European Commission, Brussels Requirements for facilities and acceptance criteria for the disposal of metallic mercury 07.0307/2009/530302 Final report 16 April 2010 BiPRO Beratungsgesellschaft für integrierte Problemlösungen DISCLAIMER: This document is distributed as prepared by BiPRO GmbH, and is the result of the scientific work carried out by its authors. Any subjective information contained therein should be perceived as expressing the views of its authors rather than those of the European Commission.
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European Commission, Brussels
Requirements for facilities and acceptance criteria for the disposal of metallic mercury
07.0307/2009/530302
Final report
16 April 2010
BiPRO Beratungsgesellschaft für integrierte Problemlösungen
DISCLAIMER:
This document is distributed as prepared by BiPRO GmbH, and is the result of the scientific work carried out by its authors. Any subjective information contained therein should be perceived as expressing the views of its authors rather than those of the European Commission.
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Content
1 Background and objectives ..................................................................................12
1.1 General background.................................................................................................12
2.2 Detailed methodology for the identification of options and the review of the state of the art; approach for information gathering..................................................25
2.2.1 Overview of information gathering............................................................................25
2.2.2 Literature search ......................................................................................................25
2.2.4 Expert interviews and site visits................................................................................28
2.2.5 Data base search .....................................................................................................29
2.3 Detailed description of the screening analysis and the selection of options including the elaboration of basic acceptance criteria ..............................................31
2.4 Detailed description of the assessment methodology including the elaboration of fine tuned acceptance criteria and the recommendation list ................................34
7 Review of immobilization, solidification and other appropriate technologies for metallic mercury waste...........................................................167
8 Screening analysis of options.............................................................................211
8.1 Identification of minimum requirements for storage options ...................................212
8.2 Feasibility of options...............................................................................................214
8.3 Acceptance criteria for metallic mercury and appropriate containment, procedure for the acceptance at the storage facility...............................................215
8.3.1 Acceptance criteria for metallic mercury.................................................................215
8.6 Option 3l: permanent storage of liquid mercury in deep underground hard rock formations...............................................................................................................232
8.7 Option 4l: temporary storage of liquid mercury in deep underground hard rock formations...............................................................................................................234
9 Summary of acceptance criteria and additional facility related requirements.........................................................................................................263
9.1 Proposed acceptance criteria for metallic mercury and additional facility related requirements ..............................................................................................264
9.2 Proposed acceptance criteria for stabilized mercury and additional facility related requirements ..............................................................................................268
10 Assessment of options........................................................................................269
10.1 Economic assessment of the options.....................................................................270
10.2 Environmental assessment of the options..............................................................274
10.3 Overview on the result of the assessment..............................................................279
11 Conclusions and Recommendations .................................................................280
12.2 Annex 2: Literature overview..................................................................................285
12.3 Annex 3: Data base research - results ...................................................................304
12.4 Annex 4: Physico-chemical properties of metallic mercury and products resulting from different immobilisation technologies...............................................313
12.5 Annex 5: Summary of technologies available in large-scale application ................315
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Index of tables
Table 1-1: Sources of mercury supply in 2005 [UNEP 2006]...........................................13
Table 1-2: EU mercury consumption estimates in 2007 (tonnes) [MEMO 08-808_EN] ..........................................................................................................13
Table 1-3: Overview of chlor-alkali plants still using mercury, September 2009 (source: Euro Chlor)........................................................................................14
Table 1-4: Estimated amount of excess mercury that has to be safely stored.................18
Table 2-1: Overview of important studies relevant for the project ....................................26
Table 4-1: Solubility of Hg and Hg compounds in water ..................................................43
Table 4-2: Change of solubility (in ppm) against the temperature [Mersade 2007A] .......47
Table 4-3: Risk phrases and classification of mercury .....................................................49
Table 4-4: Hazard class, category codes and hazard statement codes of mercury.........49
Table 4-5: Environmental Quality Standards (EQS) set for mercury in Directive 2008/105/EC ...................................................................................................56
Table 5-1: Requirements for all types of mercury storage facilities according to Directive N° EC 1102/2008 .............................................................................69
Table 5-2: General requirements for all classes of landfills according to Directive 1999/31/EC, Annex I .......................................................................................71
Table 5-3: Control and monitoring procedures for all classes of landfills according to Directive 1999/31/EC, Annex III ......................................................................73
Table 5-4: Control and monitoring procedures for all classes of landfills according to Directive 1999/31/EC, Annex III ......................................................................74
Table 5-5: Procedures for the acceptance of waste according to Decision 2003/33/EC, Annex .........................................................................................75
Table 5-6: Mercury leaching limit values for different landfill types and standards according to Decision 2003/33/EC..................................................................77
Table 5-7: Requirements for above ground mercury storage according to Regulation (EC) N° 1102/2008........................................................................81
Table 5-8: Requirements for mercury storage in above-ground disposal facilities according to Directive 1996/82/EC..................................................................82
Table 5-9: Site specific risk assessment for underground disposal according to Decision 2003/33/EC, Appendix A ..................................................................85
Table 5-10: Requirements for mercury storage in salt mines according to Directive N° EC 1102/2008 ............................................................................................87
Table 5-11: Requirements for salt mines according to Decision 2003/33/EC ....................88
Table 5-12: Requirements for mercury storage in hard rock formations according to Directive N° EC 1102/2008 .............................................................................89
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Table 5-13: Requirements for deep storage in hard rocks according to Decision 2003/33/EC .....................................................................................................90
Table 5-14: Overview of Member State legislation concerning mercury and mercury-containing waste .............................................................................................91
Table 5-15: Member States mercury leaching limit values for landfills (more stringent or additional to Decision 2003/33/EC).............................................................93
Table 5-16: Requirements for deep storage in salt mines according to German legislation ........................................................................................................95
Table 6-1: Overview of literature related to the storage of liquid mercury......................115
Table 6-2: Overview of properties of salt rock................................................................118
Table 6-3: Overview of properties of crystalline rock .....................................................127
Table 6-4: Overview of properties of Argillaceous rock, Clay / claystone ......................129
Table 6-5: Summary of Estimates of Total Storage Costs (US Dollars) for 40 Years [USEPA 2007a] .............................................................................................146
Table 6-6: Tested equipment [Muñoz, 2009], presentation: Mr. Ramos ........................156
Table 7-1: Sulphur stabilization: overview of the relevant literature ...............................170
Table 7-2: Sulphur Polymer Stabilisation/Solidification: overview of the relevant literature ........................................................................................................180
Table 7-3: Amalgamation: overview of the relevant literature ........................................189
Table 7-4: Phosphate ceramic/glass stabilization: overview of the relevant literature ...192
Table 7-5: Cement solidification: overview of the relevant literature ..............................197
Table 7-6: Overview on existing pre-treatment technologies for liquid mercury.............205
Table 8-1: Summary of the assessment of used pre-treatment technologies against minimum requirements..................................................................................249
Table 8-2: Summary of the assessment of pre-treatment technologies.........................250
Table 8-3: Assessment of feasibility requirements.........................................................253
Table 8-4: Results of the evaluation of the options for storage of liquid mercury...........259
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Figure 2-1: Overview of the methodological approach ......................................................22
Figure 2-2: Overview of possible options to be assessed .................................................23
Figure 2-3: Systematic data collection...............................................................................25
Figure 3-1: Overview of options.........................................................................................38
Figure 4-1: Relative solubility of elemental mercury in different salt water concentrations (NaCl and KCl) [GRS 2008A] .................................................44
Figure 4-2: Diagram of the biogeochemical mercury cycle ...............................................55
Figure 6-1: Illustration of possible releases of mercury related to the temporary or permanent storage of mercury ......................................................................110
Figure 6-2: Protection layers for the storage of mercury .................................................112
Figure 6-3: Metallic mercury storage at the Defense National Stockpile Center (source: DNSC).............................................................................................144
Figure 6-4: Examples of standard mercury steel containers used by Mayasa (source: Mayasa) ..........................................................................................147
Figure 6-7: Packaging instruction for liquid mercury according to ADR ..........................152
Figure 7-1: Overview of immobilisation technologies for metallic mercury......................169
Figure 7-2: Leaching behaviour of stabilized waste with different Hg loads and at different pH values. .......................................................................................194
Figure 8-1: Decision scheme for the selection of suitable pre-treatment processes .......245
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List of Abbreviations:
ADR Agreement on Dangerous Goods by Road
AISI American Iron and Steel Institute
ASTM American Society for Testing and Materials
BFS Blast furnace slag
CBPC Chemically bonded phosphate ceramic
DNSC Defense National Stockpile Center
EPA Environmental protection agency
Hg-Regulation Regulation (EC) N° 1102/2008
IATA International Air Transport Association
IMO International Maritime Organisation
MERSADE Mercury Safety Deposit
MM EIS Mercury Management Environmental Impact Statement
OPC Ordinary Portland cement
RID Regulations concerning the International Transport of Dangerous Goods by Rail
RCRA Resource Conservation and Recovery Act, US
SPC Sulphur polymer cement
SPSS Sulphur polymer stabilization/solidification
TCLP Toxicity characteristic leaching procedure
UNEP United Nations Environment Programme
WAC Waste acceptance criteria
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1 Background and objectives
1.1 General background
Metallic mercury as well as most of its compounds are highly toxic to humans and the environment.
High doses can be fatal to humans, but even relatively low doses can have serious adverse health
effects, e.g. on the reproductive system.
Mercury is considered a global persistent pollutant; once entering in the environment it cannot be
broken down to any harmless form. Mercury can be found in almost all environmental
compartments, such as the atmosphere, soil or water systems all over the world. Current
environmental concentrations are a result of anthropogenic and natural sources. Mercury is the only
metallic chemical element being liquid at standard conditions of temperature and pressure. In
particular in its gaseous form mercury is transported globally via the atmosphere. Due to its bio-
accumulation through the food chain, the consumption of fish is by far the most significant source of
mercury exposure in humans.
Due to its high toxicity to humans, ecosystems and wildlife, especially if chemically converted to
methyl mercury, there is now a world-wide common effort to reduce both demand and supply of
mercury. In 2009, the UN Environment Programme Governing Council agreed to take steps towards a
comprehensive legally binding international agreement on mercury. The Council of the European
Union had already supported this approach towards an international agreement by adopting
Conclusions on the specific issue in December 2008 [EU Council 2008].
Mercury emissions
In 2005 the global atmospheric emissions of mercury from natural sources were estimated to be
400–1,300 tonnes per year from oceans and 500–1,000 tonnes per year from land. The global
atmospheric emissions of mercury from human activities were estimated in the same range between
1,220–2,900 tonnes [UNEP 2009].
The major sources of anthropogenic mercury emissions worldwide are from fossil fuel combustion
for power and heating (878 tonnes), artisanal and small-scale gold production (350 tonnes), metal
production (ferrous and non-ferrous, excluding gold) (200 tonnes), cement production (189 tonnes),
waste incineration, waste and others (125 tonnes) [UNEP 2009].
Sources of elemental mercury
At present Kyrgyzstan is the only country mining mercury for export, China’s mercury mining is for
domestic consumption only [UNEP 2009].
Before 2003 Europe was a major exporter of mercury (around 25% of the total supply) [MEMO 08-
808_EN]. The main production site in Europe was the mine in Almadén in Spain where primary
production of metallic mercury came from cinnabar extraction. In 2003 the production of virgin
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mercury in Almadén stopped and the export of mercury from Europe declined significantly. Mercury
mining in Slovenia (Idrija mine) and Italy (Monte Amiata) ceased several years ago (1995 in Slovenia
and 1976 in Italy).
Apart from primary production from cinnabar ore, mercury can also be obtained as a secondary
product along with the production of other materials e.g. zinc or tin. Nowadays, the recovery of
mercury from waste materials containing mercury e.g. thermometers, measuring devices, etc is also
a source of elemental mercury.
The estimated average global supply (and demand) of metallic mercury is around 3,000 (2008)
tonnes per year. Based on [UNEP 2006], the main sources of mercury on the global market are
summarized in the following table:
Table 1-1: Sources of mercury supply in 2005 [UNEP 2006]
Sector Mercury supply (metric tonnes) range
Primary mercury mining 1,350-1,600
By-product 450-600
Recycled mercury from chlor-alkali
wastes
90-140
Recycled mercury – others 450-520
Mercury from chlor-alkali cells
(decommissioning)
600-800
(Stocked) 0-200
Total 3,000-3,800
Use of mercury
In 2007 the demand for mercury was estimated at more than 320 t in the 27 EU Member States. The
following table gives an overview of the most important uses of metallic mercury in Europe:
Table 1-2: EU mercury consumption estimates in 2007 (tonnes) [MEMO 08-808_EN]
sector Mercury demand (metric tonnes) range
Chlor-alkali plants 160-190
Batteries 7-25
Dental amalgam 90-110
Measuring and control equipment 7-17
Switches and electrical control 0-1
Lighting (energy-efficient lamps) 11-15
Chemicals 28-59
Other uses 15-114
Total 320-530
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In general the use of mercury is declining at both global and EU levels [EU COM 2005]. One reason is
the increased availability of mercury-free alternatives e.g. mercury-free production of chlorine or
mercury-free thermometers. On the other hand the use of mercury is increasingly being banned or
restricted by legal provisions such as restrictions for batteries (Directive 91/157/EEC1).
In Europe the most important industry related to the use of mercury is the chemical industry with its
sub-sector chlorine production. In the so called “mercury cell process” mercury is essential for the
production process of chlorine2. Currently the European chlorine industry – represented by Euro
Chlor, the European association of the chlor-alkali industry – has an agreement with the state-owned
Miñas de Almadén and y Arrayanes (MAYASA) in Spain. According to the agreement MAYASA
receives all excess mercury from western European chlorine producers and places it on the market
instead of virgin mercury. As a consequence MAYASA ceased mercury mining in 2003.
Phase out of mercury
The European chlorine industry committed itself to voluntarily phasing out the mercury-based
chlorine plants or conversion to non-mercury technologies (e.g. membrane technology) by 2020. As a
consequence, an amount of around 8,000-9,000 t of metallic mercury is expected to arise from the
decommissioned plants of the chlor-alkali industry within the next decade [Euro Chlor 2009].
Table 1-3: Overview of chlor-alkali plants still using mercury, September 2009 (source: Euro Chlor)
Country N° of plants Country N° of plants
Belgium 3 Poland 1
Czech Rep. 2 Romania 1
Finland 1 Slovak Rep. 1
France 6 Spain 7
Germany 4* Sweden 1
Greece 1 Switzerland 1
Hungary 1 UK 1
Italy 2 TOTAL 33
* In Germany, a total of 6 plants use mercury cell technology; however 2 plants are excepted from the voluntary phase out as they are not
chlor-alkali plants and have a different product range.
The ongoing substitution process of mercury in products and in particular the decommissioning of
1 Council Directive 91/157/EEC of 18 March 1991 on batteries and accumulators containing certain dangerous
substances, OJ L 078, 26.3.91 2 http://www.eurochlor.org/makingchlorine
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mercury cell plants has led to a situation in which increasing amounts of mercury are available on the
market. Therefore efforts have to be made to phase out surplus mercury; withdraw it from
circulation and find solutions for a permanent and safe final storage.
1.2 Legal background
Community Mercury Strategy
On 28 January 2005 the “Community Strategy Concerning Mercury” [EU COM 2005] was published
formulating the key objective to reduce mercury levels in the environment and human exposure as
mercury poses a threat within the Community and globally. The “mercury strategy” lists 20 actions
which should support the overall objectives. Among others, the following two actions have been
included in this strategy:
Action 5: As a pro-active contribution to a proposed globally organised effort to phase out primary
production of mercury and to stop surpluses re-entering the market as described in section 10, the
Commission intends to propose an amendment to Regulation (EC) No. 304/2003 to phase out the
export of mercury from the Community by 2011.
Action 9: The Commission will take action to pursue the storage of mercury from the chlor-alkali
industry, according to a timetable consistent with the intended phase out of mercury exports by 2011.
In the first instance the Commission will explore the scope for an agreement with the industry.
Mercury Regulation
To implement the above stated actions, the Council and European Parliament adopted on 22.10.2008
the Regulation on the banning of exports and the safe storage of metallic mercury (Regulation (EC)
No 1102/2008, OJ L304 of 14/11/08, p.75).
The export ban starts on 15 March 2011 and affects metallic mercury, cinnabar ore, mercury (I)
chloride, mercury (II) oxide and mixtures of metallic mercury with other substances including alloys
of mercury, with a concentration of at least 95 wt % Hg.
Furthermore, the Regulation lays down that from 15 March 2011 metallic mercury from the
following sources should be considered as waste (Article 2, Regulation (EC) No 1102/2008):
• Metallic mercury that is no longer used in the chlor-alkali industry
• Metallic mercury gained from the cleaning of natural gas
• Metallic mercury gained from non-ferrous mining and smelting operations
• Metallic mercury extracted from cinnabar ore in the Community as from 15 March 2011
In order to provide for possibilities of a safe storage of the above mentioned metallic mercury waste
within the Community, Article 3 of Regulation (EC) No 1102/2008 constitutes suitable options both
for permanent and temporary storage in appropriate containments (by derogation from Article 5
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(3)(a) of Directive 1999/313):
• temporary storage for more than one year or permanent storage in
o salt mines adapted for the disposal of metallic mercury, or
o in deep underground, hard rock formations providing a level of safety and
confinement equivalent to that of those salt mines; or
• temporary storage for more than one year in above-ground facilities dedicated to and
equipped for the temporary storage of metallic mercury (In this case, the criteria set out in
section 2.4 of the Annex to Decision 2003/33/EC4 shall not apply).
Article 3 (1) also sets out that all other provisions (except Article 5 (3)(a)) of Directive 1999/31/EC and
Decision 2003/33/EC shall apply to the above described storage options for liquid mercury. In
addition, in case of a temporary above ground storage Directive 96/82/EC5 (Seveso Directive, see also
chapter 5) applies to the storage facility and the corresponding requirements (e.g. establishment of a
safety management system) have to be fulfilled.
Article 4 of Regulation (EC) No 1102/2008 stipulates that the safety assessment which is required for
a safe underground storage under Decision 2003/33/EC should be complemented by specific
requirements to address the particular risks specific to the storage of metallic mercury. Furthermore,
acceptance criteria should be developed for metallic mercury either temporarily or permanently
stored in appropriate underground or above-ground facilities.
3 Council directive 1999/31/EC of 26 April 1999 on the landfill of waste (OJ L14, 20.1.2009, p.10) 4 Council Decision of 19 December 2002 establishing criteria and procedures for the acceptance of waste at
landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC 5 Council Directive 96/82/EC of 9 December 1996 on the control of major-accident hazards involving dangerous
substances (OJ L 10, 14.1.1997, p. 13–33) as amended by Directive 2003/105/EC; also referred to as the ‘Seveso II Directive’.
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Figure 1-1: Legal background
Against this background the Commission is requested, in order to ensure the proper application and
enforcement of the Regulation (EC) No 1102/2008, to propose requirements for the three specific
types of storage facilities (salt mine, hard rock, above ground) as well as acceptance criteria for
metallic mercury going to such facilities by amending annexes I, II and III of Directive 1999/31/EC.
Consequences of the Regulation
As a consequence of the Regulation large amounts of metallic mercury – which are currently
considered as raw material – will become waste, and adequate safe storage or disposal options have
to be identified. The following amounts of metallic mercury are expected to be stored/disposed of in
the next few years:
Regulation 1102/2008
- Export ban of metallic mercury
- Metallic mercury from specific sources has to be considered as waste
Underground storage permanent or temporary (>1 year)
Above-ground storage temporary (>1 year)
Amending of Annex I, II, III of Directive 1999/31/EC
Annex I: General requirements for all classes of landfills
Annex II: Waste acceptance criteria and procedures
Annex III: Control and Monitoring procedures in operation and after-care phase
Decision 2003/33/EC+
Derogation from Article 5(3)(a) of Directive 1999/31/EC
- Criteria for above ground storage - Criteria for underground storage - Site specific safety assessment (Annex A)
Definition of requirements for storage facilities and acceptance criteria for metallic mercury
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Table 1-4: Estimated amount of excess mercury that has to be safely stored
Activity Estimated amount of excess mercury which has
to be safely stored
Metallic mercury that is no longer used in the
chlor-alkali industry
~8,000 t – 9,000 t (~ 700 m³) by 2020 [Euro Chlor
2009]
Metallic mercury gained from the cleaning of
natural gas
~26t/a [Concorde 2006]
Metallic mercury gained from non-ferrous
smelting operations
~53t/a [Concorde 2006]
Metallic mercury extracted from cinnabar ore
in the Community as from 15 March 2011
No mining activities currently or anticipated
[COWI 2008] estimates that quantities of mercury in non-ferrous ores and in natural gas gives a total
of 350-410 tonnes of mercury per year potentially recoverable as a by-product from these sources, of
which 65-90 tonnes are already being recovered.
A possible extension of storage obligation to metallic mercury from other sources will be based on
the outcome of an information exchange organized by the Commission (Article 8 of the Mercury
Regulation).
In December 2008 Euro Chlor announced a voluntary agreement to ensure the safe storage of
surplus mercury from the European chlor-alkali industry, once a ban on mercury exports from the
European Union takes effect in 2011. This voluntary commitment was formally acknowledged by an
EC Recommendation on 22 December 2008 (C (2008) 8422).
According to the Regulation, no final disposal operations for metallic mercury should be permitted
until the special requirements and acceptance criteria for the storage or disposal of metallic mercury
are adopted.
1.3 Objectives of the project
The overall objective of the study is to provide the Commission with a solid knowledge base for
fulfilling the tasks resulting from Article 4 (3) of the Regulation (EC) N° 1102/2008. The Regulation
requires that for the storage options as defined in Article 3(1)(a) and (b) requirements for the
different types of storage facilities as well as acceptance criteria for metallic mercury going to such
facilities are established by amending the annexes I, II and III of Directive 1999/31/EC.
The study will provide:
• an overview of treatment techniques for metallic mercury before storage (solidification and
others), assessing the stage of development already reached (concept, laboratory phase,
pilot phase or proven large-scale application; costs),
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• an overview of feasible storage options (permanent or temporary) for metallic mercury as
well as treated (solidified/stabilized) mercury
Based on the outcome of the overview
• a set of draft requirements and draft acceptance criteria for metallic mercury
• a set of draft requirements and draft acceptance criteria for stabilized mercury
will be elaborated for the different types of permanent and temporary storage.
For the elaboration of these draft requirements and acceptance criteria the following principles – as
stated in the Mercury Regulation – will be taken into consideration:
• The storage conditions in a salt mine or in deep underground, hard rock formations, adapted
for the disposal of metallic mercury, should notably meet the principles of
o protection of groundwater against mercury
o prevention of vapour emissions of mercury
o impermeability to gas and liquids of the surroundings and
o in case of permanent storage — of firmly encapsulating the wastes at the end of the
mines' deformation process.
• The safety assessment required for underground storage under Decision 2003/33/EC will be
complemented by specific requirements and will be made applicable to non-underground
storage to ensure storage that is safe for human health and the environment.
• The above-ground storage conditions should notably meet
o the principles of reversibility of storage,
o protection of mercury against meteoric water,
o impermeability towards soils and
o prevention of vapour emissions of mercury.
• The above-ground storage of metallic mercury should be considered as a temporary solution.
To achieve the overall objective, all feasible options will be assessed and compared in order to
provide the Commission with a recommendation of how to best fulfill the tasks resulting from Article
4(3) of the Regulation (EC) N° 1102/2008.
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1.4 References
[Concorde 2004] Concorde EastWest Spr., Mercury flows in Europe and the world: the impact of decommissioned chlor-alkali plants, February 2004 http://ec.europa.eu/environment/chemicals/mercury/pdf/report.pdf [Concorde 2006] Concorde EastWest Spr., Mercury flows and safe storage of surplus mercury, 2006 http://ec.europa.eu/environment/chemicals/mercury/pdf/hg_flows_safe_storage.pdf [Concorde 2009] Concorde sprl, Assessment of excess mercury in Asia, 2010-2050, May 2009 http://www.chem.unep.ch/mercury/storage/Asian%20Hg%20storage_ZMWG%20Final_26May2009.pdf [COWI 2007] COWI, Follow-up study on the implementation of Directive 1999/31/EC on, June 2007 the landfill of waste in EU-25, Final Report - Findings of the Study http://web.rec.org/documents/ECENA/training_programmes/2008_06_budapest/session1/7-implementation_eu_25_2007_cowi_report.pdf [COWI 2008] COWI A/S and Concorde East/West Sprl, Options for reducing mercury use in products and applications, and the fate of mercury already circulating in society, December 2008 http://ec.europa.eu/environment/chemicals/mercury/pdf/study_report2008.pdf [EIA EU 2005] Communication from the Commission to the Council and the European Parliament on Community Strategy Concerning Mercury, EXTENDED IMPACT ASSESSMENT, 2005 http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=COM:2005:0020:FIN:EN:PDF [EU COM 2001] European Commission, Integrated Pollution Prevention and Control (IPPC) - Reference Document on Best Available Techniques in the Chlor-Alkali Manufacturing industry -, http://ec.europa.eu/comm/environment/ippc/brefs/cak_bref_1201.pdf [EU COM 2002] Report from the Commission to the Council concerning mercury from the Chlor-alkali industry, COM (2002) 489 final, http://eur-lex.europa.eu/smartapi/cgi/sga_doc?smartapi!celexplus!prod!DocNumber&lg=en&type_doc=COMfinal&an_doc=2002&nu_doc=489 [EU COM 2005] Communication from the Commission to the Council and the European Parliament,
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Community Strategy Concerning Mercury, COM (2005) 20 final, 28 January 2005, Brussels http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=COM:2005:0020:FIN:EN:PDF [EU COM 2005A] Commission staff working paper, Annex to the Communication from the Commission to the Council and the European Parliament, Community Strategy Concerning Mercury, Extended Impact Assessment, SEC(2005) 101, 28 January 2005, Brussels, http://ec.europa.eu/environment/chemicals/mercury/pdf/extended_impact_assessment.pdf [EU COM 2006] European Commission, Report on the International Mercury Conference - How to reduce mercury supply and demand, Brussels 26-27 October 2006, 2006 http://ec.europa.eu/environment/chemicals/mercury/conference.htm [EU COM 2006A] European Commission, Integrated Pollution Prevention and Control Reference Document on Best Available Techniques for the Waste Treatments Industries, August 2006 ftp://ftp.jrc.es/pub/eippcb/doc/wt_bref_0806.pdf [MEMO-08-808_EN] Questions & Answers on the EU Mercury Strategy, MEMO/08/808 Brussels, 22 December 2008 http://europa.eu/rapid/pressReleasesAction.do?reference=MEMO/08/808&format=HTML&aged=0&language=EN&guiLanguage=en [UNEP 2007] Draft technical guidelines on the environmentally sound management of mercury wastes, 2007, http://www.basel.int/techmatters/mercury/guidelines/240707.pdf [UNEP 2009] UNEP, Draft technical guidelines on the environmentally sound management of mercury wastes, 4th Draft, April 2009, http://www.basel.int/techmatters/mercury/guidelines/040409.doc
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2 Methodology
2.1 Overall methodological approach
Against the described background and objectives, the methodological approach of the project is visualized in the following figure: Figure 2-1: Overview of the methodological approach
For the first step of this methodology (Identification of options against the legal background) a
review of the existing pre-treatment technologies, disposal facilities for temporary and permanent
storage and of different types of containment has been carried out. With regard to disposal facilities,
apart from existing hazardous waste landfills (above ground and underground), experience from
radioactive waste disposal is also included in the review. An overview of the current status of
knowledge explains the hazardous properties and characteristics of metallic mercury with a special
focus on its behaviour in the environment. An overview of existing legal requirements, policies and
best practice related to the disposal of mercury waste in Europe as well as on an international level is
provided. With this investigation a “pool” of options is generated. The various options of the pool can
also be combined (e.g. temporary storage + pre-treatment + permanent storage) and in this way
form a broad basis for all potential solutions related to the problem of the disposal of liquid mercury.
The objective of this initial work is to acquire a current and updated status on the scientific and
technical knowledge related to the storage or disposal of mercury. The results provide various
options that all comply with the legal requirements. This outcome can be roughly characterized as
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follows and forms the basis for the further assessments, identification of necessary acceptance
criteria and combinations of options (see steps 2 and 3 of the overall methodology, Figure 2-1).
Figure 2-2: Overview of possible options to be assessed
Data and information sources for step 1 have been:
• extensive literature research
• patent analyses
• expert interviews
• site visits
• questionnaire survey
All these information sources have been used by the project team to generate the pool of options
(for more details see section 2.2.1).
Metallic mercury waste
Pre-treatment options
No pre-treatment
Options: underground storage in salt mines
Options: storage in deep underground, hard rock
formations
Options: above ground storage
Various storage possibilities according to
Directive 1999/31/EC
Solidified mercury (non metallic mercury)
Permanent Temporary Permanent Temporary Temporary
Under-ground
Above ground
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The second step of the methodology foresees a screening analysis (see Figure 2-1). One target of this
screening analysis is to exclude options from further investigation if there is no reasonable possibility
to realize them in compliance with minimum technical, environmental and economic criteria. A
second target of this step is to identify basic acceptance criteria that need to be linked to the options
(or to combinations of options) to fulfill the minimum criteria. Within the screening analysis, the
feasibility of options related to their implementation under time constraints and required resources
for realization are also investigated. The screening analysis results in a short list of feasible options
which will be further assessed.
Option Currently feasibly
I Permanent storage of liquid mercury in salt rock No / YES / ?
II Permanent storage of liquid mercury in deep underground hard
rock formations
No / YES /?
III …
For further details see section 2.3.
The third step of the methodology covers the assessment of options or combinations of options (and
corresponding acceptance criteria) that remain after the screening analysis on a short list.
Environmental and economic targets will be used to basically evaluate the options within the
assessment. After the basic evaluation, potential combinations of options and fine tuning of
corresponding acceptance criteria take place and the evaluation is repeated for a final overview on
the appropriateness of options which then found their way to the list of recommendations. Options
that are best in all or in selected criteria then find their way into the list of recommendations. The list
of recommendations will also cover the required amendments of annexes I, II and III of Directive
1999/31/EC.
The findings of the study were presented in a workshop in November 2009 and discussed with
interested stakeholders. All received comments were taken into consideration for this report.
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2.2 Detailed methodology for the identification of options and the review of the state of the art; approach for information gathering
2.2.1 Overview of information gathering
The review of the state of the art and state of the development is based on information provided by
the relevant experts on relevant studies and other systematically identified documents or
publications.
Figure 2-3: Systematic data collection
All options that could be identified with these information sources have been collected and
characterized in a “pool of options”. The results are documented in chapters 3, 4, 5 and 7 of this
report.
2.2.2 Literature search
At the beginning of the study an intensive literature search was carried out to identify relevant
information. Studies already carried out on the topic of the disposal and storage of metallic mercury
have been investigated in detail and the bibliographic references thereof were evaluated in order to
Questionnaire; expert interviews, site visits
Data base search
MS and international authorities
Industrial and scientific experts
NGOs
Patent data bases
Scientific data bases
- Environmental data bases - Technical data bases - Health data bases
Systematic data collection
Literature search
Review of important studies
Web search
Libraries
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identify further relevant literature sources and contact details of relevant experts. The following
studies provided an important input to the project:
Table 2-1: Overview of important studies relevant for the project
Reference Short description of the content
[Env Canada 2001]
National Office of Pollution prevention,
Environment Canada, The Development of
retirement and long term storage options of
mercury, Draft final report, Ontario, June 2001
Environmental Canada has published a draft report
(prepared by the Consultants SENSE) on the
development of retirement and long-term storage
options for mercury. The study evaluated 67
technologies – including disposal options in mines –
using the Kepner-Tregoe ranking technique and
reviewed a further 9 technologies but did not rank
them because there was insufficient information.
[Env Canada 2004]
Environment Canada, Mercury and the
environment, Internet document:
http://www.ec.gc.ca/MERCURY/EH/EN/eh-
i.cfm, last update 2004-02-04, accessed on 29
June 2009
This homepage provides an overview of the current
state of knowledge related to the properties of
liquid mercury.
[DNSC 2004B]
Defense National Stockpile Center, Final
Mercury Management Environmental Impact
Statement, Volume I, 2004
The Defense Logistics Agency (DLA), USA, prepared
a Mercury Management Environmental Impact
Statement (MMEIS). In 2003/2004 a Mercury
Management Environmental Impact Assessment
(MM EIS) was carried out to find the most
appropriate way of how to deal with the stored
mercury in future.
[SOU 2008A]
Statens offentliga Utredningar (SOU) 2008: 19:
Att slutförvara långlivat farligt avfall i
undermarksdeponi i berg – Permanent storage
of long-lived hazardous waste in underground
deep bedrock depositories, SOU 2008: 10 April
2008
This study – commissioned by the Swedish
government –analysed the permanent storage of
mercury in deep bedrock and salt mines. The
report provides an account of permanent storage
options for mercury-containing waste, and the
requirements and risks attendant to the permanent
storage of liquid mercury.
A summary on the key findings of the study is
available in English [SOU 2008]
[UNEP 2009]
UNEP, Draft technical guidelines on the
environmentally sound management of
These draft technical guidelines provide a broad
overview of the current state of knowledge related
to the properties of mercury and its compounds, its
behaviour in the environment but also information
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Apart from the above-mentioned studies, the world wide web has also been used for individual
searches for specific information by using specific key word combinations according to individual
search purposes. The identified documents have been evaluated related to their relevance and an
evaluation of the bibliographic references was carried out to identify further documents.
2.2.3 Questionnaire
Relevant experts of Member States authorities as well as non-EU country authorities, industrial and
scientific experts and international NGOs dealing with this topic were contacted within the scope of a
questionnaire survey in June 2009 (for a list of contacted experts, see separate excel file6). The
experts were asked to provide information on relevant research / scientific activities related to pre-
treatment techniques and disposal options of metallic mercury waste as well as on relevant contact
persons.
6 A separate excel file including the contacted institutions and experts has been provided to the European
Commission. Due to reasons of confidentiality, this list is not included as an annex to this report.
mercury wastes, 4th Draft, April 2009 on the storage of liquid mercury.
[USEPA 2002c]
Preliminary analysis of alternatives for the long
term management of excess mercury,
EPA/600/R-03/048 AUGUST 2002
This study describes a systematic method for
comparing options for the long-term management
of surplus elemental mercury in the US, using the
analytic hierarchy process. A limited scope multi-
criteria decision analysis was performed. Alternatives were evaluated against criteria that
included costs, environmental performance,
compliance with current regulations,
implementation considerations, technology
maturity, potential risks to the public and workers,
and public perception.
[DOE 2009]
U.S. Department of Energy, Interim Guidance
on Packaging, Transportation, Receipt,
Management, and Long-Term Storage of
Elemental Mercury, U.S. Department of Energy
Office of Environmental Management
Washington, D.C., November 13, 2009
This document is intended to provide general
guidance on standards and illustrative procedures
that are current, consistent, and best suited for
supporting the DOE program for the receipt,
management, and long-term storage of mercury
generated in the United States. As such, this
interim guidance provides a framework for the
standards and procedures associated with a DOE-
designated elemental mercury storage facility with
a focus on the RCRA permitting of such a facility
and planning for that storage facility’s needs.
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In total, the questionnaire (see Annex 1) was sent to 43 institutions. In total 26 questionnaires have
been sent back. The feedback on the questionnaire was quite diverse and it varied from very
extensive answers including links, documents and experts for further investigations, to very short
answers due to lack of information or no relevance of the topic.
2.2.4 Expert interviews and site visits
Received information was evaluated with respect to its content. Key persons were contacted with
the intention of obtaining specific additional information. In this way the most relevant information
sources could be systematically identified and an information exchange with selected experts was
initiated.
Expert interviews were carried out with various concerned stakeholders such as
• Treatment technology providers / developers
• Operators of underground disposal facilities
• Operators of above ground storage facilities (not landfills) for liquid mercury
• Member States’ experts on landfill and mercury
• European Associations (e.g. Euro Chlor)
In addition, site visits at an underground disposal site and treatment technology provider took place
to receive more detailed information on the disposal process and treatment technology.
This approach turned out to be the most efficient way of targeted data collection. It was additionally
supplemented by a systematic literature search in selected data bases.
Another valuable input for the project was a workshop initiated by IKIMP7. The workshop “Safe
storage and disposal of redundant mercury” (13 & 14 October, 2009) offered a good platform for
information exchange and discussion of technologies and storage options with experts.
7 IKIMP: Integrating Knowledge to Inform Mercury Policy, http://www.mercurynetwork.org.uk/
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These data bases have been systematically searched for relevant literature by using appropriate key
words (e.g. mercury, stabilization) and key word combinations (see Annex 3). Search results were
screened for their relevance for the project objectives. Relevant studies were evaluated with respect
to their content and their bibliographic references. Selected authors of key studies have been
contacted with the intention of obtaining specific additional information. The identified documents
have been evaluated based on the available abstracts.
At the end of each section the section specific references are listed. Annex 2 includes a compilation
of all identified relevant literature for this study.
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2.3 Detailed description of the screening analysis and the selection of options including the elaboration of basic acceptance criteria
The following flow chart describes the methodology for the first phase of the screening analysis:
Pool of options resulting from step 1
Acceptance criteria to be combined with
options
Technical minimum
requirements
Options that have to be excluded as they do not fulfill the minimum requirements/ acceptance criteria
Options + acceptance criteria for further investigation
Acceptance criteria to be combined with
options
Environmental minimum
requirements
Options that have to be excluded as they do not fulfill the minimum requirements/ acceptance criteria
Options + acceptance criteria for further investigation
Acceptance criteria to be combined with
options
Economic minimum
requirements
Options that have to be excluded as they do not fulfill the minimum requirements/ acceptance criteria
Options + acceptance criteria for further investigation
Candidates (options + corresponding acceptance criteria) for further
investigation
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In the first step, technical minimum requirements are established that are basically justified by the
requirements for safe and sustainable solutions.
Examples of such minimum requirements are:
- Protection of groundwater against mercury in cases of permanent underground storage
- Impermeability to gas and liquids of the surroundings (permanent underground storage)
- Large scale application or pilot plant available (applicable for pre-treatment technologies)
In relation to an option, these criteria find themselves translated into facility related requirements
and acceptance criteria for the waste, which need to be fulfilled to make the option a real solution.
Facility related requirements directly address the disposal facility or the pre-treatment technology,
such as
• Effectiveness of the geological barrier in terms of migration time for mercury to the
biosphere (permanent storage) >1 million years
• Installation of a permanent mercury vapour monitoring system
Acceptance criteria directly address the waste and its properties, the waste container or the handling
of the waste, such as
• Acceptance only of certified containers
• Purity of the mercury to be accepted: >99.9% per weight
If the defined additional acceptance criteria cannot be fulfilled by an option, the corresponding
option has to be excluded from further investigations.
The same procedure as described for the minimum technical criteria is carried out for minimum
environmental/health and minimum economic criteria. Environmental and health related minimum
criteria are for example the compliance with existing occupational exposure limits. A corresponding
facility related requirement might be the installation of a permanent monitoring system with a
certain level of sensitivity.
The following flow chart describes the methodology for the second phase of the screening analysis.
For this second phase, only options and combinations of options are considered that have not been
excluded in the first phase:
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The first criterion that is checked concerns the feasibility under the given framework of time. Feasible
solutions need to be available – together with fulfilled acceptance criteria – at the latest by 15 March
2011 for large scale applications. If options for permanent solutions cannot fulfill this feasibility
criterion they need to be combined with temporary storage options to bridge the period up to the
implementation of the option.
The second criterion covers the costs that are required to enable a large scale application. Currently,
there are some uncertainties on the quantities of liquid mercury that need to be disposed of in the
years after 2011. Feasibility under economic conditions is granted, if – with reasonable costs – a
flexibility related to the required annual capacity is provided.
Candidates as outcome of first phase of screening analysis
Option not regarded as feasible
Feasibility related to time frame
requirements for large scale
implementation
OK
Option not regarded as feasible
Feasibility related to costs required
for large scale implementation
failed
failed
OK
Feasible option + acceptance criteria for
comparative assessment
Pool of options resulting from step 1
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2.4 Detailed description of the assessment methodology including the elaboration of fine tuned acceptance criteria and the recommendation list
The screening analysis was followed by an assessment of remaining options or combinations of
options on their strengths and weaknesses. Within this assessment environmental and economic
targets have been used to basically evaluate the options. After the basic evaluation, potential
combinations of options and fine tuning of corresponding acceptance criteria took place and the
evaluation was repeated for a final overview on the appropriateness of options which then found
their way to the list of recommendations.
If an option or a combination of options fulfills all acceptance criteria, in principle it can be chosen by
industry. So the question might come up why an assessment and a following recommendation list
are necessary at all.
The answer on such questions and correspondingly the justification of the final assessment is to offer
industry an information and decision basis where they can see the advantages of options under
different criteria. This might lead to a preference of solutions that provide environmental advantages
against other options with equal costs. Also a preference might be generated for less expensive
solutions with the same level of environmental safeness.
For the assessment direct environmental and economic target criteria are set up such as:
• Hg-Emissions and corresponding risks for human health or the environment
• Risk for accidents or handling problems
• Overall costs
• Required investment costs
• Costs of temporary storage of liquid mercury prior to treatment
The final result is then summarized in the recommendation list including a written justification.
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2.5 References
[DNSC 2004B] Defense National Stockpile Center, Final Mercury Management Environmental Impact Statement, Volume I, 2004 [DOE 2009] U.S. Department of Energy, Interim Guidance on Packaging, Transportation, Receipt, Management, and Long-Term Storage of Elemental Mercury, U.S. Department of Energy Office of Environmental Management Washington, D.C., November 13, 2009, http://www.em.doe.gov/pdfs/Elementalmercurystorage%20Interim%20Guidance_11_13_2009.pdf [Env Canada 2001] National Office of Pollution prevention, Environment Canada, The Development of retirement and long term storage options of mercury, Draft final report, Ontario, June 2001 [Env Canada 2004] Environment Canada, Mercury and the environment, Internet document: http://www.ec.gc.ca/MERCURY/EH/EN/eh-i.cfm, last update 2004-02-04, accessed on 29 June 2009 [SOU 2008A] Miljödepartementet, Att slutförvara långlivat farligt avfall i undermarksdeponi i berg, ISBN 978-91-38-22922-4, 2008 [UNEP 2009] UNEP, Draft technical guidelines on the environmentally sound management of mercury wastes, 4th Draft, April 2009, http://www.basel.int/techmatters/mercury/guidelines/040409.doc [USEPA 2002c] Hugh W. McKinnon, Preliminary analysis of alternatives for the long term management of excess mercury, EPA/600/R-03/048, 2002, http://www.epa.gov/nrmrl/pubs/600r03048/600R03048.pdf
While pure mercury sulphide has a significantly lower solubility compared to elemental mercury, the
presence of HgO or HgCl2 – which might be due to impurities (< 1%) in mercury sulphide – increases
the solubility of HgS.
In 2003 a laboratory study was conducted [Sakar 2003] to investigate the solubility of mercury in the
presence of amphoteric oxides of iron, an electron acceptor. Investigations were performed with and
without chloride in solution, a rather ubiquitous component of mercury wastes. Mercury solubility
decreased in the presence of iron oxides, suggesting adsorption of mercury ions at the oxide-water
interface. There was indirect evidence of formation of ionic mercury due to oxidation of elemental
mercury in the presence of free iron in solution. Mercury solubility generally increased in the
presence of chloride in solution because of the formation of weakly adsorbing mercury-chloro
complexes.
Information related to the influence of salt and salt solutions to solubility of mercury is very limited.
In the presentation [GRS 2008A], first results have been presented on solubility of mercury at
different concentrations of NaCl and KCl. It can be seen that the solubility of mercury in pure water is
0.3 µmol/l, whereas in a saturated NaCl (~6mol/l) solution the solubility is reduced to 0.16 µmol/l.
This relationship is nearly linear but flattens with increasing NaCl concentrations. In the case of KCl,
fewer solubility values are available (5 different concentrations) at lower concentration levels (< 1
mol/l), but it can be predicted that the Hg solubility in KCl solutions is similar to that in NaCl
solutions. Some salts have a reverse effect on the solubility of mercury. NaSCN and (CH3)4NBr for
example are salts which increase the solubility of mercury with increasing salt concentration.
The solubility of pure mercury in salt solutions is illustrated in the diagram below.
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Figure 4-1: Relative solubility of elemental mercury in different salt water concentrations (NaCl and KCl) [GRS 2008A]
These data coincide with the results of other studies such as “Effects of salts on the solubility of
elemental mercury in water” [Sanemasa 1981] and “The solubility of elemental mercury vapor in
water” [Sanemasa 1975]. The main result of the studies is that there is a linear decrease – at least
until a 1 molar solution is reached – of the solubility of mercury in saturated potassium or sodium
solutions. The solubility is significantly lower (half) compared to distilled water. Tests have also been
made to demonstrate the temperature dependency of mercury vapour in pure water and sea water.
It can be seen that the solubility increases exponentially with the temperature starting with
0.1 µmol/l (19.2 µg/l) at 5°C and up to 9 µmol/l (1,800 µg/l) at 100°C. The solubility in sea water is
about 20% less than that in pure water [Sanemasa 1975].
Solubility product ((mol/l)n)
With the mean value of the solubility product (Ksp), it is possible to determine the dissolved
concentration of a solid’s constituents in solution assuming it has reached equilibrium. The solubility
product constant is the simplified equilibrium constant (Ksp) defined for equilibrium between a solid
and its respective ions in a solution. Its value indicates the degree to which a compound dissociates
in water. The higher the solubility product constant, the more soluble is the compound.
As elemental mercury only consists of one element, the solubility product is not relevant. But in the
case of pre-treatment to immobilize or solidify mercury, the solubility product of the resulting solid
form is important. The solubility products of relevant pre-treated mercury compounds (e.g. HgS) are
included in Annex 4.
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Leachability (mg/l or mg/kg)
Leachability is a specific measure to assess how a pollutant that is contained in a stored material
contributes to possible groundwater contamination if water seeps into and through the stored
material. It indicates to what extent the mercury compounds are mobilised in the waste matrix and
transported out of the stored material. The leachability of waste is often used for the classification of
a waste. Depending on the leaching behaviour, the waste is allocated to different landfill categories
(WAC Decision 2003/33/EC).
