Draft Baseline Report on ”Integrated Monitoring of dioxins & PCBs in the Baltic Region” in the framework of the European Environment and Health Strategy (COM(2003)338 final) Produced by the Technical Working Group on Integrated Monitoring subgroup Integrated Monitoring of dioxins & PCBs in the Baltic Region 05 December 2003
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Draft Baseline Report on
”Integrated Monitoring of dioxins & PCBs in the Baltic Region”
in the framework of the European Environment and Health Strategy (COM(2003)338 final)
Produced by the Technical Working Group on Integrated Monitoring
subgroup Integrated Monitoring of dioxins & PCBs in the Baltic Region
05 December 2003
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region ii
This report reflects the opinions of the members of the Working Group and it highlights
the different opinions contained within the group where appropriate. It should not be considered as an official statement of the position of the European Commission.
Further information relating to this work is available on the project website: www.environmentandhealth.org or from the Technical Secretariat: Dr Martin Adams AEA Technology Environment Culham Science Centre Abingdon Oxfordshire OX14 3ED United Kingdom Telephone +44 870 190 6402 Facsimile +44 870 190 6615 Email [email protected]
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region iii
Members of the sub-group on Integrated Monitoring of dioxins and PCBs in the Baltic Region Jouko Tuomisto, Finland, Chair Allan Astrup Jensen, Denmark, Vice Chair Rickard Bjerselius, Sweden Nathalie Bonvallot, France Francois Bordet, France Piotr Bykowski, Poland Mike Collins, United Kingdom Jean-Pierre Debruxelles, Eurofer Marc Durif, France Akos Fehervary, Hungary Veronique Garny, Euro Chlor Britta Hedlund, Sweden Dorota Jarosinska, Poland Manolis Kogevinas, Spain Evelina Nikolova, Bulgaria Jindrich Petrlik (ECN) Jacek Pietrzyk, Poland Marianne Rappolder, Germany Maria de Fátima Reis, Portugal Ott Roots, Estonia Carla Sampaio, Portugal Gabriele Schöning, European Environment Agency Pasquale Spezzano, Italy Ewa Strzelecka-Jastrzab, Poland Gerhard Thanner, Austria Cristina Tirado, Denmark (WHO) Gunther Umlauf, JRC, Italy Roel van Aalst, European Environment Agency Charmaine Vassallo, Malta Matti Verta, Finland Christine Vinkx, Belgium European Commission Katharina Spens, Frans Verstraete, Richard Bates, Barbara Gallani Technical Secretariat: Peter Coleman, Martin Adams, AEA Technology
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region iv
Executive Summary 1. This document has been produced by the Dioxins and PCBs Sub-group of the
Technical Working Group on Integrated Monitoring as part of the European Commission’s SCALE initiative (Science, Children, Awareness raising, Legal instruments, and Evaluation).
2. For this report, the sub-group has surveyed existing dioxin and PCB monitoring
activities and programmes focussing on the Baltic Sea area. An overview is provided of baseline monitoring activities, i.e. historic, current and planned. This review of monitoring activities is not comprehensive, but rather designed in order that selected activities that are relevant for integrated monitoring have been covered. The sub-group has also identified missing links in the promotion of an integrated environment and health monitoring and response system for dioxins and PCBs.
3. By using the Baltic Region as a pilot area, this report has identified and illustrated
problems and deficits with present activities. A number of the advantages of an integrated approach are also provided, specific for each chapter section.
4. An integrated approach (harmonisation of methods and co-ordination of programmes)
will result in improved knowledge on human exposure and allow for further actions, focusing on specific food items and sources (environment), to reduce exposure levels and related health risks. Such strategy will contribute to the improved health in the European Union as a whole, especially for children, who are the most susceptible group with respect to dioxins/PCBs exposure. The results and examples in this Base line report will be used to formulate the strategies in the next report, ‘Recommendations for the Commission's Action Plan 2004-2010’.
Overview 5. The Baltic Sea area is one of the most closely studied catchment areas in the world
concerning persistent organic pollutants (POPs). Until 1992, monitoring of coastal waters was considered solely as a national obligation, however, under the revised Helsinki Convention (1992), there is now an international obligation to also conduct monitoring of the coastal waters.
6. Measurement of dioxins and dioxin-like PCBs started later than PCBs, because the
environmental concentrations are much lower, and even more sophisticated measurement techniques are required. This means that time series information for dioxins and dioxin-like PCBs are not as well known as those of PCBs or some other POPs such as DDT (dichlorodiphenyltrichloroethane). Emissions have significantly decreased since 1970s due to bans on PCB and chlorophenol use, reduction or abandoning of chlorine use for pulp bleaching, and most recently due to substantial improvements in waste incineration techniques, as well as emission abatement in metal industries. Information on emission levels from other emission sources such as small-scale burning and accidental fires (e.g. at solid waste landfills) is still required.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region v
7. Members of the sub-group were requested to submit information on monitoring
programmes from their respective countries using a reporting pro-forma. The sub-group membership is broad and the general response to the call for data was encouraging. It is noted that the information returns to the study are likely to be representative of the professional interests and knowledge of the members. To an extent, the returns to the study reflect current perceptions and pre-existing priorities/drivers (i.e. legislation and/or funded international collaborative research programmes).
8. At least some information was received from nine countries in the catchment area of
the Baltic Sea, and was complemented by information from an additional five European countries. Relevant supporting information was also obtained from members of the group who represented industrial organisations, citizen’s organisations, the research community, the WHO and various European Commission services.
9. From the information received, in general it is clear that there is a substantial body of
information being generated on levels of dioxins in air, water and possibly also food, but probably not to the same extent for media such as soil and dust etc. Similarly there would appear to be relatively little target/receptor based, general public, and/or exposure information and even less that is related to children. From the information received it is difficult to comment on the comparibility of measurements – this is discussed further in the report.
10. Since more than 90 % of the human dioxin/PCB exposure derives from food, food is
central in the work of the technical working group, With respect to the Baltic region where fish comprises a significant component of the diet (and also relevant for the Mediterranean area), concentrations of dioxins and PCBs in fish are clearly the most important issue for health endpoints. From the available literature there is time series information on concentrations (especially on PCBs) in two important species of fish, Baltic herring and wild salmon, but not enough data to make good predictions on PCDD/Fs.
11. An important issue identified from the monitoring studies in the literature is that it
would be helpful to determine the relative contribution of reservoirs of these chemicals in the Blatic Sea i.e. from old storage/use of chemicals in the Baltic catchment area or from recent or contemporary air emissions and deposition to the sea. Congener analyses imply that the congener spectrum of dioxins in herring is much closer to the typical airborne congener spectrum than to the spectrum in sediments. This is of utmost importance for both predicting future levels of concentrations and also targetting of pollution abatement measures to reduce emissions at source. Air emissions can be reduced within a reasonable time frame while dioxins and PCBs in sediments will decrease very slowly during decades or centuries.
12. Human exposures and intakes seem to reflect the time trends in the environment,
although it is clear in some cases that other factors may be involved. For instance PCDD/F concentrations in breast milk in some countries have decreased faster than levels e.g. in fish (even to one tenth, from the peak levels of almost 100 pg/g to about
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region vi
10 pg/g TEq in fat). This may indicate a contribution of dietary changes. This decreasing trend has slowed down during the last few years in some countries, and it is uncertain whether this is casual or a true slowing down of the favourable development.
13. A review of the existing knowledge also makes clear that health effects of dioxins and
PCBs are still a hotly debated area, and integrated monitoring should therefore provide most useful material for the exposure assessment. The most relevant health effect seems to be developmental effects in children. Exposure can take place both during pregnancy and during breast-feeding. There is fairly good evidence that the risk of several developmental effects was real during the peak periods of dioxin and PCB concentrations, i.e. until late 1980s. It is much less clear, whether or not there is still a risk of those effects, when both environmental concentrations and intakes have decreased as also indicated by measured levels in human tissues. In high-exposure locations, such as Faroe Islands, there may still be effects associated with PCBs, although confounding by methyl mercury is difficult to rule out. At any rate the safety margins are not large, and continuous monitoring and observation of these effects is essential.
Problems and deficits 14. The working group identified a number of issues hindering the establishment of an
integrated dioxin and PCB monitoring system.
• The most important problem is considered to be a general lack of communication and cooperation between environmental, food and health researchers and authorities. Suitable international and national mechanisms need to be established in order that a unified approach can be taken.
• Environmental exposure data used for health studies is often taken from different
databanks without true collaboration with the researchers responsible for the data acquisition. Funding of well-designed multi-disciplinary research projects could encourage increased collaboration across traditional research areas.
• Integrated environmental monitoring (simultaneous measurements from air, soil,
water and wildlife) is scarce. The same is true with integrated exposure monitoring (combined environmental exposure, indoor exposure, occupational exposure, consumer exposure etc.).
• There is still a lack of reliable information on environmental dioxin and PCB
concentrations in some Accession Countries. An integrated monitoring program could help provide a clearer assessment of the environmental burden of dioxin and PCBs in these countries.
• There remain technical problems both in the standardisation of methods of analysis
and in sampling and sample preparation. Measurements from different countries are often not comparable; technology changes over the years make it difficult to compare concentrations and ascertain the time trends. There should be a fact-finding
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region vii
effort to identify existing standard methodologies (global) that potentially could form the basis of a European standard methodology. One problem is that many existing protocols are optimised for environmental measurements and not for monitoring human exposure. For long-term monitoring, methodologies that allow congener specific data would be preferable.
15. Fish is identified as the most inhomogeneous foodstuff group, as the age, size,
presence of the skin, and historic chemical exposure of the fish may all affect the measured concentration. Methodologies for the sampling and analysis of fishstocks therefore require special attention to take into account these potential sources of variation. This is especially important since the human dietary contribution of dioxins and PCBs from fish is significant for many Baltic (and also Mediterrean) countries. However, monitoring of other food groups (meat, dairy products etc) must not be neglected if dietary exposures (and particulary for those of children) are to be determined consistently.