The leachability is of particular interest for pre-treated (solidified) mercury. It is linked to the
conditions of the pre-treatment process and the stability and homogeneity of the solidified mercury
thus attained. Therefore general statements are not possible. Product-specific leaching values are
included in Annex 4.
Volatility (mg/kg) or vapour pressure (Pa)
Volatility is a measure indicating how easily a substance may be evaporated and mobilised from a
stored material and transported via an atmospheric pathway.
Mercury has a relatively high vapour pressure of 0.3 Pa at 25°C [WHO 2003] and the highest volatility
of any metal. The vapour pressure increases with temperature. The vapour is colour- and odourless
and due to its high molar mass heavier than air and therefore mercury concentration is higher at
ground level.
Reactivity of mercury with other substances
Reactivity indicates under which conditions the stored substance may react and be transformed to
other substances that may be more easily mobilised and/or transported.
Mercury can be elemental, monovalent or bivalent. Monovalent bonds are always bimolecular: Hg2X2
and bivalent bonds are always monomolecular: HgX2. Mercury has a positive redox potential which
makes it noble and therefore does not tend to oxidise. [Ho Wi 1995]
A reaction with oxygen takes place above ~300°C in air and decomposes again at 400 °C. Pure
mercury does not interact with ambient air but in the case of contaminated mercury an oxide layer is
formed on the surface of the mercury [Ho Wi 1995]. Formation of HgO should be avoided due to its
higher solubility compared to elemental mercury. [GRS 2008A]
Mercury can react with halogens and more easily with sulphur but not with phosphorus, nitrate,
hydrogen or carbon. [Ho Wi 1995]
Reaction with chlorine can result in Hg2Cl2 (low water solubility) or in HgCl2 (very high water
solubility). The formation of HgCl2 should be avoided due to its very high water solubility. In general it
can be stated that Hg(I) molecules are more stable and therefore less soluble than Hg(II) molecules.
Both kinds of chlorides can be generated by sublimation. [Ho Wi 1995]
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Mercury has a very high affinity to sulphur resulting in very stable mercury(II)sulphide (HgS). This is
the reason why natural sources of mercury are mostly HgS (cinnabar) reservoirs.
Elemental mercury cannot be attacked by dilute HCl or H2SO4 solutions, and then only slowly in the
case of dilute HNO3. [Ho Wi 1995]
Mercury combines with other metals such as copper, gold, zinc, aluminium, nickel, tin, silver or
selenium and forms mercury alloys known as amalgams. Amalgams are semi-solid solutions obtained
by dissolution of mercury in the solid metal [Mersade 2007A]. Mercury destroys the passivation layer
of aluminium which normally protects aluminium from oxidation. Blank aluminium can be oxidised
again and the corrosion process is ongoing. Therefore, aluminium is not a suitable material for the
storage of mercury. [Aluminium 2004]
Iron on the other hand does not dissolve in elemental mercury and can therefore be used as
container material. [Ho Wi 1995]
Elemental mercury does not react with glass or ceramic products. An interaction of elemental
mercury with certain plastic material is possible. [Hagelberg 2006] reported an adsorption of
elemental mercury at plastic tubes.
Within the scope of the Life project MERSADE (see chapter 6.4.1.1) a literature review has been
carried out concerning corrosion problems in mercury [Mersade 2007A]. It was concluded that
literature referring to corrosion problems on metal containment used for the storage of liquid
mercury is practically nil.
In the following, the main findings of the review are described (the information is based on
[MERSADE 2007A]):
According to the document, at low temperature and static conditions, liquid metal corrosion is not an
important factor. Therefore, steel and ceramic materials are appropriate for the storage of liquid
mercury.
Plain carbon steel is virtually unattached by mercury under non flowing conditions or isothermal
conditions. Working temperatures up to 540°C are possible. The addition of Titanium (10 ppm) might
increase the operating temperatures up to 650°C, but in this case elements with a higher affinity for
oxygen than titanium, such as Na or Mg, are required to prevent oxidation of the titanium and loss of
its inhibitive action.
On the contrary, the presence of either a temperature gradient or liquid flow might lead to a drastic
attack of the containment. It is stated that the solubility of metals (e.g. iron, nickel) in mercury
increases with temperature.
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Table 4-2: Change of solubility (in ppm) against the temperature [Mersade 2007A]
260°C 538°C
Iron 0.001 0.4
Nickel 7.0 80.0
Chromium 0,02 8.2
As a consequence, low solubility of metals in mercury results in a low corrosion rate. Although the
addition of elements such as chromium, titanium, silicon and molybdenum, alone or in combination,
show high resistance up to 600°C, other alloying elements might have a contrary effect. For example,
Nickel tends to have adverse effects on iron-based and cobalt-based alloys as it tends to form
intermetallic compounds with mercury, lead and bismuth.
In addition, experiences related to the use of liquid mercury as a target for a proton beam in a
Spallation Neutron Source (SNS) facility have been included in the report. Tests have been carried out
with various alloys, flow rates and temperatures. Due to contradicting results in the corrosion
investigations, an extrapolation to static or different dynamic conditions, other temperatures or a
long-term mercury storage condition is not recommended.
Within the scope of the Mersade project, practical investigation also took place. Storage containers
and pipe systems which have been in use for several years for the storage of liquid mercury at the
storage facility at Almadén were analysed for potential attack by the stored mercury [Muñoz, 2009].
Another important information source related to potential corrosive effects of metallic mercury with
containers are the investigations carried out by the Oak Ridge National Laboratory (ORNL), USA. The
ORNL analysed storage containers which have been used for almost 40 years for the storage of
metallic mercury.
Detailed information on the outcome and conclusions of both projects are included in sections
6.4.3.1 and 6.4.3.2.
Adsorption of mercury
Ionic forms of mercury are strongly adsorbed by soils and sediments and are desorbed slowly. Clay
minerals optimally adsorb mercury ions at pH 6. Iron oxides also adsorb mercury ions in neutral soils.
Most mercury ions are adsorbed by organic matter (mainly fulvic and humic acids) in acidic soils.
When organic matter is not present, mercury becomes relatively more mobile in acid soils and can
evaporate to the atmosphere or leach to groundwater (Ref. 1.5). [US EPA 2007]
Octanol/water partition coefficient (Kow)
The octanol/water partition coefficient is a measure to indicate the hydrophobicity of a substance. It
can give an indication of how easily a compound might be taken up in groundwater to pollute
waterways. In the field of hydrogeology it is used to predict and model the migration of dissolved
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hydrophobic organic compounds in soil and groundwater. Several studies have been carried out
concerning the 1-Octanol/Water partition coefficient of mercury.
The 1-octanol/water partition coefficient of metallic mercury was measured as a useful parameter
for predicting the environmental behaviour and fate of mercury. The partition coefficient obtained
was 4.15 ± 0.20 at 298 K [Okouchi 1985] and is indirectly proportional to the temperature, having a
value of 3.80 at 35°C. Mercury is therefore a lipophile element, which has a higher solubility in
octanol instead of water. The coefficient depends on the temperature and it decreases with an
increase in temperature. The partition coefficient of metallic mercury is very low in comparison to
non-polar organic compounds such as benzene, tetrachloromethane or PCBs. Therefore, it was
concluded that metallic mercury has a tendency for further concentration in the atmosphere.
[OKOUCHI 1985]
4.1.3 Toxic effects
The severity of mercury's toxic effects depends on the form and concentration of mercury and the
route of exposure.
Exposure to elemental mercury can result in effects on the nervous system, including tremors,
memory loss and headaches. Other symptoms include bronchitis, weight loss, fatigue, gastro-
intestinal problems, gingivitis, excitability, thyroid enlargement, unstable pulse, and toxicity to the
kidneys.
Adverse effects to human health from exposure to elemental mercury are summarised in the draft
technical guidelines on the environmentally sound management of mercury wastes (see [UNEP
2009], section 1.3.2).
Exposure to inorganic mercury can affect the kidneys, causing immune-mediated kidney toxicity.
Effects may also include tremors, loss of co-ordination, slower physical and mental responses, gastric
pain, vomiting, bloody diarrhoea and gingivitis.
Adverse effects to human health from exposure to inorganic mercury compounds are summarised in
the draft technical guidelines on the environmentally sound management of mercury wastes (see
[UNEP 2009], section 1.3.3).
Symptoms of methylmercury toxicity, also known as Minamata disease, range from tingling of the
skin, numbness, lack of muscle coordination, tremors, tunnel vision, loss of hearing, slurred speech,
skin rashes, abnormal behaviour (such as fits of laughter), intellectual impairment, to cerebral palsy,
coma and death, depending on the level of exposure. In addition, methylmercury has been classified
as a possible human carcinogen by the U.S. Environmental Protection Agency. More recently,
additional findings have described adverse cardiovascular and immune system effects at very low
exposure levels.
Prenatal exposure to organic mercury, even at levels that do not appear to affect the mother, may
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depress the development of the central nervous system and may cause psychomotor retardation for
affected children. Mild neurological and developmental delays may occur in infants ingesting
methylmercury in breast milk. Affected children may exhibit reduced coordination and growth, lower
intelligence, poor hearing and verbal development, cerebral palsy and behavioural problems.
Adverse effects to human health from exposure to inorganic mercury compounds are summarised in
the draft technical guidelines on the environmentally sound management of mercury wastes (see
[UNEP 2009], section 1.3.1).
4.1.4 Classification
The classification of mercury (EC 231-106-7; CAS 7439-97-6) according to Directive 67/548/EEC15 is as
follows:
Table 4-3: Risk phrases and classification of mercury
Classification Risk phrases
Repr. Cat. 2; R61 R61: May cause harm to the unborn child.
T+; R26 R26: Very toxic by inhalation.
T; R48/23 R48/23: Toxic: danger of serious damage to health by prolonged exposure through inhalation.
N; R50-53. R50/53: Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment.
The preliminary classification of mercury according to Regulation (EC) N° 1272/200816 is as follows:
Table 4-4: Hazard class, category codes and hazard statement codes of mercury
Hazard Class and Category Code(s)
Hazard statement Code(s)
Acute Tox. 3 * H331: Toxic if inhaled
STOT RE 2 * H373: May cause damage to organs through prolonged or repeated exposure
Aquatic Acute 1 H400: Very toxic to aquatic life
Aquatic Chronic 1 H410: Very toxic to aquatic life with long lasting effects
15 Council Directive 67/548/EEC of 27 June 1967 on the approximation of laws, regulations and administrative
provisions relating to the classification, packaging and labelling of dangerous substances, OJ 196, 16.8.1967 16 Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December 2008 on
classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006 (Text with EEA relevance), OJ L 353, 31.12.2008, p. 1–1355
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4.1.5 Occupational exposure limit values
Acute exposure (>0.1 mg⋅mercury/m3) to mercury vapour causes adverse effects to human health
[UNEP 2009].
Therefore, many EU Member States implemented occupational exposure limit (OEL, eight hour
average) values for “mercury and its inorganic divalent compounds (as Hg)” ranging from 0.03 mg/m³
in Lithuania, Sweden, Slovakia to 0.1 mg/m³ in Germany [EU OSHA 2007, GESTIS 2009, TRGS 900].
Currently, Poland is the only country with an OEL (eight hour average) for metallic vapour of mercury
with a value of 0.025 mg/m³ [GESTIS 2009].
On the European level no corresponding indicative value is available but [SCOEL 2007] recommended
an 8-hour TWA of 0.02 mg mercury/m³ for “elemental mercury and inorganic divalent mercury
compounds”. A biological limit value (BLV) of 10 µg Hg/l blood and 30 µg Hg/g creatinine in urine is
also recommended by [SCOEL 2007].
The UNEP recommended health-based exposure limit value for metallic mercury is 0.025 mg⋅Hg/m³
for long-term exposure as the time weighted average (TWA). This means the time weighted average
concentration for a normal 8-hour day and 40-hour workweek, to which nearly all workers can be
repeatedly exposed without adverse effect [UNEP 2009]. However, recent studies suggest that
mercury may have no threshold below which adverse effects do not occur [UNEP 2009].
In the USA 0.1 mg/m3 is also declared as the ceiling limit value for mercury vapour (concentration
cannot exceed this value at any time) [OSHA 2009]. Threshold limit values (TLV) are available for
elemental mercury being 0.025 mg/m³ and 0.01 mg/m3 for organic mercury [US EP 2007]. Referring
to [NIOSH 2005] the Time Weighted Average (TWA) for an 8-hour day should not exceed 0.05 mg/m3.
4.2 Hazardous properties related to the environment
4.2.1 Transformation and transport of mercury
Natural transformations and environmental pathways of mercury are very complex and are greatly
affected by local conditions. The environmental fate and the impacts of anthropogenic mercury
emissions depend on a range of biogeochemical interactions affecting mercury in its various physical
states and chemical forms.
There are two main types of reactions in the mercury cycle that convert mercury through its various
forms: oxidation-reduction and methylation-demethylation. In oxidation-reduction reactions,
mercury is either oxidized to a higher valence state (e.g. from relatively inert Hg0 to the more
reactive Hg2+) or reduced (e.g. from Hg2+ to Hg0).
Most relevant environmental pathways are short or long range atmospheric transport mechanisms
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and transport in water/sediment systems (e.g. river or marine systems).
In general, the form of mercury in the environment varies with the season, with changes in organic
matter, nutrient and oxygen levels and hydrological interactions within an ecosystem. In addition,
the quantity and forms of mercury are, to a large extent, a function of emission sources and
transportation processes. All of these variables in turn affect the global mercury budget.
Mercury oxidation
The oxidation of elemental mercury (Hg0) in the atmosphere is an important mechanism involved in
the deposition of mercury on land and water. Hg0 can volatilize relatively easily and be emitted into
the atmosphere, where it may be transported on wind currents for a year or more and be re-
deposited in the environment for further cycling. In contrast, Hg2+ has an atmospheric residence time
of less than two weeks due to its solubility in water, low volatility and reactive properties. Hence,
when (Hg0) is converted to Hg2+, it can be rapidly taken up in rain water, snow, or adsorbed onto
small particles, and be subsequently deposited in the environment through "wet" or "dry" deposition
[Selin 2009].
In the Arctic, the conversion of Hg0 to Hg2+ in the atmosphere occurs very rapidly in a phenomenon
known as "mercury depletion" at the end of dark polar winters. When the sun rises in the spring,
atmospheric Hg0 is converted photochemically to Hg2+ in the presence of reactive chemicals released
from sea salt (for example, bromine and chlorine ions) and mercury levels in the atmosphere are
"depleted" as the Hg2+ is then deposited on snow and ice surfaces. As a consequence, a pulse of
reactive mercury enters the Arctic environment when the short lived growing season is beginning. It
remains a research question as to what fraction of this reactive mercury is converted to toxic
methylmercury and taken up by animals and plants.
Mercury Methylation
In an aquatic environment under suitable conditions, mercury is bioconverted to methylmercury, by
a chemical process called Methylation [Wood 1974].
In the Methylation process, mercury is transformed into methylmercury when the oxidized, or
mercuric species (Hg2+), gains a methyl group (CH3). The methylation of Hg2+ is primarily a biological
process resulting in the production of highly toxic and bioaccumulative methylmercury compounds
(MeHg+) that build up in living tissue and increase in concentration up the food chain, from micro-
organisms like plankton, to small fish, then to fish eating-species such as otters and loons, and
humans.
The formation of methylmercury is critically important due to its highly toxic, bioaccumulative and
persistent nature. A variety of micro-organisms, particularly methanogenic (methane producing) and
sulphate-dependant bacteria are thought to be involved in the conversion of Hg2+ to MeHg under
anaerobic (oxygen poor) conditions found, for example, in wetlands and river sediments, as well as in
certain soils. Methylation occurs primarily in aquatic, low pH (acidic) environments with high
concentrations of organic matter.
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Rates of bio-methylation are a function of environmental variables affecting mercuric ion availability
as well as the population sizes of methylating microbes. Alkalinity, or pH, plays a strong role in
regulating the process because it is affected by, and in turn affects, the adsorption of various forms
of mercury on soil, clay and organic matter particles, thus influencing mercuric ion availability. Acid
rain may increase biomethylation as more MeHg is formed under acidic conditions. [Env Canada
2004].
In several reports it is stated that bioavailability of mercury for methylation is increased in the
presence of neutral dissolved Hg complexes HgS0(aq) [Benoit 1999], [Drott 2007]. It is also described
that high dissolved sulphide concentration favour the creation of disulfide complexes, primarily
HgHS2-, which reduces the bioavailability of mercury for methylation. [Hammerschmidt 2008]
[Benoit 1999]. Tests showed that not dissolved Hg or mercury sulphide gave no significant
relationship with the specific methylation rate constant. [Drott 2007] [Benoit 2001].
Some substances have been identified to have an inhibiting effect on the methylation process as iron
sulphides. This is probably due to the decrease of neutral Hg(II)-sulphide complexes via formation of
charged Hg(II)polysulfides [[Liu 2009].
However, sulphate may stimulate growth of certain methylating microbes. Organic matter can
methylation increases in warmer temperatures when biological productivity is high, and decreases
during the winter.
Atmospheric long range transport
Mercury in the atmosphere is broadly divided into gas form and particulate form. Most of the
mercury in the general atmosphere is in gas form (95% or more). Gaseous mercury includes mercury
vapour, inorganic compounds (chlorides and oxides), and alkyl mercury (primarily methylmercury
[JPHA 2001].
The volatility of elemental mercury (Hg0) enables mercury to travel in a multi-step sequence of
emission to the atmosphere, transportation, deposition and re-emission. As a result, mercury from
point source emissions may remain localized in the environment, or may be transported regionally
and even globally.
Atmospheric transport is likely the primary mechanism by which Hg0 is distributed throughout the
environment, unlike many pollutants that follow erosion or leaching pathways. Mercury can enter
the atmosphere as a gas or bound to other airborne particles and circulates until removal. Removal
occurs primarily through the "wet" deposition of Hg2+ in rainfall, however it can also occur in the
presence of snow, fog, or through direct, or "dry", deposition.
Approximately 98% of the estimated 5000 tonnes of mercury in the atmosphere is Hg0 vapour,
emitted from human activities, contaminated soils and water, as well as natural sources [Env Canada
2004]. This gas is readily transported and has a mean atmospheric residence time of about one year
to one and a half years [Selin 2009]. The transformation of insoluble Hg0 to its more reactive and
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water-soluble form, Hg2+, is thought to provide the mechanism for the deposition of Hg0 emissions to
land and water. Hg0 oxidation may also be affected by concentrations of other atmospheric
pollutants such as ozone, sulphur dioxide and soot. Additional research is needed in order to predict
corresponding mercury deposition rates.
Mercury Deposition
Following release to the atmosphere and depending on its physical/chemical form, mercury can be
either deposited in the vicinity of the emission source, or subjected to long-range atmospheric
transport via air masses. Because the uptake of Hg0 in cloud water is relatively slow, this process may
be responsible for the deposition of mercury far from its source and may be important when
considering global mercury pollution. Gaseous Hg+2 and particulate mercury (Hg(p), mercury
adsorbed onto other particulate matter) emissions generally undergo direct wet or dry deposition to
the earth's surface locally. These species have relatively short residence times in the atmosphere
ranging from hours to months. Gaseous Hg+2 has a residence time of 5 to 14 days in the atmosphere,
and may travel tens to hundreds of kilometres. Particulate forms of mercury (Hg(p)) tend to fall out
closer to the source of emissions, with larger particles falling out faster than smaller ones. The site-
specific deposition of mercury is variable, and is affected by conditions such as meteorology,
temperature and humidity, solar radiation and emission characteristics (speciation, source, stack
height, etc.).
Atmospheric Circulation
Atmospheric circulation processes may play an important role in determining where airborne
mercury is eventually deposited. Mercury, like other semi-volatile compounds such as PCBs, is
thought to participate in a global distillation phenomenon that transfers chemical emissions from
equatorial, subtropical and temperate regions to the polar regions via the "grasshopper effect".
When this phenomenon takes place, an emitted compound re-enters the atmosphere by volatilizing
after initial deposition, and continues over time to "hop" through the environment in the direction of
the prevailing winds, favouring accumulation in the colder regions of the planet. During the summer
months, major air currents in the northern hemisphere lead to the Arctic, and once there, a
contaminant can no longer gain enough heat energy for another "hop" out of the Arctic. The net
result is a concentration of contaminants in the Arctic at odds with the relative sparsity of emissions
sources in the region.
Other pathways (other than atmospheric long range transport)
In addition to atmospheric pathways, mercury can be transported through river systems in their
sediment loads, or in aqueous solution. The transport distance may be long or short. Where mercury
is carried on particles, the distance is limited by sedimentation. Transport of contaminants via
particles tends to halt at riverine lakes or reservoirs since heavy sedimentation can occur there.
Transport also occurs along ocean currents.
Transport of mercury underground depends particularly on the pH conditions in the hydrogeological
and geochemical conditions. Deep groundwater is generally neutral to alkaline, under which
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conditions Hg tends to be immobilised due to adsorption to mineral surfaces. Deep environments
tend to be reducing, under which conditions mercury tends to be immobilised due to precipitation as
sulphur compounds. The adsorption of mercury compounds is positively correlated with the cation
exchange capacity of the geo-environment. The mercury is adsorbed by certain clays (e.g. naturally
occurring clays or montmorillonite/bentonite). [Heath 2006]
The oceans are considered the ultimate sink for mercury because Hg2+ deposited from the
atmosphere can settle to oceanic depths where it is reduced and precipitates as insoluble mercuric
sulphide. It is thought that approximately one third of the total current mercury emissions cycle
between the oceans and the atmosphere, and that 20 to 30% of oceanic emissions, are re-emitted
from prior anthropogenic sources.
4.2.2 Overview of the behaviour in the environment
Mercury is a persistent, mobile and bioaccumulative element in the environment and is retained in
organisms. Mercury in the aquatic environment is changed to various forms, mainly methylmercury,
methylated from mercury. As a consequence mercury permanently exists in the environment and its
chemical form availability to living organism change over time depending on the environmental
conditions.
Figure 4-2 shows the main chemical reactions and pathways of mercury in the atmosphere, water,
soil, and in sediments and the effect of bioaccumulation.
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Figure 4-2: Diagram of the biogeochemical mercury cycle
Figure 4-2 illustrates the main chemical reactions and pathways of mercury in the atmosphere,
water, soil, and in sediments. Pathways include leaching and runoff, emission from natural and
anthropogenic sources, volatilization, deposition from the atmosphere, and sedimentation-
resuspension. Methylation-demethylation, oxidation-reduction, and complexation are the chemical
reactions shown. The diagram also illustrates bioaccumulation of mercury in a fish food chain.
(Source: Env Canada 2004)
4.2.3 Environmental limit values related to mercury
Water
Within the European Community, Directive 2008/105/EC17 on environmental quality standards in the
field of water policy establishes Environmental Quality Standards (EQS) for mercury and its
compounds.
17 Directive 2008/105/EC on environmental quality standards in the field of water policy, amending and subsequently, repealing Council Directives 82/176/EEC, 83/513/EEC, 84/156/EEC, 84/491/EEC, 86/280/EEC and amending Directive 2000/60/EC of the European Parliament and of the Council, 16 December 2008 (OJ L 348, 24.12.2008, p. 84–97)
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Table 4-5: Environmental Quality Standards (EQS) set for mercury in Directive 2008/105/EC
AA-EQS Inland surface waters (3)
AA-EQS Other surface waters
MAC-EQS Inland surface waters (3)
MAC-EQS Other surface waters
Mercury and its compounds
0.05 (9) 0.05 (9) 0.07 0.07
AA: annual average; MAC: maximum allowable concentration, Unit: [μg/l] In addition, in article 3(2)(a) an EQS for biota is set for mercury and its compounds of 20 µg/kg based
on prey tissue (wet weight), choosing the most appropriate indicator from fish, molluscs, crustaceans
and other biota. In cases where Member States do not apply the EQS for biota they shall introduce
stricter EQS for water in order to achieve the same level of protection.
On the international level [WHO 2004] is proposing a limit value of 1 μg/litre for total mercury in
water.
Air
Within the European Community no common limit value for mercury concentration is set. Directive
2004/107/EC18 establishing target values for the concentration of arsenic, cadmium, mercury, nickel
and polycyclic aromatic hydrocarbons in ambient air does not introduce specific target values for
mercury, while for the other substances such targets are introduced (Annex I of the Directive).
On the international level, the WHO prescribes an air quality guideline value of 1 μg Hg0/m3 as an
annual average concentration and 0.2 μg/m3 for long-term inhalation exposure to elemental mercury
vapour [WHO 2007]. [UNEP 2009] also describes exposure levels (RELs) for Hg0 established for the
general non-occupational population, based on US American and Canadian limits:
• 0.3 μg/m3 from the US EPA (chronic reference air concentration)
• 0.2 μg/m3 from the US Agency for Toxic Substances and Disease Registry (minimal risk level
for chronic inhalation exposure)
• 0.09 μg/m3 from the California Environmental Protection Agency (inhalation reference
exposure)
• 0.06 μg/m3 from Health Canada (chronic tolerable air concentration)
18 Directive 2004/107/EC of the European Parliament and of the Council of 15 December 2004 relating to
arsenic, cadmium, mercury, nickel and polycyclic aromatic hydrocarbons in ambient air, 16. December 2008 (OJ L 23, 26.1.2005, p. 3–16)
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4.3 Conclusions
Mercury is a persistent, mobile and bioaccumulative element in the environment and is retained in
organisms [Env Canada 2004].
In particular the methylation - transformation of mercury compounds to the highly toxic form
methylmecury – has to be taken into consideration for the storage of liquid mercury but also for
mercury compounds. Methylation occurs primarily in aquatic, low pH environments with high
concentration of organic matter but also other parameters might influence the formation of
methylmecury [Env Canada 2004], [Wood 1974]. Therefore in case of the storage of mercury a
special focus should be laid on the potential formation of methylmercury.
Metallic mercury has specific properties which have to be taken into consideration for the
assessment of possible storage options. In particular its high vapour pressure and its liquid state at
room temperature might entail problems in handling and long term storage.
Information on leaching values for mercury and mercury compounds are available in literature and
are summarized in Annex 4.
Although information is available related to the solubility of mercury and mercury compounds in
water [Hagelberg 2006], [USEPA 2007], information to the influence of salt and salt solutions to
solubility of mercury is still very limited. Results from available investigations ([GRS 2008A],
[Sanemasa 1981]) give first indications of a decreased solubility of mercury in salt solutions. But
further research is required to verify these results [GRS 2008A].
Information on the reactivity of mercury with other substances is described in chemical literature [Ho
Wi 1995]. With reference to the corrosiveness of mercury with possible container material only very
limited literature has been found [Mersade 2007A]. Most important information is available from
two projects carried out by ONRL (Oak Ridge National Laboratory), USA and within the Life Project
MERSADE19 (detailed results see 6.4.3).
Acute exposure to mercury vapour causes adverse effects to human health. Therefore occupational
exposure limit values are established in many countries [EU OSAH 2007], [GESTIS 2009]. On European
level a limit value of 0.02 mg Hg/m³ (TWA, 8 h) for elemental mercury and inorganic divalent mercury
compounds is recommended by [SCOEL 2007]. Environmental limit values are available on EU level
for water20. On international level also air quality guideline values are established [WHO 2007].
19 LIFE is the EU’s financial instrument supporting environmental and nature conservation projects throughout
the EU, as well as in some candidate, acceding and neighbouring countries, for further information see http://ec.europa.eu/environment/life/
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4.4 References
[Aluminium 2004] Corrosion of Aluminium, Christian Vargel, ISBN: 0 08 044495 4, 2004 [ATSDR 1999] U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES, Public Health Service, Agency for Toxic Substances and Disease Registry, TOXICOLOGICAL PROFILE FOR MERCURY, 1999; http://www.atsdr.cdc.gov/toxfaqs/TF.asp?id=115&tid=24 [Benoit 1999] Benoit, J.M., Mason, R.P., Gilmour, C.C., Estimation of mercury-sulfide speciation in sediment pore waters using octanol-water partitioning and implications for availability to methylating bacteria, Environmental Toxicology and Chemistry, Vol. 18, No. 10, pp. 2138-2141, 1999 http://www.serc.si.edu/labs/microbial/pubs/Benoit%20et%20al%20ET&C%201999.pdf [Benoit 2001] Benoit, J.M., Gilmour, C.C., Mason, R.P., The influence of sulphide on solid-phase mercury bioavailability for methylation by pure cultures of Desulfobulbus propionicus, (2001), Environmental Science and Technology, 35 (1), pp. 127-132, 2001 [CCOHS 1998] Canadian Centre for Occupational Health & Safety, Chemical profile mercury, preparation date 1998, copyright 2007 http://www.ccohs.ca/oshanswers/chemicals/chem_profiles/mercury/ [Drott 2007] Drott, a., Lambertsson, L., Björn, E., Skyllberg, U., Importance of dissolved neutral mercury sulfides for methyl mercury production in contaminated sediments, Environmental Science and Technology, 41 (7), pp. 2270-2276, 2007 [Env Canada 2004] Environment Canada, Mercury and the environment, Internet document: http://www.ec.gc.ca/MERCURY/EH/EN/eh-i.cfm, last update 2004-02-04, accessed on 29 June 2009 [EU OSHA 2007] Exploratory Survey of Occupational Exposure Limits for Carcinogens, Mutagens and Reprotoxic substances at EU Member States Level, European Agency for Safety and Health at Work, European Risk Observatory Report http://osha.europa.eu/en/publications/reports/548OELs [Euro Chlor 2009] Euro Chlor, Metallic mercury (Hg0) The biological effects of long-time, low to moderate exposures, Science dossier 13, February 2009 [Fraunhofer 273] M. Krus, H.M. Künzel, Das Wasseraufnahmeverhalten von Betonbaustoffen, IBP-Mitteilung 273, Fraunhofer Institut für Bauphysik http://www.ibp.fraunhofer.de/HT/pub/ibpmitt/ibp273.pdf
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[Funtikov 2009] High Temperature 2009, Vol. 47, No. 2, pp201-205, A. I. FUTNIKOV, Shock Adiabat, Phase Diagram, and Viscosity of Mercury at a Pressure up to 50 GPa. [Gestis 2009] http://www.dguv.de/bgia/de/gestis/stoffdb/index.jsp# [GRS 2008A] Gesellschaft für Anlagen- und Reaktorsicherheit (GRS) mbH, Solubility of metallic mercury and mercury compounds in saline solutions, presentation by Horst-Jürgen Herbert and Sven Hagemann GRS, Braunschweig, 2008, Germany [Hagelberg 2006] Hagelberg, Erik, Örebro University, Institutionen för naturvetenskap, Department of Natural Sciences, The matrix dependent solubility and speciation of mercury, 2006, http://oru.diva-portal.org/smash/record.jsf?pid=diva2:137047 [Hammerschmidt 2008] Hammerschmidt Chad R., Fitzgerald William F., Balcom Prentiss H., Visscher Pieter T., Organic matter and sulfide inhibit methylmercury production in sediments of New York/New Jersey Habor, Marine Chemistry 109 (2008) 165-182 [Heath 2006] Mike Heath, Health environmental and safety questions related to the underground storage/disposal of mercury over time, Presentation at the EEB Conference on EU Mercury surplus management and mercury-use restrictions in measuring and control equipment, Brussels, 19 June 2006; http://www.zeromercury.org/EU_developments/HEATH-storage.pdf [Ho Wi 1995] Lehrbuch der Anorganischen Chemie 101. Auflage Hollemann Wiberg, 1995 [JPHA 2001] Japan Public Health Association: Preventive Measures against Environmental Mercury Pollution and Its Health Effects, Japan, 2001 http://www.chem.unep.ch/Mercury/2003-gov-sub/Japan-complete-report.pdf [Liu 2009] Liu, J., Valsaraj, K.T., Delaune, “Inhibition of mercury methylation by iron sulfides in an anoxic sediment”, Environmental Engineering Science, 26 (4), pp. 833-840, 2009 [Mercury 65GPa] Rapid communication, Physical Review B, Volume 48, Number 18, 14009-14012, 1 November 1993-II, Olaf Schulte and Wilfried B. Holzapfel, Phase Diagram for mercury up to 65 GPa and 500 K [OKOUCHI 1985] Okouchi S., Sasaki, S., The 1-octanol/water partition coefficient of mercury, Bulletin of the Chemical Society of Japan, Vol.58 , No.11(1985)pp.3401-3402, http://www.journalarchive.jst.go.jp/jnlpdf.php?cdjournal=bcsj1926&cdvol=58&noissue=11&startpage=3401&lang=en&from=jnlabstract
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[Sakar 2003] Sarkar, Dibyendu, Preliminary studies on mercury solubility in the presence of iron oxide phases using static headspace analysis, Environmental Geosciences; December 2003; v. 10; no. 4; p. 151-155; DOI: 10.1306/eg.08220303015 http://eg.geoscienceworld.org/cgi/content/abstract/10/4/151 [Sanemasa 1975] Isao Sanemasa, The solubility of elemental mercury vapor in water, Bulletin of the chemical society of Japan, Vol 48(6), 1975 http://www.journalarchive.jst.go.jp/jnlpdf.php?cdjournal=bcsj1926&cdvol=48&noissue=6&startpage=1795&lang=en&from=jnlabstract [Sanemasa 1981] Isao Sanemasa, Effects of salts on the solubility of elemental mercury vapor in water, Bulletin of the chemical society of Japan, Vol 54(4), 1981 http://www.journalarchive.jst.go.jp/jnlpdf.php?cdjournal=bcsj1926&cdvol=54&noissue=4&startpage=1040&lang=en&from=jnlabstract [SCOEL 2007] SCOEL, Recommendation from the Scientific Committee on Occupational Exposure Limits for elemental mercury and inorganic divalent mercury compounds“, SCOEL/SUM/84, May 2007, http://ec.europa.eu/social/BlobServlet?docId=3852&langId=en [Selin 2009] Selin, Noelle E., Global Biogeochemical Cycling of Mercury: A Review, Department of Earth, Atmospheric, and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139-4307; Annu. Rev. Environ. Resour. 2009. 34:43–63, DOI 10.1146/annurev.environ.051308.084314 http://globalchange.mit.edu/files/document/MITJPSPGC_Reprint_09-15.pdf [SPC 2009] http://www.ktf-split.hr/periodni/en/abc/kpt.html [TRGS 900] Technische Regeln für Gefahrstoffe. Arbeitsplatzgrenzwerte. Ausgabe: Januar 2006, zuletzt geändert und ergänzt: GMBl Nr. 28 S. 605 (v. 2.7.2009), http://www.baua.de/nn_16806/de/Themen-von-A-Z/Gefahrstoffe/TRGS/pdf/TRGS-900.pdf [UNEP 2002] UNEP, Global mercury assessment, 2002, http://www.chem.unep.ch/mercury/Report/Final%20Assessment%20report.htm [UNEP 2009] UNEP, Draft technical guidelines on the environmentally sound management of mercury wastes, 4th Draft, April 2009, http://www.basel.int/techmatters/mercury/guidelines/040409.doc [USEPA 2007] U.S. Environmental Protection Agency, Treatment Technologies For Mercury in Soil, Waste, and Water, EPA-542-R-07-003, 2007, 2007 http://www.epa.gov/tio/download/remed/542r07003.pdf
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[WHO 2004] Guidelines for Drinking-water quality 3rd edition. Geneva, World Health Organization, http://www.who.int/water_sanitation_health/dwq/fulltext.pdf [WHO 2005] World Health Organisation, Mercury in Drinking-water, Background document for development of WHO Guidelines for Drinking-water Quality, 2005, http://www.who.int/water_sanitation_health/dwq/chemicals/mercuryfinal.pdf [WHO 2006] World Health Organisation, Guidelines for drinking-water quality incorporating first addendum. Vol. 1, Recommendations. – 3rd ed.Electronic version for the Web, 2006, http://www.who.int/water_sanitation_health/dwq/gdwq3rev/en/ [WHO 2007] World Health Organisation, Preventing disease through healthy environments exposure to mercury, A major public health concerns, Geneve 2007, http://www.who.int/phe/news/Mercury-flyer.pdf [Wood 1974] Wood, J.M.: Biological Cycles for Toxic Elements in the Environment, Science, 15, 1043-1048, 1974 [ZERO Hg 2006] Zero Mercury working group, EU Mercury Surplus Management and Mercury-Use Restrictions in Measuring and Control Equipment, Report from the EEB Conference, October 2006, http://www.zeromercury.org/EU_developments/0606_EEB_Mercury_Conference_ReportFINAL.pdf
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5.2 European legislation
Elemental mercury
At present, mercury is not seen as waste on the European Community level, but considered as raw
material. Excess mercury from the decommissioning of chlor-alkali plants as well as liquid mercury
gained from e.g. recycling processes of products is sold to mercury dealing companies (e.g. Mayasa)
and re-sold as raw material for various applications. Large amounts are also exported to non-EU
countries. Therefore specific requirements related to the disposal of liquid mercury have not been
needed so far.
The situation changed with the publication of Regulation (EC) No 1102/200823 on the banning of
exports and the safe storage of metallic mercury. Safe storage options for metallic mercury are
needed for the near future within the Community as the ban starts from 15 March 2011 and affects
metallic mercury, cinnabar ore, mercury (I) chloride, mercury (II) oxide and mixtures of metallic
mercury with other substances including alloys of mercury, with a concentration of at least 95 wt %
Hg (recital 5 of Regulation (EC) No 1102/2008).
In order to provide possibilities for a safe storage of the above-mentioned metallic mercury waste
within the Community, Article 3 of Regulation (EC) No 1102/2008 constitutes suitable options, both
for permanent and temporary storage in appropriate containments:
• temporary storage for more than one year or permanent storage in salt mines adapted for
the disposal of metallic mercury,
• temporary storage for more than one year or permanent storage in deep underground, hard
rock formations providing a level of safety and confinement equivalent to that of those salt
mines,
• temporary storage for more than one year in above-ground facilities dedicated to and
equipped for the temporary storage of metallic mercury.
For this purpose Article 5 (3)(a) of Directive 1999/3124 shall be derogated. In addition, Article 4 of
Regulation (EC) No 1102/2008 stipulates that the safety assessment which is required for a safe
underground storage under Decision 2003/33/EC25 should be complemented by specific
requirements resulting from the specific risk of the storage of metallic mercury. Furthermore,
acceptance criteria should be developed for metallic mercury either temporarily or permanently 23 Regulation (EC) No 1102/2008 of the European Parliament and of the Council of 22 October 2008 on the banning of exports of metallic mercury and certain mercury compounds and mixtures and the safe storage of metallic mercury (OJ L304 of 14/11/08, p.75-79), also referred to as the ‘Mercury Regulation‘. 24 Council Directive 1999/31/EC of 26 April 1999 on the landfill of waste (OJ L 182, 16.7.1999, p. 1–19), also
referred to as the ‘Landfill Directive‘. 25 Council Decision of 19 December 2002 establishing criteria and procedures for the acceptance of waste at
landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC (OJ L 11, 16.1.2003, p. 27–49), also referred to as the ‘WAC Decision‘.
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stored in appropriate underground or above-ground facilities.
So far no waste code exists for elemental mercury on the European level.
With regard to transport of liquid mercury, the containers and transport operations have to fulfil the
specific requirements set for the different types of transports inter alia stated in the European
Agreement Concerning the International Carriage of Dangerous Goods by Road (ADR), Regulations
concerning the Transport of Dangerous Goods by Rail (RID), International Maritime Organisation
(IMO) or International Air Transport Association (IATA).
“Waste containing mercury”
For waste containing mercury (not liquid), requirements concerning disposal exist at the European as
well as at Member State levels. Directive 1999/31/EC together with Decision 2003/33/EC in particular
lay down which requirements storage facilities (landfills) in general have to fulfil and which
acceptance criteria in particular have to be fulfilled for a certain type of landfill. This includes
technical standards, acceptance procedures, limit values, monitoring and control activities.
More stringent protective measures at Member States level are possible.
Several waste codes for waste containing mercury exist, depending on its source of origin listed in
the European Waste Catalogue with the following EWC numbers:
• 05 07 01* wastes containing mercury from natural gas purification,
• 06 04 04* wastes containing mercury from inorganic chemical processes,
• 10 14 01* waste from gas cleaning containing mercury,
• 16 01 08* components containing mercury,
• 16 06 03* mercury-containing batteries,
• 17 09 01* construction and demolition wastes containing mercury,
• 20 01 21* fluorescent tubes and other mercury-containing waste.
Apart from the specifically addressed mercury-containing waste other types of waste may also
contain mercury or mercury compounds such as waste types specified as ‘containing heavy metals’
or ‘containing hazardous substances’ (Directive 2000/532/EC26 ).
26 Commission Decision of 3 May 2000 replaces Decision 94/3/EC establishing a list of wastes pursuant to
Article 1(a) of Council Directive 75/442/EEC on waste and Council Decision 94/904/EC establishing a list of hazardous waste pursuant to Article 1(4) of Council Directive 91/689/EEC on hazardous waste (notified under document number C(2000) 1147) (OJ L 226, 6.9.2000, p. 3–24).
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Apart from Regulation (EC) N° 1102/2008, the following legal documents at the European level have
to be considered for evaluating the storage requirements of metallic mercury and mercury
containing waste as they are referred to in Regulation (EC) N° 1102/2008:
• Directive 2006/12/EC27 and Directive 2008/98/EC28 (‘Waste Framework Directives’)
• Directive 1999/31/EC (‘Landfill Directive‘),
• Decision 2003/33/EC (‘WAC Decision’),
• Directive 1996/82/EC 29 (‘Seveso II Directive’),
Directive 85/337/EEC32 (‘Environmental Impact Assessment Directive’) was also taken into account,
though not mentioned in the Mercury Regulation, as certain storage facilities need to comply with
this Directive.
These documents are evaluated in the following chapter with regard to possible storage facilities for
metallic mercury and mercury containing waste including above ground and underground facilities
such as salt mines and deep underground hard rock formation.
The evaluation focuses on the extraction of requirements for the various storage types laid down in
the above-mentioned legislation. However, issues such as transport and handling of mercury and
mercury waste will also be tackled within the following chapters.
Further national legislation have been screened for additional requirements for mercury disposal and
disposal of hazardous waste e.g. in underground facilities.
27 Directive 2006/12/EC of the European Parliament and of the Council of 5 April 2006 on waste (OJ L 114,
27.4.2006, p. 9–21), also referred as ‘Waste Framework Directive‘. 28 Directive 2008/98/EC of the European Parliament and of the Council of 19 November 2008 on waste
and repealing certain Directives(OJ L 312, 22.11.2008, p. 3–29), also referred as ‘new Waste Framework Directive‘.
29 Council Directive 96/82/EC of 9 December 1996 on the control of major-accident hazards involving dangerous substances (OJ L 10, 14.1.1997, p. 13–33) as amended by Directive 2003/105/EC; also referred to as the ‘Seveso II Directive’.
30 Regulation No 1013/2006 of the European Parliament and of the Council of 14 June 2006 on shipments of waste (OJ L 190, 12.07.2006, p.1-98), also referred to as the ‘Waste Shipment Regulation‘.
31 Directive 2004/35/CE of the European Parliament and of the Council of 21 April 2004 on environmental liability with regard to the prevention and remedying of environmental damage (OJ L 143, 30.4.2004, p. 56–75), also referred to as ‘Environmental Liability Directive’.
32 Council Directive 85/337/EEC of 27 June 1985 on the assessment of the effects of certain public and private projects on the environment (OJ L 175, 5.7.1985, p. 40–48) with last amendment from 25 June 2003 , also referred as ‘Environmental Impact Assessment Directive‘.
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5.2.1 Legal requirements for all storage facilities
The Mercury Regulation sets specific requirements for the disposal of metallic mercury. In general,
the provisions from the Landfill Directive and the WAC Decision are applicable with few exemptions
for specific types of landfills. The requirements listed in Table 5-1are applicable for all types of
mercury disposal facilities, while some specifications are made for above-ground facilities and for
storage in salt-mines and deep underground hard rock formations (see chapters 5.2.2 to 5.2.5).
Table 5-1: Requirements for all types of mercury storage facilities according to Directive N° EC 1102/2008
Requirements for all types of mercury storage facilities according to Regulation EC N°1102/2008
Requirement / source Specification
Objective
[Regulation 1102/2008, Recital 6]
• Safe storage should be ensured
Provisions
[Regulation 1102/2008, Recital 8 and Article 3(1)]
• All provisions of Directive 1999/31/EC shall apply; except Article 5(3)(a) (= not accepting liquid waste at landfills)
• Assuring financial security (provision in Article 8(a)(iv) of Landfill Directive) including period of closure and after care
• Directive 2004/35/CE on environmental liability applies to mercury storage facilities
Containment
[Regulation 1102/2008, Article 3 (1)]
• Storage of metallic mercury in appropriate containment
Safety assessment
[Regulation 1102/2008, Article 4(1)]
• Safety assessment for all mercury storage facilities • Covering particular risks of metallic mercury and its containment
arising from natural and long-term properties
Visual inspection
[Regulation 1102/2008, Article 4(2)]
• Permit for storage according to Landfill Directive shall include requirements for regular visual inspections of the containers,
• Installation of appropriate vapour detection equipment to detect leak
Directive 2006/12/EC and Directive 2008/98/EC (‘Waste Framework Directives’)
The new Waste Framework Directive (Directive 2008/98/EC), which has to transposed into national
law by the Member States by 12 December 2010 is repealing the old Waste Framework Directive
(Directive 2006/12/EC) and incorporating and repealing the Hazardous Waste Directive33 and the
Waste Oil Directive34.
33 Council Directive 91/689/EEC of 12 December 1991 on hazardous waste (OJ L 337, 31.12.1991, 20–27)
with last amendment from 19 November 2008, also referred as ‘Hazardous Waste Directive‘.
34 Council Directive 75/439/689/EEC of 16 June 1975 on the disposal of waste oils (OJ L 194, 25.7.1975, p. 23–25) as ‘Waste Oil Directive‘.
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The new Framework Directive requires more stringent waste reduction and waste prevention efforts.
Member States must ensure that waste is recovered or disposed of without endangering human
health and the environment and that the waste amount disposed of is reduced to a minimum by kind
of measures and effective tools to minimise waste generation.