16. From the health point of view, the most important issue for reliable predictions of
human exposure in the Baltic region is whether the source of dioxins in herring is from the old storage in the Baltic Sea, or via deposition from recent or contemporary airborne emissions. Concentrations and congener spectra may be very different in different species of fish and vary even in the same fish from different parts of the Sea. These differences can therefore potentially provide a highly useful source analysis. This may restrict the use of existing biological assay methods such as DR-Calux, because they cannot provide the highly important congener specific data.
17. A major problem concerning an integrated environmental and health monitoring
system for dioxin and PCB exposure is that health effects are very difficult to monitor in an etiological sense, as most health endpoints (i.e. notably developmental effects) are also associated to many other factors such as lifestyle factors (diet, smoking, alcohol use etc.), infections, and genetic differences. Neither spatial comparisons nor time-series comparisons may therefore be very reliable in indicating causal relationships between the exposure and the disease. Any integrated monitoring programme needs to be carefully considered in order that such issues are considered.
18. There is a lack of European research that advances our understanding in risk
comparison and risk benefit assessment. This would allow the public to make more informed decisions concerning their health and environmental exposure to chemicals. It needs to be appreciated by policy makers that risk management without a careful cost-benefit assessment involves a risk of negative total impact on public health. For example, both breast-feeding and fish consumption have clear health advantages, and if their use is discouraged on the grounds of chemical exposure, the total impact on health may be negative. It would be important to give clear and consistent messages to the public e.g., for how long breast-feeding is still beneficial, and how much fish would be more beneficial than harmful.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region viii
Advantages of integrated monitoring 19. A common system of integrated monitoring would help the risk assessment process
to assess the chemical/product in its realistic exposure scenario(s), even in the presence of factors modifying exposure and effect. Resources are often wasted both in underprotection, when an environmentally hazardous product is protected by administrative and market inertia; and in overprotection, when unnecessary restrictions deny the benefits of a product. The specialization of experts to narrow fields leads to fragmented risk assessment processes, potentially leading to risk management which is not based on balanced or comparable characteristics of the competing risks, or even considering the competing risks at all. The objective is to express the risk within the target population or ecosystem as the best available estimate. Neither requirement of complete proof nor worst-case assumptions are likely to lead to useful risk management.
20. Integrated monitoring can be envisioned to encourage innovative approaches
compared with performing separate un-linked monitoring efforts for the environmental, food, and health sectors. If different research approaches and types of expertise are combined, this will hopefully lead to improved levels of knowledge and understanding of issues.
21. Similarly, through combining and provising a common framework for the hitherto
separate measurement systems across the environment, food and health, an integrated system could potentially save resources. For instance, the use of carefully-selected indicator species (e.g. fish species) could provide information to assess the general environmental levels and trends, the ecosystem health, fish health and quantity, the quality of fish on the market and the possible exposure of humans, and risk of health effects.
22. The objective of integrated monitoring in not only to express risk. Monitoring
includes much of the official control systems. Integrated monitoring should also translate to integrated risk management. Advantages of integrated risk management are better tracing and linking, targeted risk management, and quicker problem solving.
23. Integration (harmonisation of methods and co-ordination of programmes) could also
be very useful in further actions to reduce the emissions from sources and resulting contamination of feed and food, and human exposure for dioxins and PCBs.
Requirements for an integrated monitoring system 24. In all monitoring activities, only scientifically proven methods and scientific
arguments should be used. The most important requirement for integrated monitoring is an honest discourse over the borders between scientific disciplines (environment, health) and administrative structures (regional, national and international). This is poorly done in many countries and even at international levels.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region ix
This requires sincere collaboration and appreciation of the other partners’ work and expertise.
25. Integrated monitoring is aimed at contributing relevant information for the purposes
of risk assessment. In risk assessment, the crucial determinants of risk are the dose-response of the potential adverse effect, and the relevant exposure. From strictly the health point of view, it is necessary that environmental monitoring be relevant for assessing human exposure.
26. Standardisation of analytical methodologies should guarantee that results from
different parts of Europe are comparable. Support (technical and financial) may need to be given to countries to encourage compatibility and consistency of methods. The dioxin intercalibration exercises by WHO in measuring breast milk concentrations are a good example. Protocols and methods have to be developed for combined monitoring aiming at the assessment of both ecological and human risk.
27. With the aim that monitoring of dioxins and PCBs should improve children’s health,
the identified basic requirements that could in the short term be easily addressed are: 1) integrated monitoring of dioxin and PCBs in food, 2) integrated human dietary questionnaires and 3) integrated human intake estimations.
28. Integration in this respect is harmonisation and co-ordination of the methods used for
collecting the data to be used. Dietary information is needed on population group basis, because e.g. assessment of children's risk requires information of their mother's dioxin and PCB intake during her entire life before the pregnancy as well as children's intakes.
29. New groups of chemicals are emerging, such as brominated diphenylethers and other
brominated compounds. A monitoring system needs to be responsive and allow detection of such emerging hazardous chemicals. These compounds could be included in dioxin and PCB monitoring programs. Simultaneous monitoring would be cost-effective, and an integrated approach could help in early warning of problems. Because time-course information is often important for assessing the risks of persistent chemicals, archives of samples such as eggs or fish should be maintained. A systematic archiving of sample could therefore be a useful component of an integrated monitoring system.
Possibilities to integrate existing activities and missing links
30. Existing programs such as HELCOM should introduce health expertise to add some
parameters that would be helpful in assessment of health risks, e.g. relevant types of fish that are most important for consumer viewpoint and hence help contribute to the provision of human exposure information.
31. There is still an incomplete understanding on the chain of events leading from
industrial and other emissions to food, especially Baltic fish, and possibilities to clarify these steps should be emphasised. This would give better possibilities to target
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region x
emission abatement at key emission sources that link, via environmental pathways, to human exposure.
32. As a long-term aim, stand-alone national and international databases containing
environmental and health information could be actively linked. For example, Commission database on concentrations of dioxins, dioxin-like PCBs and non-dioxin-like PCBs in food and feed should be utilised in integrated manner to predict safety of food, and the possibility to integrate health registries (such as cancer registries, birth defect registries) with environmental information should be studied both nationally and internationally.
33. There is potential for any European integrated monitoring system to be linked with
other international mechanisms linked to the environmental assessment and management of dioxins and PCBs. As an example, Annex C of the UNEP Stockholm Convention on Persistent Organic Pollutants, which contains useful information with regard to sources and measures to reduce emissions of dioxins and dioxin-like PCBs, will be used as a code of practice model for the CCFAC (2003) guidance document "Proposed Draft Code of Practice for Source Directed Measures to Reduce Dioxin and Dioxin-Like PCB Contamination of Foods".
Further details of each of the sections summarised above are contained in the main body of the report.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region xi
Contents 1 Introduction................................................................................................................... 1
1.1 Polychlorinated biphenyls, dibenzo-p-dioxins, and dibenzofurans ........................ 1 1.2 Environmental chemistry and fate of POPs ............................................................ 3 1.3 Toxicity of the dioxins and PCBs ........................................................................... 3 1.4 Risk assessment of PCDD/Fs and PCBs................................................................. 4
2 Overview of the existing monitoring activities ........................................................... 7
2.1 Role of Baltic Sea Region in Europe ...................................................................... 7 2.2 Emissions of PCB-compounds and PCDD/Fs to the Baltic Sea........................... 19 2.3 Emission regulations and examples of emission controls in Europe.................... 23 2.4 Previous information of the state of the Baltic Sea............................................... 29 2.5 Food ...................................................................................................................... 37 2.6 Feed....................................................................................................................... 44 2.7 Food monitoring activities commenced due to EU recommendations ................. 46 2.8 Human exposure studies within the catchment area of the Baltic Sea ................. 47 2.9 Health effect studies.............................................................................................. 53
3 Problems and deficits.................................................................................................. 57
3.1 Unfamiliarity of the requirements of other disciplines ......................................... 57 3.2 Problems of sampling techniques ......................................................................... 58 3.3 Fish as food – a complex matrix ........................................................................... 58 3.4 Problems with sediment profiles........................................................................... 62 3.5 Air/deposition ....................................................................................................... 63 3.6 Soil ........................................................................................................................ 64 3.7 Problems of time series information ..................................................................... 64 3.8 Problems of the TEF concept................................................................................ 65 3.9 Problems with specificity of analysis and congener spectra................................. 66 3.10 New emerging threats ........................................................................................... 67 3.11 Exposure assessment............................................................................................. 68 3.12 Problems with health effect studies ...................................................................... 68 3.13 Problems with risk assessment and risk management .......................................... 69
4 Advantages of an integrated monitoring system...................................................... 71 5 Requirements for an integrated monitoring system................................................ 72
5.1 Requirements of time series monitoring ............................................................... 73 5.2 Requirements of air monitoring ............................................................................ 73
6 Possibilities and missing links .................................................................................... 75
6.1 Links to other TWGs ............................................................................................ 75 6.2 Links to existing programs.................................................................................... 75
7 References.................................................................................................................... 77 Annex 1. Mandate of the sub-group.................................................................................. 87
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region xii
Annex 2. Country information........................................................................................... 90
7.1 Countries in catchment area of the Baltic Sea ...................................................... 90 7.2 Countries not in the immediate vicinity of the Baltic Sea .................................. 102
Annex 3. WHO Protocol for human milk studies .......................................................... 111
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 1
1 Introduction This working paper seeks to investigate integrated monitoring of dioxins and PCBs specifically in the Baltic Sea area. This could then be used as an example and guidance for other areas in Europe. Before any monitoring activities, it is of importance to make clear the purpose of the monitoring. In integrated environmental health monitoring of dioxins/PCBs the central monitoring quantity is human population exposure. The aim of the integrated risk management is to reduce the population exposure to a safe level if possible, or to a level as low as reasonably achievable. To clarify this aim, some general characteristics of dioxins/PCBs are first described. 1.1 Polychlorinated biphenyls, dibenzo-p-dioxins, and dibenzofurans Persistent organic pollutants (POP) include a number of chemicals belonging to different groups. Polychlorinated biphenyls (PCB, Fig. 1) are chemically stable organic oily compounds (technical products are mixtures of several of the 209 theoretically possible congeners with one to ten chlorines in various locations in the biphenyl structure). They have been used for a multitude of purposes because of their non-flammability, electrical insulating properties, stability, and other technical advantages. These advantages, however, are also disadvantages, because the compounds are very stable and persistent in the environment. Because they were produced in large amounts (over a million tonnes from 1930s to 1980s; IPCS, 1993), they can now be found in the environment everywhere around the globe including polar areas. Sören Jensen originally found PCBs in 1966 in the Baltic Sea biota (Jensen et al, 1969).