Amongst other issues, the new WFD provides a further clarification and differentiation of the waste
hierarchy, modifies definitions as regards e.g. the end-of-waste status, by-products and classification
of treatment operations and changes requirements for the preparation of waste management plans.
The Directive emphasizes new waste management targets, encourages waste reduction and gives a
new dimension to prevention as Member States are obliged to draw up and implement waste
prevention programmes not later than 2013.
Also the producer responsibility is extended in order to strengthen the re-use, prevention as well as
recycling and other recovery of waste. The New Waste Framework Directive also sets new recycling
targets which have to be achieved by 2020. In addition, the Directive sets out more stringent
provisions for authorisation and registration.
With the new Waste Framework Directive, the Hazardous Waste Directive is repealed with effect
from 12 December 2010. No reference in Mercury Regulation is therefore made to the Hazardous
Waste Directive. However some parts of the Hazardous Waste Directive were incorporated into
Directive 2008/98/EC, especially Annex III, describing properties of waste (which are classified as
hazardous). Annexes I (describing categories or generic types of waste which are classified as
hazardous) and Annex II (listing constitutes of waste which are classified as hazardous) are not
incorporated in the new Waste Framework Directive.
Directive 1999/31/EC (‘Landfill Directive’)
The Landfill Directive defines the relevant terms (e.g. waste, treatment options, and technical terms),
sets the scope and the landfill classes, specifies the waste and treatment options acceptable and not
acceptable at different landfill classes and explains the requirements for a permit, waste acceptance
and the control and monitoring as well as the closure and after-care procedures.
The focus of this report is only on the provisions being of relevance for the issue of mercury storage
and the deviation of specific criteria for mercury storage.
According to Directive 1999/31/EC, ‘landfill’ means a waste disposal site for the deposit of waste
onto or into land (i.e. underground), including […] a permanent site (i.e. more than one year) which is
used for temporary storage of waste (Article 2 (g)) but excluding
• Facilities where waste is unloaded in order to permit its preparation for further transport for
recovery, treatment or disposal elsewhere, and
• Storage of waste prior to recovery or treatment for a period of less than three years as a
general rule, or
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• Storage of waste prior to disposal for a period of less than one year.
According to Article 7 of Directive 1999/31/EC a landfill needs a permit, which contains information
about the identity of the applicant and the operator, the description of the types and total quantity
of waste, the proposed capacity, a description of the site, the proposed methods for pollution
prevention and control and the proposed plan for the closure and after-care procedures.
Furthermore an impact assessment following Council Directive 85/337/EEC might be required and
has to be added to the permit.
The provisions that all types of landfill have to fulfil are set out in Annex I of Directive 1999/31/EC
and summarised in Table 5-2.
Table 5-2: General requirements for all classes of landfills according to Directive 1999/31/EC, Annex I
Requirements for all classes of landfills according to Directive 1999/31/EC, Annex I
Requirement / source Specification
Location
[Directive 1999/31/EC,
Annex I, section 1]
Location of landfill must take into consideration requirements related to:
• Distance to residential and recreational areas, waterways, water bodies,
agricultural and urban sites
• Existence of groundwater, coastal water or nature protection zones
• Geological and hydrological conditions
• Risk of flooding, subsidence, landslides or avalanches
• Protection of nature or cultural patrimony
Landfill can only be authorised if requirements or measures indicate, that they do
not pose a serious risk.
Water and leachate
management
[Directive 1999/31/EC,
Annex I, section 2]
Measures (possible exceptions for inert landfills):
• Control water from precipitations entering into the landfill
• Prevent surface water and/or groundwater from entering
• Collect contaminated water and leachate (exception possible)
• Treat contaminated water and leachate
Protection of soil and
water
[Directive 1999/31/EC,
Annex I, section 3]
Measures (possible exceptions for inert landfills):
• Landfill must be situated to prevent pollution to soil, groundwater, surface
water and to ensure efficient collection of leachate
• Combination of geological barrier and bottom liner during passive phase/post-
closure
• Combination of geological barrier and top liner during operational/active
phase
• Geological barrier determined by geological and hydro-geological conditions
below and in the vicinity of a landfill providing sufficient attenuation capacity
to prevent a potential risk
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Requirements for all classes of landfills according to Directive 1999/31/EC, Annex I
Requirement / source Specification
• Landfill base and sites consist of mineral layer (specified for each class;
artificial layer possible)
• Leachate collection and sealing system including artificial sealing liner and
drainage layer (exception possible for inert waste)
• Surface sealing layer dependent on landfill class
Gas control
[Directive 1999/31/EC,
Annex I, section 4]
• Control the accumulation and migration of landfill gas
• Collection and treatment of landfill gas (for landfills receiving biodegradable
waste)
Nuisances and hazards
[Directive 1999/31/EC,
Annex I, section 6]
Measures to minimise nuisance and hazards through emissions of odours and
dust; wind-blown materials; noise and traffic; birds, vermin and insects;
formation of aerosols; fires
Stability
[Directive 1999/31/EC,
Annex I, section 6]
• Stability of the mass of waste and associated structures; avoid slippages
• Where artificial barrier, geological substratum stable to prevent settlement
that causes damage to barrier
Barriers
[Directive 1999/31/EC,
Annex I, section 7]
• Secured to prevent free access
• Gates shall be closed outside operating hours
• System to detect and discourage illegal dumping
Annex II of Directive 1999/31/EC prescribes general waste acceptance criteria proposing the
following three-level hierarchy [Directive 1999/31/EC, Annex II, section 3]:
• Basic characterisation (each type of waste, exemption for waste types where impractical)
o determination according to standardised analysis and behaviour-testing methods,
o short and long-term leaching behaviour,
o characteristic properties of the waste.
• Compliance testing (at regular intervals, at least once a year)
o periodical testing by simpler standardised analysis and behaviour-testing methods,
o determine whether a waste complies with permit conditions and/or specific
reference criteria,
o focus on key variables and behaviour identified by basic characterisation.
• On-site verification (each load of waste)
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o rapid test methods to confirm that each shipment/load of waste is the same as in the
basic characterisation and described in accompanying documents,
o visual inspection of each load of waste before and after unloading at the landfill site.
The acceptance procedures shall as far as possible be based on standardised waste analysing
methods. Furthermore, they shall respect corresponding limit values for the properties of waste to
be accepted. Therefore, Member States shall establish a national list of waste to be accepted or
refused at each class of landfills. These lists shall be used to establish site specific lists [Directive
1999/31/EC, Annex II, section 2].
The general waste acceptance procedure is concretised by Decision 2003/33/EC, Annex including
information on the function of each level of testing, the fundamental requirements, the testing
methods and the limit values to be fulfilled.
A first guideline to define what kind of waste should be accepted at each landfill class is given in the
Landfill Directive [Directive 1999/31/EC, Annex II, section 4], summarised as follows:
Table 5-3: Control and monitoring procedures for all classes of landfills according to Directive 1999/31/EC, Annex III
Preliminary criteria for waste acceptance according to Directive 1999/31/EC, Annex II
Landfill class Waste to be generally accepted
Inert waste landfills
• Only inert waste as defined in Article 2(e) accepted
(=not undergoing significant physical, chemical or biological transformations, not
dissolving, burning, physically or chemically reacting, biodegrading, adversely
affecting, no rise in environmental pollution or harm to human health,
leachability and ecotoxicity of leachate insignificant)
Non-hazardous waste
landfills • Only waste type not covered by Directive 91/689/EEC35
Hazardous waste landfills • Covered by Directive 91/689/EEC (preliminary list)
• Prior treatment required if contents or leachability is high enough to
constitute short term occupational and environmental risk
Additionally, the acceptance of waste at each landfill type depends on the leaching properties of the
waste. Leaching limit values are defined for each class of landfills in the Annex of the WAC Decision
(see description below).
Wastes which contain mercury and mercury compounds are defined as hazardous waste as they are
listed in entry C16 in Annex II of the Hazardous Waste Directive (when they fulfil the properties
described in Annex III of the same Directive). The Hazardous Waste Directive will be incorporated 35 Council Directive 91/689/EEC of 12 December 1991 on hazardous waste (OJ L 337, 31.12.1991, p. 20) with
last amendment from 19 November 2008, also referred as ‘Hazardous Waste Directive’
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and repealed by the new Waste Framework Directive (Directive 2008/98/EC) by 12 December 2010.
The new Waste Framework Directive does not adopt the list of constitutes of the wastes. However, it
adopts also in its Annex III the list of properties of waste which render it hazardous. In consequence
following the new Waste Framework Directive wastes containing mercury and mercury compounds
are defined as hazardous if fulfilling the properties listed in Annex III of Directive 2008/98/EC.
In case of stable and non-reactive waste provision 2.3 of the Annex of Decision 2003/33/EC allows
the disposal of hazardous wastes in landfills for non-hazardous waste if such wastes have been
rendered stable and non-reactive. Stable, non-reactive means that the leaching behaviour of the
waste will not change adversely in the long-term, under landfill design conditions or foreseeable
accidents (Provision 2.3 of Annex of Decision 2003/33/EC):
• In the waste alone (for example, by biodegradation),
• Under the impact of long-term ambient conditions (for example, water, air, temperature,
mechanical constraints),
• By the impact of other wastes (including waste products such as leachate and gas).
Annex III of the Landfill Directive lays down control and monitoring procedures during operation as
well as for the after-care phase of a landfill. The purpose of these procedures is to check that:
• the waste has been accepted to disposal in accordance with the criteria set for the category
of landfill in question,
• the processes within the landfill proceed as desired,
• the environmental protection systems are functioning fully as intended,
• the permit conditions for the landfill are fulfilled [Annex III, point 1 of Directive 1999/31/EC].
The control and monitoring programmes have to cover the following areas:
Table 5-4: Control and monitoring procedures for all classes of landfills according to Directive 1999/31/EC, Annex III
Control and monitoring procedures for all classes of landfills according to Directive 1999/31/EC, Annex III
Requirement / source Specification
Meteorological data
[Directive 1999/31/EC,
Annex III, section 2]
• MS decide how to collect data (in situ, national, etc.)
• If required for evaluating leachate behaviour data of precipitation,
temperature, wind, evaporation and atmospheric humidity data have to be
collected according to given schedule
Emission data
[Directive 1999/31/EC,
Annex III, section 3]
Data on water, leachate and gas control including:
• collection of leachate and surface water if present (volume and composition)
at representative points according to guidelines
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Control and monitoring procedures for all classes of landfills according to Directive 1999/31/EC, Annex III
Requirement / source Specification
• collection of surface water down- and up-stream
• gas monitoring representative for each section of landfill according to given
frequency and analysis and according to permit
Protection of
groundwater
[Directive 1999/31/EC,
Annex III, section 4]
• Sampling at measuring points for groundwater at inflow and outflow region
according to Sampling Guideline
• Monitoring based on parameters according to local conditions and level of
groundwater according to given schedule
• Determination of trigger level for change of groundwater composition in
permit
Topography
[Directive 1999/31/EC,
Annex III, section 5]
Data according to given schedule on:
• structure and composition of landfill
• setting behaviour of the landfill body
Decision 2003/33/EC (‘WAC Decision’)
Decision 2003/33/EC lays down specific requirements which have to be fulfilled by storage facilities
(landfills). Furthermore, the decision determines waste acceptance criteria for each type of waste to
be accepted at a certain type of landfill. More stringent protective measures at Member States level
are possible. This could be of particular relevance with reference to the limit values for cadmium and
mercury (see introduction to Annex of Decision 2003/33/EC).
The WAC Decision specifies in its Annex the procedure for waste acceptance at landfills as laid down
in Annex II, section 3 of the Landfill Directive. The procedures are generally applicable for all types of
landfills.
The following procedures are specified:
Table 5-5: Procedures for the acceptance of waste according to Decision 2003/33/EC, Annex
Procedures for the acceptance of waste according to Decision 2003/33/EC, Annex
Requirement / Source Specification
Function of the basic
characterisation
[Decision 2003/33/EC,
Annex, section 1.1.1]
(a) Basic information on the waste ( type and origin, composition, consistency,
leachability and where necessary and available other characteristic properties)
(b) Basic information for understanding the behaviour of waste in landfills and
options for treatment as laid out in Article 6(a) of the Landfill Directive
(c) Assessing waste against limit values
(d) Detection of key variables (critical parameters) for compliance testing and
options for simplification of compliance testing (leading to a significant decrease
of constituents to be measured, but only after demonstration of relevant
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Procedures for the acceptance of waste according to Decision 2003/33/EC, Annex
Requirement / Source Specification
information). Characterisation may deliver ratios between basic characterisation
and results of simplified test procedures as well as frequency for compliance
testing.
Fundamental
requirements for basic
characterisation
[Decision 2003/33/EC,
Annex, section 1.1.2]
Necessary data:
(a) Source and origin of waste
(b) Information on process producing waste (description, characteristics of raw
materials and products)
(c) Description of pre-treatment applied, or statement why no treatment
(d) Data on composition of waste and leaching behaviour, where relevant
(e) Appearance of waste (smell, colour, physical form)
(f) Code according to the European waste list36 (Commission Decision 2001/118/EC)
(1)
(g) Relevant hazard properties ( Annex III to Hazardous Waste Directive) for mirror
entries
(h) Information to prove that the waste does not fall under the exclusions of Article
5(3) of the Landfill Directive (liquid, explosive, corrosive etc.)
(i) Landfill class at which the waste maybe accepted
(j) If necessary, additional precautions to be taken at landfill
(k) Check if waste can be recycled or recovered
Compliance testing
[Decision 2003/33/EC,
Annex, section 1.2]
• Parameters, scope and frequency of testing determined in basic characterisation
(key variables)
• Same testing method as in basic characterisation
• Keeping of records
On-site verification
[Decision 2003/33/EC,
Annex, section 1.3]
• Visual inspection of waste before and after unloading at the landfill
• Same waste as described in accompanying documents / same as basic
characterisation
The extent of laboratory testing between basic characterisation and compliance testing is dependent
on the type of waste and if the waste is regularly generated within the same process or not. For
waste regularly generated, information on compositional range, variability of properties and key
variables are also necessary. Waste does not need testing if it is produced within the same process in
the same installation or within a defined and already tested process. There is also no testing
required, if the necessary information is well known and duly justified [Annex, Section 1.3 (a) and (b),
Decision 2003/33/EC].
36 Decision 2001/118/EC amending Decision 2000/532/EC as regards the list of wastes, 16 January 2001 (OJL
47, 16.02.2001, p. 1-31)
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In addition, short lists with EWC codes according to the European waste list are established by the
WAC Decision for wastes acceptable without testing. The acceptances of all other wastes primarily
depend on their leaching properties, which are laid down in the Annex to the WAC Decision [Section
2.1 to 2.4.]. The storage options of mercury containing waste depend mainly on the leaching limit
values for Hg as summarized for each landfill type in the following table:
Table 5-6: Mercury leaching limit values for different landfill types and standards according to Decision 2003/33/EC
Mercury leaching limit values for different landfill types according to Decision 2003/33/EC, Annex
Landfill type L/S =2 l/kg
mg/kg dry substance
L/S =10 l/kg mg/kg dry substance
C0 (percolating test) mg/l
Criteria for landfills for inert waste 0.003 0.01 0.002 Criteria for granular non-hazardous waste accepted in the same cell as stable non-reactive hazardous waste 0.05 0.2 0.03
Criteria for hazardous waste acceptable at landfills for non-hazardous waste
0.05 0.2 0.03
Criteria for waste acceptable for landfills for hazardous waste 0.5 2 0.3
Member States have the possibility to determine more stringent requirements (such as more
stringent leaching limit values, see chapter 5.3). In general, the limit values given are valid for all
kinds of storage facilities. However, in the case of hazardous waste disposed of in underground
disposal facilities, the leaching limit values are not valid. In such cases the waste has to be compliant
with the site specific safety assessment [Annex, point 2.5 of Decision 2003/33/EC].
The sampling and test methods which have to be used to determine the leachability are set in
Section 3 of the Annex to the Decision 2003/33/EC. Leaching tests have to be made in accordance
with EN 12457/1-4 ‘Leaching-Compliance test for leaching of granular waste materials and sludges.’
(Part 1: L/S=2 l/kg particle size <4mm; Part 2: L/S=10 l/kg particle size < 4mm; Part 3: L/S=2 and 8 l/kg
particle size <4mm and Part 4: L/S=2 l/kg particle size <10mm).
The WAC Decision foresees that Member States have to set criteria for monolithic waste to provide
the same level of environmental protection as for granular waste. In many Member States the
crunched monolithic waste has to fulfil the same leaching limit values as the granular waste.
The percolating test has to be carried out in accordance with prEN 14405 (CEN/TS 14405:2004)
‘Leaching behaviour test – Up flow percolation test for inorganic constituents’. Each of the Member
States has to decide which of the leaching tests shall be used.
Mercury containing waste which exceeds the indicated limit value set for a specific type of landfill
has to be treated again to reduce the content of mercury or to be stabilised to reduce the
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leachability.
Apart from the general requirements, the WAC Decision contains specific requirements for
underground disposal facilities (see chapter 5.2.3) and for salt mines (see chapter 5.2.4) and hard
The objective of the Directive on environmental liability with regard to the prevention and remedying
of environmental damage is to establish a common framework for the prevention and remedying of
environmental damage at a reasonable cost to society.
It applies to occupational activities which present a risk for environmental damage (land, water,
protected species and natural habitats), or human health [Recital 8 and 9 as well as Article 2 (1) of
Directive 2004/35/EC]. As laid down in the Mercury Regulation, it applies also to all storage facilities
for metallic mercury [Recital 8 of Regulation EC No 1102/2008]. The criteria for measuring damage
are laid down in Annex I of the Directive.
By implementing the ‘polluter pays’ principle, an operator causing environmental damage or creating
an imminent threat of such damage shall, in principle, bear the cost of the necessary preventive or
remedial measures. In cases where a competent authority acts by itself or through a third party (in
the place of an operator) the authority shall ensure that the cost incurred is recovered from the
operator [Recital 18 and Article 8(1) of Directive 2004/35/EC].
For such purposes the competent authority may require the operator to provide information on any
imminent threat or suspicion of threat of environmental damage and to take necessary preventive
measures. Additionally, the authority may give to the operator instructions to be followed on a
necessary preventive measure or to take the measure itself [Article 5 (3) of Directive 2004/35/EC].
Annex II of the Directive lays down the framework to choose the appropriate remediation measure.
Member States shall establish financial security instruments and financial guarantees enabling the
38 Directive 2004/35/EC of the European Parliament and of the Council of 21 April 2004 on environmental
liability with regard to the prevention and remedying of environmental damage (OJ L 143, 30.4.2004, p. 56–75), also referred as ‘Environmental Liability Directive ‘.
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operators to cover their responsibilities under the Directive [Article 14 of Directive 2004/35/EC].
UK / Northern Ireland [Schedule10 2007] 0.4 *Unit [mg/l] is used instead of [mg/kg]; values have been converted
In the following, the legal situation of some selected countries with underground disposal facilities is
described in more detail.
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5.3.3 Germany
Due to the lack of appropriate storage facilities, many EU Member States export Hg-containing waste
to other EU countries. Germany is the main importing country of mercury containing waste. On the
basis of information by [COWI 2008], Germany is also the only country importing mercury containing
waste for permanent storage (D12). Due to its hazardous and leaching properties Hg-containing
waste is typically disposed of in hazardous underground facilities (salt mines). Leaching requirements
for above-ground facilities are typically not met. Waste exceeding the limit values for above ground
landfills can be stored in underground facilities (no limit values related to mercury concentration, for
example) if it fulfils the site-specific waste acceptance criteria for the underground disposal site.
In Germany hazardous waste is only allowed to be deposited in salt rock due to the lack of hard rock
formations fulfilling the requirements of safe long-term storage. Therefore, in the new legislation
(see below) only requirements for underground disposals in salt rock are defined.
On 16 July 2009 the ordinance on the simplification of waste disposal regulations40 came into force.
This regulation has already taken into consideration Regulation (EC) No 1102/2008 as regards the
long-term storage of mercury. Following the regulation, the long-term storage of metallic mercury is
possible in landfill class III (above ground) and landfill class IV (underground storage). The class IV
landfills have been recently introduced for the purpose of mercury storage in Germany.
Liquid wastes are forbidden in long-term storage. An exception is made for the long-term storage of
liquid mercury (§ 23, para 2 of the Simplification Ordinance). The exception adopts the provisions set
down in Article 3 of Regulation (EC) No 1102/2008 [Kabinett 2008, questionnaire survey]. With
regard to above-ground storage (landfill class III), the landfill has to be dedicated for the storage of
mercury and needs to be operationally and technically equipped for this purpose. In the case of
underground storage (landfill class IV) the landfill has to be adapted for the purpose of disposing of
metallic mercury and this has to be taken into particular consideration in the site-specific safety
assessment. Wastes accepted into long-term storage facilities need to have a written certification
granting the planned recovery or disposal operation (§ 23, para 3 of the Simplification Ordinance).
The requirements referring to the site specific risk assessment set out in the WAC Decision, Appendix
A have been specified so far in German legislation in the Technical Instruction on Waste41. With the
Simplification Ordinance, the Technical Instruction on Waste is no longer in place since 2009. The
requirements are now set down in the Ordinance on Landfills42 which is included in the Simplification
Ordinance.
40 Verordnung zur Vereinfachung des Deponierechts vom 27. April 2009 (Bundesgesetzblatt Jahrgang 2009 Teil I
Nr. 22, ausgegeben zu Bonn am 29. April 2009), also referred to as the ‘Simplification Ordinance‘ 41 Zweite allgemeine Verwaltungsvorschrift zum Abfallgesetz (TA Abfall) vom 12. März 1991 (GMBl. Nr. 8 S. 139) last amendment on 21. März 1991. 42 Verordnung über Deponien und Langzeitlager (Deponieverordnung - DepV) vom 27. April 2009 (BGBl. I S.
900), also referred to as the ‘Landfill Ordinance‘.
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In order to obtain permission for the disposal of hazardous waste in salt rock in class IV landfills, a
long-term safety record is necessary in Germany. This concerns in particular site-specific
circumstances, including scheduled and non-scheduled (hypothetical) incidents. The long-term safety
record is essentially based on the results of the other two individual records, the:
• record of geotechnical stability, and
• safety record for the operational phase.
The record of geotechnical stability in particular plays a key role in evaluating the long-term
effectiveness and integrity of the salt barrier. If the complete enclosure has been verified by the
record of geotechnical stability, there is no need for any model calculations of unplanned incidents
and no need for a long-term safety record for model calculations on pollutant dissemination [Annex
2, 2.1.1]. The geotechnical stability has to be proven by a report from an expert in rock mechanics
requiring very detailed information about rock behaviour and rock mechanics based on geotechnical
laboratory experiments, on-site measurements and computational rock-mechanical modelling
[Annex 2, 2.1.4].
The long-time safety record summarises the information on the entire system ‘waste/underground
structure/rock body’. The record requires comprehensive information – for example about the
natural barriers of the host rock, the technical barriers and events that could endanger the whole
encapsulation (earthquakes, volcanism, leaks in boreholes etc.)
Annex 2 of the Simplification Ordinance includes instructions on the maintenance of long-term safety
records within the context of site-related safety assessments for mines in salt rock and applied in
practice. Most of the requirements have been laid down since 2002 and are already included in the
old Ordinance of Landfills43. Recently implemented are the requirements laid down in Annex 2, point
3 and 4 of the Waste Ordinance, addressing the closure of the deep underground disposal facility in
salt mines and the documentation of access to the mines after closure (including for example the
filling of pillars, introduction of a safety zone and documentation of waste filled). Table 5-16includes
the provisions for salt mines that complement the requirements of European legislation.
Table 5-16: Requirements for deep storage in salt mines according to German legislation
Requirement for deep storage in salt mines according to German Landfill Ordinance
Requirement / source Specification
Location / geological barriers
[Landfill Ordinance, Annex 2, point 1]
The salt barrier rock must have / must be:
• impermeable against gas and liquids
• adequate spatial spread
• adequate unworked salt thickness, being sufficiently large
that the barrier function is not impaired in the long term
• gradually enclosing the waste by its convergence behaviour,
43 Verordnung über Deponien und Langzeitlager (Deponieverordnung - DepV) vom 24. Juli 2002 (BGBl. I S.
2807), mit Änderungen vom 13.Dezember 2006.
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Requirement for deep storage in salt mines according to German Landfill Ordinance
Requirement / source Specification
and at the end of the deformation process, of encapsulating
it solidly
• stable cavities at least during the operational and closing
phase of the landfill
• storage is prohibited in regional areas where the earth
movement intensity of the value 8 according to the MSK-
scale44 is above 99%
Geotechnical stability
[Landfill Ordinance, Annex point 2, 2 and
2.1.4]
• In addition to the provisions set out in the WAC Decision
regarding the site-specific safety assessment (Appendix A),
the record of geotechnical stability is required (see above)
Geological properties
[Landfill Ordinance, Annex 2, point
2.1.2.1]
In addition to the provisions set out in the WAC Decision
regarding the geological assessment, the following
concretisations are made:
• Geological barrier; vertical distance from salt roof zone to
nearest upper underground, excavations; distances of
horizontal cavities from salt rock edges and vertical distance
from the footwall; thickness of the entire salt deposit or salt
rock body
• Degree of exploration of deposit
• Exploratory bore holes from above and below ground
• Stratigraphy in mining territory (including thicknesses, rock
face transitions)
• Material composition of salt deposit with ratio of salt rock to
potash rock, clays, anhydrites, carbonate rock
• Salt deposit structure/interior construction, structural
development including movements of the salt deposit and
its environment, convergence, bearings and underlays of
deposit, edge formation, transformations at surface of salt
deposit, position and formation of potential alkali
• Degree of tectonic stress on the salt structure, predominant
fault directions
• Geological cross-sections through the drifts
• Geothermal depth level
• Regional seismic activity in past and present
• Subrosion, formation of earth subsidence on surface
• Halokinesis
44 The Medvedev-Sponheuer-Karnik scale, also known as the MSK or MSK-64, is a macro seismic intensity scale
used to evaluate the severity of ground shaking on the basis of observed effects in an area of the earthquake occurrence. The scale ranges from 1 to 12. 8 denotes “damaging” (Many people find it difficult to stand, even outdoors. Furniture may be overturned. Waves may be seen on very soft ground. Older structures partially collapse or sustain considerable damage. Large cracks and fissures opening up, rock falls). See e.g. http://en.wikipedia.org/wiki/Medvedev-Sponheuer-Karnik_scale
existing exploratory bore holes from above and below
ground; insulated parts of drift and those that need to be
insulated)
Hydrological Assessment
[Landfill Ordinance, Annex 2, point
2.1.2.3]
In addition to the provisions set out in the WAC Decision
regarding the hydrological assessment, the following
concretisations are made:
• Stratigraphy, petrography, tectonics, thickness and storage
conditions of layers in the overburden and adjacent rock
• Details of the structure of aquifers and details of
groundwater movement
• Permeability and flow speeds
• Mineralisation of groundwater, groundwater chemism,
location of saltwater / freshwater boundary
• Use of groundwater, designated and planned drinking water
and healing water conservation areas and priority areas
Location, formation and properties of overground watercourses
and stagnant waterbodies and those in water-filled
underground caverns
Waste Information
[Landfill Ordinance, Annex 2, point
2.1.2.4]
In addition to the provisions set out in the WAC Decision
(Appendix A), information about waste is required (e.g. waste
types, quantities and properties, geomechanical behaviour of
waste, reaction behaviour).
Waste Information
[Landfill Ordinance, Annex 2, 2.1.2.4]
In addition to the provisions set out in the WAC Decision
(Appendix A), information about waste is required (e.g. waste
types, quantities and properties, geomechanical behaviour of
waste, reaction behaviour).
The old Ordinance on Landfills from 2002 included a leaching limit value for mercury in landfill class
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IV –disposal in rock other than salt rock - being 0,001 mg/l Hg. However, this limit value was not
transposed into the revised Landfill Ordinance (2009). Under the amended Landfill Ordinance only
salt mines are covered by the landfill class IV. Since in salt mines total containment and permanent
isolation from the biosphere is assumed, leaching limit values are not required.
Furthermore, the Federal Mining Act45 includes requirements for underground storage. Nevertheless,
it is not relevant to the storage of hazardous waste, as underground storage is defined as storage of
gas, liquid and solid materials without containment.
5.3.4 Sweden
Sweden is recognised as having the most far-reaching approach to mercury waste.
Sweden has a national environmental goal and legislation stating that the use of mercury shall be
phased out. In addition, mercury waste shall be deposited in final storage underground to eliminate
emissions and to isolate mercury from the biosphere.
Since 1 August 2005 Sweden implemented an ordinance regarding mercury in waste (Waste
Ordinance 2001:1063) which states: Waste that contains at least 0.1 percent by weight mercury and
is not in a permanent landfill shall be placed in deep underground disposal by 1 January 2015 at the
latest. It is not allowed to dispose of mercury waste before 1 January 2015 in a way that prevents
terminal storage in bedrock. [COWI 2008, questionnaire survey]
The Swedish ordinance regarding mercury in waste (Waste ordinance 2001:1063) states: Waste that
contains at least 0,1 % by weight mercury and is not in a permanent landfill shall be placed in deep
underground disposal. The rules mentioned above do not apply for mercury waste that is covered by
the Regulation (EC) 1102/2008. [personal information Mr. Carl Mikael Strauss, Swedish EPA]
The characteristics of deep underground disposal must however be viewed in the light of other
barriers such as containment, and if the waste is stabilised or not. Both salt mines and underground
hard rock formations can fulfil the requirements [Questionnaire survey, SE].
5.3.5 UK
The Environmental Permitting System of England and Wales of Regulation 200746 gives effect to the permitting requirements of Articles 9 & 10 of the EU Waste Framework Directive to ensure that waste is recovered or disposed of without endangering human health or the environment. The EU
45 Bundesberggesetz vom 13. August 1980 (BGBl. I S. 1310), mit Änderungen vom 31. Juli 2009 (BGBl. I S. 2585) 46 Environmental Permitting (England and Wales) Regulations 2007
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Landfill Directive and the WAC Decision are both implemented by Regulation 2007, Schedule 1047 for England and Wales. The provisions of both documents have been taken over with minor differences regarding the acceptance and limit values laid down in § 6 to 8 in Schedule 10. The provisions set for disposal facilities are unaffected. The same is valid for Northern Ireland48 and Scotland49.
5.4 Legislation of non-EU countries
5.4.1 Norway
Since January 2008, the Norwegian Pollution Control Authority banned the use of mercury in all
products within the country (Norwegian Product Regulation, Produktforskriften). In addition, the
importing, exporting and selling of products containing mercury or mercury compounds is forbidden.
There are limited exemptions for some areas of use until December 2010. At the moment, it is very
uncertain if elemental mercury will be allowed for export from Norway, it depends on whether the
authorities will regard elemental mercury as a product or not [Kystverket 2008].
In Norway, there is a need to store mercury containing waste from zinc-production (one site).
Mercury containing waste from zinc-production is treated for final disposal. The mercury-residue
from zinc-production is cemented in sarcophagi and placed in a bedrock hall at the production site
[NO 2005, COWI 2008]. There are no emissions of mercury reported from this activity [COWI 2008].
In the future, there might be a need to store unexpected mercury-waste, as in 2003 a submarine-
wreck from the World War II was discovered, containing large amounts of mercury. Historic
documents state that the submarine contains 65 tons of metallic mercury which is stored in steel
ampoules. The area surrounding the submarine is monitored, but so far no decision has been made
about bringing the mercury cargo up from the ocean floor.
Following the statement of [NO 2005], Norway prefers a terminal disposal in a safe manner that
meets standards for long-term environmentally sound management.
5.4.2 USA
The US approach relating to governmental as well as non-governmental surplus metallic mercury is
long-term storage (>40 years) in appropriate above ground facilities.
In 2008 the US Congress adopted the ‘Mercury Export Ban Act of 2008’ [US ban 2008]. This Act
47 Schedule 10: Provision in relation to landfill to the Environmental Permitting (England and Wales) Regulations 2007, 48 Schedule 2 (General requirements for landfills) of the Landfill Regulations (Northern Ireland) 2003 with amendments from 2004 and 2007 49 The Environment Act 1995, The Criteria And Procedures For The Acceptance Of Waste At Landfills (Scotland)
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for example recommendations on land-based sources of mercury pollution and also addressed
specific industrial sectors such as the chlor-alkali industry [PARCOM, 1981a and 1982a, 1985].
More recent agreements from OSPAR focus on the management of contaminated, dredged material
[OSPAR 2009] and the realisation of coordinated monitoring programmes [OSPAR 2008].
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5.6 References
[Basel 2010] http://www.basel.int/ Concorde 2009] Concorde sprl, Assessment of excess mercury in Asia, 2010-2050, May 2009, http://www.chem.unep.ch/mercury/storage/Asian%20Hg%20storage_ZMWG%20Final_26May2009.pdf [COWI 2008] COWI A/S and Concorde East/West Sprl, Options for reducing mercury use in products and applications, and the fate of mercury already circulating in society, December 2008 http://ec.europa.eu/environment/chemicals/mercury/pdf/study_report2008.pdf [Decreto 2003] Criteri di ammissibilità dei rifiuti in discarica. Ministero dell'ambiente e della tutela del territorio, 13 marzo 2003, Italy http://www.reteambiente.it/normativa/4355/dm-ambiente-13-marzo-2003/ [Deponieverordnung 2008] 39. Verordnung des Bundesministers für Land- und Forstwirtschaft, Umwelt und Wasserwirtschaft über Deponien, Januar 2008, Germany [DepVereinfachV 2009] Verordnung zur Vereinfachung des Deponierechts, Germany 27. April 2009, http://www.bmu.de/files/pdfs/allgemein/application/pdf/depvereinfv.pdf [DOE 2009] U.S. Department of Energy, Interim Guidance on Packaging, Transportation, Receipt, Management, and Long-Term Storage of Elemental Mercury, U.S. Department of Energy Office of Environmental Management Washington, D.C., November 13, 2009, http://www.mercurystorageeis.com/Elementalmercurystorage%20Interim%20Guidance%20(dated%202009-11-13).pdf [DNSC 2004] Defense National Stockpile Center, Record of Decision for the Mercury Management EIS, April 2004 [FNADE/ADEME 2006] Feedback on the French system, stabilisation/solidification-landfilling of hazardous waste, FNADE/ADEME, 2006 [IKIMP 2009] Briefing note for participants for "Workshop on Safe Storage and Disposal of Redundant Mercury", St Anne’s College, Oxford (UK), 13th & 14th October, 2009,
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[PARCOM 1985] PARCOM Recommendation 85/1 on Limit Values for Mercury Emissions in Water from Existing Brine Recirculation Chlor-Alkali Plants (exit of factory site), Brussels 1985 [Schedule10 2007] The Landfill (Amendment) Regulations (Northern Ireland) 2004 Statutory , Rule 2004 No. 297, The Landfill (Amendment) Regulations (Northern Ireland) 2004 [Scotland Directive 2005] The Environment Act 1995, The Criteria And Procedures For The Acceptance Of Waste At Landfills (Scotland) Direction 2005 [Seveso Guidance 2005] Guidance on the preparation of a safety report to meet the requirements of Directive 96/82/EC as amended by Directive 2003/105/EC (Seveso II), Report EUR 22113 EN, Institute for the protection and security of the citizen, Major accident hazardous bureau, European Commission, DG Joint Research Centre, 2005 http://mahbsrv.jrc.it/downloads-pdf/safety_report_guidance_EN.pdf [UNEP 2007] Draft technical guidelines on the environmentally sound management of mercury wastes, 2007, http://www.basel.int/techmatters/mercury/guidelines/240707.pdf [UNEP 2009] UNEP, Draft technical guidelines on the environmentally sound management of mercury wastes, 4th Draft, April 2009, http://www.basel.int/techmatters/mercury/guidelines/040409.doc [UNEP 2009 A] UNEP Chemicals, EXCESS MERCURY SUPPLY IN LATIN AMERICA AND THE CARIBBEAN, 2010-2050, ASSESSMENT REPORT, July 2009 http://www.chem.unep.ch/mercury/storage/LAC%20Mercury%20Storage%20Assessment_Final_1July09.pdf [UNEP 2009 B] http://www.chem.unep.ch/MERCURY/ [US ban 2008] Mercury export ban Act 2008, Public Law 110-414 - Oct, 14., 2008, 122 Stat. 4341, http://www.govtrack.us/congress/bill.xpd?bill=s110-906 [VLAREM 1995] VLAREM II: Order of the Flemish Government of 1 June 1995 concerning General and Sectoral provisions relating to Environmental Safety, 1th June 1995, Belgium
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[WHO 2005a] World Health Organisation, Policy Paper: Mercury in health care, August 2005; http://www.who.int/water_sanitation_health/medicalwaste/mercurypolpaper.pdf [WHO 2007] World Health Organisation, Preventing disease through healthy environments exposure to mercury, A major public health concerns, Geneva 2007 [WHO 2007a] World Health Organisation, risks of heavy metals from long-range transboundary air pollution, Joint WHO/Convention Task Force on the Health Aspects of Air Pollution, Germany 2007 [WHO 2008] World Health Organisation, Assessing the environmental burden of disease at national and local levels. Environmental Burden of Disease Series, No. 16, Geneva 2008
• Geochemical factors (pH, redox, other cations and complexation agents in solution)
• Retardation/attenuation processes
o Hydrodynamic dispersion
o Diffusion
o Sorption and ion exchange (pH dependent)
o Precipitation and co-precipitation (redox dependent)
o Microbiological factors
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• Establishment of distribution coefficient, ‘Kd’ (equilibrium ratio of the sorbed to dissolved
concentrations)
Experiences related to the underground storage of liquid waste mercury are not available as mercury
is still a valuable product used for various applications worldwide (see chapter 1.1). Up-to-date
relevant experience or investigations are available from
• permanent storage of mercury containing waste in salt mines (in particular German
experience from storage of hazardous waste) (see section 6.2.2)
• permanent storage in deep hard rock underground formations of hazardous waste (Swedish
experience on deep bedrock and stabilisation as HgS) (see section 6.2.3)
In addition, specific experience and investigation is available from the worldwide work on
underground disposal of radioactive waste which relies particularly on the principle of isolating the
radioactive waste from the biosphere for a very long time (see section 6.2.4).
The review related to the temporary storage of metallic mercury above ground is based on
experience from the temporary storage of liquid mercury in the USA and of Mayasa in Almadén
(former mercury mine), which stores and handles significant quantities of mercury as a product (see
section 6.3).
The containment of the waste is in particular important for the temporary storage of liquid mercury
as it has to ensure a safe containment of the waste for a certain period of time. For long-term
storage the major function of the container is to ensure a safe handling of the waste before storage
(and for a certain time period until the waste cell is closed). An overview of the containers currently
used in Europe for the transport and storage of liquid mercury (as a product) and as well as the
packaging system used in the USA for a foreseen storage period of 40 years, are described in section
6.4).
6.2 Review of underground disposal operations
Underground disposal is based on the principle of isolating waste from the biosphere in geological
formations where it is expected to remain stable over a very long time. Information on experience
from current underground storage of liquid mercury is not available. In the European Union the
acceptance of liquid waste is forbidden in landfills (Article 5(3)(a), Directive 1999/31/EC). A review of
the state-of-the-art of disposal operations for hazardous waste, and in particular metallic mercury, in
salt mines or deep underground hard rock formations can take account of experience with the
underground disposal of hazardous waste and radioactive waste.
Experience with the disposal of mercury-containing waste and other hazardous waste has been
available for several decades (e.g. underground waste disposal since 1972 in a German salt mine).
Valuable information can also be drawn from experience in the underground disposal of radioactive
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waste. In order to ensure an appropriate level of safety via the geological barrier, underground
disposal of radioactive waste is usually carried out in depths ranging from several hundred to about
one thousand metres (see e.g. [IAEA 2009]).
Although the properties of radioactive waste are somewhat different to liquid mercury,53 experiences
from research in particular related to geological requirements of host rocks like the stability are also
valid for the permanent storage of liquid mercury.
The most relevant sources of information related to the underground disposal which were consulted
are listed below:
Table 6-1: Overview of literature related to the storage of liquid mercury
53 Radioactive waste is typically solid or immobilised, partly heat generating and the hazardousness decreases
over a long period. In contrast to this, metallic mercury waste is primarily liquid, it does not generate heat and its hazardousness remains stable over unlimited time.
Review of important literature related to underground storage options
Reference Content
[BGR 2007]
BGR, Bundesanstalt für Geowissenschaften und Rohstoffe, Nuclear waste disposal in Germany - Investigation and evaluation of regions with potentially suitable host rock formations for a geologic nuclear repository, Hannover/Berlin, April 2007
This study summarizes the findings related to a geological disposal of nuclear waste in Germany including minimum requirements for the host rock.
[GRS 2008]
GRS, Gesellschaft für Anlagen- und Reaktorsicherheit (GRS) mbH, Öko-Institute e.V., Institut für angewandte Ökologie, Endlagerung wärmeentwickelnder radioaktiver Abfälle in Deutschland, Anhang Wirtsgesteine – Potentielle Wirtsgesteine und Eigenschaften, Anhang zu GRS-247, ISBN 978-3-939355-22-9, Braunschweig/Darmstadt, September 2008
This annex comprises main properties of possible host rock for the disposal of radioactive waste in Germany. It provides a broad overview of the different properties of potential host rocks including their advantages and disadvantages in view of a safe long term storage.
[IAEA 2009]
Geological Disposal of Radioactive Waste: Technological Implications for Retrievability
This report provides an overview of the current status of geological disposal of radioactive waste. The report assesses the technological implications of retrievability in geological disposal concepts. Scenarios for retrieving emplaced waste packages are considered, and the publication aims to identify and describe any related technological provisions that should be incorporated into the design, construction, operational and closure phases of a
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A list of all references used for this chapter is provided in chapter 6.5. Additional information
received personally during the research is also included in this section.
6.2.1 Potential host rocks
In Europe, many deep mines of different types of rock exist which might be generally suitable for the
storage of hazardous waste [Popov 2006]. Depending on their geological formation, mines which are
currently still in use might be used as hazardous waste disposal sites in future. Information on
existing underground disposal sites is mainly available for EU 15. But also in the Eastern European
repository.
[KEMAKTA 2007] Lars Olof Höglund and Sara Södergren, Aspects on final disposal of mercury – The need for waste stabilization, 22 March 2007
The purpose of this document was to establish background documentation for the proposal of the Hg-Regulation.
[Popov 2006]
V. Popov, R. Pusch, Disposal of Hazardous waste in underground mines, Wit Press, Southhampton, Boston, 2006
This book contains a collection of articles presenting the current experiences in the utilization of underground mines for the safe storage of hazardous waste. The book provides a broad overview of mines in Europe (active and inactive). In addition, articles by various authors to the following topics are included: Criteria for selection of repository mines, engineered barriers, stability analysis of mines, risk assessment of underground repositories.
[SOU 2008A]
Statens offentliga Utredningar (SOU) 2008: 19: Att slutförvara långlivat farligt avfall i undermarksdeponi i berg - Permanent storage of long-lived hazardous waste in underground deep bedrock depositories, , SOU 2008: 10 April 2008
This study – commissioned by the Swedish government – analyses the permanent storage of mercury in deep bedrock and salt mines. The report provides an account of permanent storage options for mercury-containing waste, and the requirements and risks attendant to the permanent storage of liquid mercury.
A summary on the key findings of the study is available in English [SOU 2008]
[SOU 2001]
NATURVÅRDSVERKET, A Safe Mercury Repository, A translation of the Official Report SOU 2001:58, Report 8105, January 2003
This report was prepared before the Hg-Regulation entered into force. It recommends that waste containing at least one percent mercury by weight be taken to a permanent deep bedrock repository (at least 400m). The repository should isolate mercury from the biosphere for a very long period, preferably more than 1,000 years. The repository should require no maintenance to avoid burdening future generations.
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countries underground disposal sites are in place (e.g. Slovenia) or planned (e.g. Poland).
Appropriate host rock for disposal of metallic mercury according to Council Decision 2003/33/EC are
salt rocks and hard rocks (igneous rocks, e.g. granite or gneiss including also sedimentary rocks e.g.
limestone or sandstone). Furthermore, deep storage in hard rock with an appropriate depth is
defined as an underground storage at several hundred metres depth (WAC Decision, Appendix A (4)).
In a geological sense, the term hard rock includes igneous rocks (e.g. granite or basalt), metamorphic
rocks (e.g. slate, marble, gneiss, schist) and sedimentary rocks (e.g. sandstone, shale, limestone). Salt
rock is a specific sedimentary rock. Further, it can be differentiated between consolidated and non-
consolidated rocks. Consolidated rocks consist of a mixture of minerals with primary solid matrix
material. Examples are breccia/conglomerate, sandstone or claystone. Non-consolidated rocks are
non-bound fragmental rocks without solid matrix material. Examples are gravel, sand or clay. Each
type of consolidated hard rock is theoretically possible for underground disposal sites for mercury.
This generally corresponds to experiences from disposal options for radioactive waste according to
which preferred host rocks could be hard rock (i.e. crystalline igneous rock), clay rock (i.e. igneous
sedimentary rock) and salt rock. Underground laboratories for testing and building confidence in
disposal technologies for the disposal of radioactive waste have been built in all types of potential
host rocks [IAEA 2009].
The host rock properties are decisive for the design and the operational and environmental safety (in
the short and long term) of an underground disposal site and other relevant aspects (e.g.
retrievability, costs, etc.). Relevant properties of potential host rocks are in particular available from
experience in underground disposal of radioactive waste (see [IAEA 2009]), [BGR 2007] and [GRS
2008].
In the following, an overview is provided on the properties, available experiences, economic and
environmental information of potential host rocks for the storage of liquid mercury.
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6.2.2 Salt rock
6.2.2.1 Properties
Salt host rocks exist in different geological formations as layered salt and salt domes, usually of a
sodium or potassium type. Both geological formations may in principle be used for disposal purposes.