Biphenyl
5'6'65
4'4
3'2'3 2
Cl
Cl
Cl
Cl
Cl
3,3',4,4',5-PCB
Fig. 1. Chemical structure of biphenyl and a non-ortho-PCB 3,3’,4,4’,5-pentachlorobiphenyl Polychlorinated dibenzo-p-dioxins (PCDD, Fig. 2) and polychlorinated dibenzofurans (PCDF, Fig. 3) consist of 210 congeners with one to eight chlorines. Those 17 of them having lateral 2,3,7,8 positions being substituted with chlorine are considered to be of toxicological importance. PCDD/Fs were never produced intentionally, but they are minor impurities in several chlorinated chemicals (e.g. PCBs, chlorophenols, chlorophenoxy acids, hexachlorophene), and are also easily produced by burning, if chlorine (with metal catalysts) is present. Municipal waste incineration in poorly controlled conditions is a notorious source of PCDD/Fs, because chlorine is abundant (PCB, PVC and other chlorine containing plastics, household waste containing chlorine), but also metal industries are an
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 2
important source. Pulp bleaching with chlorine gas also produces PCDD/Fs. So the sources are manifold and abundant, and careful analysis of emissions is needed to define the sources in order to abate them. Sources of PCDD/PCDFs emissions (Health risks of POP from long range transboundary air pollution, WHO Europe, 2003: after Fiedler, 1999)
Stationary sources Waste incineration Municipal solid waste, clinical waste, hazardous waste, sewage
sludge Steel industry Steel mills, sintering plants, hot-strip mills Recycling plants Non-ferrous metals (melting, foundry: Al., Cu, Pb, Zn, Sn) Energy production Fossil fuel power plants, wood combustion, landfill gas
Diffuse sources Traffic Cars Home heating Coal, oil, gas, wood Accidents PCB fires, fires in buildings, forest fires, volcanic eruptions
Dibenzo-p-dioxin
10 9
8
7
5 64
3
2
1O
O
2,3,7,8-TCDD
O
O
ClCl
Cl Cl
Fig. 2. Chemical structures of dibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzo-p-dioxin
2,3,4,7,8-PeCDF
O
Cl
Cl
Cl
ClCl
Fig. 3. Chemical structure of 2,3,4,7,8-pentachlorodibenzofurane Some PCBs are called dioxin-like. These have several lateral chlorines and no chlorines in ortho-position to the carbon-carbon bond between the two benzene rings (non-ortho-PCBs, no chlorines in positions 2 or 6, see Fig. 1) or only one such chlorine (mono-ortho-PCBs). ortho-Chlorines prevent planar orientation of the two phenyl rings, and because dioxin-like actions require a planar structure, only non-ortho- and to some extent mono-ortho-PCBs have dioxin-like effects. Dioxin-like PCBs are usually a small fraction of PCB mixtures.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 3
1.2 Environmental chemistry and fate of POPs Two inherent properties of PCBs and dioxins determine most of their environmental behaviour. They are chemically stable and biologically very persistent, because chlorine atoms around aromatic centres protect them from the enzymatic activity of microbes or higher organisms. Secondly they are insoluble in water but soluble in lipids resulting in very high lipid/water partition coefficients. This lipophilicity means that they bioaccumulate to any living organisms containing fats or other lipids. Biological persistence also means that while they are not effectively metabolised in the organisms or excreted, they may be passed to the next trophic level. In other words PCBs and dioxins biomagnify along the food chain, which explains their high concentrations in aquatic top predators such as seals, eagles, and polar bears. This is also true for humans. Although in modern society people usually eat a great variety of different foods compared with seals or predatory birds, we live longer. Bioaccumulation and biomagnification of various PCB and dioxin congeners will be different, and therefore the congener patterns in emissions are not the same as the congener patterns in biota such as fish, and it may also be different in different fish depending on their feeding habits. Indigenous populations in remote areas such as polar areas, whose diet consists mainly of few traditional local food items such as fish, seal or whale meat, are more exposed to PCB and dioxin than most other populations and do potentially have the highest risk for adverse effects (Deutch, 2002, Grandjean et al., 2003, Longnecker et al., 2003). These pollutants can also be a potential health problem for instance for professional or recreational fishers, who consume large quantities of their own catch from polluted waters such as the Baltic Sea (Kiviranta et al., 2002, Roots et al., 2003). In water bodies, such as the Baltic Sea, large quantities of POPs are stored in bottom sediments, accumulated during several decades (Kjeller and Rappe 1995, Verta et al. 1999, Isosaari et al. 2002). Smaller quantities are continuously discharged to the water bodies from the inlets, although releases have decreased. Atmospheric fallout also adds to this burden. It is to some extent unclear to what extent the large old storage is responsible for the present levels in biota such as fish, and to what extent more recent emissions or fallout dominate in adding to the present fish exposure. It is likely that this may also depend on the type of fish and its feeding range, whether it is plankton feeder or predatory, and whether it is mainly living in the surface waters or in the bottom (Kiviranta et al., 2000, Roots 2001). Other biota such as shellfish or molluscs may be again different in their likelihood to collect chemicals from marine environment. In integrated monitoring understanding all these issues is crucial, and monitoring should be extended to basic mechanisms of the chain of release and biomagnification and historical information of these chemicals rather than just the present situation in biota. 1.3 Toxicity of the dioxins and PCBs The most toxic dioxin, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) is one of the most studied chemicals, and it is used as a reference for all other related chemicals. Most of its effects are explained by its binding to the so called dioxin receptor (AH receptor), which is a cytosolic ligand-activated transcription factor. This activated protein, along with many other proteins, regulates the expression of several genes (Poellinger, 2000). A specific “toxicity gene” has not been found. It is believed that other PCDD/F congeners have similar
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 4
effects, albeit they are less potent than TCDD. Also some of the effects of PCB-compounds are assumed to take place due to their binding to dioxin receptors (esp. planar non-ortho-PCBs), although especially the less potent PCBs may have other effects as well (van den Berg et al, 2000). Due to belief in a similar mechanism of action, and on the assumption that the interactions are additive, a TCDD equivalency factor (TEF) concept has been developed to illustrate the total effect of all PCDD/Fs in a mixture (Ahlborg et al, 1992, van den Berg et al., 1998, 2000). The amount of each PCDD/F is multiplied by its TEF to normalise the amount to TCDD equivalent amount (TEq), and these can then be simply added to give a total TCDD equivalent amount of dioxins. TEq is basically a technical tool for risk assessment and management, and TEFs are based on convention. Therefore TEF values may change when information improves, and e.g. time series are comparable only if the individual congeners can be compared. The most relevant toxic effects of PCDD/Fs are developmental toxicity, carcinogenicity and immunotoxicity (Poland & Knutson, 1982, Pohjanvirta & Tuomisto, 1994, Birnbaum 1994). Very few toxic endpoints shown in experimental animals have been confirmed in epidemiological studies (Sweeney & Mocarelli, 2000). The best known is chloracne, a serious skin disease seen many times after high occupational exposures or after accidents (Ott & Zober 1996, Mocarelli et al, 1991, Geusau et al, 2001). Cancer risk is likely after high-exposure occupational studies (Flesch-Janys et al., 1995, Ott & Zober 1996, Kogevinas et al., 1997, Steenland et al., 1999, Kogevinas 2000) and after Seveso accident (Bertazzi et al., 1997, Bertazzi et al., 2001), although all of these studies suffer from poor exposure assessment and confounding by other chemicals, especially chlorophenols (Tuomisto et al., 2003). Several developmental effects have been shown after high accidental exposures (Feeley and Brouwer, 2000), such as the “Yucheng” incident in Taiwan (Rogan et al 1988; Yung-Cheng et al 1992; Yung-Cheng et al 1994) and some after population exposures (Alaluusua et al., 1996). The latest risk assessment of World Health Organisation was based mainly on reproductive and developmental toxicity and immunotoxicity, which were deemed to be the most sensitive toxic endpoints (Birnbaum & Tuomisto, 2000, WHO, 2000). PCBs may have some toxic effects of their own not related to AH receptor mediated dioxin-like actions, e.g. some neurotoxic and neurobehavioural effects have been proposed (Brouwer et al, 1998, Fischer et al, 1998, Feeley and Brouwer, 2000). These effects have been dealt with also in Technical Working Group on Neurotoxicity. 1.4 Risk assessment of PCDD/Fs and PCBs Several national and international authorities have assessed the risks of dioxins/PCBs over the years (Larsen et al, 2000). The risk assessment of this group has been one of the more difficult tasks in the history of risk assessment. There are several biological reasons for this. Various species are very differently sensitive to dioxins, e.g. the guinea pig is over thousand times more sensitive than the hamster, and there are over thousand-fold variations even among different strains of rats (Pohjanvirta & Tuomisto, 1994). Sensitivity of human beings is not known for certain, and species extrapolation is therefore complicated. Some accidents imply that human being is acutely not among the most sensitive species (Mocarelli et al, 1991, Geusau et al, 2001).
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 5
Toxicokinetics are also very different, e.g. the half-life of TCDD in humans is several years whereas the half-life in the rat is about three weeks. The half-life may be shorter also in humans at very high doses (Aylward et al., 2003), but the difference to rat is still remarkable. Therefore long-term exposure causes completely different cumulative behaviour in the human being as compared with rodents, and doses cannot be compared on daily dose basis. In the latest WHO risk assessment body burden was used as dose metric rather than daily dose, and it may be more reliable in species extrapolation. Representative serum concentration might be even better, because the amount of fat will influence the body burden and characteristics of kinetics. There has also been uncertainty on the most sensitive effect to be used in risk assessment. TCDD is carcinogenic in several species of experimental animals (Kociba et al., 1978, Dragan and Schrenk, 2000). There are problems in the interpretation of epidemiological studies, and epidemiological data alone do not prove TCDD a human carcinogen (IARC 1997, WHO 2000). Because of the supporting animal carcinogenicity data, however, IARC concluded in 1997 that TCDD is human carcinogen (IARC 1997). Carcinogenicity of other dioxins has not been proven (IARC 1997), so the risk of mixtures is based on analogy and the validity of TEF concept. Previous WHO estimate of the tolerable daily intake (TDI) from 1990 was 10 pg/kg/day (WHO 1991), and many countries followed similar guidelines. In most countries only TCDD was originally considered. A Nordic expert group estimated TDI in 1988, and pointed out that a daily intake recommendation is not rational because of the long-term accumulation, and set a tolerable weekly intake (TWI) at 0-35 pg/kg/week (Nord 1988). The critical endpoints considered were cancer promotion, reproductive toxicity and immunotoxicity. The difference to WHO estimate was due to 200-fold rather than 100-fold safety factor. U.S.EPA gave a radically different estimate (U.S.EPA 1985), of 0.0064 pg/kg/day based on carcinogenicity and linear multistage extrapolation. Hence the difference between the WHO estimate and EPA estimate was 1500-fold. Some European nations adopted lower TDI values (Van der Heyden et al, 1982) usually based on larger safety margins due to uncertainties. UBA (Federal Environmental Agency, Germany) and BGA (Federal Health Office) proposed 1985 TDI values of 1 –10 pg/kg/d based on the carcinogenicity study on rats (Kociba, 1976) applying safety factors of 100 – 1000 to the NOEL (UBA 1985). In 1998 a new WHO Temporary advisory group suggested a TDI value of 1-4 pg/kg/day (WHO-TEq), with 4 pg/kg/day indicating the maximal tolerable intake, and the recommended ultimate goal to reduce human intake levels below 1 pg/kg/day. In most countries average exposures are presently between 1 and 2 pg/kg/day, but variations between groups (e.g. fishermen) and individuals are large. The Scientific Committee on Food (SCF) of the EU adopted on 30 May 2001 an opinion on the Risk Assessment of dioxins and dioxin-like PCBs in food update, based on new scientific information available since the adoption of the SCF opinion of 22nd November 2000. The Committee established a group TWI for dioxins and dioxin-like PCBs of 14 pg/kg bodyweight (WHO-TEQ). This TWI is in line with the provisional Tolerable Monthly Intake of 70 pg/kg bodyweight/month established by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) at its fifty-seventh meeting (Rome, 5-14 June 2001)
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 6
and concurs with the lower end of the range TDI of 1-4 pg/kg body weight, established by the World Health Organisation (WHO) Consultation in 1998. The t-TWI (SCF opinion of 23 November 2000) was based on the most sensitive endpoints reported in animal studies. These were developmental and reproductive effects in rats and monkeys and an increase in the incidence of endometriosis in monkeys. It would also adequately protect against the carcinogenic effects of 2,3,7,8-TCDD, which require substantially higher body burdens and for which a threshold approach is applicable due to its non-genotoxic nature. It is important to note that the sensitive endpoints that drive the derivation of the t-TWI relate to body burden of dioxin in fertile women. Except for promotion of endometriosis, the group at risk is the unborn foetus, the exposure of which depends on the mother’s body burden, i.e. the result of dioxin exposure via food over many years. The SCF in its opinion of 30 May 2001 decided to base its updated assessment on the rodent studies rather than on the rodent and monkey studies and identified as the most sentitive effect of 2,3,7,8-TCDD exposure in experimental animals the developmental effects in rat male offspring. The Committee concluded that the TWI for 2,3,7,8-TCDD should be extended to include all 2,3,7,8-substituted PCDDs and PCDFs, and the dioxin-like PCBs, expressed as WHO TEQ (van den Berg et al. 1998) and established a group TWI of 14 pg/kg bw for these compounds. Because the new studies provided a firm basis for the evaluation the Committee removed the designation “temporary” from the TWI. Maximum levels were given in Council Regulation (EC) no 2375/2001 for certain contaminants in foodstuffs. The maximum level for fish was 4 ng/kg (WHO-PCDD/F in fresh weight). For the time being the maximum levels were set only for dioxins and furans and not for dioxin-like PCB, given the very limited data available on the prevalence of the latter. Because it was expected that some species of Baltic fish would exceed the limit set, and because there were indications that the exclusion of fish from the diet may have a negative health impact, Finland and Sweden were granted a derogation of this limit value until the end of the year 2006. Fish species exceeding the EU limit value cannot, however, be sold to other EU countries. U.S. Food and Drug Administration have adopted a different policy. They are not planning maximum levels for food, but consider that the weight of actions should be in decreasing emissions, and the discovery of sources is the responsibility of the government (Canady and Zorn, 2003).
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 7
2 Overview of the existing monitoring activities 2.1 Role of Baltic Sea Region in Europe The Baltic Sea has long been an important region in both economic and political terms and therefore a focus of major interests. A total of some 90 million people in fourteen different countries live in the Baltic Sea drainage basin. The nations and states within this region have shared many historical experiences in common, although the past century has also seen many sharp divisions created. Socio-economic differentiation in the Baltic region during the former regime has now become open and is carried over into the new millennium. Interactions between culture, the economy, the political circumstances and the natural environment all combine to make the Baltic Sea region and its drainage basin an interesting object for research that can be approached in many different ways and from the vantage-point of several different research traditions. The Baltic Sea is receiving an increasing attention at the national and international levels being in the future the largest water body inside the European Union, the sustainability of the natural resources and status of the marine environment of the Baltic Sea are of particular importance in the European level. As a whole there is a large amount of data on PCBs and dioxins in the Baltic Sea and its biota, both monitoring results and specific scientific studies (Tables 1 and 2). Some of the most relevant aspects are dealt with in more detail to give an impression on the development of the problem, its present level, and the trends during the recent decades, impact on human exposure and some predictions on future.
Bas
elin
e R
epor
t on
Inte
grat
ed m
onito
ring
of d
ioxi
ns a
nd P
CB
s in
the
Bal
tic R
egio
n 8
Tabl
e 1.
Mon
itori
ng a
ctiv
ities
/res
ults
on
tota
l and
indi
cato
r PC
Bs a
vaila
ble
from
diff
eren
t cou
ntri
es (d
etai
ls g
iven
in
coun
try
anne
xes a
t the
end
of
the
Doc
umen
t, a
lso
listin
g re
fere
nces
).
C
ount
ry
Sour
ces
Air
W
ater
So
il,
terr
estr
. A
nim
al fe
ed
Fish
Fo
od
Bre
ast
milk
H
uman
tis
sues
H
ealth
ef
fect
s D
enm
ark
So
urce
s (2
5-26
) A
ir em
issi
ons (
25)
Air
Leve
ls
(25)
Leve
ls in
M
usse
ls (2
7)
Seal
s (28
-29)
H
arbo
ur
porp
oise
(3
0)
Otte
rs (3
1)
Sedi
men
t (1
9,27
) H
arbo
ur sl
udge
(1
9-20
) Se
wag
e sl
udge
(1
9-20
)
Leve
ls in
soil
(19)
V
ario
us (4
0)
Fish
(3
2-37
) Fi
sh li
ver o
il (3
5-37
)
Food
(3
6-37
) M
ilk (3
8)
Hum
an m
ilk
(23-
24, 3
9,
41)
Esto
nia
So
urce
s (2
1-23
) A
ir le
vels
(3
;4) a
nd
prec
ipita
tion
(4)
Leve
ls in
W
ater
(1,2
), pl
ankt
on(1
,2),
alga
e(1,
2),
Mus
sels
(1,2
,10
), se
al (
1,2,
17-
20),
fish
(1,2
,7-1
0)
1975
-199
1 ar
ound
nor
th-
east
ern
part
of
the
Bal
tic S
ea
(her
ring,
spra
t, co
d)(1
;2).
Thre
e lo
catio
ns
1994
-200
3 (H
ELC
OM
gu
idel
ines
) for
he
rrin
g (7
) 19
98-2
002
perc
h (8
-10)
, flo
unde
r (10
).
Mea
t, po
rk,
saus
age,
etc
.(25)
, bu
tter (
26).
Hea
lth
(10,
27-3
2)
Finl
and
Air
leve
ls 1
stat
ion,
(3
), 19
96-
Bul
k de
posi
tion,
M
ay-O
ctob
er, 2
st
atio
ns ,
1993
-, (1
,2),3
rd st
atio
n 20
02-
Mus
sels
: (M
acom
a,
Myt
ilus)
eve
ry
third
yea
r, 3
stat
ions
, 198
8-
(4, 5
)
Leve
ls in
soil
(hum
us),
6 st
atio
ns, e
very
th
ird y
ear,
2000
- (14
)
Ani
mal
feed
an
alys
ed 4
3 sa
mpl
es 2
002-
2003
: -F
eed
mat
eria
l of
plan
t orig
in
Abo
ut 2
40
anal
yses
200
3,
vario
us sp
ecie
s, va
rious
lo
catio
ns, E
U
Her
ring
5-7
Mea
sure
men
ts
sinc
e 19
98??