The following table summarizes the main properties of salt rock related to its suitability as a host
rock (source: [GRS 2008], [GRS 2009], [Popov 2006]):
Table 6-2: Overview of properties of salt rock
Criteria Properties
Permeability Very low (practically impermeable)
Mechanical Strength: Medium
Deformation behaviour: Visco-plastic (creep)
Stability of cavities: Self-supporting
In situ stresses: Isotropic
Dissolution behaviour: High
Sorption behaviour: Very low
Salt rock is very dry, it contains no free water and offers very good isolation of the waste. Under
natural disposal conditions rock salt is practically impermeable to gases and liquids. Together with an
overlying and underlying impermeable rock strata (e.g. claystone), it acts as a geological barrier
intended to prevent groundwater entering the landfill and, where necessary, effectively to stop
liquids or gases escaping from the disposal area (see Council Decision 2003/33/EC). On the other
hand, salt rocks are highly soluble, thus any access of water would cause severe consequences on the
host rock. Salt rock is perfectly impermeable with respect to water and gas [Popov 2006] as a
consequence no gas producing materials should be stored to avoid an increase of pressure in the
rock. Recent research give indications that in case of gas generation there will be no “explosion” and
the gas will not escape via a macroscopic fracture – as assumed so far. According to [Popp 2007]
recent research micro fractures occur in the near field along existing grain boundaries with the effect
that an increased volume is available for the generated gas. It can be concluded that the permeability
of the surrounding salt rock decreases in the near field and is only relevant for a defined area around
the stored material. It stops as soon as the pressure does not increase anymore. [Brückner 2003,
Popp 2007]
Salt rocks generally have a low sorption capability (see [GRS 2009]. Information related to its sorption
capacity for mercury has not been identified.
The hydraulic conductivity of rock salt is very low. In [GRS 2008] the following values have been
indicated for rock salt:
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Hydraulic conductivity (Kf in m/s) Average depth of
samples
N° of
samples Range Median value
Rock salt 300 – 841 m 75 9.81 x 10-17 - 2.94 x 10-10 5.50 x 10-14
A liner is usually not required in salt formations. Here, rock creep is a continuous process leading to
rock deformation in response to lithostatic pressure. Salt creep will close the void space around
waste packages in the emplacement cells, leading to complete encapsulation. The creep rate
depends on in situ stress (increasing with depth) and temperature.
The investigation of the structure of layered salt mines is easier – compared to salt domes, and well
established investigation methods are available [GSR 2008]. In particular, the presence of brine in
local lenses or irregular structures or fissures may cause difficulties for a safe storage. Therefore, the
presence of such structures has to be excluded via a site-specific safety assessment. [Popov 2006].
Due to its plastic deformation behaviour the salt rock encapsulates wastes in the long term. The
encapsulation process is enhanced by backfill material. Given that salt encapsulation is one of the
main safety elements of a disposal concept in salt, it is advantageous to backfill the emplacement
cells rapidly after waste emplacement, and keeping the disposal cells open has never been
considered in the German salt based repository concept (for disposal of radioactive waste) [IAEA
2009]. The most appropriate backfilling material for salt rock is crushed salt rock with a major barrier
function [Popov 2006]. At the German underground Herfa-Neurode waste disposal site, salt dams are
filled up or stone walls are built in order to separate the storage cells and to facilitate the ventilation
of the disposal site.
The operators of the Herfa-Neurode disposal site assume that the galleries of the underground salt
mine will be completely closed within some thousand years54.
Long-lasting seals in the form of plugs in the shafts leading down to the repository level are required
since water inflow from shallow soil and rock can cause very difficult problems [Popov 2006]. The
plug system has to be adapted to site specific requirements.
6.2.2.2 Experience of underground disposal of hazardous waste in salt mines
Hazardous wastes including mercury contaminated solid wastes have been deposited in underground
salt mines for several decades in Europe. Therefore, an extensive knowledge base on all repository
relevant properties of rock salt and salt formations is available (in particular in Germany).
In Europe, salt mines are currently authorised for the underground disposal of hazardous waste only
in Germany and the UK. Poland is currently considering using specific salt mines for the disposal of
hazardous waste.
54 Personal Communication, Dr. Lukas, K&S Entsorgung GmbH, 5.11.2009
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In France, the first underground landfill was opened in February 1999 in a potash-salt mine in
Wittelsheim, France-Alsace, with a licensed capacity of 320,000 tons (for 30 years). 13 different
waste types including galvanisation sludge, spent catalysts and residues from waste incineration
were licensed. The deposit of explosive and flammable wastes was forbidden. In September 2002, a
fire broke out in the underground landfill which may have been caused by improper disposal. As a
consequence of the fire, the landfill and the adjacent mine were closed. [UBA DE 2004]
Salt mine in the UK
A relatively new salt mine deposit for the storage of hazardous waste has been operating in
Winsford, Cheshire, United Kingdom since 2005 (Minosus rock salt mine). The site is permitted
according to the IPPC directive and has a licence for selected waste codes.
At Minosus rock salt mine, waste disposal takes place at a specific 30-hectare worked-out area of the
mine and its activities will have no impact upon either continuing rock salt extraction or upon the
area dedicated to and used for archiving and document storage.
The site consists of a 200 million year-old bed of rock salt formation and the hazardous waste is
disposed of at a depth of 170m. The storage capacity of the mine is 2 million tonnes of hazardous
waste over the next 20 years including incinerator and heavy industry waste and asbestos. Up to
100,000 tonnes of suitably packaged wastes can be handled each year. [Minosus 2009]
The facility is licensed to handle different categories of waste – including hazardous waste such as air
pollution control residues – some of which will be disposed of and some stored. The range of waste
accepted includes ashes with dangerous substances, which might also be mercury. Currently, the
facility is not permitted to receive mercury wastes (source: questionnaire survey reply UK).
Under its Environment Agency permit, Minosus can accept 42 different categories of waste included
in the European Waste Catalogue. A further 24 potential waste categories are permissible but are
subject to Environment Agency improvement orders. [Minosus 2009]
While the Minosus facility is exempt from the need to meet the leaching limit values imposed by the
Waste Acceptance Criteria Decision, the company does have its own parameters for waste
acceptance55. The waste acceptance procedure follows the provisions of Directive 2003/33/EC (see
chapter 5). The containers will be opened upon arrival for further sampling to verify their contents
and then sealed again before being taken underground.
Before the permit was given to the Minosus mine extensive research and assessments have been
carried out related to the long-term safety of the storage site. “No other waste management facility,
save for those in the nuclear industry, has been as deeply researched and assessed as the Minosus
facility” [extract of the report commissioned by the Environment Agency and prepared by Cranfield
University in 2004, [Minosus 2009]. The elaborated scenarios look forward as far as 50,000 years into
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In accordance with Decision 2003/33/EC, waste is only accepted if random tests have proven that the
waste has the identity as indicated in the corresponding waste documents and fulfils the waste
acceptance criteria. Otherwise the disposal of the waste is rejected.
Depending on the waste identity the waste is disposed of in appropriate containers (steel panel
barrels, steel panel containers or large bags) and eventually an appropriate inner packaging in order
to facilitate the handling of the waste (e.g. during sampling) and/or to protect the containers from
corrosive waste.
Salt mines are typically equipped with a ventilation system. According to the information received
from the operator of Herfa-Neurode, the salt mine is equipped with a permanent monitoring system
which – apart from other parameters – already monitors the mercury concentration in the air.
6.2.2.3 Economic information – hazardous waste in salt mines
According to information from the operators of the disposal sites Herfa-Neurode, Zielitz,
Niederrhein, Heilbronn and Sondershausen (all in Germany), the costs for disposal of 1 tonne of
hazardous waste is approximately 260-900 euros, irrespective of the hazardousness of the disposed
waste (e.g. metallic mercury or pre-treated mercury). The only condition is that the site-specific
waste acceptance criteria are fulfilled. The upper end of the price already includes additional costs
which might result from specific storage requirements for hazardous waste (e.g. separate chamber,
isolated area). The prices are based on recent conditions. Depending on additional requirements that
facilities have to fulfil for the storage of liquid mercury (e.g. regular monitoring and inspection), the
price might be higher. The costs for temporary storage in salt mines depend on the necessary
additional monitoring, inspection requirements and the costs for the retrieval of the stored material.
6.2.2.4 Environmental and safety aspects related to the storage of hazardous waste in salt mines
Due to its plastic deformation behaviour, salt rock may completely enclose metallic mercury in a gas-
tight and impermeable geological barrier. Under natural disposal conditions, rock salt is practically
impermeable to gases and liquids. [BGR 2007]
A study [Siemann 2007] investigated the origin and migration behaviour of mineral bonded gases in
evaporite (salt rock). The study concludes that gases which have been generated during the
sedimentation and diagense (forming of the rock) have not moved significantly before they have
been finally fixed in the investigated salt rock. This means that the gases have been fixed in the salt
rock for 250 million years. Undisturbed salt rock can therefore be seen as gas tight even in cases of
the easily migrating hydrogen molecule.
58 http://www.ks-entsorgung.com/export/sites/ks-
entsorgung.com/de/pdf/annahmebedingungen_utd_zielitz.pdf (in German) 59 http://gses.de.server378-han.de-nserver.de/uploads/media/UTD-Annahmebedingungen_07-2006.pdf (in
German)
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In long term storage, the only effective barrier to prevent hazardous waste entering the environment
is the salt rock and its specific isolation criteria. Therefore, a minimum thickness of the salt layer is
needed around the waste to ensure the safe encapsulation of it. For short-term storage, additional
engineered barriers, such as containment or constructed barriers, can be applied.
For the storage of radioactive waste, minimum requirements for the thickness of the host rock have
been established to ensure a safe storage [BRG 2007]. These criteria are included in section 6.2.4.1.
On the basis of literature available on the subject (e.g. [Popov 2006], [IAEA 2009]), salt mines in
general are seen as appropriate for the storage of hazardous waste. But only mines located several
hundred metres below the ground surface should be considered as appropriate for storage of
hazardous waste [Popov 2006].
[Env Canada 2001] also included the disposal of mercury waste in conventional mines and solution
mines in its analysis. While solution mines60 have been assessed as less appropriate with regard to
health, safety, environment and plant operations, the disposal of mercury waste in conventional
mines (e.g. slat, potash, gypsum, limestone or underground granite) has been assessed as highly
suitable for the disposal of excess mercury. But only on condition that pre-treated waste containing
mercury is placed in a stable semi-soluble form in containers. According to [Env Canada 2001]
conventional mines could also be used as a long-term underground warehouse, if retrievability for
recycling were desired.
[USEPA 2002c] included in the analysis of alternatives for the long-term management of excess
mercury the temporary storage of liquid (bulk) mercury as well as the disposal of pre-treated
(stabilised) mercury waste. In particular, the temporary storage of liquid mercury in an already
existing mine cavity has been evaluated as an appropriate storage option for liquid mercury.
In Germany, the disposal of liquid mercury in salt mines is seen as a long term safe solution as long as
all legal requirements are fulfilled and the long-term assessment of the underground facility allows
the storage of liquid mercury (source: questionnaire survey German EPA).
However, until now only very limited information is available related to the behaviour of liquid
mercury in salt rock. First research results relating to the solubility of metallic mercury and mercury
compounds in saline solutions are available but have to be further investigated [GRS 2008A,
personnel information: Mr. Hagemann, GRS]. Indications suggest that the solubility of mercury in salt
solutions is lower compared to pure water [GRS 2008A] but is nevertheless significantly higher
compared to mercury sulphide for example, see also section 4.1.2.
According to information from German authorities, a project is planned to test the behaviour of
metallic mercury in salt and salt solutions. The intended start of this project is in 2010 (source:
60 Mines which have been created by solution mining which means the extraction of the materials from the
earth by leaching and fluid recovery.
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questionnaire survey German EPA, personal communication Ms. Hempen, BMU61). According to the
information received from the German Environment Ministry, permanent storage of metallic
mercury in a German salt mine would not be authorised before the results of the study are available.
Most probably the planned project also includes investigations about the behaviour of stabilised
mercury or mercury compounds in salt rock.
There are also concerns related to salt host rock as a permanent storage site for liquid mercury.
A Swedish report [SOU 2008] states that salt mines have properties which enable the waste to be
completely enclosed. But for this to occur it is important that “the deformations occur without
cracks, and the shafts, inspection drill-holes and the like that link the terminal storage facility to
flowing groundwater are properly sealed. If waste contamination leaks from the salt formation, it is
crucial that the surrounding rock has a natural ability to immobilise it, to ameliorate the effects of a
leak.”
In the report, possible scenarios for the permanent underground storage of liquid mercury in salt
mines and related potential environmental risks (see [SOU 2008] “Safety analysis and scenarios for
salt mine storage”) are described. The main concerns are:
• Possible sinking of the “heavy” mercury (which is seen as a long process that can take place
over hundreds or thousands of years) and thus increased risk of liquid mercury coming in
contact with open fissures
• Salt rock formations are affected by convergence, thus the waste is subject to pressure over
time which might result in it being squeezed out, into the access shaft for example.
• Fissures in the salt rock might result in a release of the liquid mercury or mercury vapour into
the biosphere.
• Chemical reaction in the storage site (e.g. reaction between mercury and containment) might
result in gas formation and a corresponding pressurisation with the risk of mercury being
pressed out through sealing plugs, fissures or pores of the rock. Corrective measures and
retrieval of waste is more difficult in cases where liquid mercury is stored without containers;
in addition, mercury might very efficiently leach through existing pores and fissures and the
ability of mercury to penetrate might also cause new pores and fissures.
• Possible plug leaks due to very high petrostatic pressure at greater depths. As a consequence
an effective enclosure of the mercury at a depth of 500 m would require plugs with a very
dense structure (max. pore radius: 68-80 nm).
61 BMU: Bundesministerium für Umwelt, Naturschutz und Reaktorsicherheit (Federal Ministry for the
Environment, Nature Conservation and Nuclear Safety, Berlin)
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During a workshop at Oxford in October 200962 in particular the lack of information related to the
behaviour of mercury and mercury compounds in salt rock has been raised as major concern. No
post-closure models related to the long term behaviour of liquid mercury or other mercury
compounds are available up to now. According to expert opinions expressed during the workshop,
post-closure models developed for the disposal of radioactive waste could be adapted to the specific
characteristics of mercury.
6.2.2.5 Conclusions: salt rock
Valuable information on the properties of salt rock is available in particular from the research for a
safe nuclear waste disposal ([GRS 2008], [BGR 2007]). In particular, the salt rock properties such as
gas and liquid impermeability, total encapsulation of the waste, very low hydraulic conductivity and
high stability of cavities qualify salt rock as a host rock for metallic mercury as well as for other
mercury compounds [GRS 2008], [Popov 2006]. Apart from the rock properties the stability of the
formation, the overlying impermeable strata and the exclusion of water entering the storage site are
crucial for underground storage sites in salt mines [Popov 2006], [WAC Decision].
The geological properties of existing underground disposals sites in salt rock in Europe which might
be relevant for the permanent or temporary storage of liquid mercury are well investigated to reduce
the probability of unexpected incidents. A site-specific risk assessment – as outlined in the WAC
decision, Appendix A and prepared by independent experts or institutions – is crucial to determine
the effectiveness of the host rock as a geological barrier and its capability to isolate the waste from
the biosphere over a very long time. Based on the site specific risk assessment a list of waste is
derived which is allowed to be stored in the salt mine. In salt mines only waste can be stored which is
specifically permitted for the site.
In Europe currently 5 underground salt mines are authorised as underground disposal sites for
hazardous waste. Experience with regard to the storage of liquid mercury as well as large amounts of
stabilised mercury (e.g. mercury sulphide) in salt rock is not yet available. The only experience
available is from storage of mercury containing waste in a salt mine in Germany over several
decades.
Several studies ([USEPA 2002c], [Env Canada 2001]) assessed salt mines as an appropriate option for
stabilised mercury. [USEPA 2002c] evaluated the temporary storage of metallic mercury in existing
cavities in salt mines as a possible option.
In general salt mines are seen as safe disposal options for hazardous waste ([Popov 2006], [IAEA
2009], but concerns related to a permanent storage of metallic mercury still remain [SOU 2008] due
to its specific properties. Up to now, specific studies or risk assessments related to the behaviour of
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6.2.3 Hard rock formations
6.2.3.1 Properties of crystalline hard rocks
In the following, the most important properties of crystalline rock (e.g. granite and metamorphic
rocks) are summarised (source: [GRS 2008], [GRS 2009], [Popov 2006]:
Table 6-3: Overview of properties of crystalline rock
Criteria Properties
Permeability Very low (unfractured) to high (fractured)
Hydraulic conductivity Very low to high
Mechanical Strength: High
Deformation behaviour: Brittle
Stability of cavities: High (unfractured) to low (strongly fractured)
In situ stresses: Anisotropic
Dissolution behaviour: Very low
Sorption behaviour: Medium to high
The hydraulic conductivity of crystalline rock depends to a great extent on its physical state (whether
fractured or not). Unfractured crystalline rock has a low hydraulic conductivity. In [GRS 2008] the
following values have been indicated for crystalline rock:
Hydraulic conductivity (Kf in m/s) Average depth of
samples
N° of
samples Range Median value
Granite 302 – 1.480 m 605 2.23 x 10-15 - 4.00 x 10-04 2.80 x 10-08
Gneiss 301 – 1.498 271 4.70 x 10-15 – 1.20 x 10-05 3.00 x 10-10
The permeability of the rock is highly dependent on whether it is fractured or not.
In situ stress (anisotropic) in hard rock formations and the typical deformation behaviour (brittle)
may lead to fractures in the host rock (see [GRS 2009]).
Hard rocks are effectively self-supporting and minimal engineered support and maintenance is
required to prevent failure of the rock walls in the emplacement cells and access drifts. Maintenance
of rock support, if necessary at all, is not expected to be required over extended periods (see [IAEA
2009]). Crystalline rock has excellent stability of the drifts and rooms even at large depths but it has a
relatively high permeability [Popov 2006]. The creep potential of crystalline rock is very low and thus
self-healing is unimportant.
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In the case of hard-rocks (crystalline and sedimentary), total containment is not possible (due to its
brittle deformation behaviour, cracks and faults in the host rock may occur and liquids and gases
could escape from a hard rock depository). In such cases, an underground storage needs to be
constructed in a way that natural attenuation of the surrounding strata mediates the effect of
pollutants to the extent that they have no irreversible negative effects on the environment. This
means that the capacity of the near environment (engineered barriers) to attenuate and degrade
pollutants as well as the state of the waste (e.g. solid waste with a low solubility and volatility) will
determine the acceptability of a release from such a facility (see Council Decision 2003/33/EC).
The investigation of the rock structure of crystalline rock (granite) is very limited in particular with
respect to hydraulic conductivity [GSR 2008]. The homogeneity of the rock is strongly site-related and
examination of a homogenous rock structure is very complex [GRS 2008]. Low permeability is only
guaranteed in unfractured rocks. In the case of fractured rocks, engineered barriers (such as
appropriate containers, backfillings) are required to avoid contamination of the environment.
For the backfilling of rooms and drifts, dense clay material rich in smectites seem to be the most
appropriate material for crystalline rock. Following an article by Pusch published in [Popov 2006]
German Friedland Ton appears to represent an optimum with respect to costs and good isolating
properties. The article refers to a study – published in 2007 by Roland Pusch [Pusch 2007] – which
investigated whether toxic, non-radioactive chemical waste can be safely stored underground.
A major issue of the study was to develop techniques for the isolation of hazardous waste – primarily
mercury – in solid and solidified form (batteries). Various techniques for preparation and application
of the clay-based materials have been tested and found to be very effective as “near-field” isolation
of solid waste represented by mercury batteries. The best isolating medium turned out to be dense
clay material applied in the form of pre-compacted blocks of clay powder or as on-site compacted
clay layers.
According to the study, deep abandoned mines appear to be suitable for the disposal of solid
hazardous waste because of low costs and suitable chemical conditions. The study concluded that
solid or solidified mercury waste and other solidified hazardous waste can be isolated from the
biosphere for hundreds of thousands of years and that subsequent groundwater contamination will
be lower than stipulated by the EU. The study also covers estimations of the rock mechanical stability
around drifts and rooms suitable for disposal of such waste.
Dense clay (bentonite) is also recommended by [BGR 2007] as appropriate backfilling material for
crystalline rock.
Experiences related to the storage of waste in crystalline rock are available but only for stabilised
waste.
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6.2.3.2 Properties of other sedimentary hard rocks (e.g. claystone)
Argillaceous rock covers a wide range of rock types from plastic clays, with transitional types, to
strongly consolidated and partially fractured claystones. Argillaceous rock formations in France
(Callovo-Oxfordian), Canada (Ordovician argilites) and Switzerland (Opalinus Clay) are highly
consolidated sediments.
In the following, the most important properties of argillaceous rock (e.g. granite and metamorphic
rocks) are summarised (source: [GRS 2008], [GRS 2009], [Popov 2006]):
Table 6-4: Overview of properties of Argillaceous rock, Clay / claystone
Properties Argillaceous rock, Clay / claystone
Permeability Very low to low
Hydraulic conductivity Very low
Mechanical strength Low to medium
Deformation behaviour Plastic to brittle
Stability of cavities Artificial reinforcement required
In situ stresses Anisotropic
Dissolution behaviour Very low
Sorption behaviour Very high
Argillaceous rock has a very low hydraulic conductivity but poor stability and the vicinity of the drifts
may be very conductive. In [GRS 2008] the following values related to hydraulic conductivity have
been indicated for argillaceous rock:
Hydraulic conductivity (Kf in m/s) Average depth of
samples
N° of
samples Range Median value
Argillaceous rock 313 – 1.474 m 36 5.50 x 10-15 - 2.05 x 10-10 9.50 x 10-13
Argillaceous rock formations possess relatively high mechanical strength, depending on the particular
structure (fracturing) and mineralogy of the rock. However, these may exhibit some plastic
behaviour, which progressively reduces fracturing but they may also lead to excavation damage
zones around excavations in the repository, depending on the support and rock characteristics.
Appropriate support would be required for operational safety, although it is considered that
excavations could be kept open with suitable maintenance over extended periods. In argillaceous
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rock, short term support (from a few months to some years) is often provided by means of rock bolts
with metallic arches, metallic meshes and/or shotcrete. Concrete linings can subsequently be
deployed to provide mechanical stability for a longer period.
In the case of Boom Clay in Belgium, mechanical support by liner systems is required. Regular
maintenance of the excavation lining may be necessary should the access to excavation remain open
to enable easy access to the waste emplacement cell. The frequency and scale of any maintenance
work will depend on the deformation rate of the rock at the proposed depth and on the design and
properties of the lining.
In-situ-stress in clay rock formations (anisotropic) and the typical deformation behaviour (plastic to
brittle) may lead to fractions in the host rock. Cavities are often not self-stable but must be
supported by mechanical structures (see [GRS 2009]).
The investigation of the rock structure of consolidated argillaceous rock is possible by means of
boreholes and other geophysical methods as they have a limited thickness and composition [GRS
2008].
According to [GRS 2008] argillaceous rock is generally assumed to have adequate strength for the
construction and maintenance of underground drifts, but the stability of drifts can only be
guaranteed by additional reinforcement and supporting measures. These measures are particularly
complex and expensive in unconsolidated clays, therefore storage in consolidated clays is more
appropriate.
Analogous to crystalline rock, clay material rich in smectites are particularly relevant as backfilling
material due to their high isolating potential. [Popov 2006]. See also backfilling crystalline rock.
Argillaceous rocks have proven their long-term effectiveness as geological barriers where they form
tight seals, for example above hydrocarbon reservoirs. Mineralogical, geochemical and geotechnical
investigations of argillaceous rocks are currently being conducted in international rock laboratories.
Little information is available due to a lack of mining experience with these rocks [GRS 2008].
6.2.3.3 Experience of underground disposal of mercury in hard rock formations
Although several hard rock mines (active and inactive) exist in Europe, experience with the disposal
of mercury in hard rock formations is very limited. In deep underground hard rock formations
typically solid industrial waste such as fly-ash from incineration plants is stored [Popov 2006]. These
waste types might contain small amounts of Hg but only in a solid matrix.
Sweden
There is no underground disposal for mercury waste at the moment in Sweden. However it has been
assessed that Swedish bedrock should be able to meet specific requirements [SOU 2008].
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The Swedish government has commissioned an inquiry into permanent deep bedrock storage of
mercury-containing waste. The inquiry commenced in mid-2005 and a final report was presented on
31 January 2008. The report analyses the permanent storage of mercury in deep bedrock and salt
mines. A summary of the report (in English) provides an account of permanent storage options for
mercury-containing waste, and the requirements and risks attendant to the permanent storage of
liquid mercury [SOU 2008].
According to the report, the technical conditions to build secure underground depositories in stable
geological formations are very good. Deep bedrock deposition in mines or at an existing bedrock
facility enables the permanent storage of long-lived hazardous waste, providing both technical
advantages and extensive safety margins. The latter point is naturally dependent on the enclosure of
the waste in a massive geological barrier. Deposition of long-lived, potentially hazardous waste in
underground depositories provides safety advantages that markedly exceed the current European
practice of surface storage for this type of waste. [SOU 2008]
This report states further that all waste, including metallic mercury, must be appropriately stabilised
prior to deposition. Direct deposition of metallic mercury for example in steel containers – as an
alternative to the storage of stabilised mercury – has disadvantages in terms of safe deposition, and
raises new issues which currently lack an adequate knowledge base. Clarification of these key issues
is required to consider the deposition of liquid mercury as a serious alternative. Therefore the report
states that for practical adaptation, it is reasonable that the necessary safety analyses in case of the
deposition of liquid mercury demonstrate that safety margins correspond to what can be achieved
with stabilised mercury deposited in deep geological formations, such as Swedish bedrock [SOU
2008].
Norway
According to a Norwegian report [Kystverket 2008], it could be a problem to find a suitable location
for “deep” geological disposal in Norway. Though Norwegian storage locations may fulfil the criteria
of stable physical and chemical conditions there is the problem that most storage locations in rock
are relatively shallow (<100 m) and not at several hundred metres depth as required in the WAC
Decision.
In Norway there is a need to store mercury containing waste from zinc-production (one site).
Mercury from zinc-production is a by-product and is treated as waste for final disposal. The mercury-
residue from zinc-production is cemented into sarcophagi and placed in a bedrock hall at the
production site. [NO 2005]
Another Norwegian study has investigated the environmental, safety and health consequences from
salvaging mercury and mercury-contaminated sediments from a sunken submarine [Kystverket
2008]. At least two facilities have permits for disposal of mercury containing waste (mercury content
max. 10%). Possible storage locations and costs for the disposal of hazardous waste are included in
the study. The following possible underground storage locations are cited in the study:
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NOAH AS, Langøya, Norway
NOAH is Norway’s largest disposal facility for hazardous waste. It has a permit to receive a total
of 622,000 metric tons of different types of waste per year, including 322,000 metric tons of
inorganic hazardous waste per year. Since the year 2000, NOAH has received approximately
200,000 tons of mercury waste (10% Hg). It has developed a stabilisation method in
cooperation with the University of Oslo, where mercury is absorbed into gypsum and iron
hydroxide. The maximum allowed discharge of mercury to water is 0.0013 kg/day. NOAH is
situated on the island of Langøya and waste can be transported directly to the island by ship.
Miljøteknikk Terrateam AS, Mo i Rana, Norway
Miljøteknikk Terrateam has a large disposal facility in the rock caverns of the former steel
works in Mo i Rana. Miljøteknikk Terrateam has a permit to receive 70,000 metric tons of
inorganic hazardous waste per year. The waste has to be stabilised/solidified before placement
into the rock cavern. Maximum allowed leaching of waste containing mercury which has been
stabilised/solidified is 0.01 mg Hg/l. The leached amount is determined by using the United
States TCLP63 (Toxicity Characteristic Leaching Procedure) test.
There are also other possible disposal facilities in Norway:
Boliden Odda AS, Odda Boliden
Odda has large rock caverns for disposal of mainly jarosite-bearing sludge from smelters, but
also other waste streams containing mercury sulphide compounds. They have 14 large rock
caverns and each is 75,000-220,000 m3. The waste is placed in plastic drums and is then cast in
concrete in the rock caverns.
BIR (Bergen Interkommunale Renholdsverk), Hordaland
BIR has a disposal facility for hazardous waste in a rock cavern in Stendafjellet. Its permit would
probably have to be revised to be able to receive mercury.
Disposal of mercury waste in Norway (allowed for waste with max 10% Hg) will need stabilisation
prior to disposal. According to [Kystverket 2008] binders for stabilisation could be gypsum, cement,
sulphur and sulphides.
The report recommends a temporary storage while immobilisation technologies are developed.
Temporary storage could typically be in salt mines (which are already available), rock caverns,
preferably in deep bedrock permanent depositories in order to achieve non-oxidative conditions
[Kystverket 2008].
63 The leaching tests of various literatures refer to different standards, which make a direct comparison of the
results impossible. In the United States the toxicity characteristic leaching procedure (TCLP) is typically used, whereas in Europe the leaching standard (EN 12457/1-4) is used. (The rarely-used percolating test (prEN 14405) is also possible.)
With the American TCLP test, a liquid/solid ratio of 20 is used whereas the European leaching test uses a liquid/solid ratio of 10 or 2. Hence, the same material results in higher concentration values in the European measurements.
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6.2.3.4 Economic information – hazardous waste in hard rock
In 2001 the report [SOU 2001] published by the Swedish EPA estimated the cost of a deep bedrock
repository having a capacity of about 1,000-20,000 tonnes of high-level mercury waste to be about
SEK64 200-300 million. This represents a cost of approximately SEK 250,000-650,000 per tonne of
pure mercury. The higher figure represents storage of mixed waste such as process waste containing
1-10% mercury. The report [SOU 2008A] contains updated and more detailed information relating to
expected storage costs of stabilised mercury.
The figures below were received from Johan Gråberg, Swedish Ministry of Environment, and give an
overview of estimated costs for the construction of a permanent deep bedrock storage of mercury-
containing waste in connection with an existing bedrock facility (all cost figures have been converted
from SEK to Euro by using an exchange rate of ~0.1 euro = 1 SEK).
- The estimated investment cost for a deep bedrock storage established adjacent to an existing
or former mine or bedrock facility is around 900-1,500 euros per m³ at 10,000m³ stored
volume or 150-190 euros per m³ at 100,000 m³ deposited volume.
- The construction of an entrance ramp is estimated to cost around 5,000 euros/meter.
- The cost for an underground deep bedrock depository is around 50 euros per excavated m³
volume.
- Further costs for equipment such as pumps, cables, ventilation, lights etc should be added to
these costs. The investment cost for equipment is estimated at 20-25 percent of the
construction cost. In addition to this, operational costs should be added for pumping and
ventilation (100,000-200,000 euros/year), staff (100,000-200,000 euros/year) as well as costs
for loading, unloading and transportation of the waste (20,000 euros/year). In total,
operative expenses amount to 250,000-500,000 euros/year.
The report [Kystverket 2008] did not make any assumptions about costs relating to the storage of
elemental mercury. The report only refers to the assumptions made in the Swedish Report [SOU
2001].
6.2.3.5 Environmental and safety aspects related to the storage of hazardous waste in hard rock
Total enclosure of the waste by the host rock is not possible in hard rock depositories [SOU 2008].
Due to its brittle deformation behaviour, hard rock cannot encapsulate metallic mercury or mercury
compounds.
Therefore, additional artificial or engineered barriers are needed to ensure a safe encapsulation of
64 Exchange rate (October 2009): 10 SEK = around 1 euro
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the hazardous waste over a very long time. Although hard rock has a very low hydraulic conductivity
and gas permeability – under the condition it is unfractured– the investigation on the homogeneity
of the rock is very complex [GRS 2008]. It is difficult to exclude the occurrence of fractures or faults
for a relevant dimension of the host rock [GRS 2008].
Containers, which for instance might provide an important additional safety factor for the storage of
metallic mercury, cannot be considered for long-term storage (see Decision 2003/33/EC, Appendix A,
point 1.2.7). Therefore considerations for long-term safety might be based solely on engineered
barriers.
A presentation prepared by the Swedish environmental agency [Eriksson 2006] made the following
recommendation relating to underground storage in bedrock (the Swedish solution for mercury
waste):
- the responsibility for safe storage rests on the waste owners
- mercury in waste streams should be extracted and converted into an insoluble form
- the storage facility should be located at least 400m below ground in granite bedrock
The Swedish EPA concluded as Swedish mercury strategy [Eriksson 2006] that it should;
• Reduce emissions as far as possible
• Phase out use in products and processes
• Collect mercury already in use
• Effect terminal disposal
In addition, the fundamental properties of the surrounding bedrock have been defined as follows (for
• All doors fitted with 3 inch containment dikes that are incorporated into floor sealant
systems
• Heat, smoke and fire detection system – monitored continuously
• Fire protection system (active fire suppression system, fire extinguisher and alarm system)
• Closely controlled access (Security systems)
• Regular monitoring (routine monitoring and inspections of mercury)
• Protective equipment and supplies
• Emergency procedures (spill prevention control and response procedures)
• Positive contact intrusion detection on all doors, windows and vents – monitored
continuously
• Ramped containment dikes
Figure 6-3: Metallic mercury storage at the Defense National Stockpile Center (source: DNSC)
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The warehouses at the Hawthorne Army Depot are constructed with concrete support columns, steel
roof trusses, and transite roofing. The warehouses have concrete floors and walls (resistant to fire).
Another option at the Hawthorne Army Depot is the use of earth-mounded storage buildings
(igloos).The site has 393 empty, usable igloos. The igloos are made of steel-reinforced concrete and
covered with about 2ft (1m) of soil. The mercury could be stored in about 125 igloos.
Analogues to the existing warehouses the new site will have approved Spill Prevention Control and
Countermeasures and Installation Spill Contingency Plans to ensure that the appropriate response to
a spill is made. State and local emergency response teams are aware of the mercury storage. In case
of a mercury spill, an appropriate response would occur and the spill would be cleaned up to
applicable standards.
Public access to the storage site is restricted by a security system, including guards, locked
warehouses, and other measures. Warehouses are kept locked except for inspections and other
periodic maintenance work. In addition to security, perimeter fencing, and closely controlled access
comparable to the levels of protection at the current mercury storage sites, DNSC would work with
local authorities to ensure that even the most unlikely scenarios would be handled properly.
Maintenance and Inspection Apart from the technical safety measures, periodic maintenance activities and inspections of the
stored mercury by appropriately trained DNSC or contract personnel are essential to ensure that it is
safe and secure. Inspections have to be conducted by trained personnel and include the following
methods:
• visual examinations
• mercury vapor monitoring using state-of-the-art equipment.
In 2002, the DNSC issued the Environmental Inspection Plan for Mercury in Storage (Appendix 4–A in
the Defense National Stockpile Operations and Logistics Storage Manual). The main purpose of this
manual is to improve the inspection and reporting process for mercury storage. The plan also
documents the correct storage and control measures that are required for the protection, safety, and
health of workers and the public, and protection of the environment. The manual provides
procedures for:
• Frequency of inspections
• Temperature, barometric pressure, and humidity measurement
• Vapour monitoring
• Visual inspection
• Documentation and records
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• Corrective action
In case the DNSC action level of 0.025 mg Hg/m³ is exceeded or if metallic mercury is found during a
visual inspection, an investigation has to be initiated to determine the cause. Any defects in the
packaging have to be quickly corrected.
Costs
The facility at Hawthorne will be operated by a contractor. DNSC estimates that storage of mercury
at Hawthorne will cost $.0515 per lb per year, for a total of a little more than $500,000 per year for
the military's entire stockpile of mercury [Hogue 2007].
Cost estimates are also available associated with the permanent, private sector storage of elemental
mercury as a method of safe management of excess non-federal mercury supply. The USEPA study
[USEPA 2007a] examined the costs of private sector storage under two storage scenarios: a storage
facility that uses rented warehouses and a storage facility that includes construction of warehouses
specifically for mercury storage. Estimates of total storage costs assume that over a 40-year period,
either 7,500 or 10,000 metric tons of excess mercury supply will require storage.
Table 6-5: Summary of Estimates of Total Storage Costs (US Dollars) for 40 Years [USEPA 2007a]
Storage Capacity
Total Cost Estimates Rent Scenario Build Scenario
7,500 ton Total Project Costs (undiscounted) 59.5 - 144.2 million 50.0 - 137.7 million
Net Present Value of Total Project Costs 18.5 - 39.9 million 17.8 - 41.0 million
Annualized Costs 1.4 - 3.0 million 1.3 - 3.1 million
Annualized Costs per pound 0.084 - 0.181 0.081 - 0.186
10,000 ton
Total Project Costs (undiscounted) 69.8 - 183.9 million 57.3 - 174.9 million
Net Present Value of Total Project Costs 21.3 - 50.9 million 20.0 - 51.9 million
Annualized Costs 1.6 - 3.8 million 1.5 - 3.9 million
Annualized Costs per pound 0.072 - 0.173 0.068 - 0.177
Note: present value calculation assumes a seven percent discount rate.
6.4 Review of containment
6.4.1 Container systems currently in use
The packaging system is an integrated element of a safe storage of metallic mercury – in particular in
the case of temporary storage. It is an engineered barrier which is designed to ensure operational
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safety during interim storage, transport and waste package handling operations, and may provide a
long term containment function [IAEA 2009].
In the following, the standard steel containers used in Europe for the transport and stockpile of liquid
mercury as raw material are described.
In addition, the foreseen packaging system for the storage of metallic mercury at the DNSC is
described. The system is designed to be safe for a period of 40 years.
6.4.1.1 Europe
The information related to the packaging of liquid mercury is based on the information available,
personal information from Mr. M. Ramos, Mayasa.
Currently, for the transport and stockpile of liquid mercury standard gas and liquid-tight steel flasks
(34.5 kg net70) and containers (1 metric ton net) are in use in Europe. Both are UN-approved (see also
section below) and meet the requirements for transport on the road (ADR71), by rail (RID72) and ship
(IMO73). In addition, the smaller flasks meet the requirements for the shipment by air (IATA74). Both
containers are made of steel with a lacquered interior. For further information on the container
material see section 6.4.3.
Figure 6-4: Examples of standard mercury steel containers used by Mayasa (source: Mayasa)
70 The international unit of measurement of mercury, a 34.5 kg flask, is originally from Almadén and equal to
three old Castilian arrobas of 11.5 kg 71 Agreement on Dangerous Goods by Road 72 Regulations concerning the Intl Transport of Dangerous Goods by Rail 73 International Maritime Organisation 74 International Air Transport Association
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The flasks are suitable for strapped to standard wooden pallets (115 cm X 115 cm x 13.5 cm). The 1
metric tonne containers have a height of 66.2cm and a diameter of 70cm.
Costs:
The costs for the current carbon steel flask mainly used (34.5 kg) are around €10/flask, for a 1 tonne
container the costs are around €700 [personal information: M. Ramos, Mayasa]. Other figures vary
from €600 to €1,100 (stainless steel) for the 1 tonne container [personal information by Euro Chlor].
6.4.1.2 USA (DNSC)
The information relating to the packaging of liquid mercury is based on the information available
from the MM EIS [DNSC 2004B], [DNSC 2007], [Hogue 2007] and personal information from Mr.
Dennis Lynch (DNSC).
The DNSC has 4,436 metric tons of mercury in inventory. The purity of the mercury is between 99.5
and 99.9%. In total, the metallic mercury is stored in 128,662 steel flasks. The mercury inventory is
contained in flasks made of 0.2-in (0.5-cm) thick, low-carbon steel. Each flask contains 34.5kg (76lb)
of liquid mercury and is sealed with a threaded pipe plug. Figure 6-5 shows the dimensions of a
typical flask. Currently, two types of flasks are in use. Newer flasks are seamless and thus they are
not as susceptible to leakage as the older, welded flasks. The older flasks have already been in use for
Special provisions: 5 kg (maximum net quantity per inner packaging in case of combination
packaging)
packaging group: III (substance presenting low danger)
Packaging instructions: P800
Mixed packaging provisions: M15
The following packaging instructions apply for the transport of liquid mercury (UN N° 2809):
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Figure 6-7: Packaging instruction for liquid mercury according to ADR
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In the case of elemental mercury no longer being transported as a product but as waste, additional
provisions have to be taken into consideration, in particular:
• Regulation 1013/2006/EC75 on shipment of waste requiring a notification procedure for all
wastes destined for disposal involved in transboundary transport (see chapter 5 “legal
assessment”)
• Directive 91/689/EEC76 on hazardous waste and Directive 2006/12/EC77 on waste requiring a
record of waste including information on quantity, nature, origin, destination, frequency of
collection, mode of transport and treatment method. Documentary evidence that the
management operations have been carried out to be kept for at least three years
• The specific requirements laid down for waste transports according to ADR
• National requirements for signing waste transport, e.g. according to the German legislation78,
signing the transport with an “A” for waste
Improper handling of metallic mercury might result in mercury emissions with adverse effects to
workers and the environment. No mercury specific provisions are implemented on EU level but the
general established occupational and health regulations have to be taken into consideration during
the handling and transport of metallic mercury (e.g. compliance with existing occupational limit
values for mercury).
To avoid improper handling – which might result in mercury releases – Euro Chlor has implemented
the following specific requirements for the safe handling and transport of liquid mercury to Almadén
(Annex 2 – Technical requirements to the Euro Chlor Voluntary Agreement on Safe Storage of
Decommissioned Mercury):
General
- Mercury shall be delivered to the storage site as a liquid in hermetically sealed containers ready
for storage.
- The containers will be placed in a dedicated area in the storage site.
75 Regulation N 1013/2006 of the European Parliament and of the Council of 14 June 2006 on shipments of
waste (OJ L 190, 12.07.2006, p.1-98), also referred as the ‘Waste Shipment Regulation‘ 76 Council Directive 91/689/EEC of 12 December 1991 on hazardous waste (OJ L 337, 31.12.1991, p. 20) with
last amendment from 19 November 2008, also referred as ‘Hazardous Waste Directive‘ 77 Directive 2006/12/EC of the European Parliament and of the Council of 5 April 2006 on waste (OJ L 114,
27.4.2006, p. 9–21) 78 Act for Promoting Closed Substance Cycle Waste Management and Ensuring Environmentally Compatible
Waste Disposal (Kreislaufwirtschafts- und Abfallgesetz - KrW-/AbfG), 27 September 1994 (BGBl I 1994, 2705)
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Containers:
- The containers will be made of steel, with top connection only (no bottom valves) and should
have ADR/RID approval for transportation. The containers will normally have a capacity in the
region of 1 tonne of mercury. Containers of other capacities may be used if appropriate.
- The containers will be used for transportation and storage to avoid further manipulation of
mercury on the storage site.
- The containers will have a visible indication of their empty and full weights.
Preparation and filling operation:
- Before filling the containers, residual sodium concentration in the mercury will be checked to
ensure that there is no risk of hydrogen production.
- The container shall not be completely filled to avoid overpressure by thermal expansion.
- After filling, the container will be hermetically closed. The filled containers will be weighted for
the quantity of mercury; sealed and properly identified: product with UN code, danger signs,
amount, sender, date and reference number to trace the origin.
Loading and unloading of containers
- During loading and unloading trucks or rail wagons, all precautions will be taken to avoid any
spill and emergency aspiration equipment will be ready to collect accidental spillage.
All members of Euro Chlor still operating chlor-alkali plants using the mercury technology, signed the
agreement and thus have to take into consideration the above stated requirements.
Furthermore Euro Chlor published “Guidelines for the preparation for permanent storage of metallic
mercury above ground or in underground mines” [Euro Chlor 2007] including detailed information on
required quality, containment and packaging of mercury resulting from decommissioned chlor-alkali
plants. It is stated in the document that “Mercury [… ] may be contaminated, so it is necessary to
purify it before transfer to storage containers. The most likely contaminants are water-soluble
(specifically sodium, which has the potential to generate hydrogen in storage)”. In addition the
presence of radioactive traces, which are used to measure the plant mercury inventory, should be
avoided. [Euro Chlor 2007]
Mercury from decommissioned chlor-alkali plants have some small metallic contaminants, like iron,
nickel, copper … usually not detectable (< 20 mg/kg each) [personal information by Euro Chlor].
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6.4.3 Container material
Containers must withstand all anticipated levels of handling, storage, stacking, loading and unloading
conditions and should not become adversely affected by changes in atmospheric conditions,
pressure, temperature and humidity [UNEP 2009].
With respect to the containment of metallic mercury the following primary aspects have to be
fulfilled:
• Reaction stability against its content (also in case of impurities)
• Reaction stability against the surrounding environment
• Mechanical stability
• Suitability for transport (avoidance of additional re-filling)
• Air and liquid tightness
• Monitoring possibilities
Container suitability is largely related to the form and foreseen storage period of the metallic
mercury. In the case of permanent underground storage, the containment is not seen as a protection
measure anymore as the stability of any packaging system cannot be expected for a period of >1,000
years.
Apart from the above described steel containers currently in use, glass containers are also discussed
as possible containers for liquid mercury since glass will not react with mercury. However, due to its
low pressure resistance, fragility and strength, appropriate surrounding packaging (casing) has to be
designed to avoid breakage during transport and handling. Teflon might also be suitable. No specific
information has been found to packaging systems made of glass and teflon.
Pure iron flasks might also be an appropriate material for the storage of liquid mercury as iron does
not react with mercury and it is more stable than glass. The problem with iron is that – depending on
the storage environment (e.g. saline solutions) – iron might corrode. An appropriate coating or
second layer might by necessary. No specific information on pure iron flasks could be identified.
In the case of storage of liquid mercury over a long time, possible reactions of mercury with the
containment have to be taken into consideration. Although for example pure iron does not react
with pure mercury, impurities in the mercury may result in a possible reaction and thus an attack of
the containment.
For pre-treated metallic mercury, the requirements to be fulfilled would be different than those
applying to metallic mercury. Solidified mercury might either be stored in drums or large packs
depending on the structure of the final product.
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In the following, the preliminary findings of the MERSADE project relating to corrosion by liquid
mercury of the container material are described. One objective of the MERSADE project is to identify
appropriate container material for the safe long term storage of metallic mercury. Apart from a
literature review (see section 4.1.2), practical investigations also took place with tanks and flasks in
use for several years.
The Oak Ridge National Laboratory (ORNL) also carried out an extensive assessment of mercury
containers to identify the most appropriate container material as well as container size.
6.4.3.1 Corrosion by liquid mercury of the container material (steel) – Preliminary results of the MERSADE project
The following information is based on [Muñoz, 2009] and [Mersade 2009A] and additional personal
information from Mr. Ramos, Mayasa.