? M
onito
ring
2002
-20
03 E
U
WH
O si
nce
1987
R
esea
rch
proj
ects
, fa
t, se
rum
, pl
acen
ta
Res
earc
h pr
ojec
ts,
canc
er,
toot
h de
fect
s, cl
eft
Bas
elin
e R
epor
t on
Inte
grat
ed m
onito
ring
of d
ioxi
ns a
nd P
CB
s in
the
Bal
tic R
egio
n 9
Isop
od:
(Sad
uria
), 3
stat
ions
, 199
1-
(4)
Sedi
men
ts, 3
0 st
atio
ns, m
ostly
su
rfac
e/de
ep, 5
co
res (
2, 1
2)
Sedi
men
t tra
ps,
seve
ral l
ocat
ions
(2
) Po
pula
tions
of
grey
seal
, rin
ged
seal
and
whi
te-
taile
d ea
gle
(4,
13)
-Fis
h m
eal
-Fis
h oi
l -O
ther
feed
m
ater
ial o
f ani
mal
or
igin
-M
iner
als
-Tra
ce e
lem
ents
-P
rem
ixtu
res
-Com
poun
d fe
edin
gstu
ff fo
r: -C
attle
-P
igs
-Pou
ltry
-Fur
ani
mal
s -F
ish
feed
stat
ions
, 198
5-
Nor
ther
n pi
ke 7
st
atio
ns, 1
992-
(4
, 5, 6
, 7)
Salm
on (9
, 10)
(S
alm
on fr
om
1980
's-19
90's
unde
r ana
lysi
s)
pala
te,
cryp
torc
hidi
sm
Ger
man
y Se
wag
e sl
udge
(1,
7)
sew
age
slud
ge a
nd
com
post
(4
-6)
Air
emis
sion
pro
ject
s (4
,8,9
) 5
Haz
ar-d
ous w
aste
in
cine
-rat
ors 2
003-
2004
(6)
Mon
itorin
g A
mbi
ent A
ir le
vels
15
site
s de
posi
tion
15 s
ites
som
e si
nce
1989
(1
,2,1
0)
ambi
ent a
ir le
vels
an
d de
posi
tion
36
site
s 200
2-20
03 (1
1)
Indo
or 1
2 lo
catio
ns
in 2
003
– 20
04 (4
,6)
Riv
er se
dim
ents
(2
) R
etro
spec
tive
mon
itorin
g H
errin
g gu
ll eg
g, e
elpo
ut
mus
cle
(3, 1
2)
Perm
anen
t so
il m
onito
ring
>600
sam
ples
(1
,2)
Bio
mon
itorin
g:
Spru
ce
need
les s
ince
19
92, (
1,2)
G
rass
, gre
en
cabb
age
sinc
e 19
95 (1
,2)
Proj
ects
G
rass
, gre
en
cabb
age
(4-6
)
Mon
itorin
g of
gr
ass,
hay,
sila
ge,
each
5 sa
mpl
es
sinc
e 19
96 (2
) Pr
ojec
t: Fe
edin
g st
uff
com
pone
nts7
0 sa
mpl
es 1
994/
95
(14)
Pr
ojec
t: Fo
rage
cr
ops,
feed
ing
stuf
f 40
sam
ples
200
3-20
04 (6
) N
atio
nal c
ontro
l pr
ogra
m fo
r fe
edin
g st
uff s
afet
y in
200
3: 3
175
sam
ples
Her
ring
9 po
oled
sam
ples
B
altic
Sea
in
1999
H
errin
g 2
– 5
sam
ples
1
loca
tion
sinc
e 19
96
Bre
am, 1
4 lo
catio
ns, 1
995
+ 20
00
Fres
hwat
er fi
sh
15 sa
mpl
es
annu
ally
92 sa
mpl
es E
U-
food
mon
itorin
g 19
99 –
200
2;
vario
us
mon
itorin
g ac
tiviti
es in
the
Länd
er (1
9),
spec
ial
mon
itorin
g pr
ogra
ms f
or e
ggs
and
milk
in th
e lä
nder
pl
anne
d pr
ojec
t fo
r foo
d an
d fe
edin
g st
uff 1
000
sam
ples
(15)
Bre
ast m
ilk:
No
regu
lar
mon
itorin
g,
Indi
vidu
al
sam
ples
> 8
0 an
nual
ly (2
, 18
)
Blo
od o
f 10
year
old
pu
pils
, 16
pool
ed
sam
ples
, bi
annu
ally
si
nce
1993
(2
, 16)
R
etro
spec
tive
m
onito
ring
hum
an
bloo
d 20
sa
mpl
es
annu
ally
, 19
77 –
19
99 (1
7)
Lat
via
Emis
sion
in
vent
ory
2001
/200
2 ba
sed
on
Non
e?
HEL
CO
M:
Mac
oma
balti
ca
(4 st
atio
ns in
the
Gul
f of R
iga)
,
Sam
plin
g in
so
ils,
sedi
men
ts a
nd
fres
hwat
er
Yes
? M
onito
ring
of
diox
ins a
nd
diox
in-li
ke
PCB
s in
fish
and
Mea
t, fis
h, m
ilk,
eggs
, wild
gam
e,
hone
y
No
mon
itorin
g N
o m
onito
ring
No
rese
arch
Bas
elin
e R
epor
t on
Inte
grat
ed m
onito
ring
of d
ioxi
ns a
nd P
CB
s in
the
Bal
tic R
egio
n 10
emis
sion
fa
ctor
s. U
NEP
C
hem
ical
’s
tool
kit.
No
mea
sure
me
nts.
perc
h m
uscl
e (7
st
atio
ns –
4
balti
c/3
Gul
f of
Rig
a), h
errin
g (1
ar
ea in
the
Gul
f of
Rig
a)
Dio
xin
and
fura
ns in
fish
fr
om B
altic
Sea
an
d G
ulf o
f R
iga:
Spr
at, c
od,
herr
ing.
16
sam
ples
.
fish.
If
prob
lem
→
mon
itorin
g w
ill b
e de
velo
ped.
fishe
ry p
rodu
cts
(her
ring,
cod
, sp
rat)
acco
rdin
g to
EC
re-
com
men
datio
n 20
02/2
01. T
wic
e a
year
sinc
e 20
02.
Lith
uani
a Em
issi
on
inve
ntor
y 20
01/2
002
base
d on
em
issi
on
fact
ors.
No
mon
itorin
g 14
lake
s sin
ce
1994
, 39
river
s si
nce
1996
, W
ater
: H
ELC
OM
3
stat
ions
B
lue
mus
sels
, he
rrin
g an
d co
d liv
er (5
st
atio
ns/y
ear)
No
mon
itorin
g
HEL
CO
M 3
st
atio
ns
Mea
t, fis
h, m
ilk,
eggs
, wild
gam
e,
hone
y 7
PCB
s acc
ordi
ng
to d
irect
ive
96/2
3/EC
. Fro
m
2002
.
WH
O 1
992
PCB
s in
hum
an m
ilk
and
new
born
bl
ood.
92
pai
rs o
f sa
mpl
es.
1995
-199
8.
Mon
itorin
g of
nut
ritio
n of
Lith
uani
an
popu
latio
n:
PCB
s in
cons
umpt
ion
of fo
od
grou
ps/d
ay
1997
.
Pola
nd
Bal
tic h
errin
g an
d sp
rat 1
996-
2002
, re
f [1-
12,1
4-15
], A
ppen
dix
2,
App
endi
x 3,
Bas
elin
e R
epor
t on
Inte
grat
ed m
onito
ring
of d
ioxi
ns a
nd P
CB
s in
the
Bal
tic R
egio
n 11
Rus
sia
W
HO
199
2,
2001
Swed
en
Sew
age
treat
men
t pl
ants
, ye
arly
20
03-
Air
leve
ls 3
stat
ions
19
95/6
- A
ir de
posi
tion
3 st
atio
ns 1
995/
6-
16 sa
mpl
ing
stat
ions
, con
c. in
se
dim
ent.
Popu
latio
n of
gr
ey se
als,
bree
ding
of s
ea
eagl
es, o
ne si
te
conc
. in
guill
emot
egg
s
No
mon
itorin
g pr
ogra
mm
es,
som
e da
ta o
n re
med
iatio
n pr
ojec
ts
Pilo
t pro
ject
s 19
99-,
mon
itorin
g 20
03-,
50 sa
mpl
es,
EU
Four
loca
tions
ye
arly
197
8/80
- he
rrin
g m
uscl
e (H
ELC
OM
gu
idel
ines
)
54 sa
mpl
es/y
ear
2003
- B
reas
t milk
fr
om
prim
ipar
ae
mot
hers
, ev
ery
2. y
ear,
WH
O
No
regu
lar
mon
itorin
g.
Pilo
t and
re
sear
ch
proj
ects
, bl
ood
sam
ples
C
B 1
53
from
you
ng
mal
es,
ever
y 2-
3 ye
ar
No
mon
itorin
g, p
ilot
and
rese
arch
pr
ojec
ts
Aus
tria
In
cine
rato
r an
d la
rge
com
bust
ion
plan
t co
ntro
l
Air
8 si
tes i
ndic
ator
PC
B
Fo
rest
soils
, ag
ricul
tura
l so
ils,
indi
cato
r
Feed
and
feed
co
mpo
nent
s 70
sam
ples
/a
indi
cato
r PC
B
M
ilk 3
0 sa
mpl
es/a
in
dica
torP
CB
, ot
her f
ood
star
t 20
04, 4
5 sa
mpl
es
Bel
gium
Em
issi
ons
inve
ntor
y re
gula
rly
upda
ted
Rou
tine
mea
sure
men
ts o
f em
issi
ons o
f dio
xins
fo
r inc
iner
ator
s and
ris
k in
dust
ries.
D
epos
ition
m
easu
rem
ents
of
diox
ins s
ince
199
5,
incl
ude
now
PC
B12
6. M
any
loca
tions
, sev
eral
tim
es a
yea
r.
Nor
th S
ea:
OSP
AR
; fr
eshw
ater
en
viro
nmen
t (r
iver
s).
Bio
indi
cato
rs
such
as e
el a
nd
shel
lfish
, se
abird
, mar
ine
mam
mal
s;
wat
er,
sedi
men
ts.
No
rout
ine
mon
itorin
g, in
ca
se o
f su
spic
ion
and
one
rese
arch
pr
ojec
t (29
sa
mpl
es o
f so
il).
Hig
h nu
mbe
r of
rout
ine
sam
ples
si
nce
2000
. In
2002
, 111
68
sam
ples
for n
on-
diox
in-li
ke P
CB
s an
d 78
7 sa
mpl
es
for
PCD
D/F
.Mon
itori
ng o
f dio
xin-
like
PCB
s sin
ce 2
003.
Incl
uded
in
regu
lar f
ood
mon
itorin
g an
d in
mon
itorin
g of
w
ater
en
viro
nmen
t
Mon
itorin
g of
PC
DD
/F in
milk
si
nce
1990
. Hig
h nu
mbe
r of f
ood
sam
ples
for
anal
yses
on
non-
diox
in-li
ke P
CB
s, di
oxin
s and
di
oxin
-like
PC
Bs
sinc
e 20
00 (2
002:
20
5 an
alys
es fo
r di
oxin
s and
di
oxin
-like
PC
Bs;
15
00 a
naly
ses
non-
diox
in-li
ke
PCB
s)
Expo
sure
es
timat
es m
ade
(inta
ke fr
om
food
).