One major objective of Mersade was to identify appropriate container material for the storage of
liquid mercury. Therefore, in a first step the storage containers that have been in use for several
years for the storage of liquid mercury at Almadén have been analysed for potential effects resulting
from the mercury. The stored mercury at Almadén has a purity of 99.9%.
The following equipment has been investigated.
Table 6-6: Tested equipment [Muñoz, 2009], presentation: Mr. Ramos
Capacity Thickness
container
material
Container material In use since
Flask 1 34.5 kg Not indicated Plain carbon steel (low
C, Mn, P steel, DD13)
>7 years
Flask 2 34.5 kg Not indicated Plain carbon steel (low
C, Mn, P steel, DD13)
6 years
Flask 30 34.5 kg 4mm Plain carbon steel (low
C, Mn, P steel, not
DD13)
30 years
Container 1 1 tonne Not indicated AISI 316L79 >10 years
Container 2 1 tonne Not indicated AISI 304L79 6 years
Deposit of scale Not indicated 7mm AISI 30479 steel (304L
C Content limit)
Not indicated
Bulk tank-25 Not indicated 8mm AISI 304 steel 25 years
Pipes / 3.5mm AISI 30479 steel 25 years
79 Classification according to AISI = American Iron and Steel Institute
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In addition, two samples of the stored mercury have been analyzed to identify possible impurities. In
particular one sample shows bismuth, sodium, manganese and potassium concentrations of around
200 ppm and calcium was identified in a concentration of up to 250 ppm. Other substances such as
Ag, Pb, Zn, Al have been found in concentrations below 10 ppm. The following conclusions have been
drawn:
Conclusions: packaging (flasks, containers)
• samples had a good optical appearance with no significant damage
• FLASK 1: some iron oxides were observed on the damaged areas as well as below the
protective coating on specimens taken from non damaged areas
• Profile depletion by the GDOES technique for Cr, Ni and Mn shows that for CONT.-1 (AISI
316L) the depleted areas are deeper (2,5 μm) than for CONT.-2 (AISI 304) (1 μm).
Additionally, for CONT.-1 the depth of the affected zone increases up to 4 μm when the
specimens evaluated were taken from the bottom of the tank.
• FLASK-30 shows a deeper damage since the average thickness of the iron oxide layer may
reach 30-40μm which is about 1% of the thickness of the steel, reaching up to 200μm, 5% of
the thickness.
Conclusions: Installations (pipes, tanks):
• Intergranular attack on the surface, but the depth of damage on the steel is rather small
• Bulk tank 25, which has been used for Hg storage for 25 years, showed small amounts of
damage of 40µm depth (0,5% of the total thickness) --->max 5,000 years (8mm thickness)
• The deposit of scale showed the same results: 20µm (<0,3% of the total thickness) - max.
8,750 years (7mm thickness)
• Pipe: Under flowing conditions, the attack was more severe, resulting in a regression of the
surface and increased roughness of the surface.
• Due to the elevated presence of impurities in the mercury, it is not possible to conclude that
the identified attacks can be attributed exclusively to the mercury.
Preliminary overall conclusion resulting from the MERSADE project:
“Stainless steel AISI 304 shows a good performance in metallic mercury under static and isothermal
conditions, since after 25 years the steel only shows a slight attack on the surface. These results
suggest that this steel grade seems suitable for constructing the long term storage depository.”
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The planned prototype for a bulk storage container will be constructed with stainless steel AISI 304.
6.4.3.2 Assessment of mercury storage containers by the Oak Ridge National Laboratory (ORNL)
The ORNL has been working for several years on the assessment of mercury storage containers to
identify the most appropriate container material as well as container size for the storage of liquid
mercury. In the following, a summary of the research activities is provided, based on presentations
[ORNL 2009] and [ORNL 2009A].
The main findings of the research are:
- Mild steel and stainless steel containers are immune to pure mercury (purity >99,5%)
for anticipated exposure conditions and are appropriate for long-term storage
- Avoid acceptance of “unknown” compositions of Hg, at least until more information
is available
- Mercury is compatible with iron and mild steel up to ~400°C (solubility of iron in Hg
<< 0.1 ppm at RT, mercury does not chemically wet steel at RT in the presence of air)
- The evaluation of flasks with a life time of up to ~50 years service confirmed the
absence of steel interaction with mercury
- Welds are likely to be the weakest point in containers
The outcome of the research activities has been used as input for research on the design of
appropriate storage containers.
As acceptable container materials, carbon steel (ASTM A36 minimum) or stainless steel (~316L) have
been identified. Carbon steel is recommended as it has further advantages compared to stainless
steel. Stainless steel
• is more than twice the cost of carbon steel
• has lower material strength
• but provides better exterior corrosion protection than carbon steel
The purity of the stored mercury should be at least 99.5% and the remaining impurities within it
should not be capable of corroding carbon or stainless steel (i.e., nitric acid solutions, chloride salt
solutions, or water).
For a protective coating for the exterior surface of the containers, epoxy paint or electro plating are
recommended. For the inner surface, no protective coating is required for as long as mercury meets
purity requirements and no water is present inside the container.
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For a plug, a National Pipe Thread (NPT) plug with Teflon® tape is recommended, as it provides an
excellent seal at low cost.
The presentation [ORNL 2009A] also includes a comparison of storage containers with different sizes
(3 l flask, 1, 2, 3 and 10 metric tonne containers) and the pros and cons relating to their storage
function.
Based on the results of the above described investigations, DOE published in November 2009
“Interim Guidance on Packaging, Transportation, Receipt, Management, and Long-Term Storage of
Elemental Mercury” [DOE 2009].
The document provides a framework for the standards and procedures associated with a DOE-
designated elemental mercury storage facility (see chapter 5.4.2) with a focus on the RCRA (Resource
Conservation and Recovery Act) permitting of such a facility and planning for that storage facility’s
needs. This document provides general guidance on standards and illustrative procedures that are
current, consistent, and best suited for supporting the DOE program for the receipt, management,
and long-term storage of mercury generated in the United States. The document lays down that a
detailed analysis of the purity of the elemental mercury has to be prepared. This purity analysis shall
“confirm a minimum purity of 99.5% (per volume) and list all impurities and their weight percent of
content. The total liquid shipment per container is on a volume basis, and the percent impurities are
on a weight basis. The impurities shall not be capable of corroding carbon or stainless steel. To
prevent degradation of the container, nitric acid solutions, chloride salts solutions, water, and other
possible corrosion agents are prohibited. The mercury shall be free of any added radiological
components.”
6.4.4 Conclusions
Above ground storage of the “product” liquid mercury has already been practiced for several years
and experiences with the storage of large quantities of liquid mercury are available in particular in
the USA and Spain. Also experiences are available related to the handling, packaging, transport of
metallic mercury.
In Europe, the Spanish state-owned company Miñas de Almadén (MAYASA), the operator of the
former mercury mine, is the major company dealing with liquid mercury. According to an agreement
with Euro Chlor, MAYASA receives all excess mercury from western European chlorine producers.
The required minimum purity for the acceptance of mercury is > 99.9%.
Currently, for the transport of liquid mercury, standard gas and liquid-tight steel flasks (34.5 kg net)
and containers (1 metric ton net) are in use in Europe. The storage at Almadén also takes place in
bulk tanks which are stored in collecting basins capable to collect all mercury included in the bulk
tanks.
In the USA, government owned liquid mercury (more than 5,500 metric tons) which is no longer used
for military purposes has already been stockpiled for more than 40 years in four above-ground
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warehouses. It is planned to store this metallic mercury for another 40 years in a selected warehouse
[DNSC 2004]. The selection of the warehouse was accompanied by intensive research related to
minimum requirements for the storage site and the containment ([ONRL 2009], [ONRL 2009A]). The
purity of the stored mercury is above 99.5%.
Intensive research related to appropriate containers for the storage of metallic mercury has been
carried out in specific projects in the US ([ONRL 2009], [ONRL 2009A]) and in Spain ([Muñoz, 2009],
[Mersade 2009A]).
Within both projects, containers actually used since several years/decades for the storage of metallic
mercury have been analysed on possible effects by the stored mercury. Based on the results from the
analytical investigations of the storage containers, requirements related to container material
suitable for long term storage have been derived. Both concluded that suitable container material is
available for a temporary storage of metallic mercury.
Recently, the Department of Energy (DOE) published “Interim Guidance on Packaging,
Transportation, Receipt, Management, and Long-Term Storage of Elemental Mercury” [DOE 2009]
which is based on the outcome of the above described investigations.
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6.5 References
[BGR 2007] BGR, Bundesanstalt für Geowissenschaften und Rohstoffe, Nuclear waste disposal in Germany - Investiagtion and evaluation of regions with potentially suitable host rock formations for a geologic nuclear repository, Hannover/Berlin, April 2007, http://www.bgr.bund.de/nn_335086/EN/Themen/Geotechnik/Downloads/WasteDisposal__HostRockFormations__en,templateId=raw,property=publicationFile.pdf/WasteDisposal_HostRockFormations_en.pdf [BMU 2009] Bundesministerium für Umwelt, Natur und Reaktorsicherheit, Sicherheitsanforderungen an die Endlagerung wärmeentwickelnder radioaktiver Abfälle, Berlin, 2009, http://www.bmu.de/files/pdfs/allgemein/application/pdf/endfassung_sicherheitsanforderungen_bf.pdf [Brückner 2003] Brückner, D.; Lindert, A., Wiedemann, M., The Bernburg Test Cavern - A Model Study of Cavern Abandoment, SMRI Fall Meeting, 5 - 8. Oct. 2003, Chester, UK, 69 – 89, 2003 [Council Decision 2003/33/EC] Council Decision, of 19 December 2002 establishing criteria and procedures for the acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC (2003/33/EC) [DNSC 2003] Defense National Stockpile Center, Draft Mercury Management Environmental Impact Statement, 2003 [DNSC 2004] Defense National Stockpile Center, Record of Decision for the Mercury Management EIS, April 2004 [DNSC 2004A] Defense National Stockpile Center, Final Mercury Management Environmental Impact Statement, Executive Summary, 2004 [DNSC 2004B] Defense National Stockpile Center, Final Mercury Management Environmental Impact Statement,Volume I, 2004 [DNSC 2004C] Defense National Stockpile Center, Human Health and Ecological Risk Assessment Report for the Mercury Management EIS, Volume II, 2004 [DNSC 2007] Defense National Stockpile Center, Fact Sheet: Mercury Over-Packing, Storage & Transportation, May 2007 [DNSC 2007A] Defense National Stockpile Center, Fact Sheet: Somerville Depot, February 2007
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[DOE 2009] U.S. Department of Energy, Interim Guidance on Packaging, Transportation, Receipt, Management, and Long-Term Storage of Elemental Mercury, U.S. Department of Energy Office of Environmental Management Washington, D.C., November 13, 2009, http://www.mercurystorageeis.com/Elementalmercurystorage%20Interim%20Guidance%20(dated%202009-11-13).pdf [Env Canada 2001] National Office of Pollution prevention, Environment Canada, The Development of retirement and long term storage options of mercury, Draft final report, Ontario, June 2001 [Eriksson 2006] L. Eriksson, Swedish policy for a mercury free environment, presentation, Swedish Environmental Protection Agency [Euro Chlor 2007] Euro Chlor, Guidelines for the preparation for permanent storage of metallic mercury above ground or in underground mines, Env Prot 19, 1st Edition, October 2007 [EU COM 2001] European Commission, Integrated Pollution Prevention and Control (IPPC) - Reference Document on Best Available Techniques in the Chlor-Alkali Manufacturing industry -, http://ec.europa.eu/comm/environment/ippc/brefs/cak_bref_1201.pdf [FZK 2007] Forschungszentrum Karlsruhe in der Helmhotz - Gemeinschaft: Schwerpunkte zukünftiger FuE-Arbeiten bei der Endlagerung radioaktiver Abfälle (2007 - 2010), Förderkonzept des BMWT, Dezember 2007 http://www.fzk.de/fzk/groups/ptwte/documents/internetdokument/id_064588.pdf [Gibb 2000] Fergus Gibb, A new scheme for the deep geological disposal of high-level radioactive waste, Journal of the Geological Society, Jan 2000 http://jgs.geoscienceworld.org/cgi/content/abstract/157/1/27 [GRS 2008] GRS, Gesellschaft für Anlagen- und Reaktorsicherheit (GRS) mbH, Öko-Institute e.V., Institut für angewandte Ökologie , Endlagerung wärme entwickelnder radioaktiver Abfälle in Deutschland, Anhang Wirtsgesteine – Potentielle Wirtsgesteine und Eigenschaften, Anhang zu GRS-247, ISBN 978-3-939355-22-9, Braunschweig/Darmstadt, September 2008 http://www.fzk.de/fzk/groups/ptwte/documents/internetdokument/id_067981.pdf [GRS 2009] GSR Gesellschaft für Anlagen- und Reaktorsicherheit, Legislation and Technical Aspects of Regulations on Waste Containing Mercury in Europe and Germany, presentation by Thomas Brasser at the Latin American Mercury Storage Project Inception workshop, Montevideo, Uruguay, April 22-23, 2009 [Heath 2006] Mike Heath, Health environmental and safety questions related to the underground storage/disposal of mercury over time, Presentation at the EEB Conference on EU Mercury surplus management and
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mercury-use restrictions in measuring and control equipment, Brussels, 19 June 2006; http://www.zeromercury.org/EU_developments/HEATH-storage.pdf [Hogue 2007] Cheryl Hogue, Mercury Excess, congress and EPA probe possibility of long-term storage of liquid metal, Chemical & Engineering News, July 2, 2007, Volume 85, Number 27, pp. 21-23 http://pubs.acs.org/cen/government/85/8527gov1.html [Höglund 2009] Höglund, Lars Olof, Underground storage and disposal in hard rock based on a chemically-stable mercury solid, Presented at Workshop of Safe Storage and Disposal of Redundant Mercury, St Anne’s College, Oxford, 13th and 14th October, 2009; http://www.mercurynetwork.org.uk/wp-content/uploads/2009/10/Hoglund1.pdf [IAEA 1994] SITING OF GEOLOGICAL DISPOSAL FACILITIES - A Safety Guide, 1994, http://www-pub.iaea.org/MTCD/publications/PDF/Pub952e_web.pdf [IAEA 2002] Issues relating to safety standards on the geological disposal of radioactive waste, Proceedings of a specialists meeting held in Vienna, 18–22 June 2001, June 2002, http://www-pub.iaea.org/MTCD/publications/PDF/te_1282_prn/t1282_part1.pdf [IAEA 2003] Technical Reports Series No. 413, Scientific and Technical Basis for the Geological Disposal of Radioactive Wastes, Vienna 2003 http://www-pub.iaea.org/MTCD/publications/PDF/TRS413_web.pdf [IAEA 2007] Disposal Aspects of Low and Intermediate Level Decommissioning Waste, Results of a coordinated research project 2002–2006, IAEA-TECDOC-1572, December 2007 http://www-pub.iaea.org/MTCD/publications/PDF/TE_1572_web.pdf [IAEA 2009] Geological Disposal of Radioactive Waste: Technological Implications for Retrievability http://www-pub.iaea.org/MTCD/publications/PDF/Pub1378_web.pdf [IAEA 2009b] Joint Convention on the Safety of Spent Fuel Management and on the Safety of Radioactive Waste Management, Third Review Meeting of the Contracting Parties 11 to 20 May 2009, Vienna, Austria, SUMMARY REPORT, 20 May 2009 http://www-ns.iaea.org/downloads/rw/conventions/third-review-meeting/final-report-english.pdf [IfG 2007] Institut für Gebirgsmechanik GmbH, Gebirgsmechanische Zustandsanalyse des Tragsystems der Schaftanlage Asse II, Kurzbericht, November 2007 [K+S 2009] K+S, Underground Waste Disposal, presentation by Alexander Baart at the Latin American Mercury Storage Project Inception workshop, Montevideo, Uruguay, April 22-23, 2009; http://www.chem.unep.ch/mercury/storage/Inception_workshop_LatinAmerica.htm
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[KEMAKTA 2007] Lars Olof Höglund and Sara Södergren, Aspects on final disposal of mercury - The need for waste stabilisation, 22 March 2007 [Kystverket 2008] Det Norske Veritas AS, Kystverket Norwegian Coastal Administration - Salvage of U-864 - Supplementary studies - disposal, report NO. 23916-6, Revision N° 01, 2008 http://www.kystverket.no/arch/_img/9818145.pdf [Mersade 2007] M. Ramos, Estimation of figures for total quantity for possible storage from EU countries and in adhesion process taking in account the caustic-soda industry and others., Status Report Literature review, T 1.2, Life Project Number Life06 ENV/ES/PRE/03, July 2007; http://www.mayasa.es/Archivos/Mersade/WEB%20Estimated%20quantity%20of%20Hg%20to%20store%20INSIDE%20EU%20after%20export%20ban%20MAYASA.pdf [Mersade 2007 A] M. Ramos, Literature review concerning corrosion problems in mercury and stabilisation of liquid Hg, Status Report Literature review, T 1.3 and T 1.4, Life Project Number Life06 ENV/ES/PRE/03, February 2007; http://www.mayasa.es/Archivos/Mersade/WEB%20Literature%20review%20concerning%20to%20mercury%20corrosion%20and%20stabilisation%20of%20liquid%20Hg.pdf [Mersade 2007 B] P. Higueras, J. M. Esbrí, Literature review concerning environmental mercury monitoring, Status Report, Life Project Number Life06 ENV/ES/PRE/03, March 2007; http://www.mayasa.es/Archivos/Mersade/WEB%20Literature%20review%20concerning%20environmental%20mercury%20mon….pdf [Mersade 2009] Process for the Stabilization of Liquid mercury, via mercury sulfide, by the use of polymeric sulfur, F.A. López, A. López-Delgado and F.J. Alguacil, Consejo superior de investicadiones cientificas (CSIC), Centor nacional de investigations metalúrgicas (CENIM) [Minosus 2009] http://www.veoliaenvironmentalservices.co.uk/pages/minosus_main.asp [Muñoz, 2009] C. Muñoz, M.T. Dorado, A. G´mez-Coedo, J.J. de Damborenea, A. Conde, Corrosión en depsitos de almacenmiento de mercurio, 2009, http://www.mayasa.es/Archivos/Mersade/Poster-LIFE.pdf [Nirex 2004] United Kingdom Nirex Limited: A Review of the Deep Borehole Disposal Concept for Radioactive Waste, Nirex Report no. N/108, June 2004 [NO 2005] Stakeholder meeting in Brussels 8 September 2005, Additional questions, Answers from the Norwegian authorities http://ec.europa.eu/environment/chemicals/mercury/doc/norway_2.doc
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[öko institut 2007] Methodenentwicklung für die ökologische Bewertung der Entsorgung gefährlicher Abfälle unter und über Tage und Anwendung auf ausgewählte Abfälle, 30.11.2007 http://www.oeko.de/oekodoc/730/2007-110-de.pdf?PHPSESSID=rphc29st47qbq49u3paetrc2t7 [ORNL 2009] Pawel S. J., Oak Ridge National Laboratory, Assessment of Mercury Storage Containers, Presentation October 2009, http://www.mercurynetwork.org.uk/ikimp-safe-storage-and-disposal-workshop-13-14-oct-2009-presentations/ [ORNL 2009A] Carroll, Adam J., Oak Ridge National Laboratory, Design of Mercury Storage Containers, Presentation October 2009, http://www.mercurynetwork.org.uk/ikimp-safe-storage-and-disposal-workshop-13-14-oct-2009-presentations/ [Popov 2006] V. Popov, R. Pusch, Disposal of Hazardous waste in underground mines, Wit Press, Southhampton, Boston, 2006 [Popp 2007] Popp. T.; Wiedemann, M.; Böhnel, H., Minkley, W.; Manthei, G., Untersuchungen zur Barriereintegrität im Hinblick auf das Ein-Endlager-Konzept ,Institut für Gebirgsmechanik GmbH, Leipzig, UFOPLAN-Vorhaben: SR 2470, Ergebnisbericht, 2007 [Pusch 2007] Pusch, Roland, Project on underground disposal of toxic chemical waste like mercury batteries, Roland Pusch, Geodevelopment International AB, Lund, 2007 [Siemann 2007] M. Siemann, Herkunft und Migration mineralgebundener Gase der Zechstein 2 Schichten in Zielitz, Technische Universität Clausthal Institut für Endlagerforschung Fachgebiet Mineralogie, Geochemie, Salzlagerstätten, published in Kali und Steinsalz, ISSN 1614-1210, Heft 3/2007, page 26, http://www.vks-kalisalz.de/images/pdfs/K_Stein_3_07.pdf [SKB 1999] Deep repository for long-lived low- and intermediate-level waste, Preliminary safety assessment. Swedish Nuclear Fuel and Waste Management Co (SKB), Stockholm, 1999 [SKB 2000] What requirements does the KBS-3 repository make on the host rock? Geoscientific suitability indicators and criteria for siting and site evaluation. Swedish Nuclear Fuel and Waste Management Co (SKB), Stockholm, 2000 [SOU 2001] NATURVÅRDSVERKET, A Safe Mercury Repository, A translation of the Official Report SOU 2001:58, Report 8105 • January 2003, http://www.naturvardsverket.se/Documents/publikationer/620-8105-5.pdf [SOU 2008] Statens offentliga Utredningar (SOU) 2008: 19 Permanent storage of long-lived hazardous waste in underground deep bedrock depositories, Summary of key findings, SOU 2008: 10 April 2008
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[SOU 2008A] Miljödepartementet, Att slutförvara långlivat farligt avfall i undermarksdeponi i berg, ISBN 978-91-38-22922-4, 2008 [Spiegel 2007]
Gau in der Grube, Michael Fröhlingsdorf, Sebastian Knauer, 17/2007
[UBA DE 2004] Umweltbundesamt, Background paper on permanent storage in salt mines prepared by the Federal Environment Agency, Berlin, Germany, 29 July 2004; http://www.basel.int/techmatters/popguid_may2004_ge_an1.pdf [UNEP 2009] UNEP, Draft technical guidelines on the environmentally sound management of mercury wastes, 4th Draft, April 2009, http://www.basel.int/techmatters/mercury/guidelines/040409.doc [USEPA 2002c] Hugh W. McKinnon, Preliminary analysis of alternatives for the long term management of excess mercury, EPA/600/R-03/048, 2002, http://www.epa.gov/nrmrl/pubs/600r03048/600R03048.pdf [USEPA 2004] Application of the analytic hierarchy process to compare alternatives for the long-term management of surplus mercury, Paul Randall, Linda Brown, Larry Deschaine, John Dimarzio, Geoffrey Kaiser, John Vierow, 6 January 2004 USEPA 2007a] US EPA, Mercury Storage Cost Estimates, final report, November 2007 http://earth1.epa.gov/mercury/stocks/Storage_Cost_Draft_Updated_11-6-final.pdf
General description of the SPSS process for a surrogated sludge contaminated with 5000 ppm Hg
Advances in Encapsulation Technologies for the management of Mercury-contaminated Hazardous Wastes [EPA 2002b]
General description of different immobilization techniques and cost estimates
Economic and Environmental analyses of technologies to treat mercury and dispose of it in a waste containment facility [USEPA 2005]
General information about costs and techniques for sulphur stabilization, sulphur polymer stabilization/solidification and amalgamation.
Treatment Technologies for Mercury in Soil, Waste and Water [USEPA 2007]
General description of techniques and cost estimates
Determination of acute Hg emissions form solidified-stabilized cement waste forms [ORNL 2002]
General information about SPSS
Using Sulphur Polymer Stabilisation/Solidification Process to Treat Residual Mercury Wastes form Gold Mining Operations [Brookhaven-Newmont 2003]
Batch scale SPSS treatment.
Advances in Encapsulation Technologies for the Management of Mercury-Contaminated Hazardous Wastes [USEPA 2002b]
Comparison of different stabilization techniques (SPSS, CBPC, Macroencapsulation) from different literature sources.
Sulphur polymer solidification/stabilization of elemental mercury waste. [Waste Management 2001]
Tests for SPSS by adding triisobutyl phosphine and sodium sulphide are presented.
Process for the stabilization of liquid mercury, via mercury sulphide, by the use of polymeric
Physical and chemical data of SPSS of mercury
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Relevant literature overview for Sulphur Polymer Stabilisation/Solidification
Reference Content
sulphur [Mersade 2009]
Emerging Technologies in Hazardous Waste Management [ACS Kazakhstan 2000]
Production of SPC and encapsulation of contaminated phosphor gypsum
Mercury wastes evaluation of bulk elemental Mercury [USEPA 2002a]
Comparison of three vendors stabilizing bulk elemental mercury
Mercury wastes evaluation of Treatment of mercury surrogated waste [USEPA 2002]
Comparison of four different stabilizing surrogated sludges
Treatment of mercury containing waste [US6399849 B1]
Stabilizing mercury containing waste with SPC and encapsulation
Method and apparatus for stabilizing liquid elemental mercury [US 6403044 B1]
Detailed experiment description of stabilizing elemental mercury with sulphur and calcium polysulphide to receive a monolithic product.
Process for the encapsulation and stabilization of radioactive, hazardous material [US 5678234]
General description of encapsulation with sulphur cement
7.2.1 Technical background
Sulphur polymer stabilization is a modification of sulphur stabilization. Within this process elemental
mercury reacts with sulphur to mercury(II)sulphide. Simultaneously, the HgS is encapsulated and
thus the final product is a monolith. The process relies on the use of ~95 wt% of elemental sulphur
and 5% of organic polymer modifiers also called sulphur polymer cement (SPC). The SPC can be
dicyclopentadiene or oligomers of cyclopentadiene.
The process has to be carried out at a relatively high temperature of about 135°C, which may lead to
some volatilization and thus emission, of the mercury during the process. In any event, the process
requires the provision of an inert atmosphere in order to prevent the formation of water soluble
mercury(II)oxide.
In the case of SPC, beta-HgS is obtained. The addition of sodium sulphide nonahydrat results in
alpha-HgS as a product.
A relatively high Hg load of the monolith (~70%) can be achieved with this process, as there is no
chemical reaction of the matrix required to set and cure. The process is robust and relatively simple
to implement and the product of it is very insoluble in water, has a high resistance to corrosive
environment, is resistant to freeze-thaw cycles and has a high mechanical strength. During the
process, volatile losses are liable to occur and therefore appropriate engineering controls are
needed. Engineering controls to avoid possible ignition and explosions are also necessary.
Additionally, the volume of the resulting waste material is considerably increased.
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Polysulphide is added to elemental mercury and sulphur in order to obtain a monolithic product, but
the synthesis of a mercury polysulphide complex, with a higher leaching value compared to mercury
sulphide, shall be avoided. This can be done by adding the sulphur first and in a second step the
sulphur polymer. Formation of mercury polysulphide can also be avoided by adding a polysulphide
inhibitor.
The generation of toxic H2S can be inhibited by limiting the exposure of the stabilizing inorganic
sulphur compounds to air and sunlight or by adding antioxidants.
7.2.2 Economic information
According to various studies, the costs vary from 2.88 $/kg (~2 €/kg) elemental mercury
[USEPA2002b] and between 2.6 $ and 26 $/kg (~€2 and €20/kg) [USEPA 2005] of treated elemental
mercury. The wide range of costs from the report [USEPA 2005] is due to variation of different
parameters, which are: technology (ADA or DOE process, whereas the ADA process is considered to
be twice expensive compared to the DOE process), mobile and stationary construction, with or
without macroencapsulation and considered amount of mercury to be treated (5,000 or 25,000
tonnes).
7.2.3 Environmental information
The physical chemical properties of the products have been collected and included in Annex 4.
Available data about the leachability of the SPSS product are in the range of ~0.02mg/l [Brookhaven-
Newmont 2003] and the volatility is about 0.41-0.74mg/kg (18°C) [Waste Management 2001].
7.2.4 Use of the technology
Using Sulphur Polymer Stabilisation/Solidification Process to Treat Residual Mercury Wastes from Gold Mining Operations [Brookhaven-Newmont 2003]
Two experiments are described, which have been performed with 500 and 250ml mercury and a
waste load of 33 to 37%. 2% of hydrated sodium sulphide and 65 to 61% SPC have been used. The
products were approximately cylindrical pellets with a largest dimension of 9.5mm. The TCLP results
for Hg have been between 0.009 and 0.039mg/l.
Advances in Encapsulation Technologies for the Management of Mercury-Contaminated Hazardous Wastes USEPA 2002b], Sulphur polymer solidification/stabilization of elemental mercury waste. [Waste Management 2001]
In this reports the same process is described, which is the SPSS treatment of radioactive Hg° with
different additives.
The report includes examples for the optimisation of the SPSS process with additives in a 5 gallon,
heavy gauge steel drum. Triisobutyl phosphine sulphide and sodium sulphide have been tested as
additives. The additives (except pure Triisobutyl phosphine) improved the leaching behaviour as well
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as the reaction time. Instead of 16 hours, the process could be finalized within 8 hours. This process
is a two step single-vessel process. Mercury SPC and quartz cobbles were placed in the drum, which
was covered and then purged with argon through one of the vents. In the first step equal weights of
mercury and SPC were mixed in the reaction vessel assuring a six fold, molar excess of sulphur to
mercury which facilitates a faster reaction. Prior to mixing the reaction vessel was purged with argon.
The vessel was heated to ~ 40 °C with agitation to accelerate the mercuric sulphide reaction. Once
the mercury had completely reacted with the sulphur, extra SPC was added and the temperature was
increased to 135.5 ± 5 °C with agitation, until the mixture melted. The molten product was then
poured into metal cans where it cooled into a monolithic waste form. The final product had a
mercury load of 33.3°%.
The untreated material had a TCLP of 2.64mg/l whereas the SPSS treated material had a TCLP of
between 0.02 and 0.4mg/l. Adding 3% triisobutyl phosphine to the SPC changed the TCLP to >0.4mg/l
and using 3% Na2S.9H2O to the SPC resulted in a TCPL of between 0.0013 to 0.05mg/l. Therefore,
adding 3% of Na2S.9H2O generated the best results. Additional information is available on the pH
dependency.
Process for the stabilization of liquid mercury, via mercury sulphide, by the use of polymeric sulphur [Mersade 2009]
In this study, the physical characterization and durability of a SPSS concrete with approximately 50%
of filler, sand and gravel as well as 30% of mercury are measured. It has been tested that the
comprehensive strength is about 57 N/mm2, the flexural strength is about 8.5 N/mm², the density is
about 3.1g/cm³ and the porosity is less than 2%.
Emerging technologies in hazardous waste management [ACS Kazakhstan 2000]
This report includes the production of SPC and its use for the stabilization of phosphorgypsum sand
waste. In the described process, molten sulphur (140°C) was reacted with a mixture of 2.5% of
polyester grade dicyclopentadiene and 2.5% of a proprietary reactive polymer. After 4 hours, the
molten SPC was cooled and solidified. The use of 3% sodium sulphide resulted in a TCLP mercury
concentration of 26µg/l. Based on the observation from different tests at different times, it is
assumed that leachable mercury may decrease over time.
Mercury wastes evaluation of bulk elemental Mercury [USEPA 2002a]
The technologies compared in the report are: SPSS sulphur stabilization with micro and macro
encapsulation and amalgamation.
The SPSS process is conducted in two stages. The first step is a reaction between elemental mercury
and powdered sulphur polymer cement to generate mercuric sulphide (HgS). During reaction the
vessel is placed under inert nitrogen gas to prevent mercuric oxide (HgO) formation and heated to 40
°C to enhance the sulphide formation. The purpose of this first step is to chemically stabilize the
mercury. The purpose of the second step is to solidify the product. The mixture is heated to 130 °C to
melt the thermoplastic sulphur binder. It is then poured into a mould. On cooling the reacted
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sulphide particles become microencapsulated within the monolithic sulphur matrix
The mercury content of the product from the SPSS process was 33 wt% and had an therefore an
increase of 203% by weight. The volume increase is 1,500%. The final form was monolithic and it was
estimated that mercury losses to air were about 0.3%. The leaching values for the final pellets are
dependent on the pH value and were about 0.01 mg/l at pH=2, ~30 mg/l at pH = 8, 0.01mg/l at pH =
11 and ~140mg/l at pH = 12.
7.2.5 Overview of patents
Treatment of mercury containing waste [US6399849 B1]
In this patent, several examples for a SPSS have been performed. The tests were made with 5kg of
elemental mercury and 5kg SPC (containing 5% elemental sulphur). Additionally, 3% of the additives
sodium sulphide, triisobutyl phosphine sulphide and a 1:1 mixture of both have been added.
Untreated mercury had a TCLP concentration of 2.64mg/l and SPC without any additive had a TCLP
concentration of 0.02mg/l (if the processing time was enough for a complete reaction). Adding 3%
triisobutyl phosphine sulphide resulted in a TCLP concentration of 0.42mg/l whereas 3% sodium
sulphide resulted in a TCLP concentration of 0.026. By adding 1.5% triisobutyl phosphine sulphide
and 1.5% sodium sulphide to the mixture, the final product had a TCLP concentration of 0.064mg/l.
Vapour tests show that the vapour pressure of Hg sharply decrease over the span of one week from
approximately 37µg/l to approximately 3µg/l. The decrease in Hg vapour is explained by the theory
of an ongoing curing process of elemental mercury with free sulphur in the matrix.
Process for the encapsulation and stabilisation of radioactive, hazardous material [US 5678234]
The patent provides a detailed description of the process of encapsulation of hazardous waste. The
waste loading is about 40 w/w% waste, 52.5% modified sulphur cement, 7% anhydrous sodium
sulphide and 0.5 % glass fibres to increase the physical strength of the product. Compressive strength
and leaching tests were performed but the focus is not set on mercury.
Method and apparatus for stabilizing liquid elemental mercury [US 6403044 B1]
In this work various tests with elemental mercury containing waste and mercury chlorine were
performed. A promising example was the experiment to combine 13.5kg of mercury with 6.75kg of
elemental sulphur, 2.7 litres of calcium polysulphide and 6.75kg of sand. The leaching test resulted in
0.1mg/l; whereas a test without the sand resulted in 2mg/l.
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7.2.6 Further details concerning realization of the process
Two companies have been identified which apply the SPSS process at least on a laboratory scale and
which could provide additional information on technical, environmental and economic aspects of the
technology.
The information included is based on personal communication with the companies.
7.2.6.1 SPSS According to ADA Technology
ADA Technology is the owner of the technology only. The licensee is M&EC, a company in Oak Ridge,
TN.
Process description and equipment
Reactants The reactants of the process are elemental mercury, sulphur, polysulfide
(calcium polysulphide, or sodium polysulphide) and sand
Process description It is a batch process consisting of combining elemental mercury with a
proprietary sulphur mixture in a pug mill. Treatment of the liquid mercury
was conducted by adding powdered sulphur to the pug mill, while a pre-
weighed amount of mercury was poured into the mill. As the mill
continues to mix and the reaction takes place, additional substances as
sand or water can be added to provide temperature control and sufficient
volume for efficient mixing to take place. While the processing of mercury
in the pug mill is performed without heating, the reaction of mercury with
sulphur is exothermic at room temperature. and the temperature of the
mixture increases but shall not exceed 100 °C.
Process conditions No further information than that provided in the process description
could be provided for the process conditions.
Throughput A batch size of 50 kg has already been used which would result in a daily
throughput of 250 kg/day. A scale up to 375kg/batch is considered
possible by the vendor. In this case the yearly throughput is expected to
be 1,000t/year if five mixers are used in parallel.
All together, 10 metric tonnes of radioactive mercury has already been
stabilized by the Company.
Emissions Off-gas is passed through a High Efficiency Particulate Airfilter (HEPA),
and then passed through a sulphur-impregnated carbon filter. Mercury
vapour concentration above the plug mill is below the threshold limit
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Process description and equipment
value (TLV) of 50 mg/m3.
Energy consumption No information could be provided for energy consumption.
Expected operational
costs
No information could be provided for operational costs.
Implementation costs No information could be provided for implementation costs.
Patent US 6,403,044 B1
Implementation time 10t of waste have already been stabilised by 50 kg/batch. But no
information could be provided for a larger facility e.g. 375 kg/batch
Resulting product
Final product The final product is a granular waste, which consist of HgS and sulphur
polymer cement, and can be poured into drums.
Product stability For this product, only leaching values (TCLP) at different pH values are
available. The lowest leaching behaviour can be achieved at a pH value of
2 with 0.001 mg/l. In a more or less linear trend the leaching value
reaches a maximum of ~0.1 mg/l at pH value of 12.
Volume and weight The weight of the material increases by about 100 % and the volume
increases by about 2200 %.
Emissions from the
product
No emissions from the product except leaching are known.
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7.2.6.2 SPSS according to DOE
The patent assignee is Brookhaven Natural Laboratory, which is one of ten laboratories overseen and
primarily funded by the office of science of the U.S. Department of energy (DOE). The process results
in a product containing traces of mercury, further investigations are on hold due to economic
reasons.
Process description and equipment
Reactants The reactants are elemental mercury, sulphur polymer cement (SPC) and
sodium sulphide.
Process description This process is a two stage single vessel (vertical mixer/dryer) batch process
that results in mercuric sulphide stabilised in a sulphur polymer matrix. In
the first step, mercury is reacted with powdered sulphur polymer cement
and additives to form a stable mercury sulphide compound. Next, the
chemically stabilized mixture is melted in a sulphur polymer matrix, mixed
and cooled to form a monolithic solid waste form in which the stabilized
mercury particles are microencapsulated within a sulphur polymer matrix
[USEPA 2002c].
Process conditions In the first reaction step the reactor is heated to 40- 70 °C and in a second
step to 135 °C. The whole process takes place under an inert gas atmosphere
(nitrogen or argon).
Throughput A 1 ft3 (0.03 m3) mixer has already been realized, capable of stabilizing about
20 kg mercury per shift. Assumptions have been provided for the following
mixer sizes. 10 m3 mixers could stabilize about 7,600 kg/day, 1.8 m3 mixers
have a daily throughput of 1,400 kg and 0.28 m3 mixers have a daily
throughput of 270 kg/day. All these assumptions are based on an average
batch time of twelve hours and two shifts per day.
Emissions The process produces some mercury vapour, so a ventilation system is
required to filter out the vapour. Since the process is carried out at a high
temperature (135°C), heat exchangers are included in the ventilation system.
A liquid nitrogen cryogenic trap condenses the mercury vapour and it is
recycled back into the process. Trials have shown that 99.7 % of the mercury
is retained in the product.
Energy consumption No information could be provided for the energy consumption of the
process.
Expected
operational costs
No information could be provided for the expected operational costs of the
process. From a different study [USEPA 2003] an estimated full scale cost is
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Process description and equipment
provided with about 2.88 $/kg (~2,000 €/t).
Implementation
costs
No information could be provided for the implementation costs of the
process.
Patent US 6,399,849
Implementation
time
No information could be provided for the implementation time of the
process.
Resulting product
Final product The product is a monolithic structure with a mercury content of 33%, 65%
sulphur polymer cement and 2% sodium sulphide.
Product stability
In order to determine leaching behavior, the TCLP process was used for
different pH values. The results have been in a range of 0.005 and 45 mg/l.
The reason for this wide range of leaching behaviour was not the pH
dependency but a small amount of elemental mercury which was still
existing in the final product. It is considered by the inventors that by
adjusting the processing methodology (e.g. mixing method, introduction of
waste material) the product quality can be increased and that the process
can be controlled better. No further work has been done so far in this field.
Volume and weight
The Volume of the product is about 15-18 times the original elemental
mercury whereas the weight increased by a factor of 3. The mercury content
of the final product is 33 %
Emissions from the
product
No emissions from the product except leaching are known.
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7.3 Amalgamation
Many metals interact with liquid mercury and an alloy is formed. These alloys are called amalgams. If
the amount of the non-mercury metal is small, the amalgam is still liquid and the viscosity of the
amalgam increases with higher concentration of the non-mercury metal in the amalgam.
Table 7-3: Amalgamation: overview of the relevant literature
Relevant literature overview for amalgamation
Literature Content
Treatment Technologies for Mercury in Soil, Waste and Water [USEPA 2007]
General description of techniques and cost estimates
Advances in Encapsulation Technologies for the management of Mercury-contaminated Hazardous Wastes [USEPA 2002b]
General description of different immobilization techniques and cost estimates
Determination of acute Hg emissions from solidified-stabilised cement waste forms [ORNL 2002]
General description of the volatile behaving of mercury after amalgamation.
Economic and Environmental analyses of technologies to treat mercury and disposed of in a waste containment facility [USEPA 2005]
General information about costs and techniques for sulphur stabilisation, sulphur polymer stabilisation/solidification and amalgamation.
Mersade Mercury Safety Deposit [Mersade 2007a]
General description about different stabilization, solidification techniques, among others amalgamation.
Mercury wastes evaluation of Treatment of mercury surrogated waste [USEPA 2002]
Comparison of four different stabilizing surrogated sludges
Mercury wastes evaluation of Bulk elemental Mercury [USEPA 2002a]
Comparison of three vendors stabilizing bulk elemental mercury
Process for treating mercury in preparation for Disposal [US5034054]
Mercury is mixed with an inorganic powder (copper, zinc, nickel and sulphur) resulting in a permanent bonding of the mercury to the powder in a solid form.
Treatment of elemental mercury [WO2005092447 A2] and [US20080234529 A1]
Amalgamation as a first step , followed by a cementation process with Ordinary Portland Cement (OPC)
7.3.1 Technical background
Amalgamation means the dissolution and solidification of mercury in other metals such as copper,
selenium, nickel, zinc and tin, resulting in a solid, non-volatile product. The amalgamating metal is
preferably provided in the form of a fine powder, thereby providing the maximum surface area and
promoting increased efficiency of reaction. In general, the preferred amalgamation metal is copper.
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Amalgamation is a subset of solidification technologies and does not involve a chemical reaction.
Different amalgamation processes exist: aqueous and non-aqueous. The non-aqueous process is
suitable for elemental mercury. This process involves the mixing of finely divided powder into liquid
mercury, forming a solidified amalgam. This technology is a speedy process for the treatment of
elemental mercury. However, mercury in the resulting amalgam is susceptible to volatilization or
hydrolysis. Therefore, amalgamation is typically used in combination with an encapsulation
technology.
Disadvantages come from the difficulties to scale up and the need for dilute nitric acid to achieve
high efficiency.
The use of nickel has to be considered critically due to its hazardous properties. In addition, prices of
potentially suitable metals are relatively high.
7.3.2 Economic background
The prices of the metals used for the amalgamation (Cu ~€3/kg, Zn ~€1 /kg, Sn €9/kg) [LME] as well
as the adverse raw material/elemental mercury ratio of suggested 3:1 result in relatively high costs
of this technology. (HgCu = €9/kg treated mercury, HgZn = €3/kg and HgSn €27/kg).
7.3.3 Environmental background
The physical-chemical properties of the products have been collected and included in Annex 4.
Available data about amalgams is mainly indicated at 0.2 mg/l (TCLP) and a further encapsulation
step is therefore recommended.
7.3.4 Use of the technology
Mercury wastes: evaluation of treatment of mercury surrogated waste [USEPA 2002]
The technologies compared in this report are: sulphur stabilisation, SPSS, amalgamation and
formation of mercuric sulphide followed by cement-containing stabilization.
The waste load for the amalgamation process followed by a precipitation of stable salt was ~45 wt%
and had an increase of 120% by weight. The final form was soil-like and it was estimated that the
mercury loss to air was about 0.05%.
Mercury wastes: evaluation of Bulk elemental Mercury [USEPA 2002a]
The technologies compared in this report are: sulphur stabilisation, SPSS and amalgamation.
The waste load for the amalgamation process followed by a precipitation of stable salt was ~20 wt%
and had an increase of 400% by weight. The final form was monolithic. The leaching values for the
final pellets are dependent on the pH value and have been about 30 mg/l at pH=2, ~0.2mg/l at pH =
8, 0.1mg/l at pH = 11 and ~0.02mg/l at pH = 12.
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In a separate test, mercury and selenium were heated and allowed to react in the vapour phase. The
leaching value of the mercuric selenide was tested at different chlorine concentrations in the water.
At pH 7 the addition of 500 ppm of chloride increased solubility from 0.007mg/l to 0.021mg/l.
7.3.5 Overview of patents
Process for treating mercury in preparation for disposal [US5034054]
In different experiments, amalgamation of 1 pint of mercury was tested. In the case of amalgamation
with copper it was determined, that a compound agitation with a copper/mercury ratio of 3:1 for 40
minutes provided an optimum result. The product is a powder with a copper appearance,
satisfactory for disposal in landfills (for US conditions). In the case of a copper/mercury ratio of 1:1
elemental mercury remained even after 45 min of compound agitation. Another test showed that 2
hours of reciprocal agitation with a copper/mercury ratio of 3:1 yielded an unacceptable high
amount of liquid mercury.
In a final experiment, sulphur was used instead of copper. After 20 minutes of compound agitation of
a mixture with a sulphur/mercury ratio of 3:1 the mercury was solidified. However a mercuric
sulphide gas was noticed.
Treatment of elemental mercury [WO2005092447 A2] and [US20080234529 A1]
Amalgamation tests have been performed and the greatest success was observed when copper was
added to mercury in a ratio of 2:3. In addition, a 1:1 w/w of a 0.1 M diluted aqueous nitric acid
should be employed for optimum results. This mixture was subjected to vigorous agitation until the
amalgam reaction was completed. The amalgam sludge is suitable for treatment with an appropriate
cementitious particulate filler material such as OPC (or a mixture of a blast furnace slag (BFS) with
Ordinary Portland Cement in a ratio of 3:1). The whole process is conducted at room temperature.
The amalgamation stage is complete after 5-10 minutes whereas the curing of the BFS and OPC takes
24 to 48 hours. The mercury concentration of the final product is about 14%. The final product shall
be suitable for immediate disposal (according to the US legal requirements).
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7.4 Phosphate ceramic/glass stabilization: Chemical bonded phosphate ceramic (CBPC)
The first efforts to stabilize mercury or mercury compounds with phosphate glass started in 1970. In
the relevant patent, HgO was stabilized with different phosphates and metal oxides. The product of
this technology is a Chemically Bonded Phosphate Ceramic (CBPC).