WH
O 1
987-
, In
200
0 tw
o po
oled
sa
mpl
es (6
-10
mot
hers
ea
) for
W
HO
. In
200
0-20
01, 2
0 in
divi
dual
sa
mpl
es
anal
ysed
.
Stud
y pe
rfor
med
on
blo
od
sam
ples
ne
ar
inci
nera
tors
. Stud
y on
goin
g to
in
vest
igat
e th
e di
ffer
ence
in
di
oxin
/PC
B
leve
ls in
se
rum
from
be
fore
and
af
ter
PCB
/dio
xin
inci
dent
in
Firs
t st
udy
star
ted
in
1999
. C
urre
ntly
se
cond
st
udy
ongo
ing
focu
sing
on
in
dica
tors
fo
r ex
posu
re
(ser
um
leve
ls,
cord
bl
ood)
an
d of
ef
fect
on
heal
th
Bas
elin
e R
epor
t on
Inte
grat
ed m
onito
ring
of d
ioxi
ns a
nd P
CB
s in
the
Bal
tic R
egio
n 12
Bel
gium
. (im
mun
olog
ic, …
) in
di
ffer
ent
age
grou
ps
and
diff
eren
t re
gion
s. In
clud
es
diox
ins
and
PCB
s. Fr
ance
Em
issi
on
inve
ntor
y 19
90-2
002
Emis
sion
s aro
und
hot
spot
s, no
dep
ositi
on
Min
. of
Envi
ronm
ent,
over
view
199
9-20
00, n
o co
ntin
ued
mon
itorin
g,
RN
O 2
001-
2002
No
natio
nal
mon
itorin
g
See
food
Fo
od m
onito
ring,
M
arke
t bas
ket
stud
y 19
99, 2
003,
M
ilk a
roun
d in
dust
rial p
lant
s
Nat
iona
l st
udy
1998
-99
, no
mon
itorin
g
Blo
od in
pl
anni
ng
2004
-200
6
No
spec
ific
mon
itorin
g, st
udy
on h
ealth
pa
ram
eter
s nea
r in
cine
rato
rs
Ital
y Pi
lot
proj
ect:
seco
ndar
y m
etal
in
dust
ry
(200
0-20
02)
No
regu
lar
mon
itorim
g So
me
scat
tere
d da
ta
Sedi
men
t and
m
usse
ls in
co
asta
l are
as, 7
3 sa
mpl
ing
site
s, 20
00-2
003.
M
onito
ring
prog
ram
mes
in
hot s
pots
(i.e
. th
e la
goon
of
Ven
ice)
So
me
data
from
re
sear
ch
proj
ects
.
Som
e da
ta
from
rese
arch
pr
ojec
ts.
Som
e da
ta o
n co
ntam
inat
ed
site
s.
Mon
itorin
g (5
1 sa
mpl
es in
200
1).
Seaf
ood
from
th
e A
dria
tic S
ea
(199
7-19
98).
Mon
itorin
g (N
atio
nal P
lan
for
Res
idue
s in
food
).
Hum
an m
ilk,
WH
O
Res
earc
h pr
ojec
ts
(adi
pose
tis
sue,
ce
ntra
l Ita
ly)
Uni
ted
Kin
gdom
N
atio
nal
emis
sion
A
ir co
ncen
tratio
n an
d de
posi
tion,
6 si
tes
NM
MP
1998
, 20
03,
UK
Soi
l and
H
erba
ge
EC c
oord
inat
ed
prog
ram
, 200
3,
Mar
ine
and
fres
hwat
er fi
sh,
Mar
ket b
aske
t st
udy,
199
7, 2
001,
N
o na
tiona
l pr
ogra
mm
e
Bas
elin
e R
epor
t on
Inte
grat
ed m
onito
ring
of d
ioxi
ns a
nd P
CB
s in
the
Bal
tic R
egio
n 13
inve
ntor
y 19
90-2
001,
En
viro
nme
nt A
genc
y
(dep
os. d
isco
ntin
ued
1993
) Po
lluta
nt
Surv
ey (s
oil
and
gras
s).
Ava
ilabl
e 20
04
Loca
l aut
norit
y sa
mpl
ing
and
anal
ysis
200
1-20
02
10 sp
ecie
s 199
6,
Mar
ine
and
fres
hwat
er fi
sh,
31 sp
ecie
s, sh
ellfi
sh 7
sp
ecie
s, 20
03-
2004
, Fis
h oi
ls
2000
-200
2
EU sa
mpl
ing
prog
ram
me
2003
, In
fant
form
ulae
, 20
03
Cou
ntry
So
urce
s A
ir
Wat
er
envi
ronm
ent
Soil,
terr
estr
. en
viro
nmen
t A
nim
al fe
ed
Fish
Fo
od
Bre
ast m
ilk
Hum
an
tissu
es
Hea
lth
effe
cts
Bas
elin
e R
epor
t on
Inte
grat
ed m
onito
ring
of d
ioxi
ns a
nd P
CB
s in
the
Bal
tic R
egio
n 14
Tabl
e 2.
Mon
itori
ng a
ctiv
ities
/res
ults
on
diox
ins a
nd d
ioxi
n-lik
e PC
Bs a
vaila
ble
from
diff
eren
t cou
ntri
es (d
etai
ls g
iven
in c
ount
ry a
nnex
es a
t the
en
d of
the
Doc
umen
t, a
lso
listin
g re
fere
nces
).
C
ount
ry
Sour
ces
Air
W
ater
So
il, te
rres
tr.
Ani
mal
fe
ed
Fish
Fo
od
Bre
ast
milk
H
uman
tis
sues
H
ealth
ef
fect
s D
enm
ark
Gen
eral
m
ass f
low
s (1
-6)
Prod
ucts
(1
-4, 7
)
Air
emis
sion
s (8
-16)
A
ir le
vels
(15-
17)
Air
depo
sitio
n (1
4,16
-17)
Lake
/fior
d w
ater
(16)
R
ain
wat
er (1
6)
Perc
olat
e (1
6)
Sedi
men
t (16
,19)
H
arbo
ur sl
udge
(19-
20)
Sew
age
slud
ge (1
9-20
)
Leve
ls in
soil
(14,
16
-19)
V
eget
atio
n (1
4,
16-1
7)
Com
post
(16
) B
io a
sh
(16)
C
ows m
ilk (1
6)
Var
ious
(40)
Fi
sh (2
1)
Food
(21-
22)
Hum
an
milk
(23-
24, 4
1)
Est
onia
So
urce
s (2
4)
PCD
D/F
s in
soil
near
land
fill
2003
(res
earc
h pr
ojec
t)(5;
6)
20
02-4
93 h
errin
g sa
mpl
es (2
0poo
ls)
and
246
spra
t sa
mpl
es (8
poo
ls)
PCD
D/F
s in
Bal
tic
herr
ing
(with
out s
kin
4 re
gion
s) (1
1,12
);
PCD
D/F
s in
balti
c he
rrin
g(4
regi
ons)
an
d sp
rat (
3 re
gion
s) 2
002
with
sk
in (1
3-15
);in
2003
(her
ring,
sp
rat,
perc
h,
pike
-per
ch (1
6).
H
ealth
(2
8,32
)
Finl
and
B
ulk
depo
sitio
n,
sum
mer
, 2 st
atio
ns
1998
- (1
,2),
3rd
stat
ion
2002
-
Mus
sels
: (M
acom
a,
Myt
ilus)
eve
ry th
ird
year
, 1st
atio
n, 1
991-
(4
) Se
dim
ents
, 30
stat
ions
, mos
tly
surf
ace/
deep
, 5 c
ores
(2
, 11,
12)
Se
dim
ent t
raps
,
Abo
ut 2
40
anal
yses
200
3,
vario
us sp
ecie
s, va
rious
loca
tions
, EU
R
esea
rch
proj
ects
H
errin
g ,3
stat
ions
, 19
90-
Nor
ther
n pi
ke, 3
Mea
sure
men
ts
sinc
e 19
98??
? M
onito
ring
2002
-200
3 EU
WH
O si
nce
1987
R
esea
rch
proj
ects
, fat
, se
rum
, pl
acen
ta
Res
earc
h pr
ojec
ts,
canc
er,
toot
h de
fect
s, cl
eft p
alat
e,
cryp
torc
hid
ism
Bas
elin
e R
epor
t on
Inte
grat
ed m
onito
ring
of d
ioxi
ns a
nd P
CB
s in
the
Bal
tic R
egio
n 15
seve
ral l
ocat
ions
(2,
7)
stat
ions
, 199
2-
(4, 5
) Sa
lmon
(9, 1
0)
(Sal
mon
from
19
80's-
1990
's un
der a
naly
sis)
G
erm
any
Com
post
(2
2 sa
mpl
es)
and
sew
age
slud
ge (1
0 sa
mpl
es) i
n 20
01-2
002
(4-5
)
Air
emis
sion
pr
ojec
t (4)
5
haza
rdou
s was
te
inci
nera
tors
pro
ject
(2
003-
4) (6
) A
mbi
ent a
ir le
vels
15
site
s, de
posi
tion
15 si
tes,
som
e si
nce
2000
(10)
Pr
ojec
t: am
bien
t ai
r lev
els a
nd
depo
sitio
n 36
site
s 20
02-2
003
(11)
In
door
12
loca
tions
Pr
ojec
t 200
3-20
04
(4,6
)
Ret
rosp
ectiv
e m
onito
ring
Her
ring
gull
egg,
ee
lpou
t mus
cle
(3,
12)
Perm
anen
t soi
l m
onito
ring
in
2003
: 200
sam
ples
Pr
ojec
ts: G
rass
, gr
een
cabb
age
2001
-200
4 (4
-6)
Proj
ect:
Fora
ge c
rops
, fe
edin
gstu
ff
40 sa
mpl
es
2003
-200
4 (6
)
Her
ring
9 po
oled
sa
mpl
es B
altic
Sea
in
199
9, B
ream
14
loca
tions
, 199
5 +
2000
92 sa
mpl
es E
U
Food
mon
itorin
g 19
99-2
002,
va
rious
m
onito
ring
activ
ities
in th
e Lä
nder
(19)
, sp
ecia
l m
onito
ring
prog
ram
s for
eg
gs a
nd m
ilk in
th
e Lä
nder
pl
anne
d pr
ojec
t fo
r foo
d an
d fe
edin
g st
uff
1000
sam
ples
(1
5)
WH
O
1987
-
Lat
via
Emis
sion
in
vent
ory
2001
/200
2 ba
sed
on
emis
sion
fa
ctor
s. U
NEP
C
hem
ical
’s
tool
kit.
No
mea
sure
me
nts.
Non
e?
HEL
CO
M: M
acom
a ba
ltica
(4 st
atio
ns in
th
e G
ulf o
f Rig
a),
perc
h m
uscl
e (7
st
atio
ns –
4 b
altic
/3
Gul
f of R
iga)
, her
ring
(1 a
rea
in th
e G
ulf o
f R
iga)
D
ioxi
n an
d fu
rans
in
fish
from
Bal
tic S
ea
and
Gul
f of R
iga:
Sp
rat,
cod,
her
ring.
16
sam
ples
.
Sam
plin
g in
soils
, se
dim
ents
and
fr
eshw
ater
fish
. If
prob
lem
→
mon
itorin
g w
ill b
e de
velo
ped.
Yes
? M
onito
ring
of
diox
ins a
nd d
ioxi
n-lik
e P
CB
s in
fish
and
fishe
ry
prod
ucts
(her
ring,
co
d, sp
rat)
acco
rdin
g to
EC
re
-com
men
datio
n 20
02/2
01. T
wic
e a
year
sinc
e 20
02.
Mea
t, fis
h, m
ilk,
eggs
, wild
gam
e,
hone
y
No
mon
itorin
g N
o m
onito
ring
No
rese
arch
Lith
uani
a Em
issi
on
inve
ntor
y N
o m
onito
ring
14 la
kes s
ince
199
4,
39 ri
vers
sinc
e 19
96,
No
mon
itorin
g
HEL
CO
M 3
st
atio
ns
Mea
t, fis
h, m
ilk,
eggs
, wild
gam
e,
WH
O 1
992
Bas
elin
e R
epor
t on
Inte
grat
ed m
onito
ring
of d
ioxi
ns a
nd P
CB
s in
the
Bal
tic R
egio
n 16
2001
/200
2 ba
sed
on
emis
sion
fa
ctor
s.
Wat
er: H
ELC
OM
3
stat
ions
B
lue
mus
sels
, her
ring
and
cod
liver
(5
stat
ions
/yea
r)
hone
y
Pola
nd
Ref
18
Ref
18
B
altic
her
ring
and
spra
t 200
2 an
d 20
03, R
ef 1
3
Ref
17
WH
O 1
987
Rus
sia
W
HO
19
92, 2
001
Swed
en
N
o m
onito
ring
16 sa
mpl
ing
stat
ions
, co
nc. i
n se
dim
ent.
One
site
con
c. in
gu
illem
ot e
ggs
No
mon
itorin
g pr
ogra
mm
es, s
ome
data
on
rem
edia
tion
proj
ects
Pilo
t pro
ject
s 19
99-,
mon
itorin
g 20
03-,
50
sam
ples
, EU
Four
loca
tions
ye
arly
198
1/95
- he
rrin
g m
uscl
e
54 sa
mpl
es/y
ear
2003
- B
reas
t milk
fr
om
prim
ipar
ae
mot
hers
W
HO
19
97, e
very
2.
yea
r,
Res
earc
h pr
ojec
ts, n
o re
gula
r m
onito
ring
No
mon
itorin
g,
pilo
t and
re
sear
ch
proj
ects
Aus
tria
In
cine
rato
r an
d la
rge
com
bust
ion
plan
t co
ntro
l
Air
8 si
tes
PCD
D/F
, dio
xin-
like
PCB
Feed
and
feed
co
mpo
nent
s 70
sam
ples
/a
PCD
D/F
, di
oxin
-like
PC
B
M
ilk 3
0 sa
mpl
es/a
PC
DD
/F,
diox
in-li
ke P
CB
, ot
her f
ood
star
t 20
04, 4
5 sa
mpl
es
Bel
gium
EC
Rep
ort
2003
R
outin
e m
easu
rem
ents
for
inci
nera
tors
and
ris
k in
dust
ries,
depo
sitio
n si
nce
1995
Mon
itorin
g pr
ogra
mm
e 20
01-
2003
PC
DD
/F, P
CB
No
rout
ine
mon
itorin
g, in
cas
e of
susp
icio
in
Hig
h nu
mbe
r of
rout
ine
sam
ples
sinc
e 20
00, b
oth
PCB
and
PC
DD
/F
Incl
uded
in re
gula
r fo
od m
onito
ring
Hig
h nu
mbe
r of
food
sam
ples
si
nce
2000
(2
001
abou
t 16
00 P
CB
an
alys
es,
diox
ins 2
00/a
)
WH
O
1987
-, In
20
00 tw
o po
oled
sa
mpl
es (6
-10
mot
hers
ea
)
Seru
m
sam
ples
nea
r in
cine
rato
rs
Res
earc
h pr
ojec
ts
Fran
ce
Emis
sion
in
vent
ory
1990
-200
2
Emis
sion
s aro
und
hot s
pots
, no
depo
sitio
n
Min
. of E
nviro
nmen
t, ov
ervi
ew 1
999-
2000
, no
con
tinue
d m
onito
ring,
RN
O
2001
-200
2
No
natio
nal
mon
itorin
g
See
food
Fo
od
mon
itorin
g,
Mar
ket b
aske
t st
udy
1999
, 20
03, M
ilk
arou
nd
indu
stria
l pla
nts
Nat
iona
l st
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Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 19
2.2 Emissions of PCB-compounds and PCDD/Fs to the Baltic Sea PCB and PCDD/F emissions to the Baltic Sea have been both airborne and from the multitude of waterways. Airborne emissions derive from a number of burning processes, incineration of municipal waste, metal industries, fossil energy production, small scale burning, traffic, chemical industries, and other sources both in Central Europe and in the Nordic and Baltic Countries, and Russia. Prevailing winds in the area are from the southwest, emphasising to some extent the heavily industrialised Central Europe, also practising municipal waste incineration, in contrast to less densely populated Nordic Countries mostly dumping their waste to dumpsites. The worst sources in Russia seem to be distant from the Baltic Sea area (e.g. Chapayevsk, Dzersinsk, UFA), but there are some poorly characterised sources in St. Petersburg, Leningrad oblast area, and Kaliningrad. On the other hand, the waterway pollution can be attributed to a large extent to forest industries, where chlorine was used for pulp bleaching in large amounts until early 1990s in the Nordic countries (Finland, Sweden). Also associated with forest industries is the production of chlorophenols, which have polluted e.g. Kymijoki River in Finland very badly during 1940s through 1980s. The total release was 26,000 g WHO-TEq, of which 13,600 g is situated along the river deeps and 12,400 g WHO-TEq has entered the Gulf of Finland (Isosaari et al, 2002, Verta et al. 2003). Multiple emission sources render it highly desirable to carefully analyse both spatial and temporal distributions of this pollution in the Baltic Sea and the most important inlet waterways. Table 3. Estimates of dioxin emissions in different countries around the Baltic Sea. Country/year of information
Total air emissions g WHO-TEq
Total waterway emissions to the Baltic Sea g WHO-TEq
Denmark 2000-2002
11-163*** 0.4-1.4***
Estonia** 14*** 0.15*** Finland 2001 31 (UNECE) 44 (River Kymijoki, Verta et al., 2003) Germany 2000 <70 (UBA) <0.5 (UBA) Latvia** 23*** 0.18*** Lithuania** 17*** 0.1*** Poland** 490*** 1.2*** Russia** 6900-10800*** Sweden 2002 >14-21 >0.03-0.5 Austria 2001 52.25*** n.a. Belgium 2001 164*** n.a. France 2002 405*** n.a. UK 2001 357*** n.a. **Lassen et al., 2003 ***I-TEq
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 20
2.2.1 Air emissions The sources to atmosphere of dioxins and PCBs are different. Dioxins are emitted as unintentional byproducts. In the early 1970s the major sources were waste incineration, use of chemical products and the metal industry. The decline in use of organochlorine pesticides has reduced emissions from that particular source. Since then, the implementation of pollution abatement controls has reduced emissions dramatically. This led, in the early 1990s, to a decrease in atmospheric concentrations. In recent years, for the UK at least, the continuing slight decline in emissions does not appear to have led to a corresponding decrease in air concentrations (see following figure).
PCDD/F Emissions (I-TEQ) and Air Concentrations at UK Urban TOMPs Sites 1991-2002
0
200
400
600
800
1000
1200
1990 1992 1994 1996 1998 2000 2002
UK
Est
imat
ed A
nnua
l Em
issi
ons
of
PC
DD
/F to
Atm
osph
ere
(g I-
TEQ
nd=
dl)
0
20
40
60
80
100
120
140
160
180
200
220
Ann
ual M
ean
Air
Con
cent
ratio
n (fg
I-TE
Q m
-3)
Total EmissionsManchesterMiddlesbroughLondon
Note: 1995 higher concentrations possibly due to the prevailing meteorological conditions. 2.2.2 Soil contamination due to chlorophenols
The use of wood preservative "Ky-5" (mixture of 2,3,4,6-tetrachlorophenol. pentachlorophenol and 2,4,6-trichlorophenol) has led in Finland to soil and sediment contamination by chlorophenols and PCDD/Fs at many sawmills and landfill and disposal sites for wood preservative wastes (Assmuth & Vartiainen 1994, Assmuth & Vartiainen 1995, Kitunen & Salkinoja-Salonen 1990, Vartiainen et al. 1995). Concentrations of 2,3,7,8-chlorinated PCDD/Fs as high as 3 200 ng/g or 94 ng I-TEQ/g d.w. have been reported in sawmill soil (Assmuth & Vartiainen 1995). Ky-5 was also used in Sweden. The maximum concentration of 2,3,7,8-chlorinated PCDD/Fs in the samples collected from two sawmill sites was 490 ng/g d.w. (3.9 ng WHO-TEQ/g d.w.) (Persson et al. 2003).