Table 7-4: Phosphate ceramic/glass stabilization: overview of the relevant literature
Relevant literature overview for phosphate ceramic/glass stabilization
Literature Content
Method for producing chemically bonded phosphate ceramics and for stabilizing contaminants encapsulated therein utilizing reducing agents[USWagh Singh]
General information about CBPC and magnesium potassium phosphate (MKP) and examples with different wastes.
Advances in Encapsulation Technologies for the Management of Mercury contaminated Hazardous Wastes [USEPA 2002b]
General description of different immobilization techniques and cost estimates
Polymer coating for immobilizing soluble ions in a phosphate ceramic product [US6153809A]
General description for CBPC and applying a polymer coating to the exterior surface of the CBPC product
Evaluation of chemically bonded phosphate ceramics for mercury stabilization of mixed synthetic waste [USEPA 2003]
Leaching tests of CBPC containing Hg- and HgCl2 contaminated wastes. Cost estimation
Chemically bonded phosphate ceramics for stabilization and solidification of mixed waste [USWagh]
Experience on bench scale stabilization of various waste streams containing Hg in the CBPC process.
Mercury stabilization in chemically bonded phosphate ceramics [USWagh 2000]
Detailed explanation for producing a CBPC with mercury contaminated waste and improvement by adding Na2S or K2S.
Mercury containing phosphate glass [US3499774]
Process description of the production of mercury phosphate glass with the reactants HgO, P2O5 and a metal of Group I-II, lead or aluminum.
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7.4.1 Technical background
Chemically bonded phosphate ceramics (CBPCs) are fabricated by an acid-base reaction between
calcinated magnesium oxide (MgO) and mono-potassium-phosphate (KH2PO4) in solution to form a
hard dense ceramic of magnesium potassium phosphate hydrate. For this purpose calcinated
magnesium oxide powder and monopotassium phosphate is stirred under an aqueous condition to
produce Magnesium potassium phosphate (MKP). In a second step, the MKP is combined with the
mercury. The process temperature is low (<80°C) and therefore little hazardous off-gasses arise and
no secondary waste is generated.
CBPC treatment of elemental Mercury will form low solubility chemical bonded phosphate solids
(Hg3(PO4)2), but a further improved stabilization by forming HgS in a first step, can be realised with a
small amount of sodium sulphide (Na2S) or potassium sulphide (K2S). The sulphides significantly
improve the performance of the final CBPC waste and are therefore recommended. An excess of
sulphide will increase the leachability and therefore careful processing is needed.
The product of the CBPC process can have a mercury load as high as 78% with a density of 1.8g/cm³.
The immobilisation is a result of chemical stabilisation and a physical encapsulation (solidification).
Studies have been carried out to show stabilization of waste streams only, which were contaminated
with small amount of mercury. In the case of elemental mercury, some significant work will have to
be carried out to develop a process to treat mercury in large quantities, though theoretically this can
be achieved.
An advantage for phosphate glass is the high physical stability.
7.4.2 Economic background
The total costs, including raw materials, labour and disposal for the CBPC process is about 15.45 $/kg
(~€10/kg) elemental mercury [USEPA 2002b].
7.4.3 Environmental background
The physical-chemical properties of the products have been collected and included in Annex 4. The
solubility of Hg3(PO4)2 is 1.4*10-8 mol/l and for HgHPO4 = 2.8*10-7. This is equal to a mercury
concentration of 2.8 and 56µg/l respectively. Even though these values are very low, the leaching
value of HgS is much lower (4.5 *10-25 mol/l or 10-16 µg/l) [USWagh 2000].
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7.4.4 Use of technology
Evaluation of chemically bonded phosphate ceramics for mercury stabilization of mixed synthetic waste [USEPA 2003]
In this evaluation, CBPCs of elemental mercury with a concentration of 50% and 70% Hg in the
stabilised waste form have been produced.
For the 50% load, 300g Hg were mixed with 2g Na2S and 160g water. After 10 minutes of mixing, it
was combined with 300g MKP binder.
For the 70% load, 400g Hg were mixed with 2.67 g Na2S and 120g water. After 10 minutes of mixing,
it was combined with 172g MKP binder.
These mixtures were transferred into plastic vertical cylindrical moulds and allowed to set until
solidified. The moulds were cured by air-drying for about three weeks.
In the case of untreated Hg the leaching behaviour is ~250mg/l at pH of 2 and ~35µg/l at pH 12.
Stabilised waste with 50% Hg had a leaching concentration of ~3mg/l at pH 2 and ~8µg/l at pH 12.
Stabilised waste with 70% Hg had a leaching concentration of ~6mg/l at pH 2 and ~1.4 mg/l at pH 12.
The results are shown in Figure 7-2.
Figure 7-2: Leaching behaviour of stabilized waste with different Hg loads and at different pH values.
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Chemically bonded phosphate ceramics for stabilization and solidification of mixed waste [USWagh]
In this report the CBPC technology to encapsulate different wastes is described. Among other wastes,
the encapsulation of Hg-contaminated wastes from light bulbs is also presented. The examples were
performed in 5-gals drums with a waste load of about 40%. For the Hg-contaminated wastes,
potassium sulphide was added. The final product had a TCLP leaching value of 0.05 ppb of Hg in the
leaching water.
Mercury stabilization in chemically bonded phosphate ceramics [USWagh 2000]
This report describes different types of wastes that have been treated to form CBPC and to bind
mercury as Hg3(PO4)2 within the ceramic. It was shown that the limit value of TCLP 0.2 mg/l could not
be reached. Therefore, it is recommended to add a sulphide as Na2S or K2S to receive HgS which is
encapsulated within the ceramic. An excess of sulphide favours the formation of HgSO4 which has a
disadvantageously high solubility product. The waste was added to the binder mixture (K2S, MgO,
and KH2PO4) and to a stoichiometric amount of water. The mixture was mixed for 30 minutes and
poured into a mould to set within 2 hours. The hard and dense ceramic was stored for 3 weeks for
good curing. Leaching tests and long term leaching tests delivered sufficient stability for EPA limits.
7.4.5 Overview of patents
Mercury containing phosphate glass [US3499774]
In this patent different combinations of HgO, Li2O and P2O6 have been used to produce phosphate
glass. The focus was to produce a glass with good optical characteristics. The mercury content in the
different glasses is between ~30 to 70% with a density between 3 to 6.5g/cm3.
7.5 Solidification/encapsulation
The following techniques are used for hazardous waste treatment. No reports have been published
which cover the encapsulation of elemental mercury but the processes shall be briefly described here
for a complete overview of stabilisation encapsulation techniques. All these processes only
encapsulate mercury but do not interact chemically with the mercury:
Polyethylene Encapsulation [US-EPA2002]
The polyethylene encapsulation is dependent on the extruder used, a macro-encapsulation process
or a combined micro- and macro-encapsulation process. Low density polyethylene (LDPE) is less
prone to cratering and cracking than high density polyethylene (HDPE). The resulting material has a
high mechanical strength, flexibility and chemical resistance. The waste load can be up to 70% and
the equipment is commercially available. The disadvantage is that this process requires higher
temperature and therefore Hg emissions from the process can occur. This technique can be
combined with a stabilisation process.
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Encapsulation with Asphalt [US-EPA2002]
Asphalt micro-encapsulation can be used for encapsulation of different wastes. For mercury
containing waste, cold-mix asphalt seems to be more appropriate than hot-mix asphalt due to the
possible volatilization of mercury. As there is no chemical reaction between the asphalt and the
mercury a stabilizing pre-treatment step is necessary.
Encapsulation with Polyester and Epoxy resin [US-EPA2002]
With polyester and epoxy resin encapsulation, waste loads of 50% have been reported but no
information for the usability for metallic mercury is available. As there is no chemical reaction
between the polyester nor the epoxy resin with the mercury, a stabilizing pre-treatment step is
necessary.
Encapsulation with Synthetic Elastomers [US-EPA2002]
Synthetic rubbers have been used for microencapsulation and stabilisation of metal contaminated
waste. As there is no chemical reaction between the synthetic elastomer with the mercury a
stabilizing pre-treatment step is necessary.
Encapsulation with Polysiloxane [US-EPA2002]
Polysiloxane or ceramic silicon foam (CSF) have been used for the encapsulation of waste and
consists of 50 wt% vinylpolydimethyl-siloxane, 20 wt% quartz, 25 wt% proprietary ingredients and
less than 5 wt% water. The material sets at room temperature and is resistant to extreme
temperatures, pressures and chemical exposure. The waste loading can be up to 50 wt%. As there is
no chemical reaction between polysiloxane and the mercury, a stabilizing pre-treatment step is
necessary.
Sol gels encapsulation [US-EPA2002]
Sol gels are a combination of organic polymers and inorganic ceramics. The polymer and silicon
dioxide are combined first and then mixed with the waste and then solidified to encapsulate the
waste. The temperature for this process is about 70°C and a waste loading of 30 to 70% can be
achieved.
DolocreteTM encapsulation [US-EPA2002],
DolocreteTM is a calcined dolomitic binder material that can be used for microencapsulation of
inorganic, organic and low-level radioactive waste.
Encapsulation with calcium carbonate and magnesium oxide (CaCO3-MgO) [US6399848 B1]
The hazardous waste material is added to a settable composition forming a slurry and allowing the
slurry to set to encapsulate the waste material. The settable composition is a powdered, flowable
cement composition, containing calcium carbonate and a caustic magnesium oxide. Different
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additives such as aluminium sulphate of citric acid can be added to increase the performance.
Encapsulation with ladle furnace slag [WO2005039702 A1]
When ladle furnace slag is subjected to an alkali-activated (2M NaOH) process with thermal
treatment, the non-reactive ladle furnace slag undergoes a chemical reaction and forms a durable
cementitious matrix capable of advantageously stabilizing mercury ions. The mercury ions are
precipitated into stable heavy metal compounds such as mercury sulphides and are encapsulated by
the matrix slurry as the matrix slurry sets into a monolith structure. The amount of mercury in
comparison to the ladle furnace slag is ≤ 1%.
7.6 Encapsulation of stabilized mercury with cement
Cement solidification is an encapsulation technique as listed in section 7.5. This technique is
described separately because tests with a starting material of metallic mercury, which was pre-
treated before encapsulation, have already been carried out and a patent is available. This technique
has only been realised on a laboratory scale.
Table 7-5: Cement solidification: overview of the relevant literature
Relevant literature overview for ordinary Portland cement solidification
Literature Content
Method for producing inorganic hardened body [JP2002255671]
General description of inorganic hardened body by using fibre and cement.
Treatment of elemental mercury [WO2005092447 A2]
Describes the encapsulation technique with ordinary portland cement (OPC). A pre-treatment technique is recommended.
Encapsulation process [Lopez 2009] Description of a sulphur stabilization technology, combined with a cement encapsulation.
Procedimiento de estabilizacion de mercurio liquid mediante cemento polimerico de azufre, via sulfuro de mercurio [P200930672]
Patent application for a process of a sulphur stabilization technology, combined with a cement encapsulation
7.6.1 Technical background
Cement (e.g. ordinary Portland cement [OPC]), acting as the cementitious filler material is used for
the encapsulation of elemental mercury. To improve the leaching properties, a previous stabilisation
step (amalgamation with Cu) is carried out. Additional inorganic fillers can be added to this process
as pulverised fuel ash, hydrate lime, finely divided silica, limestone flour and organic and inorganic
fluidizing agent and especially blast furnace slag (BFS). The ratio of the inorganic filler to the
cementitious filler material can be in the range of 3:1 w/w. The immobilised mercury shall be mixed
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in a ratio of 1:1 w/w with the filler material.
7.6.2 Economic background
The cost estimate is $16.37 per kg for conventional Portland cement stabilization (including disposal)
[US-EPA 2003]
7.6.3 Environmental background
No relevant environmental data have yet been found for the OPC encapsulation of mercury.
7.6.4 Overview of patents
Treatment of elemental mercury [WO2005092447 A2]
In a first experiment, 80g of amalgam sludge (20g Hg, 30g Cu and 30ml dilute nitric acid) are stirred
with 40g OPC and 120g BFS. Water was added to this mixture as necessary. The mixture was covered
and allowed to stand for 48 hours at ambient temperature. The product was suitable for immediate
disposal according to the US legislation requirements.
In a second experiment, 100g mercury, 150g copper and 150ml 0.1 M nitric acid were intensively
stirred for 30 minutes to receive an amalgam sludge. This sludge was mixed with 300 g BFS and 100 g
OPC resulting in a Hg load of 14%. The mixture was poured into a mould and left for 24 hours for
curing.
7.6.5 Further details concerning realization of the process
One institution has been identified which applies the sulphur stabilization in combination with the
encapsulation technique, which could provide additional information on technical, environmental
and economic aspects of the technology.
7.6.5.1 Cement encapsulation technique according to MERSADE
The information included is based on personal communication with the companies.
The process was developed in the context of the EU Life-project Mersade. The technology is until
now only performed on a semi-laboratory scale. A larger scaling up has not yet started.
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Process description and equipment
Reactants The reactants are elemental mercury, elemental sulphur, polymeric
sulphur, coarse and fine gravel, sand and CaCO3. The concrete block has a
mercury content of 30%.
Process description The stabilization takes place in a two-step process. In the first step the
elemental mercury is stabilized with sulphur to meta-cinnabar with a
planetary ball mill. In a second step this meta-cinnabar is incorporated in
a polymeric S-concrete matrix, composed of gravel, sand, filler, elemental
sulphur and modified sulphur.
Process conditions The concrete matrix is prepared at 140°C and at room temperature
Throughput The facility is still only on a small scale, producing 6 kg of a final product
per batch and a throughput of 4 kg/
Emissions Due to the laboratory scale, emissions can occur during the milling of
sulphur and liquid mercury
Energy consumption No information could be provided for the energy consumption of the
process.
Expected operational
costs
The cost for the stabilization of metallic mercury at a full scale application
is estimated to be between 15,000 and 17,000 €/tonne metallic mercury.
Implementation costs No information could be provided for the implementation costs of the
process.
Patent Patent application N° P200930672, priority date: 9 September 2009
[P200930672]
Implementation time No information could be provided for the implementation time of the
process.
Resulting Product
Final Product The final product is prepared in the form of a monolithic material of
16x16x4 cm. The shape of the ashlars can also be changed.
Product stability The concrete blocks have a water absorption by capillary of 0.07 g/cm2.
The water permeability under low pressure (RILEM) shows no water
absorption under low pressure. To determine the leaching behaviour the
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Resulting Product
TCLP procedure was used and the average value was ~0,102mg/l. The
concrete block shows very good mechanical properties with a
comprehensive strength of 57.2 ± 44 N/mm2 and a flexural strength of
8.5 ± 1.17 N/mm2.
Volume and weight
The density of the concrete block is about 3.1-3.2 g/cm3 and has a total
porosity of ~2% and a closed porosity of ~0.6%. The mercury loaded
concrete blocks have a higher density and lower pore volume than a
mercury free reference. The reason is that it is expected that meta-
cinnabar particles fill interparticle interstices and the higher size pores
which exist in the initial S-concrete. The volume of the product is
approximately 13 times higher than elemental mercury and the weight is
increased by a factor of 3.
Emissions from the
product No emissions from the product except leaching are known.
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7.7 Conclusion
Based on an extensive literature search including patent data bases, scientific data bases and other
relevant recent publications numerous pre-treatment technologies have been identified. Wherever
possible, the authors or companies, developing the technologies, have been approached directly to
receive the most recent information on the state of the art of the technology and their state of
implementation.
The identified technologies could be allocated to 6 categories depending on the used technology or
stabilization process (see Table 7-6).
Apart from the technologies already realised in large scale application only very limited information
on costs or environmental aspects of the process are available.
An evaluation of the technologies against technical, environmental and economic requirements is
included in section 8.
In particular the sulphur stabilization and the SPSS technologies are already well developed and
available at a full-scale application. Detailed data on operation conditions and final products as well
as some information concerning costs are available and included in the previous section. In addition,
an overview on the most important information related to technologies already realised in large-
scale application is compiled in Annex 5.
Sulphur stabilisation
The stabilisation with sulphur has been widely described in literature such as [DE453523],
[USEPA 2002], [GRS 2009A] and [USEPA 2005]. Literature refers to the stabilisation of metallic
mercury but also to mercury-containing waste.
In general sulphur is seen as an appropriate stabilisation agent and the stabilisation process with
sulphur is considered to be an effective stabilisation process. If testing results have been presented in
literature [US EPA 2005], the sulphur containing stabilisation techniques show good test results with
respect to the stability of the product. Due to intensive research work a continuous improvement of
the process could be observed.
At present, only two companies realised this process on a large-scale application, SAKAB/DELA,
Germany and Bethlehem Apparatus, USA. Literature available related to the latest process conditions
are patents, presentations [DELA 2009] or direct information from the companies.
DELA has published some patents on the production of mercury sulphide. Patents are available for a
continuous process [EP 2072 468 A2] as well as for a discontinuous process [EP 2072 467 A2]. The
currently realised process refers to patent No. EP 2072 467 A2 (batch process).
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Details of the process have been gathered by telephone conversation, e-mails and a visit. During
2009 the process was continuously developed and the parameters have been adjusted.
Since the end of 2009, stable and low leaching values are realised and the mercury concentration in
the gaseous phase was measured and was below the limit of detection of the used analysis
instrument (0.003 mg/m³).
In February 2010 a large-scale application (installed capacity: 1,000 t/year) has been installed by the
company DELA80. At the moment no test results of the product could be provided.
Recently, a patent of Bethlehem Apparatus concerning the stabilisation of metallic mercury with
sulphide has been approved and an official number is expected in the near future81. All the data
related to the process developed by Bethlehem Apparatus has been gained by telephone
conversation and a filled in questionnaire from the company.
The quality of the stabilised product is comparable to the product resulting from the SAKAB/DELA
process. The leaching value is in the same range and no unreacted metallic mercury could be
detected when analysed with x-ray diffraction or by computer aided tomography. With both
methods no mercury could be detected82.Sulphur polymer stabilisation/solidification (SPSS)
The different literatures ([Brookhaven_Newmont 2003], [US6399849B1], [ACS Kazakhstan 2000],
[USEPA 2002a]) describing the SPSS process developed by the Department of Energy (DOE) evaluate
this pre-treatment technology as a stable process which is fully developed. Only one report ([USEPA
2002a, vendor A]) indicated leaching values - measured at different pH values – which seemed higher
than expected. After direct contact with DOE83 it turned out that this technique still needs some R&D
to optimize the technology and improve quality control (i.e. to ensure complete reaction of all the Hg
and therefore consistently low leachability). The high leaching values reported in the report result
from an incomplete stabilisation of the metallic mercury. Only 99.7% of the mercury is retained in
the product.
Apart from DOE another company (ADA Technology) has been identified which has developed a pre-
treatment process based on SPSS. The process is described in detail in literature (e.g. [USEPA 2002a,
vendor B], [USEPA 2005]). In addition several discussions and e-mail exchanges took place with ADA
Technologies as well as with M&EC, the licence holder of this technology. The installation costs of the
facility are stated in the report [USEPA2005] to be about 2,000,000 € and the estimated cost per year
(for 1,000 t/year) have been set at about 2,700,000 €. According to ADA Technology this economic
calculation of the report [USEPA 2005] is considered to be rather conservative. ADA Technology
which has 15 years of experience in developing mercury stabilisation solutions indicated that on the
80 E-mail: Miriam Ortheil, DELA GmbH, 6 January 2010 81 E-mail: Bruce J. Lawrence, president, Bethlehem Apparatus Co. Inc., 5 January 2010, U.S. Patent Application
No. 12/255,403 82 E-mail: Bruce J. Lawrence, president, Bethlehem Apparatus Co. Inc., 19 August 2009 83 E-mail statement from Mr. Kalb, Division Head, Brookhaven National Laboratory, 28.08.2009
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basis of their experience mercuric sulphide is the most stable and least soluble form of mercury.84
Amalgamation
Technologies based on amalgamation of mercury with other metals are widely described (especially
[USEPA 2007], [USEPA 2002a], [WO2005092447 A2] [US5034054]), but the stability and suitability of
the resulting amalgam for a final storage are highly questionable. Report [USEPA 2002a] compares
leaching limit values of different pre-treatment technologies. The leaching values indicated for the
amalgamation process (vendor C) are higher compared to the other pre-treatment technologies
using sulphur as a stabilisation agent. Especially at lower pH values (pH <4) the poor quality of this
stabilisation technology can be recognised. No information on a potential commercial use has been
found. The poor stabilisation performance of amalgams is a general accepted opinion [USEPA 2002a]
and no expert could be found who would favour amalgamation as a stabilisation technique. In many
cases as in the patent [US5034054] amalgamation is combined with an encapsulation step.
CBPC
The stabilisation of metallic mercury by chemical bonded phosphate ceramic processes are well
described in the literature, e.g. [US Wagh], [US Wagh Singh], [USWagh]). Evaluating the literature,
the reader has the impression that this technology is ready to be used to stabilise metallic mercury.
To verify this information Mr. Wagh was contacted. The following statement has been received by e-
mail85: “The phosphate bonded ceramic technology has not been used or demonstrated for
elemental mercury. We have developed detailed solubility models to produce suitable formulation
for treating metals, but we have not carried out any experimental work.” It was also stated that still a
lot of work has to be done to develop a process to treat mercury in large quantity, though
theoretically this would be possible.
Encapsulation
A lot of information related to encapsulation processes has been identified. In particular [USEPA
2002b] describes encapsulation processes in detail. But all technologies deal with the encapsulation
of mercury containing waste. Investigations using an encapsulation technique with metallic mercury
could not be found. Numerous patents are available describing encapsulation of mercury
contaminated waste (e.g. [WO2005 039702 A1]). A rough screening of these patents was carried out
but no suitable technologies for the treatment of pure metallic mercury have been identified. Due to
its liquid state, metallic mercury is completely different to mercury-contaminated waste (solid) and
therefore stabilisation technologies cannot be easily transferred.
Only one encapsulation technology with a prior sulphur stabilization of the metallic mercury shows
promising results [Mersade 2009A]. It can be considered that the main stabilisation is due to the
sulphurisation and not the encapsulation [Mersade 2007A]. Currently information only is available
from the institution developing this technology.
84 E-Mail statement from Mr. Jim Butz, vice president of Operations from ADA Technology, Inc. 06.07.2009 85 e-mail from Mr. Wagh, dated 23.06.2009
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A patent promoting the encapsulation of immobilised mercury (either by sulphur stabilisation,
sulphur polymer stabilisation/solidification, chemically bonded phosphate ceramic or copper) with
Ordinary Portland Cement (OPC) is described by [WO 2005092447 A2]. A practical use of this
technology could not be found.
In the following table a short overview on the realised pre-treatment per categories is given:
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Table 7-6: Overview on existing pre-treatment technologies for liquid mercury
Existing pre-treatment technologies Process Company Elemental mercury
per batch Daily Throughput for one existing line
Complete stabilisation
Hg content in product
Comments
DELA 5 kg 60 kg/day 84 wt% Large scale application available but not tested yet.
Sulphur stabilisation
Bethlehem apparatus
50 kg 275 kg/day 84 wt% No scaling up is planned but the parallel use of many small lines is proposed to meet quantity needs, when needed
DOE 20 kg 40 kg/day X 33 wt% Incomplete reaction, presence of elemental mercury in the product
Amalgamation X X X X X
The technology is currently not economically used for Hg stabilisation
CBPS X X X X X
The technology is currently not economically used for Hg stabilisation
Encapsulation without stabilisation
X X X X X The technology is currently not economically used for Hg stabilisation
Sulphurisation / Encapsulation
MERSADE 2 kg 100 kg/day 30 wt% Needed time period for a large scale application: 3-5 years
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7.8 References
[ACS Kazakhstan 2000] Emerging Technologies in Hazardous Waste Management 8 D. William Tedder and Frederick G. Pohland, 2000 [Brookhaven Newmont 2003] Using the Sulfur Polymer Stabilization/Solidification Process to Treat Residual Mercury Wastes from Gold Mining Operations B. Bowerman, J. Adams, P.Kalb, R-Y Wan and M. LeVier 24-26 February 2003, http://www.bnl.gov/isd/documents/25533.pdf [CA1011889] McCord, Andrew T. and Wagner, lois E., Disposal of wastes containing mercury, Chem-Trol pollution Services
[CENIM 2009]
The application of sulphur concrete to the stabilization of Hg-contaminated soil, 1st Spanish national
conference on advances in materials recycling and eco-energy, F.A. López, C.P. Román, I. Padilla, A.
López-Delgado and F.J. Alguacil, 2009
[DELA 2009] Workshop on the safe storage and disposal of redundant mercury, Stabilisation of mercury for final disposal by formation of mercury sulphide, Miriam Ortheil, DELA, St Anne´s College, Oxford (UK), 13th & 14th October, 2009 [DE453523] Herstellung von lichtecher Zinnober aus den Elementen, Deutsches Reich, Alexander Eibner, 7. April 1925 [EP 2 072 467 A2] Verfahren und Vorrichtung zur Herstellung von Quecksilbersulfid zur anschließenden Entsorgung, Bonman Christian, EP2 072 467 A2 [EP 2 072 468 A2] Verfahren und Vorrichtung zur Herstellung von Quecksilbersulfid zur anschließenden Entsorgung, Bonman Christian, EP2 072 468 A2 [GRS 2009A] GSR Gesellschaft für Anlagen- und Reaktorsicherheit, Technologies for the stabilization of elemental mercury and mercury-containing wastes, Final Report, GRS – 252, ISBN 978-3-939355-27-4, October 2009 [JP2002255671] Method for producing inorganic hardened body, Suzuki Shinchi, Watanabe Hiroshi, Shimada Kyoko, JP2002255671, 2002 [Kystverket 2008] Det Norske Veritas AS, Kystverket Norwegian Coastal Administration - Salvage of U-864 -
[Lopez 2008] F.A. López, F.H. Alguacil, C.P. Roman, H. Tayibi and A. López-Delgado, Disposal of elemental mercury via sulphur reaction by milling, 2008 ; http://digital.csic.es/bitstream/10261/7692/1/DISPOSAL%20ELEMENTALHg.pdf [Lopez 2009] Stabiliszation of mercury by sulphur concrete: Study of the Durability of the Materials obtained, F.A. López, C. Pérez, A. Guerrero, S. Goñi, F.J.Alguacil and A. López-Delgado, 1st Spanish National Conference on Advances in Materials Recycling and Eco-Energy, Madrid, 12-13 November 2009 [Mercury Bakeoff 1999] Mercury Bakeoff: Technology Comparison for the Treatment of Mixed Waste Mercury Contaminated Soils at BNL] P.D. Kalb, J.W. Adams, L.W. Milian, G. Penny, J. Brower, A. Lockwood Brookhaven National Laboratory 2 March 1999 [Mersade 2007 A] M. Ramos, Literature review concerning corrosion problems in mercury and stabilisation of liquid Hg, Status Report Literature review, T 1.3 and T 1.4, Life Project Number Life06 ENV/ES/PRE/03, February 2007; http://www.mayasa.es/Archivos/Mersade/WEB%20Literature%20review%20concerning%20to%20mercury%20corrosion%20and%20stabilisation%20of%20liquid%20Hg.pdf [Mersade 2007 B] P. Higueras, J. M. Esbrí, Literature review concerning environmental mercury monitoring, Status Report, Life Project Number Life06 ENV/ES/PRE/03, March 2007; http://www.mayasa.es/Archivos/Mersade/WEB%20Literature%20review%20concerning%20environmental%20mercury%20mon….pdf [Mersade 2009] Process for the Stabilization of Liquid mercury, via mercury sulfide, by the use of polymeric sulfur, F.A. López, A. López-Delgado and F.J. Alguacil, Consejo superior de investicadiones cientificas (CSIC), Centor nacional de investigations metalúrgicas (CENIM) [ÖREBRO 2006] Margareta Svensson, Mercury immobilisation, A requirement for permanent disposal of mercury waste in Sweden, http://www.sakab.se/upload/dokument/pdf/Laddningsbara%20filer/Forskning%20&%20utveckling/Mercury_immobilization.pdf 3rd February 2006 [ORNL-2002] MEASUREMENTS OF MERCURY RELEASED FROM SOLIDIFIED/STABILIZED WASTE FORMS–FY 2002 http://www.clu-in.org/download/contaminantfocus/mercury/DOE-Measurements-of-Mercury115769.pdf
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[ORNL 2002a] Determination of acute Hg emissions form solidified -stabilized cement waste forms, C.H. Mattus, 2002 [P200930672] López FA, López-Delgado A, Alguacil FJ and Alonso M., Procedimiento de estabilizacion de mercurio liquid mediante cemento polimerico de azufre, via sulfuro de mercurio, P200930672 (2009) [SAKAB/ DELA 2009] Stabilization of metallic mercury, Fact sheet, Susanne Kummel, 2009 [SPC 2009] http://www.ktf-split.hr/periodni/en/abc/kpt.html [Spiegel 2007] Gau in der Grube, Michael Fröhlingsdorf, Sebastian Knauer, 17/2007 [UNEP 2009] UNEP, Draft technical guidelines on the environmentally sound management of mercury wastes, 4th Draft, April 2009 [UNEP 2009 B] http://www.chem.unep.ch/MERCURY/ [USEPA 2002] Mary Cunningham, John Austin, Mike Morris, Evaluation of Treatment of Mercury Surrogate waste, final report, 2002 [USEPA 2002a] Mary Cunningham, John Austin, Mike Morris, Greg Hulet, Mercury wastes evaluation of treatment of bulk elemental mercury, 2002 [USEPA 2002b] Paul M. Randall, Sandip Chattopadhyay, Wendy E. Condit, Advances in encapsulation technologies for the management of mercury-contaminated hazardous wastes, 2002 [USEPA 2002c] Hugh W. McKinnon, Preliminary analysis of alternatives for the long term management of excess mercury, EPA/600/R-03/048, 2002, http://www.epa.gov/nrmrl/pubs/600r03048/600R03048.pdf [USEPA 2003] Evaluation of chemically Bonded Phosphate Ceramics for Mercury Stabilization of a Mixed Synthetic Waste, Land Remediation and Pollution Control Division National Risk Management Research Center Sandip Chattopadhyay, Paul M. Randall, March 2003 http://www.epa.gov/nrmrl/pubs/600r03113/600r03113.pdf [US EPA 2005] Paul Randall, Economic and Environmental Analysis of Technologies to Treat Mercury and Dispose in a Waste Containment Facility, April 2005 http://www.epa.gov/nrmrl/pubs/600r05157/600r05157.pdf
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[USEPA 2007] U.S. Environmental Protection Agency, Treatment Technologies For Mercury in Soil, Waste, and Water, EPA-542-R-07-003, 2007, 2007 http://www.epa.gov/tio/download/remed/542r07003.pdf [US20080019900 A1] Christelle Riviere-Huc, Vincent Huc, Emilie Bosse, Method for stabilisation of metallic mercury using sulphur, Oblon, Spivak, Mccleland Maier & Neustadt, 24. January 2008 [US20080234529 A1] Treatment of elemental mercury, Moore & Van Allen PLLC, Henry Boso Chan, Raymond Hall, 25. Sep. 2008 [US3061412] Preparation of mercuric sulfide, Anthony Giordano, 30. October 1962 [US3499774] Mercury-containing phosphate glass University Park Woldemar A. Weyl 10. March 1970 [US3704875] Removal of mercury from effluent streams, Penwalt Corporation, Paul Francis Waltrich,05. December 1972 [US5034054] Process for treating mercury in preparation for disposal, Ecoflo Inc., Jeffrey C. Woodward, 23 July 1991 [US5347072] Stabilizing inorganic substrates, Harold W. Adams, 13. September 1994 [US5562589] Stabilizing inorganic substrates Harold W. Adams, 8. October 1996 [US5569153] Method of immobilizing toxic waste material and resultant products, Southwest Research Institute, William A. Mallow, Robert D. Young, 29. October 1996 [US5678234] Process for the encapsulation and stabilization of radioactive, hazardous and mixed wastes, Peter Colombo, Paul D. Kalb, John H. Heisser, US 5,678,234, 1997 [US6399848 B1] Encapsulation of hazardous waste materials, Dolomatrix International Limited, Dino Rechichi, 04. July 2002 [US6399849 B1] Treatment of mercury containing waste, Brookhaven Science Associates LLC, Paul D. Kalb, Dan Melamed, Bhavesh R Patel, Mark Fuhrmann, 04 July 2002
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[US6153809A] Polymer coating for immobilizing soluble ions in a phosphate ceramic product, Dileep Singh, Arun S. Wagh, Kartikey D. Patel, US 6,153,809, 2000 [US6403044 B1] John E. Litz, Thomas Broderick, Robin M. Stewart, Method and apparatus for stabilizing liquid elemental mercury, ADA Technology Inc., 11. July 2002 [US Wagh] Chemically Bonded Phosphate Ceramics for Stabilization and Solidification of mixed waste, Energy Technology Division Arun S. Wagh, Dileep Singh, Seung-Young Jeong, [US Wagh 2000] Mercury Stabilization in Chemically Bonded Phosphate Ceramics; Energy Technology Division Argonne National Laboratory Dilep Singh, Arun Wagh, Seung Young Jeong http://www.anl.gov/techtransfer/Available_Technologies/Material_Science/Ceramicrete/wagh-mercury.pdf [US Wagh Singh] Method for producing chemically bonded phosphate ceramics and for stabilizing contaminants encapsulated therein utilizing reducing agents; United States Government; Dileep Singh, Arun Wagh, Seung-Young Jeong http://www.osti.gov/bridge/purl.cover.jsp;jsessionid=5971569EAD6B8B9106D1BE27F5F19563?purl=/782750-nscUTZ/webviewable/ [Wagh-1] Personal information Mr. Wagh [Waste Management 2001] Sulfur Polymer Solidification/Stabilization of elemental mercury waste M. Fuhrmann, D. Melamed, P.D. Kalb, J.W. Adams, L.W. Milian 14 August 2001 [Waste Management 2001]
- Outer side of the container must be resistant against the storage conditions
- Containers should be certified for the storage of mercury
- Welds should be avoided as far as possible
Justification:
The type of container material is based on experiences and investigations related to appropriate
container material (MERSADE, see chapter 6.4.3.1 and ORNL, see chapter 6.4.3.2).
Only containers should be allowed which are gas and liquid tight, so no mercury or mercury vapour is
able to escape from the container. The container should be certified for the storage of mercury. This
can either be proven by a paper certificate from the producer including the type number or indicated
in a data plate which is fixed at the container. These recommendations are technically obvious (see
chapter 6.4) and required to adequately protect workers health and the environment.
For above-ground storage long-term experience are in particular available from an existing above-
ground warehouses/storage facilities for liquid mercury in Europe (Almadén) and in the USA (DNSC),
see also chapter 6.3. These containers are also seen as appropriate for storage in underground
disposal sites in particular in the dry atmosphere of salt mines.
Welds are the weakest point in the container and should therefore be avoided as far as possible (see
chapter 6.4.3.2).
Each facility can define which size of containers is acceptable (depends on the facility conditions).
8.3.3 Acceptance procedure
The standard waste acceptance procedure as defined in Directive 1999/31/EC and Decision
2003/33/EC shall apply for metallic mercury. Metallic mercury is only allowed to be accepted if it is
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addressed in the site-specific risk assessment and included in the list of waste authorized to be
stored at a specific site. Prior to the shipment of the mercury an approval by the facility operator is
necessary. For this purpose the waste owner has to send information on the amount and
characteristics of the waste to the storage facility.
In addition, the following requirements shall be fulfilled:
- Only acceptance of metallic mercury which fulfils the minimum requirements as set out in
section 8.3.1 (verification required either by sampling or a certificate issued by a certified
person)
- Visual inspection of the container, no acceptance of damaged, leaking or corroded containers
- Only acceptance of containers with adequate labelling (at least according to the transport
requirements)
- Only acceptance of containers with a certificate which confirms the appropriateness for the
storage of liquid mercury
Justification:
In order to ensure that a container fulfils the minimum requirements as mentioned in chapter 8.3.2 a
certificate is needed. By the mean of this certificate the operator of the storage facility is able to
verify if the container is appropriate for the storage of liquid mercury.
The certificate – might also be a plate permanently fixed on the container - should include as a
minimum, identification number of the container, container material, producer of the container,
date of production and a confirmation that only mercury has been stored/transported in the
container (exclusion of storage of products which might react with mercury or the container
material).
The acceptance procedure at underground storage facilities typically includes visual inspection,
sampling and analysis of the received waste (WAC Decision). To avoid the opening of the mercury
containers and thus possible mercury emissions, it is recommended that the acceptance of sealed
containers accompanied by a certificate – issued by a certified person - which verifies the quality of
the mercury is possible.
In the case of the acceptance of sealed containers it is crucial that there is a reliable proof that the
containers only contain mercury which fulfils the minimum acceptance criteria as mentioned in
section 8.3.1. To avoid mercury is accepted which does not fulfil the minimum criteria, the filling and
the sealing of the containers should be supervised by a certified person. It is essential that the
supervising person has basic knowledge on the process and required quality of the mercury. With the
requirement that a certified person should supervise the filling and sealing on the one hand it is
assured that the person has a basic knowledge on the process and required quality of the mercy. On
the other hand incorrect information or misuse of the certificate could be avoided.
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The certificate, which has to be issued by the certified person, should include at least:
- Name and address of the company (waste owner)
- Place and date of packaging
- The purity of the mercury (min. >99.9%) and, if relevant, description of the impurities
(analytical report has to be provided)
- Quantity of the mercury
- Any specific comments
- Signature
One major advantage of the acceptance of sealed containers is that mercury emissions occurring
during the opening process can be reduced and thus a possible exposure of workers with mercury
can be avoided. In addition the risk of damaging of the plugs or improper re-closing of the flask -
which might result in a release of small amounts of mercury during the storage - can be significantly
reduced. On the other hand there is the risk that mercury is stored which does not fulfil the
minimum quality requirements due to wrong information included in the certificate. In case of any
suspicion that the quality criteria might not be met random samples should be carried out.
Sealed containers accompanied by an incomplete certificates or certificates issued by unknown
certification institutions have either to be rejected or the waste acceptance procedure as required by
the WAC has to be applied.
Record keeping
In general the recordkeeping for hazardous waste is designed to track hazardous waste from its
generation to final disposition.
With respect to the record keeping of the basic characterisation and compliance testing no specific
time frame is given in the Annex of the WAC Decision. Each Member State has to determine the
period of time these records have to be kept. The time for sample keeping from the on-site
verification is set by the WAC Decision for a minimum of one month.
In case of temporary storage it is recommended that the documents have to be stored for at least 3
years after the termination of the storage.
In case of a permanent storage of liquid mercury the Member State specific requirements should
apply but the records should at least be kept until the closure of the disposal site.
A plan of the storage area should be kept also after the closure of the storage site.
Records and plans must be available for inspection by regulators.
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8.4 Option 1l: permanent storage of liquid mercury in salt mines
In chapter 6.2.2, an overview is provided on basic characteristics of salt rock formations and their
qualification as a permanent disposal facility for hazardous waste.
In the following, an evaluation of the options conforming to the minimum requirements described in
chapter 8.1 is carried out. As already stated above, metallic mercury is only allowed to be stored in
facilities which fulfil the requirements of the landfill directive and the WAC decision.
8.4.1 Technical minimum requirements
In the case of permanent underground storage in salt mines, the potential storage site needs a
permit as an underground landfill, including a site specific risk assessment as outlined in Appendix A
of the WAC decision. The site-specific risk assessment has to include the following:
1. geological assessment;
2. geomechanical assessment;
3. hydrogeological assessment;
4. geochemical assessment;
5. biosphere impact assessment;
6. assessment of the operational phase;
7. long-term assessment;
8. assessment of the impact of all the surface facilities at the site
9. assessment of other risks (e.g. protection of workers)
More detailed information on the site-specific risk assessment is included in section 5.2.3.
Based on the site-specific risk assessment, the list of acceptable waste has to be derived for each
storage site. As a consequence, the storage of liquid mercury in underground facilities is only possible
when it is demonstrated that the level of isolation from the biosphere is acceptable (WAC Decision,
Appendix A, Nr. 2.3).
Salt rock fulfils the requirement to be impermeable to gas and liquids (WAC Decision, Appendix A, Nr.
3.2). Therefore, in cases of vapour emissions of mercury from the waste after the sealing of the mine
or disposal cell, these should then still remain enclosed in the salt rock.
Due to its plastic properties, salt rock has a creeping potential, and thus a firm encapsulation of the
waste at the end of the mines’ deformation process is possible. Decision 2003/33/EC describes the
role of salt mines as follows: With the overlying and underlying impermeable rock strata (e.g.
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anhydrite), it acts as a geological barrier intended to prevent groundwater entering the landfill and,
where necessary, effectively to stop liquids or gases escaping from the disposal area.
Its function as a geological barrier to protect groundwater against mercury strongly depends on the
geological conditions of the salt rock. In particular the thickness and composition of the salt rock as
well as the overlying and underlying impermeable strata (e.g. anhydrite or claystone) define the
protection level of the storage facility. Therefore, minimum requirements for theses parameters – in
addition to the requirements already included in Decision 2003/33/EC – are recommended to be
established to prevent mercury from entering the biosphere due to inappropriate geological
conditions.
Although the disposal of radioactive waste is carried out under different conditions compared to
metallic mercury, one principal aspect is the same – the safe long-term isolation of the hazardous
waste material from the biosphere. Intensive research related to safe storage of radioactive waste in
geological deposits has been carried out (see section 6.2.4). Valuable information is available in
particular on minimum requirements related to the geological effectiveness of salt rocks. Based on
the findings of this research, exclusion and minimum requirements have been defined which an
underground disposal site should fulfil for safe storage (see section 6.2.4.2). Some of these minimum
criteria, which are not already covered by the site-specific assessment as outlined in Appendix A of
the WAC decision, are also seen as being relevant for the storage of liquid mercury. In particular, the
minimum thickness of the isolating salt rock being at least 100m, as well as the minimum depth of
the storage site being 300m, these conditions should be fulfilled as additional safety factors.
In case a storage site does not fulfil these criteria (300m minimum depth and 100m minimum
thickness of the isolation rock) it has to be proven by a separate document that due to other
geological criteria or measures this deficit can be compensated. The determination of the
effectiveness of the geological salt rock barrier by a time factor is seen as an appropriate criterion for
the safe storage of liquid mercury in salt mines. It is proposed to set a time limit for which the
geological barrier has to protect the biosphere against the entry of mercury from the storage site. For
radioactive waste, a similar approach is currently being discussed (see section 6.2.4). Following the
recommendations of 6.2.4.2, the radioactive waste has to be safely enclosed for one million years.
Due to the fact that the hazardousness of mercury, in contrast to the hazardousness of radioactive
waste, will not decrease over time, it is recommended to apply at least the same period of time for
mercury as for radioactive waste.
Therefore, a site-specific safety assessment has to be carried out including a long term safety
assessment which verifies the effectiveness of the geological barrier against liquid mercury. By
means of the assessment, it has to be proven that mercury will not pass the overlying impermeable
strata and thus enter the biosphere for a period of time in the order of magnitude of one million
years.
The storage of liquid mercury has to take place in a separate cell to avoid any reaction of the storage
containers with other chemicals. The cells have to be separated by salt barriers or other adequate
artificial barriers. As a minimum, a distance of 100m should be kept from access shafts and other
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waste storage areas to ensure a safe encapsulation.
The container also has to fulfil the minimum requirements as set out in chapter 8.3.2. Its main
function is to ensure a safe handling and storage at least until the closure of the cell.
During the operational phase of the storage cell, in case of spills or leaks, it is important that
adequate measures are established to prevent liquid mercury from entering other parts of the salt
mine. It is recommended to store the containers in collecting basins which are able to capture the
total amount of the stored liquid mercury. The collecting basins can be constructed as pits in the salt
rock or other constructed basins. Adequate linings and slopes should be installed which allow an easy
collection of the mercury.
The following table presents a summary of the outcome of the evaluation including the minimum
requirements and the identified additional facility-related requirements. The last column of the table
indicates if an option fulfils the requirements – either due to the application of already existing
provisions and/or by applying the identified additional requirements.
Technical minimum
requirements
Additional facility related requirements Minimum
requirements
fulfilled
Geological barrier enables the
protection of groundwater
against mercury
Geological barrier enables the
prevention of vapour emissions
of mercury
Geological barrier ensures
impermeability to gas and
liquids of the surroundings
The salt rock ensures a firm
encapsulation of the waste at
the end of the mines'
deformation process
- Effectiveness of the geological barrier in
terms of migration time for mercury to the
biosphere >1 million years (verification by a
site-specific assessment including a long
term safety verification)
- Minimum thickness of the isolating salt rock:
100m (justified exemption possible)
- Minimum depth of the storage area: 300m
(justified exemption possible)
- Minimum distance from access shafts and
other waste storage areas: 100m
- No storage together with other waste
- Storage of the liquid mercury containers in
collecting basins able to catch the whole
amount of stored mercury
The check mark (“ ”) does not mean that any existing landfill does already fulfil the minimum
requirements for the storage of metallic mercury. It simply indicates that if the storage site fulfils the
described additional facility-related requirements (together with the requirements set out in the
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landfill directive and the WAC Decision) it would be suitable for the storage of metallic mercury.
If existing storage facilities are available which already fulfil the requirements or if there is still need
for further investigation/research or approval by the authorities, this will be assessed under the
category “feasibility of implementation”.
8.4.2 Environmental minimum requirements
The criteria that no existing environmental limit values are allowed to be exceeded is not relevant for
the permanent storage of liquid mercury in salt mines as the technical minimum requirements
already imply a total enclosure of the liquid mercury in salt rocks for a certain time period.
The protection of workers has to be ensured during the whole operational phase of the storage cell.
Therefore, during this phase, adequate monitoring, control measures and inspection schemes have
to be defined to avoid mercury emissions from the stored mercury due to leaking storage containers
or improper handling. Proper ventilation is required and in case of any incidents, adequate
protection equipment and emergency plans have to be available. In addition, workers have to be
adequately informed and trained in case of any incidents.
Mercury vapour monitoring system
Annex III of the landfill directive already foresees specific requirements relating to a monitoring and
after-care control.
Where there is permanent storage of liquid mercury in salt mines, monitoring is only necessary
during the operational phase of the storage cell. After the closure of the salt mine, no after-care
measures are necessary, because the salt rock is considered to provide total containment and the
waste will only come into contact with the biosphere in the event of an accident or an event in
geological time (e.g. earth movement) (Nr. 3.2, Appendix A, WAC). By means of failure scenarios the
possible consequences of accidents or geological events have to be included in the site-specific risk
assessment. In the site-specific risk assessment, the probability of such accidents or events has to be
assessed.
During the operational phase, a continuous mercury vapour monitoring system has to be established
which should have a minimum sensitivity ensuring the recommended indicative limit value of 0.02mg
mercury/m³ (8 hour TWA) [SCOEL 2007] is not exceeded.
The vapour detection equipment should be installed at head level and near to the ground as mercury
vapour is heavier than air and thus the concentration of mercury is higher at ground level. The
monitoring system should be equipped with a visual as well as an acoustic alert system in case the
limit value is exceeded. The proper functioning of the monitoring system has to be checked at least
once every 12 months.
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Regular inspection
Apart from the continuous monitoring system, also regular visual inspections of the containers
should be carried out by an authorised inspector. These regular visual inspections should also include
a control ensuring proper installation of the necessary minimum requirements as stated in the
permit for the storage of liquid mercury. The inspection interval should not be more than 12 month.
After the detection of a leak, all relevant emergency measures – as laid down in internal instructions
manuals – have to start immediately. The operator of the facility has to take any measures to prevent
that workers are exposed to mercury emissions and to avoid mercury or mercury vapour entering the
environment. Within one month after the detection of the leak and the subsequent remedial actions
an inspection should take place to ensure that the origin of the leak has been eliminated and a
proper operation of the storage facility is ensured. A documentation of any leak and the subsequent
activities is required.
Emergency plans
The WAC decision foresees an assessment of the operational phase to identify possible risks for the
storage facility as well as for the workers (WAC, Appendix A, 1.2.6 and 1.2.9). Potential incidents
have to be described, evaluated and appropriate contingency measures have to be implemented.
Where there is storage of metallic mercury, emergency plans addressing the specific risks of metallic
mercury have to be established and adequate personal protection equipment has to be available. In
addition, workers have to be adequately informed and trained in case of any incidents.
Environmental minimum
requirements
Additional facility-related requirements or
acceptance criteria
Minimum
requirements
fulfilled
No exceeding of current
environmental limit values
Protection of workers during
operational phase (monitoring and
regular inspection)
Installation of a permanent mercury vapour monitoring systems - with a sensitivity of at least 0.02 mg
mercury/m³ - visual and acoustic alert system - annual maintenance and control of the
system - sensors have to be installed at ground
level and head level Regular visual inspection of the container and the storage site by a certified person - max. interval: 12 months, or - 1 month after detection of a leak Availability of emergency plans and adequate protective equipment suitable for
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Environmental minimum
requirements
Additional facility-related requirements or
acceptance criteria
Minimum
requirements
fulfilled
metallic mercury Information and training of workers on how to deal with liquid mercury
8.4.3 Economic minimum requirements
Disposal in salt mines, compared to other storage options, entails moderate costs. The permanent
storage of liquid mercury in appropriate containment would result in costs between €260-€900/t for
the storage (see section 6.2.2.3) and between 600 – 1,100 €/t mercury (see section 6.4.1) for the
container.
The economic minimum requirements are fulfilled without additional requirements.
8.4.4 Feasibility of implementation
In the European Community, 5 underground disposal sites in salt rock have been identified which are
permitted to accept hazardous waste. The remaining capacity of each underground disposal site
would be sufficient for the storage of the expected volume of liquid mercury (700 m³ net, without
packaging). According to information from the operators of the mines, storage would probably only
be possible in two of these mines (one site is currently not in use, the other sites envisage problems
in obtaining a permit).
Experience related to the storage of hazardous waste in salt rock is available in Germany in
particular. For more than 20 years, Germany has disposed of hazardous waste in salt mines.
Up to now, none of the existing facilities has a permit for the storage of pure metallic mercury, since
it was excluded from the storage due to its liquid status. However, German salt mines for example
have a permit to accept waste containing mercury, such as “fluorescent tubes and other mercury-
containing waste” (waste code 20 01 21*).
Quite extensive information is available on the properties of possible host rocks, information related
to the specific behaviour of liquid mercury in underground conditions is still very limited. Extensive
experiences, models and simulations are available for the storage of radioactive waste. The models
related to the post-closure safety of geological disposal sites are well developed and might also be
applicable to liquid mercury. According to experts, the adaption of the radioactive waste models to
liquid mercury is expected to take around 3-5 years (see section 6.2.4.2) under the precondition that
sufficient reliable data on the behaviour of metallic mercury is available.
German authorities generally consider the storage in salt mines as safe, but very little is currently
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known on the long-term behaviour of metallic mercury under storage conditions in salt rock (e.g.
behaviour in case of increased pressure, possible interactions with the host rock). Therefore,
according to information from German authorities, a project is planned to test the behaviour of
metallic (and probably also of solidified) mercury in salt rock. The outcome of this study is an
essential input to the site specific risk assessment for salt mines required for the application for a
permit to store liquid mercury. Only based on this information a safe encapsulation of the metallic
mercury can be ensured for a timeframe of 1 million years.
The intended start of this project is in 2010 (source: questionnaire survey German EPA, personal
information by Ms. Hempen). Following the information received from the German EPA, the
permanent storage of metallic mercury in a German salt mine before the results of the study are
available would not be authorised.
Relevant legal requirements like the adaption of the long-term safety assessment and the formal
permit to be allowed to store liquid mercury will need additional time. Therefore, it is not expected
that this procedure will be finalized before 2011. The time for the preparation of disposal cells in the
salt mines is expected to be relatively short, since for example, ventilation and monitoring systems
have already been installed in mines formerly used for the exploitation of salt.
The costs for the implementation of the option depend on the additional requirements which have
to be implemented, but they are expected to be comparatively low.
The option 1 l “permanent storage of liquid mercury in salt mines” is promising because there are
suitable sites that fulfil the technical, environmental and economic minimum requirements – under
the precondition that the additional facility related requirements and acceptance criteria are
fulfilled.”
With regard to the feasibility of implementation by 2011 there are doubts due to the fact that
reliable information on the long-term behaviour of liquid mercury in salt mines is still lacking.
Therefore, problems are expected for availability of this option in good time (expressed by “?”).
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8.5 Option 2l: temporary storage of liquid mercury in salt mines
In chapter 6.2.2, an overview is provided on basic characteristics of salt rock formations and its
qualification as a permanent disposal facility for hazardous waste.
In the following, an evaluation of the option is carried out in view of the minimum requirements
described in section 8.1. As already stated above, metallic mercury is only allowed to be stored in
facilities which fulfil the requirements of the landfill directive and the WAC decision.
8.5.1 Technical minimum requirements
With regard to the protection of groundwater against mercury, prevention of vapour emissions of
mercury and impermeability to gas and liquids of the surroundings, the same requirements apply as
for permanent storage of liquid mercury.
In contrast to permanent storage, the temporary storage option has to fulfil the technical minimum
requirements only over a certain time period, thus a long-term safety verification of the effectiveness
of the geological barrier for 1 million years is not necessary for temporary storage. However, during
the defined storage time, the relevant technical minimum requirements have to be fulfilled. As a
consequence, the effectiveness of the container to prevent mercury emissions will mainly determine
the feasibility of this option. The salt rock surrounding is only an additional safety factor in case of
spills or any unforeseeable events which would result that the stored mercury would be released
from the container. In this case the gas and liquid impermeable salt rock would act as additional
geological barrier. Because even in the worst case that not all spilled mercury could be recovered the
salt rock system still would act as geological barrier in the long term and prevent the liquid mercury
entering the biosphere.
The minimum criteria set for the permanent storage related to the depth and minimum thickness of
the geological barrier are not relevant for the temporary storage as the container provides the main
safety for the storage.
The container has to fulfil the minimum requirements as set out in chapter 8.3.2. Its main function is
to ensure a safe handling and storage. In case of a temporary storage the liquid mercury has to be
stored in a way that a subsequent processing of the liquid mercury is not hindered or made
impossible. This can be achieved by appropriate containment, which does not, or only to a very
limited extent, react with the mercury.
Storage of liquid mercury has to be in a separate cell to avoid any reaction of the storage containers
with other chemicals. The cells have to be separated by salt barriers or other adequate artificial
barriers.
In addition, the reversibility of the storage of liquid mercury has to be fulfilled, which means that the
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cavities where the liquid mercury is stored have to be stable enough for a defined storage time.
Although salt rock has a high creeping potential, the convergence of drifts lasts several hundred
years until the drift is closed. The stability and the secure access to the cavities should be guaranteed
for at least 100 years.
Adequate measures have to be established to avoid spills or leaks allowing liquid mercury to enter
other parts of the salt mine. It is recommended that containers are stored in collecting basins which
are able to capture the whole amount of the stored liquid mercury. The collecting basins can be
constructed as pits in the salt rock or in other construction forms. Adequate linings and slopes should
be installed which allow an easy collection of the mercury.
Technical minimum requirements Additional facility related requirements or
acceptance criteria
Minimum
requirements
fulfilled
Protection of groundwater against
mercury
Prevention of vapour emissions of
mercury
Impermeability to gas and liquids of
the surroundings
Retrievability of waste
- Cavity stability and secure access to the
storage area >100 years
- No storage together with other waste
- Minimum distance to access shafts and
other waste storage areas: 100 m
- Storage of the liquid mercury
containers in collecting basins able to
catch the whole amount of stored
mercury
8.5.2 Environmental minimum requirements
During the whole temporary storage time adequate monitoring, control measures and inspections
schemes have to be defined to avoid mercury emissions from the stored mercury due to untight
storage containers or improper handling. Proper ventilation is required and in case of any incidents
adequate protection equipment and emergency plans have to be available. In additions workers have
to be adequately informed and trained in case of any incidents.
The same monitoring, inspection and emergency requirements apply as for the permanent storage of
metallic mercury in salt mines (see chapter 8.4.2).
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Environmental minimum
requirements
Additional facility related requirements or
acceptance criteria
Min.
requirements
fulfilled
No exceeding of current
environmental limit values
Protection of workers during
operational phase
Installation of permanent mercury vapour monitoring systems - with a sensitivity of at least 0.02mg
mercury/m³ - visual and acoustic alert system - annual maintenance and control of the
system - sensors have to be installed at ground
level and head level Regular visual inspection of the container and the storage site by a certified person - max. interval: 12 months, or - 1 month after detection of a leak Availability of emergency plans and adequate protective equipment suitable for metallic mercury Information and training of workers in how to deal with liquid mercury
8.5.3 Economic minimum requirements
Disposal in salt mines, compared to other storage options, entails moderate costs. Temporary
storage of liquid mercury in appropriate containment would result in the same costs as for
permanent storage, between €260 and €900/t for the storage and between €600 and €1,100/t for
the container. Additional costs will result for the retrieval of the waste after the temporary storage
time.
The economic minimum requirements are fulfilled without any additional requirements.
8.5.4 Feasibility of implementation
In the European Community, 5 underground disposal sites in salt rock have been identified which are
permitted to accept hazardous waste. The remaining capacity of each underground disposal site
would be sufficient for the storage of the expected volume of liquid mercury. According to
information from the operators of the mines the storage would probably only be possible in two of
these mines (one site is currently not in use, the other sites envisage problems in obtaining a permit).
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Experience related to the storage of hazardous waste is available in Germany in particular. For more
than 20 years, Germany has disposed of hazardous waste in salt mines. But no experience is available
for the temporary storage of liquid mercury.
The preparation time for the cells and the implementation of the waste acceptance procedure are
expected to be relatively short as for example ventilation and monitoring systems are already
installed in mines formerly used for the exploitation of salt (see chapter 6.2.2.2). The adaptation of
these systems to the required standards should be possible within a short time.
In Germany, the possibility of long-term storage of liquid mercury in salt mines is already foreseen in
national laws (see section 5.3). According to German law, long-term storage in salt mines (landfill
class IV) is possible under the precondition that the landfill is adapted for the purpose of disposing of
metallic mercury and this aspect is taken into particular consideration in the site-specific safety
assessment.
In addition, an application for a permit for the temporary storage of liquid mercury is required,
including the additional requirements for a safe storage of it. An expertise has to be provided by the
owner of the mine to ensure the proper implementation of the minimum requirements. Although
such a permit is currently not yet available, there are no doubts that it will be provided within the
required time frame. The application time is expected to be not more than 1 year.
The costs for the implementation of the option depend on additional requirements which have to be
implemented, but they are expected to be comparatively few.
Geological barrier enables the prevention of vapour
emissions of mercury No
Geological barrier ensures impermeability to gas and
liquids of the surroundings No
Firmly encapsulating the waste at the end of the
mines' deformation process
No
Equal level of safety and confinement to those of salt
mines
No
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8.6.2 Summary: option 3l
Minimum requirements Additional facility-related requirements or acceptance
criteria required
Minimum requirements
fulfilled
Technical minimum requirements no no Environmental minimum requirements / /
Economic minimum requirements / /
Feasibility of implementation / /
For option 3l “permanent storage of liquid mercury in deep underground hard rock formations,” no
sites could be identified in the scope of this study that would fulfil the technical minimum
requirements for the storage of liquid mercury. Also involved stakeholders could not suggest any
suitable site.
8.7 Option 4l: temporary storage of liquid mercury in deep underground hard rock formations
In chapter 6.2.3, an overview is provided on basic characteristics of hard rock formations and their
qualification as permanent disposal facilities for hazardous waste.
In the following, an evaluation of the options pertaining to the above-described criteria is carried out.
As already stated above, metallic mercury is only allowed to be stored in facilities which fulfil the
requirements of the landfill directive and the WAC decision.
8.7.1 Technical minimum requirements
With regard to the protection of groundwater against mercury, prevention of vapour emissions of
mercury and impermeability to gas and liquids of the surroundings, the same requirements apply as
for the permanent storage of liquid mercury in underground hard rock formations. When looking at
the assessment of option 3l, it is obvious that hard rock formations do not fulfil the minimum
requirements for a permanent safe storage of liquid mercury.
In contrast to permanent storage, the temporary storage option has to fulfil the technical minimum
requirements only over a certain time period, thus a long-term safety verification of the effectiveness
of the geological barrier is not necessary for temporary storage. However, during the defined storage
time, the relevant technical minimum requirements have to be fulfilled. As a consequence, the
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effectiveness of the artificial barriers (near environment, container) in particular, to attenuate and
degrade pollutants will determine the feasibility of this option.
According to the information available, it would be possible to build storage cavities fulfilling these
requirements, although practical experiences in underground storage sites are not available (see
section 6.2.3.2).
The container has to fulfil the minimum requirements as set out in chapter 8.3.2. In the case of a
temporary storage, the liquid mercury has to be stored in such a way that a subsequent processing of
the liquid mercury is not hindered or made impossible. This can be achieved by appropriate
containment, which does not, or only to a very limited extent, react with the mercury.
The storage of liquid mercury has to take place in a separate cell to avoid any reaction of the storage
containers with other chemicals. The cells have to be separated by adequate artificial barriers.
The reversibility of the storage of liquid mercury has to be fulfilled, which means that the cavities
where the liquid mercury is stored have to be stable enough for a defined storage time. The stability
of cavities is, in particular, given for crystalline hard rock formations. In argillaceous rock, the cavity
stability is not given and thus it would have to be stabilised by engineered barriers. The stability of
cavities should be guaranteed for at least 100 years.
Adequate measures have to be established to avoid spills or leaks allowing liquid mercury to enter
the rock. It is recommended to store the containers in collecting basins, which are able to capture
the total amount of the stored liquid mercury. Adequate linings (Hg resistant sealing or material able
to attenuate mercury like bentonite, see chapter 6.2.3.1and slopes should be installed, which
facilitate an easy collection of the mercury.
The most critical point is seen in possible spills or vapour emissions that might result in an intrusion
of mercury into the host rock. Mercury, once entering the host rock, might enter the biosphere due
to possible fractures in the rock body.
Technical minimum requirements Additional facility-related requirements or
acceptance criteria
Minimum
requirements
fulfilled
Protection of groundwater against
mercury ?
Prevention of vapour emissions of
mercury ?
Impermeability to gas and liquids of
the surroundings ?
Reversibility of storage
- Cavity stability and secure access to the
storage area for >100 years
- No storage together with other waste
- Minimum distance to access shafts and
other waste storage areas
- Storage of the liquid mercury
containers in collecting basins able to
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Technical minimum requirements Additional facility-related requirements or
acceptance criteria
Minimum
requirements
fulfilled
capture the stored mercury
- Proof that in cases of spills and leaks no
mercury enters the host rock
8.7.2 Environmental minimum requirements
During the entire temporary storage time, adequate monitoring, control measures and inspection
schemes have to be defined to avoid mercury emissions from the stored mercury due to leaking
storage containers or improper handling. Proper ventilation is required and in the case of any
incidents, adequate protection equipment and emergency plans have to be available. In addition,
workers have to be adequately informed and trained for such incidents.
With regard to compliance with environmental limit values, it has to proven by adequate model
calculations that possible mercury emissions will not exceed existing environmental limit values.
The same monitoring, inspection and emergency requirements apply as for the permanent storage of
metallic mercury in salt mines.
Environmental minimum
requirements
Additional facility-related requirements or
acceptance criteria
Minimum
requirements
fulfilled
No exceeding of existing
environmental limit values
Model calculation to prove the compliance with environmental limit values
Protection of workers during
operational phase (monitoring and
regular inspection)
Installation of a permanent mercury vapour monitoring systems - with a sensitivity of at least 0.02mg
mercury/m³ - visual and acoustic alert system - annual maintenance and control of the
system - sensors have to be installed at ground
level and at head level Regular visual inspection of the containers and the storage site by a certified person - max. interval: 12 months, or - 1 month after detection of a leak Availability of emergency plans and adequate protective equipment suitable for
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Environmental minimum
requirements
Additional facility-related requirements or
acceptance criteria
Minimum
requirements
fulfilled
metallic mercury Information and training of workers on how to deal with liquid mercury
8.7.3 Economic minimum requirements
Storage costs for the temporary storage of liquid mercury in hard rock formations are seen as
relatively low. However, the costs for the preparation of the cells and the artificial barriers seem to
be significantly higher compared to salt rock facilities. Costs are expected in a dimension that this
solution - considering also the less sustainable environmental performance of this option - will have
difficulties to fulfil economic minimum requirements. However, it cannot be excluded that an
economically viable solution can be established in Europe. Cost estimates relating to the preparation
of a storage cell are available in section 6.2.3.4.
Though there might be feasible hard rock formations for a temporary storage of liquid mercury, the
assumed high investment costs to prepare an appropriate cell have to be taken into consideration.
Looking at the cost information received from the Swedish Ministry of Environment (see chapter
6.2.3.4) the preparation costs and operation costs might be very high for a limited period of time and
a limited volume of liquid mercury (700 m³).
8.7.4 Feasibility of implementation
Euromines86 indicated that the underground disposal site in Odda, Norway might be an option for the
temporary storage of liquid mercury. No information on the precise depth of this disposal site could
be identified but one report [Kystverket 2008] indicated that the disposal sites might not fulfil the
criteria of several hundreds of meters of depth as stated in the WAC Decision for deep underground
hard rock formation.
Currently this underground disposal site has only a permit to store e.g. mercury sulphide (see chapter
6.2.3.3). Other relevant storage sites could not be identified in the scope of this study.
Potential storage sites have to be prepared for the storage of liquid mercury and a permit for a
temporary storage has to be issued. It is highly questionable whether within the given timeframe
adequate storage facilities will be identified, also preparing adequately the corresponding waste cells
will be rather unlikely within the given time frame.
86 Personal Information of Euromines (European Association of Mining Industries)
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8.7.5 Summary: option 4l
Minimum requirements Additional facility-related requirements or acceptance criteria required
Given the experience already gained in storing other hazardous wastes in hard-rock formations, the
temporary storage of liquid mercury in hard rock formations would be a possibility in case adequate
capacities are available and permits for the storage of liquid mercury are available at the latest until
2012.
Based on the assessment of the current situation in the EU, however, this solution – although
feasible – seems to be very unlikely to be implemented within the given time frame.
8.8 Option 5l: temporary storage of liquid mercury in above-ground facilities
In chapter 6.3, an overview is provided on the current state of the art of above-ground storage of
metallic mercury.
In the following, an evaluation of the options concerning the criteria described in section 8.1 is
presented.
8.8.1 Technical minimum requirements
The Hg-Regulation sets out that temporary storage of liquid mercury is possible at above-ground
facilities that are dedicated and equipped for the storage of it.
In addition, the Hg-Regulation lays down that all provisions of the landfill directive as well as of the
WAC decision (except WAC Nr. 2.4) apply to these facilities. As a consequence, storage sites for the
temporary storage of liquid mercury need a valid landfill permit in case the storage takes place for
more than 1 year prior to disposal and for more than 3 years prior to recovery or treatment
(confirmation of a subsequent disposal or recovery/treatment is required).
The provisions set out in the landfill directive in Annex I (General requirements for all classes of
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landfills), thus apply for storage facilities for metallic mercury. In addition, the Hg-Regulation sets out
that the liquid mercury should be protected against meteoric water.
According to Regulation (EC) N° 1102/2008 the Seveso Directive (Directive 96/82/EC, see chapter
5.2.2) shall apply for the temporary above ground storage of liquid mercury. The Seveso directive
aims at the “prevention of major accidents which involve dangerous substances, and the limitation of
their consequences for man and the environment, with a view to ensuring high levels of protection”
(Article 1, Directive 96/82/EC).
The Seveso Directive requires that the possible risks of the storage of liquid mercury have to be
identified and evaluated in a safety report by taking into consideration the specific properties of
liquid mercury. In particular, the risks of accidental release have to be taken into consideration and
adequate measures have to be implemented to reduce on the one hand, the risk of accidental
releases, and on the other hand to minimize subsequent potential negative effects to the
environment. The assessment under the Seveso directive also includes possible scenarios in cases of
natural disasters such as floods but also man-made threats such as terrorist attacks. Adequate
management plans have to be established to fulfil these requirements.
Currently, the storage of liquid mercury takes place in warehouses. In order to protect the stored
liquid mercury against meteoric water and to guarantee impermeability towards the soil, the best
option for the above-ground storage seems to be construction of a building with engineered barriers
to protect the environment against mercury emissions.
The protection of the soil can be achieved by sealed floors, with a mercury-resistant sealer, which
can prevent the intrusion of mercury into the soil, for example in cases of accidental spills. In
addition, the containers have to be stored in areas where – in case of an accidental release of the
mercury – the total amount of the stored mercury can be collected and retrieved. This can either be
achieved by storing the containers with the liquid mercury in an appropriate collecting basin or by
implementing appropriate other measures, for example by ramped containment dikes that are
incorporated into the floor sealant and connected to appropriate collecting basins.
Above-ground storage is only seen as temporary storage, therefore the liquid mercury has to be
stored in such a way so that a subsequent processing of it is not hindered or made impossible. This
can be achieved by appropriate containment that fulfils the minimum requirements as set out in
chapter 8.3.2).
The storage of liquid mercury has to take place in a separate area to avoid any reaction of the
storage containers with other chemicals. The areas have to be separated by adequate barriers, for
example concrete walls. In addition adequate fire protection and ventilation systems should by
installed.
To avoid any unauthorised removal of the stored mercury the storage area should be secured.
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Technical minimum requirements Additional facility related requirements or
acceptance criteria
Minimum
requirements
fulfilled
Reversibility of storage
Protection of mercury against
meteoric water
Impermeability towards soil
Prevention of vapour emissions of
mercury
- Storage in constructed building with
engineered barriers to protect the
environment against mercury emissions
- Storage of the liquid mercury
containers in collecting basins able to
catch the whole amount of the stored
mercury
- Hg-resistant sealants for the floor and
installation of a slope towards a
collection sump
- Fire protection system
- Ventilation system
- No storage together with other waste
- Area should be secured to prevent
unauthorised removal of the mercury
8.8.2 Environmental minimum requirements
During the entire temporary storage time, adequate monitoring, control measures and inspection
schemes have to be defined to avoid mercury emissions from the stored mercury due to leaking
storage containers or improper handling. Proper ventilation is required and in cases of any incidents
adequate protection equipment and emergency plans have to be available. In addition, workers have
to be adequately informed and trained in such cases.
The same monitoring, inspection and emergency requirements apply as for the permanent storage of
metallic mercury in salt mines.
To avoid any negative impacts of the surrounding area due to mercury emission, in addition to the
continuous on site measurements, immission measurements should take place before the temporary
storage starts and after 1 year. Based on this information it can be decided if additional measures to
protect the environment might be required.
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Minimum requirements Additional facility related requirements or
acceptance criteria
Min.
requirements
fulfilled
No exceeding of existing
environmental limit values
Hg-limit values for air (WHO)
Installation of a regular immission monitoring system of the surrounding of the storage facility
Protection of workers during
operational phase (monitoring and
regular inspection)
Installation of permanent mercury vapour monitoring systems - with a sensitivity of at least 0.02mg
mercury/m³ - visual and acoustic alert system - annual maintenance and control of the
system - sensors have to be installed at ground
level and at head level Regular visual inspection of the container and the storage site by a certified person - min. interval: 12 months, or - 1 month after detection of a leak Availability of emergency plans and adequate protective equipment suitable for metallic mercury Information and training of workers on how to deal with liquid mercury
8.8.3 Economic minimum requirements
The costs related to this option highly depend on the availability of existing facilities and the
possibility to adapt these facilities to secure above-ground landfills for the storage of liquid mercury.
If existing warehouse facilities can be used which have already implemented parts of the required
standards, then the costs seem to be acceptable. If construction of new buildings is necessary, then
the costs will be significantly higher.
8.8.4 Feasibility of implementation
Currently, in the European Community no landfill site has been identified which fulfils the
requirements for the storage of liquid mercury waste. The most appropriate facility for a central
storage is the warehouse of Almadén, which is currently used for the storage of the product liquid
mercury. The currently installed capacity for the storage of liquid mercury is below 8,000t.
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The owner of the Almadén warehouse has long-term experience with the handling of liquid mercury
and has already installed monitoring systems and safety measures to prevent mercury releases from
the facility. But the facility does not fulfil the requirements of a landfill and also does not have a
permit for the storage of waste. Thus, a permit has to be requested which might be very time
consuming.
In Germany, the possibility of long-term storage of liquid mercury in above ground landfills dedicated
to the storage of hazardous waste is already foreseen in national law (see section 5.3). According to
German law, long-term storage in above-ground disposal sites for hazardous waste (landfill class III)
is possible under the precondition that the landfill has to be explicitly appointed for the storage of
mercury and needs to be operationally and technically equipped for this purpose.
Apart from Almadén, other companies also have experience with the storage of liquid mercury as a
product. In particular, recycling companies extracting mercury from waste as well as operators of
chlor-alkali plants have experience related to the handling and storage of liquid mercury but typically
only with smaller amounts. In principal, other companies could also apply for a permit for the
temporary storage of liquid mercury. The potential storage sites have, on the one hand, to fulfil the
requirements laid down in the landfill directive and the WAC decision (permit as landfill), implement
the requirements of the Seveso Directive and they also have to provide adequate storage conditions
for liquid mercury. No information is available on existing storage capacities.
In particular already permitted landfills could be potential storage sites as they already fulfil the
requirements of the landfill directive and WAC Decision. The application process for an
amendment/extension of an existing permit is seen by far less time consuming and cost intensive as
the application for an entire permit as landfill.
The implementation costs and time widely depend on the possibility to use already existing facilities.
It is expected that adequate facilities will be available until 2011.
Implementation time Has to operate before March 2011
Capacity 8,000-9,000 tonnes within 9 years =>
~ 1,000t/year
Approval of authorities is
given
?
Recently (January 2010) the German company using the technology of Option 6a “Sulphur
stabilization“ has realised a full size facility, but has not tested it yet. The open engineering tasks for
this new facility are considered by the company to be negligible. Due to the experience with similar
plants, this statement can be considered as reliable. The expected throughput is considered to be
about 1,000 tonnes per year, and would therefore be able to treat the total expected amount of
liquid mercury within 8 to 9 years, provided that the elemental mercury is delivered in a more or less
constant stream. A permit is submitted and should be accepted within 2010.
For the technology developed in Spain recently (9 September 2009), an application for a patent has
been made on 9 of September 2009 with the application N° P200930672 [P200930672]. From their
point of view, an industrial scale facility would take about 3 to 5 years. No data is available for the
throughput of one full scale stabilisation line.
8.9.8 Minimum acceptance criteria for stabilised mercury
Based on the above assessment it is recommended to establish the used environmental minimum
requirements as minimum acceptance criteria for stabilised mercury:
- vapour pressure of the stabilised metallic mercury < 0.003mg/m³
- leaching value below 2mg/kg dry mass (L/S=10 l/kg; EN 12457/1-4).
These criteria could be implemented by establishing a specific waste code for waste from the
stabilisation of metallic mercury.
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8.9.9 Feasibility of permanent storage of pre-treated elemental mercury
The main purpose of the pre-treatment of metallic mercury is to change the liquid state into a solid
form to improve the handling, reduce possible risks by reducing the volatility and toxicity and to
reduce possible environmental risks by improving the leaching properties. As a consequence, after
the pre-treatment process, a stabilized and solid (waste) product is the result with quite different
properties than metallic mercury.
The storage requirements set out in Regulation (EC) N° 1102/2008 only apply to metallic mercury.
Therefore, for the pre-treated metallic mercury, the provisions of this Regulation are no longer valid.
After the pre-treatment process of the metallic mercury, only the provisions and requirements laid
down in the landfill directive (1999/31/EC) and the WAC Decision (2003/33/EC) apply to storage.
Decision 2000/532/EC87 foresees the following waste code for stabilised waste:
19 03 stabilised/solidified wastes
19 03 04* wastes marked as hazardous, partly stabilised88
19 03 05 stabilised wastes other than those mentioned in 19 03 04
Therefore, depending on its properties, different storage options are possible following existing legal
requirements. A temporary storage of the pre-treated mercury is not foreseen as it does not provide
the requested type of solution. Therefore, after pre-treatment only permanent storage options are
considered further. The following permanent storage options in combination with the feasible pre-
treatment option are possible:
Option 6l-1s: Permanent storage of mercury sulphide in salt rock formations
Option 6l-3s: Permanent storage of mercury sulphide in hard rock formations
Option 6l-7s: Permanent storage of mercury sulphide in above-ground facilities
Acceptance of stabilised mercury in underground facilities is only possible after a positive site-
specific risk assessment (Nr. 2.3, Appendix A, Decision 2003/33/EC). The site specific assessment has
to be carried out as outlined in the WAC Decision and has to demonstrate that the level of isolation
from the biosphere is acceptable.
Therefore, in the case of storage of stabilised mercury in underground storage sites (hard rock
87 Commission Decision of 3 May 2000 replacing Decision 94/3/EC establishing a list of wastes pursuant to Article 1(a) of Council Directive 75/442/EEC on waste and Council Decision 94/904/EC establishing a list of hazardous waste pursuant to Article 1(4) of Council Directive 91/689/EEC on hazardous waste (2000/532/EC), OJ L 226, 6.9.2000, p. 3 88 The asterisk indicates that the waste is classified as hazardous
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formations or salt mines) potential risks related to the storage of stabilised mercury should be
addressed adequately. The assessment is based on the assumption that the stabilised waste fulfils
the minimum acceptance criteria as recommended in the previous section. The acceptance and
sampling procedures apply as defined in the WAC decision.
8.9.9.1 Option 6l-1s: Permanent storage of mercury sulphide in salt rock formations:
The storage of mercury containing waste in salt mines has already been practiced for several years
(see also chapter 6.2.2.2). Therefore, the permanent storage of stabilized mercury in the form of
mercury sulphide is seen as a feasible option. The only requirement is that the storage of mercury
sulphide has to be taken into consideration in the site-specific assessment and – if the storage site
has been assessed as suitable – it has to be included in the permit.
In Germany, at least 3 salt mines already have a permit which includes the storage of the waste
codes N° 19 03 04 and 19 03 05.
The storage of mercury sulphide in salt rock formations has to take place in a separate area to avoid
any reaction of the storage containers with other chemicals. The areas have to be separated by
adequate barriers.
8.9.9.2 6l-3s Permanent storage of mercury sulphide in hard rock formations:
Following the safety philosophy for hard rock of Appendix A of the Decision 2003/33/EC, protection
of the groundwater can only be fulfilled by demonstrating the long-term safety of the installation.
For a deep storage in the hard rock, this requirement is respected in that any discharges of hazardous
substances from the storage will not reach the biosphere, including the upper parts of the
groundwater system accessible for the biosphere, in amounts or concentrations that will cause
adverse effects. Therefore, in particular, the water flow paths to and in the biosphere should be
evaluated (Appendix A, section 4.1, Decision 2003/33/EC) (see also section 5.2.5 of this report).
In the case of the storage of stabilised mercury (e.g. in form of mercury sulphide), the hydraulic
situation has to be taken into consideration very carefully to avoid non-acceptable emissions from
the storage site to the biosphere via groundwater flows. In the site-specific assessment the storage
of mercury sulphide should be addressed and at least the compliance with the currently existing
environmental limit values should be assured. The acceptance of stabilised mercury has to be
included in the permit.
Information on the existing storage of mercury containing waste in hard rock formations is very
limited (see section 6.2.3.3). But a Swedish study [SOU 2008] concluded that Swedish hard rock
formations would be suitable for the storage of mercury sulphide (see chapter 6.2.3.3). In addition,
two facilities in Norway have a permit for the storage of mercury containing waste (max. 10% Hg).
Therefore, the permanent storage of stabilized mercury as mercury sulphide is seen as a feasible
option.
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8.9.9.3 6l-7s Permanent above ground storage of pre-treated elemental mercury:
In the case of an above-ground storage of stabilised mercury, the provisions of the landfill directive
and the WAC decision have to be fulfilled. Stabilised mercury is only allowed to be stored at a landfill
if it fulfils the requirements set out for the specific storage site. In general, stabilised waste with a
waste code 19 03 04 or 19 03 05 can be disposed of on existing above ground landfills, but some
additional precautions might be considered in the case of mercury sulphide.
In the case of above-ground disposal, the long term behaviour of waste is more crucial compared to
underground storage due to the partially higher interaction with the environment. It is possible that
a reaction of metallic mercury with water and bacteria could take place and the very toxic
methylmercury could be formed. The minimum requirement of the vapour pressure below 0.003
mg/m³ in the stabilised products indicates that the amount of metallic mercury is negligible and
therefore this reaction should not take place. However, concerns remain, since little is known of the
long-term behaviour and stability of the product, especially at higher temperatures or pressures. For
this purpose, additional safety measures should be considered for above-ground disposal.
To exclude or at least minimise the risk of conversion or interaction of the stored material in the case
of an above-ground storage of stabilised waste, the following additional facility requirements are
recommended:
1) Storage in separated cells, no storage together with other waste (especially biodegradable
waste or waste with a high pH value, e.g. above pH = 10)
2) The cell shall be sufficiently self-contained
3) Appropriate measures shall be taken to limit the possible uses of the land after closure of the
landfill in order to avoid human contact with the waste
4) After closure, a plan shall be kept of the location of the landfill/cell indicating that stabilised
mercury waste has been deposited
5) No works shall be carried out on the landfill/cell that could lead to a release of the stabilised
mercury (e.g. drilling of holes)
6) A final top cover shall be put on the landfill/cell.
Justification:
Ad 1)/2):
As already stated above, little is known on the long-term behaviour of stabilised mercury and
possible interactions with other wastes. In particular biodegradable waste might pose a risk to
interact with HgS as it might include bacteria, water and other unknown constituents and still an
active decomposition process might be ongoing. Tests show, that in case of mercury sulphide,
mercury concentration in leachate increases sufficiently above a pH value of 10, as described in
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section 7.1.4, 7.2.4. and 12.5. Therefore it is recommended to store stabilised mercury in separated
and self contained cells to avoid contact with other wastes.
Ad 3)/4):
After the closure of the landfill the risk increases of unintentional removal or re-entering of the
stored mercury due to human activities. For example, in case the landfill area is not adequately
isolated and protected against human intrusion (e.g. drilling, excavation) an uncontrolled distribution
of the stored waste might occur. Therefore appropriate long term measure should be implemented
(e.g. documentation and record keeping of the stored waste at a separate location). It is also
recommended to keep plans of the storage location after closure of the landfill, to facilitate
corrective measures in case of any kind of unforeseen incidence or of a significant increase of
mercury compounds in the surrounding of the landfill area is detected.
Ad 5)
Any release of the stored material from the storage cell has to be avoided to prevent exposure of
workers. Another reason of such releases is that any kind of uncontrolled long or short time release
of the stored material from the landfill body increases the risk of methylmercurate formation.
As a consequence it is necessary to implement measures which prevent any destruction of the
storage cell and its protection against unintended releases (e.g. due to drilling activities).
Ad 6)
The final top cover will serve to prevent dispersion and will reduce potential leachate via reduction
caused by meteoric water.
An advantage of above ground storage is that emission control and counter measures are easier,
compared to underground storage systems.
With regard to the control and monitoring procedures in operation and in the after-care phase, the
requirements set out in Annex III of the WAC decision should apply. To avoid any negative effects on
the environment it is recommended to include in the leachate testing the parameter
“methylmercury”. Recently (October 2009), a quick test method was published to measure trace
amounts of methylmecury, which might be feasible for testing. [Ramon-Knut 2009]
In any case, the WAC decision requires that the basic characterisation of the stabilised metallic
mercury has to include information to understand the behaviour of waste in landfills. This concerns
especially the co-disposal of carbon containing (biodegradable) wastes and wastes with high pH
values.
One possible safety measure could be the establishment of a separate EWC code for stabilized
metallic mercury waste. This would have the advantage that this type of waste can be specifically
defined and linked to specific requirements. Another advantage is the immediate and clear
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identification of this waste type, highlighting the exceptional position of it compared to other
stabilized wastes. This would reduce the chance of a possible mismatch with other stabilized wastes
and incorrect disposals thereof. Furthermore a separate waste code would facilitate to track the final
destination of stabilised mercury.
It is also recommended to further investigate the long-term behaviour of metallic mercury under
landfill conditions with a special focus on potential methylation effects.
8.9.10 Summary Option 6l and its permanent storage
From the assessment of the technologies against the minimum requirements, it was determined that
two different pre-treatment technologies already exist in Europe that are able to fulfil all necessary
minimum requirements. It was investigated in the feasibility study, that the realisation of a large-
scale application of Option 6p still needs about 3 to 5 years.
In the case of Option 6a, a pilot plant demonstrated the reliability of this technology and a full-scale
application has been established. The permit as well as the proper function and the product quality
of the full-scale application are still lacking. The operator stated that the shortcomings will be solved
within the year 2010. Due to their experience in the field of treating mercury contaminated waste,
handling metallic waste and the proper function of the pilot plant this seems reasonable.
As a consequence the following conclusion is valid:
“An appropriate technology for pre-treating elemental mercury is available but not realised on a
scale to handle the quantity from the industry of elemental mercury to be stabilised/encapsulated. It
is expected that it could be realised by March 2011.”
Stabilized mercury can be disposed of in salt rock and hard rock, as well as above ground, following
the existing legal requirements. In the case of above-ground disposal, additional safety requirements
should be considered to avoid any kind of decomposition of the stabilized waste.
Minimum acceptance criteria for stabilised metallic mercury are recommended. In addition elaborate
BAT-Reference documents should be prepared for pre-treatment technologies for metallic mercury.
These documents should include information on how the process has to be performed in the best
way in order to avoid mercury emissions during handling and processing, and to ensure the quality of
the end product. In addition, adequate monitoring measures should be described.
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8.10 Summary of the screening analysis
In the screening analysis, the identified options have been evaluated against minimum requirements
and on their feasibility of implementation. Several options fulfil the minimum requirements but
problems are seen relating to an implementation by 2011. Therefore, in the following table a
differentiation has been made between the fulfilment of the technical, environmental and economic
minimum requirements and the feasibility of implementation of the option by 2011. The question
marks in the table stand for uncertainty concerning implementation being on time.
Table 8-4: Results of the evaluation of the options for storage of liquid mercury
Option Technical,
environmental and
economic minimum
requirements fulfilled
Implementation
feasible by 2011
1l Permanent storage of liquid mercury in salt
mines
Yes ?
2l Temporary storage of liquid mercury in salt
mines
Yes ?
3l Permanent storage of liquid mercury in deep
underground hard rock formations
No /
4l Temporary storage of liquid mercury in deep
underground hard rock formations
?89 /
5l Temporary storage of liquid mercury in above-
ground facilities
Yes ?
6l-1s Pre-treatment + permanent storage of
stabilised mercury in salt mines
Yes ?
6l-3s Pre-treatment + permanent storage of
stabilised mercury in deep underground hard
rock formations
Yes ?
6l-7s Pre-treatment + permanent storage of
stabilised mercury in above-ground facilities
Yes ?
When considering permanent solutions, the permanent storage in salt rock as well as the pre-
treatment options with a subsequent permanent storage are considered to be feasible against
89 Due to expected high costs and the difficulties to identify an adequate site it seems unlikely that this option
will be realised.
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technical, environmental and economic criteria – on condition that the elaborated additional criteria
and facility requirements are fulfilled.
For some permanent solutions, uncertainties remain relating to their availability in March 2011. If
these uncertainties – which might result from the lack of research data or uncertainties relating to
the duration required to apply for a specific permit – are solved by 2011, then these options are seen
as feasible. The option “permanent storage of liquid mercury in deep underground hard rock
formations” does not fulfil the minimum requirements as deep underground hard rock facilities will
not provide the equal level of safety and confinement for metallic mercury as salt mines.
Uncertainties in case of a permanent storage in salt rock refer in particular to the behaviour of
metallic mercury in salt rock. Currently no sufficient information is available on the behaviour of
metallic mercury under storage conditions in salt rock such as the behaviour in case of increased
pressure or possible interactions with the host rock. A study is planned by the German Ministry of
Environment which should investigate the behaviour of metallic mercury in salt rock. The outcome of
this study is an essential input to the site specific risk assessment for salt mines required for the
application for a permit to store liquid mercury. Only based on this information a safe encapsulation
of the metallic mercury can be ensured for a timeframe of 1 million years.
The evaluation of pre-treatment technologies resulted in the conclusion that technologies are
available which fulfil the technical, environmental and economic minimum requirements. Different
technologies based on sulphur stabilization have been assessed as a suitable pre-treatment option.
The availability of at least one technology on an industrial scale in 2011 is seen as very probable.
There are other technologies developed enough to be available on an industrial scale within the next
3-5 years. It has to be noted that the assessment of the feasibility of pre-treatment options was
carried out bearing in mind that in 2011 the export ban for metallic mercury enters into force and the
mercury from specific applications has to be considered as waste. Therefore, it was necessary to
check whether appropriate pre-treatment technologies would be available by this date.
Technologies that have been assessed as not feasible by 2011 are not necessarily excluded in the
future. The assessment provides only an overview of which technologies are available at that date.
It is recommended to elaborate BAT-Reference documents for pre-treatment technologies.
For the final disposal of stabilized mercury underground disposal sites in salt mines, deep hard rock
formations as well as above ground landfills are seen as feasible options. In particular in case of
above ground storage missing information related to the long-term behaviour of stabilized mercury
and/or possible interaction with other stored waste requires additional research.
In order to reduce the existing uncertainty about implementation feasibility being on time
combinations of options in the sense of “temporary options + permanent options” are also possible.
The possibility of temporary storage for liquid mercury should be limited to a certain time period. In
order to determine the time period, the availability of appropriate permanent storage options is the
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main criteria. Looking at the expected availability of permanent options (with or without pre-
treatment) a timeframe of 5 years is recommended for a temporary storage.
A review of the Regulation (EC) N° 1102/2008 is foreseen as being published not later than 15 March
2013 (Article 8 (2)). Therefore, an update on the availability of pre-treatment technologies fulfilling
the minimum criteria is recommended in the context of this review. Based on this review, it has to be
decided if a temporary storage still has to be kept as a possible storage option for metallic mercury as
currently foreseen in the Hg-Regulation. With a timeframe of 5 years for the temporary storage of
metallic mercury the industry has a good basis for future plannings and negations with temporary
storage facilities. In addition in case of any delays in the review process of the Regulation (EC) N°
1102/2008 there is still enough buffer to avoid any problems or additional costs as the maximum
temporary storage time is exceeded
With regard to the temporary storage options, the storage of liquid mercury in salt mines and the
storage in above ground facilities fulfil the technical, environmental and economic minimum criteria.
The temporary storage in salt mines has been assessed as a feasible option in relation to the
implementation time as it is expected that the relevant permits and approval will be available in
time. The feasibility of above-ground storage of liquid mercury is determined by the availability of
capacities and the time to apply for a permit. The application time for a permit to store metallic
mercury is difficult to estimate as it depends on the actual permit of the site. If the site already has a
permit as landfill the application time is not expected to be more than 0.5 - 1 year. If no permit for a
landfill is available it is estimated that the application time will be more than 1 year.
The option “temporary storage of liquid mercury in deep underground hard rock formations” might
fulfil the minimum requirements. But due to the expected high cost and the difficulties to identify an
adequate site within the given timeframe, it seems very unlikely that this option will be realised.
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8.11 References
[DOE 2009] U.S. Department of Energy, Interim Guidance on Packaging, Transportation, Receipt, Management, and Long-Term Storage of Elemental Mercury, U.S. Department of Energy Office of Environmental Management Washington, D.C., November 13, 2009, http://www.em.doe.gov/pdfs/Elementalmercurystorage%20Interim%20Guidance_11_13_2009.pdf [Euro Chlor 2007] Euro Chlor, Guidelines for the preparation for permanent storage of metallic mercury above ground or in underground mines, Env Prot 19, 1st Edition, October 2007 [Höglund 2009A] Höglund, Lars Olof Assessing the behaviour and fate of mercury should it be released from a disposal facility, Presented at Workshop of Safe Storage and Disposal of Redundant Mercury, St Anne’s College, Oxford, 13th and 14th October, 2009, http://www.mercurynetwork.org.uk/wp-content/uploads/2009/10/Hoglund2.pdf [Jerome 431] ARIZONA INSTRUMENT LLC, JEROME® 431-X mercury vapor analyzer, Operation manual, April 2009 http://www.azic.com/pdf/manual_700-0046.pdf [P200930672] López FA, López-Delgado A, Alguacil FJ and Alonso M., Procedimiento de estabilizacion de mercurio liquid mediante cemento polimerico de azufre, via sulfuro de mercurio, P200930672 (2009)
[Ramon-Knut 2009]
The Determination of Methylmercury in Real Samples Using Organically Capped Mesoporous
Inorganic Materials Capable of Signal Amplification, Estela Climent, M. Dolores Marcos, Ramón
Martínez-Máñez, Félix Sancenón, Juan Soto, Knut Rurack, Pedro Amorós, Angew. Chemie, 121/45
- Outer side of the container must be resistant against the storage conditions
- Containers should be certified for the storage of mercury
- Welds should be avoided as far as possible
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Salt mine with valid permit as underground storage facility for hazardous waste (DHAZ) Above ground storage site with valid permit for the storage of hazardous waste,
- Only acceptance of metallic mercury which fulfils the minimum acceptance criteria as set out above (verification required either by sampling or a certificate issued by a certified person)
- Visual inspection of the container, no acceptance of damaged, leaking or corroded containers
- Only acceptance of containers with adequate labelling (at least according to the transport requirements)
- Only acceptance of containers with a certificate which confirms the appropriateness for the storage of liquid mercury
The certificate – might also be a plate permanently fixed on the container - should include as a minimum, the identification number of the
container, container material, producer of the container, date of production and a confirmation that only mercury has been stored/transported in
the container (exclusion of storage of products which might react with mercury or the container material).
In the case of sealed containers, the filling and the sealing of the containers should be supervised by a certified person, which confirms that only
mercury of the required specification is contained in the sealed containers. The certificate, which has to be issued by the certified person, should
include at least:
- Name and address of the company (waste owner)
- Place and date of packaging
- The purity of the mercury (min. >99.9%) and, if relevant, description of the impurities (analytical report has to be provided)
- Quantity of the mercury
- Any specific comments
- Signature
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Salt mine with valid permit as underground storage facility for hazardous waste (DHAZ) Above ground storage site with valid permit for the storage of hazardous waste,
Record keeping Documents referring to the metallic mercury (e.g.
basic characterization, compliance testing) shall be
kept at least until the closure of the disposal site.
A plan of the storage area should be kept also after
the closure of the storage site.
Documents referring to the metallic mercury (e.g. basic characterization, compliance
testing) shall be kept at least 3 years after the termination of the storage.
Facility related requirements
- Effectiveness of the geological barrier in terms of
migration time for mercury to the biosphere >1
million years (verification by a site-specific
assessment including a long term safety
verification)
- Minimum thickness of the isolating salt rock:
100m (justified exemption possible)
- Minimum depth of the storage area: 300m
(justified exemption possible)
- Minimum distance from access shafts and other
waste storage areas: 100m
- No storage together with other waste
- Storage of the liquid mercury containers in
collecting basins able to catch the whole amount
of stored mercury
- Cavity stability and secure access to the
storage area >100 years
- No storage together with other waste
- Minimum distance to access shafts and
other waste storage areas: 100 m
- Storage of the liquid mercury containers
in collecting basins able to catch the
whole amount of stored mercury
- Storage in constructed building with
engineered barriers to protect the
environment against mercury
emissions
- Storage of the liquid mercury
containers in collecting basins able to
catch the whole amount of the stored
mercury
- Hg-resistant sealants for the floor and
installation of a slope towards a
collection sump
- Fire protection system
- Ventilation system
- No storage together with other waste
- Area should be secured to prevent
unauthorised removal of the mercury
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Salt mine with valid permit as underground storage facility for hazardous waste (DHAZ) Above ground storage site with valid permit for the storage of hazardous waste,
Installation of a permanent mercury vapour monitoring systems - with a sensitivity of at least 0.02 mg mercury/m³ - visual and acoustic alert system - annual maintenance and control of the system - sensors have to be installed at ground level and head level
Regular visual inspection of the container and the storage site by a certified person
- max. interval: 12 months, or - 1 month after detection of a leak
Availability of emergency plans and adequate protective equipment suitable for metallic mercury Information and training of workers on how to deal with liquid mercury
Installation of a regular immission monitoring system of the surrounding of the storage facility. Installation of permanent mercury vapour monitoring systems - with a sensitivity of at least 0.02mg
mercury/m³ - visual and acoustic alert system - annual maintenance and control of
the system - sensors have to be installed at ground
level and at head level Regular visual inspection of the container and the storage site by a certified person - min. interval: 12 months, or - 1 month after detection of a leak
Availability of emergency plans and adequate protective equipment suitable for metallic mercury Information and training of workers on how to deal with liquid mercury
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9.2 Proposed acceptance criteria for stabilized mercury and additional facility related requirements
Storage option Salt mine with valid permit as underground storage facility for
hazardous waste (DHAZ)
Hard rock formation with valid permit as underground storage
facility for hazardous waste (DHAZ)
Above ground storage site (with valid permit)
Waste acceptance criteria for stabilised Hg
- A Vapour pressure (e.g. < 0.003 mg/m³) to guarantee a metallic mercury free, stabilised product
- Leaching limit value of the stabilized product <2mg/kg dry mass (L/S =10 l/kg; EN 1247/1-4)
Waste acceptance procedure
Standard waste acceptance procedure applies as defined in the landfill directive and the WAC decision.
Facility related requirements
- Storage of stabilised mercury has to be taken into consideration in the site-specific assessment
- Storage of stabilised mercury in salt rock formation has to take place in a separate area to avoid any reaction with other waste
- Storage area has to be separated by adequate barriers
- Site-specific assessment has to be carried out for the safe storage of stabilised mercury and a long term proof has to be provided which indicates at least the compliance with the currently existing environmental limit values
- Storage of stabilised mercury in hard rock formations has to take place in a separate area to avoid any reaction with other chemicals.
- The areas have to be separated by adequate barriers
- Storage in separated cells, no storage together with other waste (especially biodegradable waste or waste with a high pH value, e.g. above pH = 10)
- The cell shall be sufficiently self-contained
- Appropriate measures shall be taken to limit the possible uses of the land after closure of the landfill in order to avoid human contact with the waste
- After closure, a plan shall be kept of the location of the landfill/cell indicating that stabilised mercury waste has been deposited
- No works shall be carried out on the landfill/cell that could lead to a release of the stabilised mercury (e.g. drilling of holes)
- A final top cover shall be put on the landfill/cell
Monitoring and control
Standard monitoring and control procedures apply as defined in the landfill directive and the WAC decision.
In addition “Methylmercury” should be included as parameter in the leachate control.
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10 Assessment of options
The goal of the study is to identify a “permanent solution for the long-term storage of liquid mercury
with minimized environmental impacts to acceptable costs” and to set up corresponding acceptance
criteria. The results so far show that there might be more than one acceptable permanent solution.
Therefore an environmental and economic assessment of the options is carried out to highlight the
advantages and disadvantages of the various options and option combinations. If an option or a
combination of options fulfills all acceptance criteria, it can be chosen by industry. So the question
might come up why an assessment and a consequent recommendation list are necessary at all.
The answer on this question and correspondingly the justification of the final assessment is to offer
industry an information and decision basis where they can see the advantages of options under
different criteria. This might lead to a preference of solutions that provide environmental advantages
against other options with equal costs. Also a preference might be generated for less expensive
solutions with the same level of environmental safeness.
It should be emphasised that the results of the assessment can serve as a decision basis for
concerned companies and authorities, the exclusion of options is not a target of this investigation.
The options and option combinations which have been considered to fulfil the minimum
requirements from Section 8 are used as a basis for the assessment. The following table gives an
overview of all remaining relevant option combinations:
Option / option
combination
Description
1l Permanent storage of liquid mercury in salt mines
6l-1s Pre-treatment + Permanent storage of stabilised mercury in salt mines
6l-3s Pre-treatment + permanent storage of stabilised mercury in deep underground hard rock formations
6l-7s Pre-treatment + permanent of stabilised mercury in above ground facilities
2l-1l Temporary storage of liquid mercury in salt mines + Permanent storage of liquid mercury in salt mines
2l-6l-1s Temporary storage of liquid mercury in salt mines + Pre-treatment + permanent storage of stabilised mercury in salt mines
2l-6l-3s Temporary storage of liquid mercury in salt mines + Pre-treatment + permanent storage of stabilised mercury in deep underground hard rock formations
2l-6l-7s Temporary storage of liquid mercury in salt mines + Pre-treatment + permanent of stabilised mercury above ground storage
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Option / option
combination
Description
5l-1l Temporary storage of liquid mercury in above ground facilities + Permanent storage of liquid mercury in salt mines
5l-l6-1s Temporary storage of liquid mercury in above ground facilities + Pre-treatment + permanent storage of stabilised mercury in salt mines
5l-6l-3s Temporary storage of liquid mercury in above ground facilities + Pre-treatment + permanent storage of stabilised mercury in deep underground hard rock formations
5l-6l-7s Temporary storage of liquid mercury in above ground facilities + mines + Pre-treatment + permanent of stabilised mercury above ground facilities
10.1 Economic assessment of the options
In the following a rough assessment of the cost for each option has been carried out. For the
economic assessment the following costs of each option have been estimated and evaluated:
- Permanent storage costs (incl. Engineering and construction costs if necessary)
- Costs of a temporary storage of metallic mercury
- Costs for maintaining, monitoring and inspection of the permanent storage site
before its final closure (time period depends on the expected closure time of the
storage site)
- Transportation costs
- Capital costs for the pre-treatment facility
- Operating and maintenance costs for the pre-treatment process
The assessment is based on information available. For many parameters only estimates are possible
as no quantification is available.
The most cost effective solution is a permanent option without any further treatment. Each option
including temporary storage and/or pre-treatment is more cost intensive as additional handling,
processing and transports are required. Storage costs charged for the disposal in salt mines are
expected to be in a range between 260 - 900 € per tonne (see chapter 6.2.2.3). Storage costs at hard
rock formations are in general low but highly depend on the necessary engineering and construction
measures which have to be implemented for the specific waste and/or location.
Specific containers are only required for the storage of metallic mercury. Costs for these containers
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are in a range between 600 - 1,100 Euros per tonne. For stabilised products big bags or drums are
used which are significantly cheaper (~ 10 €/t).
The costs for a temporary storage depend on the need for additional constructions (e.g. construction
of a storage building) and the duration of the storage. Also costs for the retrieval of the waste and
the necessary rebuilding measures of the storage site have to be taken into consideration. In addition
costs for staff working at the facility are relevant.
Within the investigation some technologies have already been assessed as suitable for the pre-
treatment of mercury. Therefore the duration of the temporary storage is expected to be in a frame
of 3-5 years.
Transport costs are in particular relevant for combined options which means options including a
temporary storage and/or pre-treatment and a subsequent permanent storage. Transport costs for
8,000 – 9,000 t of metallic mercury are expected in a range between 1.1 – 1.3 million Euro
(calculations based on actual transport costs received from Mayasa). The transport capacity of a
truck is 22 t of metallic mercury.
The availability of storage sites only plays a minor role in case of metallic mercury. As the main
producers of metallic mercury waste (chlor-alkali plants) are spread around Europe (see chapter 1.1)
the existence of several storage options for metallic mercury would not significantly reduce the costs
but would require additional costs for the preparation of storage sites for a relatively low volume of
waste (700 m³ not including container).
In case of a temporary storage prior to a pre-treatment the costs will increase significantly as
additional transports (from the temporary storage site to the pre-treatment site to the final disposal
site) are necessary. The pre-treatment results in a product with higher volume and weight compared
to metallic mercury. As a consequence transport costs and the number of transports significantly
increase. Therefore it is advantageous to have short distances from the pre-treatment site to the
storage site. As for pre-treated products different types of landfills (salt mines, hard rock
underground formations, above ground) are possible the transport costs might be reduced by
selecting the nearest adequate site.
Cost estimates are available for the sulphur stabilisation process. According to DELA the pre-
treatment inclusive transport costs and final disposal of the product would be around 2,000 €/t
metallic mercury (see chapter 7.1.4). These costs also include the capital costs and the operational
costs for the plant.
The costs for the inspection should be rather low in case of annual inspection routine by certified
inspectors.
The costs for a permanent monitoring of the air should also be rather low. Suitable technology is
available which allows a permanent surveillance of the storage area including acoustic and visual
alert systems.
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Option 1l: Permanent storage of liquid mercury in salt mines
This option is considered to be the most beneficial economic solution. Storage costs are expected to
range between 300 – 900 €/t Hg plus the costs for the container with around 600 – 1,100 €/t Hg. The
transport costs are relatively low as only one transport from the waste generator to the salt mines is
required.
Option 2l-1l (Temp. storage in salt rock + perm. storage in salt rock)
Temporary storage of metallic mercury prior to a permanent storage in salt mine is considered to be
nearly as economic beneficial as option 1l – in case both take place in the same mine. No additional
transport or handling costs are required. If this is not the case additional transport costs and handling
costs for retrieval of the waste occur.
Option 6l-1s (Pre-treatment + perm. storage in salt rock)
The pre-treatment process is the most cost intensive part of this option. The costs for the
stabilisation, the transport to the disposal site and the final disposal costs are at least 2,000 €/t
metallic mercury. Currently only one company offers this price. All other technologies seem to be
more expensive.
A cost advantage of option 6l-1s compared to option 1l is the containment as no specific container is
required. The stabilized product can be disposed in relatively cheap big bags or drums. On the other
hand the storage cost will increase significantly due to the increased amount of waste which has to
be stored. Storage costs are typically charged per tonne of waste. Each stabilisation process results in
higher volume as well as increased weight compared to metallic mercury. For the sulphur
stabilisation an elevation of the weight (at least 16%) and volume (around 500%) has to be
considered.
The transport costs are higher compared to option 1l and option 2l-1l as additional transports are
required. The transport costs from the pre-treatment plant to the final disposal site depend on the
distance and the number of available storage site.
Option 6l-3s (Pre-treatment + perm. storage in hard rock)
The economic situation of option 6l-3s is very similar to the above described option 6l-1s. The mere
disposal costs of pre-treated mercury in hard rock or salt rock formations are relatively low
compared to the other costs. No information is available on the number of sites fulfilling the
requirements for the storage of stabilised mercury in hard rock formations.
Option 6l-7s (Pre-treatment + perm. above ground)
Also this option is comparable with option 6l-1s with regard to the costs. Although the above-ground
disposal is economically beneficial compared to underground disposal, the difference is expected to
have only a small consequence on the overall expenses. The storage is recommended in separated
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cells which result in additional costs.
This option might result in lower transport costs as it can be expected that several suitable hazardous
waste landfills are available all over Europe.
Option 2l-6l-1s (Temp. storage in salt rock + pre-treatment + perm. storage in salt rock)
This option is comparable to option 6l-1s but additional expenses arise due to additional handling,
transports and monitoring expenditures during the temporary storage phase.
Option 2l-6l-3s (Temp. storage in salt rock + pre-treatment + perm. storage in hard rock)
The expenditure of this option is comparable with option 2l-6l-1s. Again the disposal costs only have
a low effect on the overall costs.
Option 2l-6l-7s (Temp. storage in salt rock + pre-treatment + perm. above ground)
Also this option is comparable with option 2l-6l-1s due to the negligible effect of the disposal costs.
Option 5l-1l (Temp. storage above ground + perm. storage in salt rock)
Compared to option 2l-1l higher costs result for this option due to additional transport costs of the
metallic mercury. In addition it is expected that significantly higher costs for the construction of
storage site are required compared to salt mines. The storage costs of this option highly depend on
the availability of already existing suitable storage sites. In case a building has to be constructed or
rebuilt the costs for this option rise significantly. Also additional handling (retrieval of the waste) and
staff costs (operation of the storage site) increase the overall costs of this option compared to option
2l-1l.
Option 5l-6l-1s (Temp. storage above ground + pre-treatment + perm. storage in salt rock)
The pre-treatment costs and storage costs of this option are comparable to option 2l-6l-1s The
temporary storage costs of this option highly depend on the availability of already existing suitable
storage sites. In case a building has to be constructed or rebuilt the costs for this option rise
significantly.
Option 5l-6l-3s (Temp. storage above ground + pre-treatment + perm. storage in hard rock)
This option is similar to option 5l-6l-1s. Again the mere disposal costs either in salt rock or hard rock
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Questions
1. Do you know recent or ongoing research / scientific activities related to disposal options of metallic mercury waste?
If available, please indicate contact persons, documents or links.
2. Do you know recent or ongoing research / scientific work related to pre-treatment techniques for metallic mercury waste?
If available, please indicate contact persons, documents or links.
3. What is the current legal framework related to the disposal and /or treatment of metallic mercury in your country?
4. What are the current ways of treatment of metallic mercury and disposal of metallic mercury within your country?
5. Are there any national preferences as regards the options stated in Regulation (EC) N° 1102/2008 (salt mines, deep underground hard rock formations) in which way metallic mercury should permanently be disposed of?
If yes, please indicate reasons for the preferences.
6. Do you have appropriate storage possibilities in your country?
7. Do you have specific experiences related to the underground storage of hazardous waste?
8. Which type of containment should be used for the storage (permanent or temporary)?
9. Do you see a pre-treatment of metallic mercury (e.g. solidification) as essential before a safe storage?
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10. Do you have any experiences and/or preferences related to pre-treatment technologies of metallic mercury?
If yes, please indicate relevant contact persons, documents or links.
11. Which aspects are most important for you related to the revision of the annexes I, II and III of Directive 1999/31/EC on landfill of waste?
e.g. any specific suggestions on what would especially need to be revised, any additional options
12. Which further items related to the disposal of metallic mercury would be of special interest for you?
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12.2 Annex 2: Literature overview
[ACS Kazakhstan 2000] Emerging Technologies in Hazardous Waste Management 8 D. William Tedder and Frederick G. Pohland, 2000 [Aluminium 2004] Corrosion of Aluminium, Christian Vargel, ISBN: 0 08 044495 4, 2004 [ATSDR 1999] U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES, Public Health Service, Agency for Toxic Substances and Disease Registry, TOXICOLOGICAL PROFILE FOR MERCURY, 1999; http://www.atsdr.cdc.gov/toxfaqs/TF.asp?id=115&tid=24 [Benoit 1999] Benoit, J.M., Mason, R.P., Gilmour, C.C., Estimation of mercury-sulfide speciation in sediment pore waters using octanol-water partitioning and implications for availability to methylating bacteria, Environmental Toxicology and Chemistry, Vol. 18, No. 10, pp. 2138-2141, 1999 http://www.serc.si.edu/labs/microbial/pubs/Benoit%20et%20al%20ET&C%201999.pdf [Benoit 2001] Benoit, J.M., Gilmour, C.C., Mason, R.P., The influence of sulphide on solid-phase mercury bioavailability for methylation by pure cultures of Desulfobulbus propionicus, (2001), Environmental Science and Technology, 35 (1), pp. 127-132, 2001 [BGR 2007] BGR, Bundesanstalt für Geowissenschaften und Rohstoffe, Nuclear waste disposal in Germany - Investigation and evaluation of regions with potentially suitable host rock formations for a geologic nuclear repository, Hannover/Berlin, April 2007, http://www.bgr.bund.de/nn_335086/EN/Themen/Geotechnik/Downloads/WasteDisposal__HostRockFormations__en,templateId=raw,property=publicationFile.pdf/WasteDisposal_HostRockFormations_en.pdf [BMU 2009] Bundesministerium für Umwelt, Natur und Reaktorsicherheit, Sicherheitsanforderungen an die Endlagerung wärmeentwickelnder radioaktiver Abfälle, Berlin, 2009, http://www.bmu.de/files/pdfs/allgemein/application/pdf/endfassung_sicherheitsanforderungen_bf.pdf [Brookhaven 2001] P.D. Kalb, J.W. Adams and L.W. Milian, Sulfur Polymer Stabilization/Solidification (SPSS) Treatment of Mixed-Waste Mercury Recovered from Environmental Restoration Activities at BNL, January 2001 [Brookhaven 2002] Discover Brookhaven, Volume 1 number 1 spring 2002, page 7, Paul Kalb, Spring 2002 [Brookhaven Newmont 2003] Using the Sulfur Polymer Stabilization/Solidification Process to Treat Residual Mercury Wastes from Gold Mining Operations B. Bowerman, J. Adams, P.Kalb, R-Y Wan and M. LeVier 24-26 February 2003, http://www.bnl.gov/isd/documents/25533.pdf
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[Brückner 2003] Brückner, D.; Lindert, A., Wiedemann, M., The Bernburg Test Cavern - A Model Study of Cavern Abandoment SMRI Fall Meeting, 5 - 8. Oct. 2003, Chester, UK, 69 – 89, 2003 [CA1011889] McCord, Andrew T. and Wagner, lois E., Disposal of wastes containing mercury, Chem-Trol pollution Services
[Caucus 2003] Quicksilver Caucus, Mercury Stewardship Best Management Practices, 2003, http://www.ecos.org/files/720_file_QSC_BMP_Oct_03.pdf. [CCOHS 1998] Canadian Centre for Occupational Health & Safety, Chemical profile mercury, preparation date 1998, copyright 2007 http://www.ccohs.ca/oshanswers/chemicals/chem_profiles/mercury/ [CENIM 2009] The application of sulphur concrete to the stabilization of Hg-contaminated soil, 1st Spanish national conference on advances in materials recycling and eco-energy, F.A. López, C.P. Román, I. Padilla, A. López-Delgado and F.J. Alguacil, 2009, http://digital.csic.es/bitstream/10261/18465/1/S02_3.pdf [Concorde 2004] Concorde EastWest Spr., Mercury flows in Europe and the world: the impact of decommissioned chlor-alkali plants, February 2004 http://ec.europa.eu/environment/chemicals/mercury/pdf/report.pdf [Concorde 2006] Concorde EastWest Spr., Mercury flows and safe storage of surplus mercury, 2006 http://ec.europa.eu/environment/chemicals/mercury/pdf/hg_flows_safe_storage.pdf [Concorde 2009] Concorde sprl, Assessment of excess mercury in Asia, 2010-2050, May 2009 http://www.chem.unep.ch/mercury/storage/Asian%20Hg%20storage_ZMWG%20Final_26May2009.pdf [Council Decision 2003/33/EC] Council Decision, of 19 December 2002 establishing criteria and procedures for the acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC (2003/33/EC) [COWI 2007] COWI, Follow-up study on the implementation of Directive 1999/31/EC on, June 2007 the landfill of waste in EU-25, Final Report - Findings of the Study http://web.rec.org/documents/ECENA/training_programmes/2008_06_budapest/session1/7-implementation_eu_25_2007_cowi_report.pdf [COWI 2008] COWI A/S and Concorde East/West Sprl, Options for reducing mercury use in products and
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applications, and the fate of mercury already circulating in society, December 2008 http://ec.europa.eu/environment/chemicals/mercury/pdf/study_report2008.pdf [DE453523] Herstellung von lichtecher Zinnober aus den Elementen, Deutsches Reich, Alexander Eibner, 7. April 1925 [Decreto 2003] Criteri di ammissibilità dei rifiuti in discarica. Ministero dell'ambiente e della tutela del territorio, 13 marzo 2003, Italy http://www.reteambiente.it/normativa/4355/dm-ambiente-13-marzo-2003/ [DELA 2009] Workshop on the safe storage and disposal of redundant mercury, Stabilisation of mercury for final disposal by formation of mercury sulphide, Miriam Ortheil, DELA, St Anne´s College, Oxford (UK), 13th & 14th October, 2009 [Deponieverordnung 2008] 39. Verordnung des Bundesministers für Land- und Forstwirtschaft, Umwelt und Wasserwirtschaft über Deponien, Januar 2008, Germany [DepVereinfachV 2009] Verordnung zur Vereinfachung des Deponierechts, Germany 27. April 2009, http://www.bmu.de/files/pdfs/allgemein/application/pdf/depvereinfv.pdf [DNSC 2004] Defense National Stockpile Center, Record of Decision for the Mercury Management EIS, April 2004 [DNSC 2004A] Defense National Stockpile Center, Final Mercury Management Environmental Impact Statement, Executive Summary, 2004 [DNSC 2004B] Defense National Stockpile Center, Final Mercury Management Environmental Impact Statement, Volume I, 2004 [DNSC 2004C] Defense National Stockpile Center, Human Health and Ecological Risk Assessment Report for the Mercury Management EIS, Volume II, 2004 [DNSC 2007] Defense National Stockpile Center, Fact Sheet: Mercury Over-Packing, Storage & Transportation, May 2007 [DNSC 2007A] Defense National Stockpile Center, Fact Sheet: Somerville Depot, February 2007 [DOE 1999] U.S. Department of Energy, Mercury Contamination – Amalgamate (contract with NFS and ADA) - Stabilize Elemental Mercury Wastes - Summary report, DOE/EM-0472
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[UNEP 2009] UNEP, Draft technical guidelines on the environmentally sound management of mercury wastes, 4th Draft, April 2009 [UNEP 2009 A] UNEP Chemicals, EXCESS MERCURY SUPPLY IN LATIN AMERICA AND THE CARIBBEAN, 2010-2050, ASSESSMENT REPORT, July 2009 http://www.chem.unep.ch/mercury/storage/LAC%20Mercury%20Storage%20Assessment_Final_1July09.pdf [UNEP 2009 B] http://www.chem.unep.ch/MERCURY/ [US ban 2008] Mercury export ban Act 2008, Public Law 110-414 - Oct, 14., 2008, 122 Stat. 4341, http://www.govtrack.us/congress/bill.xpd?bill=s110-906 [USEPA 2000] Mercury stabilization in chemically bonded phosphate ceramics, Arun S. Wagh, Dileep Singh and Seung Young Jeong, March 2000 [USEPA 2000a] Proceedings and Summary Report, Workshop on Mercury in Products, Processes, Waste and the Environment: Eliminating, Reducing and Managing Risks from Non-Combustion Sources, 22-23 March 2000 [USEPA 2002] Mary Cunningham, John Austin, Mike Morris, Evaluation of Treatment of Mercury Surrogate waste, final report, 2002 [USEPA 2002a] Mary Cunningham, John Austin, Mike Morris, Greg Hulet, Mercury wastes evaluation of treatment of bulk elemental mercury, 2002 [USEPA 2002b] Paul M. Randall, Sandip Chattopadhyay, Wendy E. Condit, Advances in encapsulation technologies for the management of mercury-contaminated hazardous wastes, 2002 [USEPA 2002c] Hugh W. McKinnon, Preliminary analysis of alternatives for the long term management of excess mercury, EPA/600/R-03/048, 2002, http://www.epa.gov/nrmrl/pubs/600r03048/600R03048.pdf [USEPA 2003] Evaluation of chemically Bonded Phosphate Ceramics for Mercury Stabilization of a Mixed Synthetic Waste, Land Remediation and Pollution Control Division National Risk Management Research Center Sandip Chattopadhyay, Paul M. Randall, March 2003 http://www.epa.gov/nrmrl/pubs/600r03113/600r03113.pdf [USEPA 2004] Application of the analytic hierarchy process to compare alternatives for the long-term management
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of surplus mercury, Paul Randall, Linda Brown, Larry Deschaine, John Dimarzio, Geoffrey Kaiser, John Vierow, 6 January 2004 [US EPA 2005] Paul Randall, Economic and Environmental Analysis of Technologies to Treat Mercury and Dispose in a Waste Containment Facility, April 2005 http://www.epa.gov/nrmrl/pubs/600r05157/600r05157.pdf [USEPA 2007] U.S. Environmental Protection Agency, Treatment Technologies For Mercury in Soil, Waste, and Water, EPA-542-R-07-003, 2007, 2007 http://www.epa.gov/tio/download/remed/542r07003.pdf USEPA 2007a] US EPA, Mercury Storage Cost Estimates, final report, November 2007 http://earth1.epa.gov/mercury/stocks/Storage_Cost_Draft_Updated_11-6-final.pdf [US20080019900 A1] Christelle Riviere-Huc, Vincent Huc, Emilie Bosse, Method for stabilisation of metallic mercury using sulphur, Oblon, Spivak, Mccleland Maier & Neustadt, 24. January 2008 [US20080234529 A1] Treatment of elemental mercury, Moore & Van Allen PLLC, Henry Boso Chan, Raymond Hall, 25. Sep. 2008 [US3061412] Preparation of mercuric sulfide, Anthony Giordano, 30. October 1962 [US3499774] Mercury-containing phosphate glass University Park Woldemar A. Weyl 10. March 1970 [US3704875] Removal of mercury from effluent streams, Penwalt Corporation, Paul Francis Waltrich, 05. December 1972 [US3804751] Disposal of wastes containing mercury, Chem-Trol Pollution Services Inc., Andrew T. mc Cord and Louis E. Wagner [US4230486] Process for removal and recovery of mercury from liquids, Olin Corporation, Italo A. Capuano, Patricia A. Turley, 28. October 1980 [US4354942] Jerry J. Kaczur, James C. Tyler Jr., John J. Simmons, Stabilization of mercury in mercury-containing materials, Olin corporation, 19. October 1982 [US4844815] Stabilisation of mercury containing-waste, Chemical Waste Management Inc, Milton Ader, Edward F. Glod, Edward G. Fochtman, 04. Juni 1989
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[US5034054] Process for treating mercury in preparation for disposal, Ecoflo Inc., Jeffrey C. Woodward, 23 July 1991 [US5347072] Stabilizing inorganic substrates, Harold W. Adams, 13. September 1994 [US5562589] Stabilizing inorganic substrates Harold W. Adams, 8. October 1996 [US5569153] Method of immobilizing toxic waste material and resultant products, Southwest Research Institute, William A. Mallow, Robert D. Young, 29. October 1996 [US6153809] HS in phosphate glass, The united States of America as represented by the United States Department of Energy, Dileep Singh, Arun S, Wagh, Kartujey D, Patel, 28. November 2000 [US6399848 B1] Encapsulation of hazardous waste materials, Dolomatrix International Limited, Dino Rechichi, 04. July 2002 [US6399849 B1] Treatment of mercury containing waste, Brookhaven Science Associates LLC, Paul D. Kalb, Dan Melamed, Bhavesh R Patel, Mark Fuhrmann, 04 July 2002 [US6153809A] Polymer coating for immobilizing soluble ions in a phosphate ceramic product, Dileep Singh, Arun S. Wagh, Kartikey D. Patel, US 6,153,809, 2000 [US6403044 B1] John E. Litz, Thomas Broderick, Robin M. Stewart, Method and apparatus for stabilizing liquid elemental mercury, ADA Technology Inc., 11. July 2002 [US Wagh] Chemically Bonded Phosphate Ceramics for Stabilization and Solidification of mixed waste, Energy Technology Division Arun S. Wagh, Dileep Singh, Seung-Young Jeong, [US Wagh 2000] Mercury Stabilization in Chemically Bonded Phosphate Ceramics; Energy Technology Division Argonne National Laboratory Dilep Singh, Arun Wagh, Seung Young Jeong http://www.anl.gov/techtransfer/Available_Technologies/Material_Science/Ceramicrete/wagh-mercury.pdf [US Wagh Singh] Method for producing chemically bonded phosphate ceramics and for stabilizing contaminants encapsulated therein utilizing reducing agents; United States Government; Dileep Singh, Arun Wagh, Seung-Young Jeong http://www.osti.gov/bridge/purl.cover.jsp;jsessionid=5971569EAD6B8B9106D1BE27F5F19563?purl=/782750-nscUTZ/webviewable/
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[VLAREM 1995] VLAREM II: Order of the Flemish Government of 1 June 1995 concerning General and Sectoral provisions relating to Environmental Safety, 1th June 1995, Belgium [Wagh-1] Personal information Mr. Wagh, 23.06.2009, e-mail [Waste Management 2001] Sulfur Polymer Solidification/Stabilization of elemental mercury waste M. Fuhrmann, D. Melamed, P.D. Kalb, J.W. Adams, L.W. Milian 14 August 2001 [Waste Management 2002] Sulfur polymer stabilization/solidification (SPSS) treatability of simulated mixed-waste mercury contaminated sludge J.W: Adams, B.S. Bowerman, P.D. Kalb 24-28 February 2002 http://www.wmsym.org/archives/2002/Proceedings/11/511.pdf [Webmin] http://webmineral.com [WHO 2003] World Health Organization Geneva, Concise International Chemical Assessment Document 50, ELEMENTAL MERCURY AND INORGANIC MERCURY COMPOUNDS: HUMAN HEALTH ASPECTS, 2003 [WHO 2004] Guidelines for Drinking-water quality 3rd edition, Geneva, World Health Organization, http://www.who.int/water_sanitation_health/dwq/fulltext.pdf [WHO 2005] World Health Organisation, Mercury in Drinking-water, Background document for development of WHO Guidelines for Drinking-water Quality, 2005 [WHO 2005a] World Health Organisation, Policy Paper: Mercury in health care, August 2005; http://www.who.int/water_sanitation_health/medicalwaste/mercurypolpaper.pdf [WHO 2006] World Health Organisation, Guidelines for drinking-water quality incorporating first addendum. Vol. 1, Recommendations. – 3rd ed.Electronic version for the Web, 2006 [WHO 2007] World Health Organisation, Preventing disease through healthy environments exposure to mercury, A major public health concerns, Geneva 2007 [WHO 2007a] World Health Organisation, risks of heavy metals from long-range transboundary air pollution, Joint WHO/Convention Task Force on the Health Aspects of Air Pollution, Germany 2007 [WHO 2008] World Health Organisation, Assessing the environmental burden of disease at national and local levels. Environmental Burden of Disease Series, No. 16, Geneva 2008
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[WO2005039702 A1] A method and composition for stabilizing waste mercury compounds using ladle furnace slag, Nanyang Technological University Sun, Darren Delai, Tay, Joo Hwa, Cheong, Hee Kiat, 06. May 2005 [WO2005092447 A2] Treatment of elemental mercury, Nuclear Fuels PLC, Chan, Henry, Boso 22. March 2005 [Wood 1974] Wood, J.M.: Biological Cycles for Toxic Elements in the Environment, Science, 15, 1043-1048, 1974 [ZERO Hg 2006] Zero Mercury working group, EU Mercury Surplus Management and Mercury-Use Restrictions in Measuring and Control Equipment, Report from the EEB Conference, October 2006
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12.3 Annex 3: Data base research - results
A systematic data base research was carried out to identify relevant literature for this study. The
following scientific data bases have been screened for relevant literature:
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12.4 Annex 4: Physico-chemical properties of metallic mercury and products resulting from different immobilisation technologies
The following list provides an overview on physic-chemical properties of metallic mercury as well as for relevant productions resulting from discussed immobilization technologies. This will be successively updated with new information received during the project running time.
Physico - chemical properties of the products received from different immobilisation techniques
Product CAS Density [g/cm³] Hg conc. [wt%] Solubility product KSP Compressive strength Solubility
Hg 7439-97-6 13.534 g/cm3 at 25°C [WHO 2003]
100 Not applicable Not applicable 5.6*10-2 mg/l at 25 °C [USEPA 2007]
No data available No data available No data available No data available
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12.5 Annex 5: Summary of technologies available in large-scale application
The following table provides an overview of the information received from the companies developing or running the process.
Sulphur stabilization according to
SAKAB / DELA Sulphur stabilization according to Bethlehem Apparatus
SPSS According to ADA Technology
SPSS according to DOE Cement encapsulation technique according to MERSADE
Process description and equipment Reactants technical sulphur and technical
elemental mercury which was received from the chlor-alkali industry and was not further processed before treatment
sulphur and elemental mercury; use of polyethylene to produce pellets was abandoned
elemental mercury, sulphur, polysulfide (calcium polysulphide, or sodium polysulphide) and sand
elemental mercury, sulphur polymer cement (SPC) and sodium sulphide
elemental mercury, elemental sulphur, polymeric sulphur, coarse and fine gravel, sand and CaCO3; the concrete block has a mercury content of 30%.
Process description
The process which is used by DELA is a sulphuring method capable of treating elemental mercury. The receiver tanks are filled with elemental sulphur (slight surplus) and mercury, and if needed, with additives. The inner atmosphere of the facility is filled with nitrogen. The process is carried out with 0.1 bar absolute, which is 0.9 bar below ambient pressure. The whole amount of the sulphur is added into the reaction vessel. Afterwards, the elemental mercury is continually added to the sulphur within approximately 15 to 20 minutes. The temperature is monitored and cooling of the exothermic reaction can be carried out. After about two hours the product can be removed from the vessel.
Elemental mercury is brought into contact with elemental sulphur, resulting in HgS (Cinnabar). The crystal formation is considered to be very sensitive to temperature and pressure changes.
It is a batch process consisting of combining elemental mercury with a proprietary sulphur mixture in a pug mill. Treatment of the liquid mercury was conducted by adding powdered sulphur to the pug mill, while a pre-weighed amount of mercury was poured into the mill. As the mill continues to mix and the reaction takes place, additional chemicals are added. While the processing of mercury in the pug mill is performed without the addition of heat, the reaction of mercury with sulphur is exothermic at room temperature, and the mixture increases in temperature during processing.
This process is a two stage single vessel (vertical mixer/dryer) batch process that results in mercuric sulphide stabilised in a sulphur polymer matrix. In the first step, mercury is reacted with powdered sulphur polymer cement and additives to form a stable mercury sulphide compound. Next, the chemically stabilized mixture is melted in a sulphur polymer matrix, mixed and cooled to form a monolithic solid waste form in which the stabilized mercury particles are microencapsulated within a sulphur polymer matrix [USEPA 2002c].
The stabilization takes place in a two-step process. In the first step the elemental mercury is stabilized with sulphur to meta-cinnabar with a planetary ball mill. In a second step this meta-cinnabar is incorporated in a polymeric S-concrete matrix, composed of gravel, sand, filler, elemental sulphur and modified sulphur.
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Sulphur stabilization according to SAKAB / DELA
Sulphur stabilization according to Bethlehem Apparatus
SPSS According to ADA Technology
SPSS according to DOE Cement encapsulation technique according to MERSADE
Process conditions
Most of the tests so far have been performed without heating. Additional heating of the HgS at the end of the process (~250 °C) leads to good process results. It is foreseen that the pilot-scale facility will have a heating option and that the whole process will work at a temperature between 100 and 200°C.
No information available No further information than that provided in the process description could be provided for the process conditions.
The process is heated in the second step to a temperature of 135 °C. Oxidation of mercury does not occur as the mercury has already been stabilized with sulphur in the first step.
The concrete matrix is prepared at 140°C and at room temperature
Throughput Currently, a laboratory scale facility with a reaction volume of about 5 liters exists. The process is carried out in batches with a processing time of about 120 minutes (90-240 min) per batch.
Early runs have been batch sizes of about 22.5kg of mercury. The last few runs have been in the range of 90kg. It was decided to work with 45kg batches due to easy processability and possible reruns in 24 hour periods. It is planned to attach 10 or 20 units to a single mercury feed. At such a time, the operating system will be capable of processing 500 to 1000kg of mercury per day.
A batch size of 50kg has already been used which would result in a daily throughput of 250 kg/day..A scale up to 375kg/batch is considered possible by the vendor. In this case the yearly throughput is expected to be 1,000t/year if five mixers are used in parallel. All together, 10 metric tonnes of radioactive mercury has already been stabilized by the Company.
A 1 ft3 (0.03 m3) mixer has already been realized, capable of stabilizing about 20 kg mercury per shift. Assumptions have been provided for the following mixer sizes. 10 m3 mixers could stabilize about 7,600 kg/day, 1.8 m3 mixers have a daily throughput of 1,400 kg and 0.28 m3 mixers have a daily throughput of 270 kg/day. All these assumptions are based on an average batch time of twelve hours and two shifts per day.
The facility is still only on a small scale, producing 6 kg of a final product per batch and a throughput of 4 kg/
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Sulphur stabilization according to SAKAB / DELA
Sulphur stabilization according to Bethlehem Apparatus
SPSS According to ADA Technology
SPSS according to DOE Cement encapsulation technique according to MERSADE
Emissions Due to the use of a vacuum (100 mbar) in the reaction vessel, a filter system and an activated carbon filter, the Hg-emissions should be close to zero (no measurement results available).
The process takes place in a sealed container and no emissions should occur. This container is capable of holding 1-10 bar pressure at 530°C.
Off-gas is passed through a High Efficiency Particulate Airfilter (HEPA), and then passed through a sulphur-impregnated carbon filter. Mercury vapour concentration above the plug mill is below the threshold limit value (TLV) of 50 mg/m3.
The process produces some mercury vapour, so a ventilation system is required to filter out the vapour. Since the process is heated (135°C), heat exchangers are included in the ventilation system. A liquid nitrogen cryogenic trap condenses the mercury vapour and it is recycled back into the process. Trials have shown that 99.7 % of the mercury is retained in the product.
Due to the laboratory scale, emissions can occur during the milling of sulphur and liquid mercury
Energy consumption
The energy consumption has not been evaluated. A three phase electrical power is necessary.
No information is provided for energy consumption.
No information could be provided for energy consumption.
No information could be provided for the energy consumption of the process.
No information could be provided for the energy consumption of the process.
Expected operational costs
According to estimations, the costs will be about €2,000/tonne, packaging, transport and final disposal underground of the produced HgS included.
The stabilization costs are about 5-6 $ / pound which are about 8,000 to 9,000 €/tonne of elemental mercury.
No information could be provided for operational costs.
No information could be provided for the expected operational costs of the process. From a different study [USEPA 2003] an estimated full scale cost is provided with about 2,000 €/t.
The costs for the stabilization of metallic mercury at a full scale application is estimated to be between 15,000 and 17,000 €/tonne metallic mercury.
Patent DE 10 2008 006 A1, EP 2072 467, EP2072 468 A2
It is expected that the official patent number will be available by beginning of February 2010.
No information could be provided for implementation costs.
No information could be provided for the implementation costs of the process.
No information could be provided for the implementation costs of the process.
Implementation time
It is envisaged to install a pilot-scale facility with a volume of 500 l and a capacity of about three tonnes per day (three shifts) by January 2010.
No information is provided for the implementation time.
US 6,403,044 B1 US 6,399,849 P200930672
Implementation costs
No information is provided for implementation costs.
About €700,000 for a facility to stabilize 300t per year.
No information could be provided for implementation time.
No information could be provided for the implementation time of the process.
No information could be provided for the implementation time of the process.
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Sulphur stabilization according to SAKAB / DELA
Sulphur stabilization according to Bethlehem Apparatus
SPSS According to ADA Technology
SPSS according to DOE Cement encapsulation technique according to MERSADE
Resulting Product Final product The final product is cinnabar (red).
No elemental mercury (silver) or meta-cinnabar (black) could be detected in an X-ray structure analyses. It is a fine powder with a density of 2.5-3.0g/cm3. The single crystals have a density of about 8.2g/cm3.
The product is a powder with the bulk of the material of approximately 50 mesh size. It easily breaks down into less than 250 mesh size. When removed from the reaction chamber there are also clumps with a diameter of approximately 1cm. The product of the treatment is cinnabar and was compared with data on file for naturally occurring cinnabar using x-ray diffraction. The results show complete similarity. No elemental mercury could be detected when a pellet was analysed in computer aided tomography.
The final product is a granular waste, which consist of HgS and sulphur polymer cement, and can be poured into drums.
The product is a monolithic structure with a mercury content of 33%, 65% sulphur polymer cement and 2% sodium sulphide.
The final product is prepared in the form of a monolithic material of 16x16x4 cm. The shape of the ashlars can also be changed.
Product stability
The leaching limit values from test runs under stable conditions range between 0.01 mg/kg and 0.04 mg/kg with an average value of 0.026 mg Hg/kg (EN12457/1-4).. Thermal information of the product shows that it is stable up to 350 °C. In its current state, the product of the laboratory-scale facility could be disposed of on hazardous and non-hazardous landfills according to the WAC Decision 2003/33/EC (hazardous landfills 0.2 mg/l (2 mg/kg) and non-hazardous 0.02 mg/l (0.2 mg/kg)).
The leaching values which were measured had an average of 0.0143 mg/kg (EPA TCLP)
For this product, only leaching values (TCLP) at different pH values are available. The lowest leaching behaviour can be achieved at a pH value of 2 with 0.001 mg/l. In a more or less linear trend the leaching value reaches a maximum of ~0.1 mg/l at pH value of 12.
In order to determine leaching behavior, the TCLP process was used for different pH values. The results have been in a range of 0.005 and 45 mg/l. The reason for this wide range of leaching behaviour was not the pH dependency but a small amount of elemental mercury which was still excising in the final product. It is believed that this inconsistency can be avoided by changing the processing methodology (e.g. mixing method, introduction of waste material) but no further work has been done so far in this field.
The concrete blocks have a water absorption by capillary of 0.07 g/cm2. The water permeability under low pressure (RILEM) shows no water absorption under low pressure. To determine the leaching behaviour the TCLP procedure was used and the average value was ~0,102mg/l. The concrete block shows very good mechanical properties with a comprehensive strength of 57.2 ± 44 N/mm2 and a flexural strength of 8.5 ± 1.17 N/mm2.
Volume and weight
The volume of the cinnabar powder is about six times the
The powder density is about 5g/cm3.
The weight of the material increases by about 100 % and
The Volume of the product is about 15-18 times the original
The density of the concrete block is about 3.1-3.2 g/cm3.
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Sulphur stabilization according to SAKAB / DELA
Sulphur stabilization according to Bethlehem Apparatus
SPSS According to ADA Technology
SPSS according to DOE Cement encapsulation technique according to MERSADE
volume of elemental mercury. The weight is increased by about 16%.
the volume increases by about 2200 %.
elemental mercury whereas the weight increased by a factor of 3.
And has a total porosity of ~2% and a closed porosity of ~0.6%. The mercury loaded concrete blocks have a higher density and lower pore volume than a mercury free reference. The reason is that it is expected that meta-cinnabar particles fill interparticle interstices and the higher size pores which exist in the initial S-concrete. The volume of the product has approximately 13 times more volume than the elemental mercury and the weight is increased by a factor of 3.
Emissions from the product
Mercury vapour tests have been performed. However, no mercury vapour could be detected (LOD=0.003 mg/m3). If additives are introduced, the product form can be changed into a granular form (1-4mm). Thus, dust emissions could be further reduced and handling facilitated.
No emissions from the product (except leaching) are known.
No emissions from the product except leaching are known.
No emissions from the product except leaching are known.
No emissions from the product except leaching are known.
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