In Poland, the production of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), sodium pentachlorophenate, pentachlorophenol and 2,4,5-trichlorophenol was started in 1969 in Neratovice. Dumping of chemical wastes around the production facility led to soil contamination with 2,3,7,8-TCDD levels up to 29.8 ng/g (Holoubek et al. 2000).
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 21
2.2.3 Pulp industries in the Baltic Sea catchment area
Fig. 4a,b. Pulp industries in Sweden and Finland in 2001. There are 48 pulp and paper mills in Sweden producing 12.1 million tonnes of pulp in a year (2001). In Finland there are 46 pulp and paper mills, and 13.9 million tonnes of pulp are produced. There are 27 Swedish and 15 Finnish pulp/paper mills along the coast of the Gulf of Bothnia (Fig. 4), and 14 produce bleached pulp (http://www.baltic.vtt.fi). Previously many of these used chlorine for bleaching. In addition there are metal industries in the area (iron and steel mills, metal smelters of non-iron heavy metal, and aluminum). There are 17 pulp and paper plants in the catchment area of the Gulf of Finland in Russia, as well as mining industries and chemical and aluminium plants. Many of them have substantial atmospheric and waterway emissions. In Finland there are 29 pulp and paper mills in this sub-region (Fig. 4b). Five mills are on the coast and eight on the banks of rivers that directly affect the coastal waters. Two of these mills produce bleached kraft pulp. Both air and water emissions of these industries have been drastically reduced during the latest decades. In Estonia there are two paper and pulp mills and two large oil shale burning power plants affecting large atmospheric emissions. In the Northern Baltic proper area there are 15-20 major industrial plants, most importantly large steelworks. In the Western Gotland basin there is only one major kraft pulp mill. In the
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 22
Gulf of Riga area there are a number of chemical plants, some major polluters, but only one pulp/paper mill, and no bleached pulp production or other typical sources of chlorinated persistent compounds.
Fig. 5. Paper and pulp mills in Poland especially on the Rivers Oder and Vistula with inlets to the Baltic Sea. There are 9 pulp and paper mills and 35 pulp mills with a total pulp production of 1 million tonnes (2001). Along the Nemunas river there are many industries, including some pulp and paper mills and chemical industries. Some of these are old and with limited possibilities for modernization and pollution abatement. In Kaliningrad there are many major enterprises including four pulp and paper mills. The problem is outdated technology and lack of wastewater treatment. Along the Vistula River chemical and pulp and paper industries are the most problematic (Fig. 5). Most of the wastewaters are treated but only by mechanical treatment and in 45 % biological treatment. There are several industrial plants along the Polish coast, including chemical, metal and forest industries. The Odra/Oder River carries some discharges from forest industries, but most of the steel industries and sources of air pollution are in the Southern part (Katowice) as well as in Czech Republic. Also in the Eastern parts of Germany discharges have been high but drastically reduced after the reunification.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 23
Mean annual concentrations of the sum of PCBs (µg/l) in the Oder and Vistula rivers between 1992-2001 (data from the State Environmental Monitoring, Institute of Meteorology and Water Management, Poland) Year Vistula Oder Krakow Warszawa Kiezmark Chalupki Wroclaw 1992 0,0275 0,0078 0,0075 0,0018 0,0014 1993 0,0138 0,0103 0,0072 0,0037 0,0039 1994 0,0234 0,0125 - 0,0079 0,0080 1995 0,0129 0,0090 0,0011 0,0171 0,0097 1996 0,0134 0,0099 0,0184 - 0,0080 1997 0,0137 0,0110 0,0088 0,0040 0,0114 1998 0,0112 0,0138 0,0088 - 0,0096 1999 0,0127 0,0136 - - 0,0198 2000 0,0170 0,0141 - 0,0015 0,0158 2001 0,0078 0,0082 - 0,0098 0,0157 Mean 0,0153 0,0110 0,0086 0,0065 0,0103 2.2.4 Local specific point sources An example of a local problem was vinyl chloride production in Sköldvik, Southern Finland (Isosaari et al., 2000). The main component was OCDF, and the total release over the years of vinyl chloride production was 32 g (I-TEq), OCDF being responsible of 59 %. This is an example of the sensitivity of valuations of these compounds, since the decrease of OCDF-TEF from 0.001 to 0.0001 also reduces the TEq amount as WHO-TEq to about one half. 2.3 Emission regulations and examples of emission controls in Europe 2.3.1 International Conventions and EU-Regulations With regard to POPs two international conventions are to be mentioned namely the UNECE-Protocol and the Stockholm Convention. The UNECE-Protocol focusses on a list of 16 substances with the objective to eliminate all discharges, emissions and losses of POPs. The protocol has been signed by all present member states and most of the candidate countries. The UNECE-Protocol went into effect on 23rd October 2003. The Stockholm Convention on POPs was signed by the EC in 2001. All EU Member States and most of the candidate countries have signed the Convention. By March 2003, 30 countries worldwide had ratified the convention. It will go into effect with the fifth ratification. The overall objective of the convention is to protect human health and the environment from POPs. It lists 12 substances, which are also included in the UNECE-Protocol, and provides a mechanism to include new substances fulfilling the criteria for POPs. Member states to the convention are obliged to prepare National Action Plans to meet the provisions of the treaty.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 24
With regard to unintentionally produced POPs several community rules already exist:
• Directive 96/61/EC, better known as IPPC directive covering the major stationary resources
• Commission Decision 2000/479/EC giving provisions for the establishment of an European pollutant emission register (EPER)
• Directive 2000/76/EC covering waste incineration facilities • Directive 2001/80/EC covering large combustion plants • Directive 96/82/EC on prevention of accidental release of hazardous substances,
better known as Seveso II Directive • Council Directive 76/464/EEC on pollution of water bodies caused by discharges of
certain dangerous substances. This list is not exhaustive. There are also several directives restricting marketing, production, export/import of POPs. With respect to the wide range of EU-regulations on POPs, which are in some cases redundant, or worse, contradictory, the commission has decided to initiate a harmonisation process. The first draft proposal has already been published in June 2003 (COM(2003) 333 final, 12.6.2003). 2.3.2 National Emission Inventories From the beginning of the 1990s European countries made much effort to compile existing emission data, to evaluate it and to draw conclusions how to limit dioxin releases to the environment and to identify major sources. These efforts resulted in so called national emission inventories, mainly based on the CORINE (COoRdination d’INformation Environmentale) scheme for air comprising app. 270 single activities, divided into 11 major groups and 36 subgroups. Several other countries used their own, national, definitions of emission activities. Another shortcoming of the inventories is the fact, that most of the emission data are based on estimates. The quality of these estimations varies strongly for different activities. Estimates for known and well investigated sources like waste incineration, ferrous and non-ferrous production processes can be assumed as almost accurate, whereas estimates for small sources like domestic wood-, coal-, coke combustion are less accurate due to a wide range of reported emission factors. Meanwhile at least a harmonisation of reporting formats took place, mainly driven by the adoption of the UNECE/CLRTAP. In 1996 the North Rhine–Westphalia State Environment Agency started a re-evaluation of European emission inventories funded by the DG ENV. The final report of stage II of this project, published in 2001, gives an estimate for industrial sources of 1589 to 2516 g I-TEQ/year and 846 to 2144 g I-TEQ/year for non-industrial sources, based on data from 2000. As can be seen from Tables 4-7 presenting emission data from Austria, Belgium, France and Germany there is a clear downward trend of Dioxin-emissions in the beginning of the 1990s, mainly caused by closing down and/or retrofitting of MSWIs and other large combustion facilities. Waste incineration, at least in those Member States who fully adopted the relevant EC-regulations, can be presently considered a minor emission source for dioxins and PCBs. The remaining relevant sources are processes of metal production and treatment, especially sinter plants, and industrial and residential combustion.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 25
Table 4. The time trend for Austrian emission estimates for 1990 to 2001 expressed as g I-TEQ Source 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 Energy production 0,73 0,76 1,06 0,28 0,30 0,34 0,39 0,41 0,41 0,44 0,46 0,49
small combustion sources
45,14 49,25 44,01 42,49 37,73 39,44 41,52 36,52 34,03 33,10 30,13 33,22
Industry 91,12 61,97 26,56 20,98 15,37 16,21 15,34 20,61 19,15 16,37 17,61 17,19 road traffic 3,43 3,30 2,76 2,38 2,05 1,73 1,58 1,29 1,25 1,04 0,96 0,93 Agriculture 0,35 0,35 0,35 0,35 0,35 0,35 0,35 0,35 0,35 0,35 0,35 0,35 Others 19,25 18,79 0,55 0,24 0,08 0,08 0,08 0,08 0,08 0,08 0,08 0,08 Sum 160,02 134,42 75,28 66,73 55,89 58,16 59,26 59,27 55,27 51,38 49,59 52,25 Table 5. Emission estimates for Flanders (Belgium) for 2000 Source private sector (open fires, heating of buildings) 73% trade and services (e.g. waste incineration) 13% industry (ferrous and naon ferrous industry, etc.) 14% SUM 98,4 g I-TEQ/a Table 6. German emission estimates for 1994 and 2000 expressed as g I-TEQ Emission source
Quantity released per year g TEQ /a (1994)
Quantity released per year g TEQ /a (2000)
Metal production and treatment (sum) 220 2) 40 2)
Sinter plants 168 1) < 20 3) Iron and steel production without sinterplants 10 1) < 5 1)
Non – Ferrous metal industry 91 1) Targ. emission val.: 0.1 ng TEQ/m³ 3 1)
Waste incineration Municipal Hazardous Medical Sewage sludge
Sum 32 1)
30 1)
2 1) 0,1 1)
< 0,1 1)
sum < 0,5 2)
0.4 2)
0.04 2)
0.0002 2)
0.03 2)
Chemical industry – VC production 0.1 1) 0.1 1) Power stations (all fuels) 5 2) < 3 2) Industrial combustion 15 2) < 10 2) Residential combustion 15 2) 10 2)
Traffic (sum) 4 2) 2 2)
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 26
Crematories 2.3 1)
2 2) <2 2)
Landfill gas incineration 0.3 1) <0.3 2) Total air emission 330 << 70
Total water emission 0.5 < 0.5 Sources: 1) Fiedler, H. (2001): Existierende Dioxininventare weltweit und neue Methodik zur Erstellung von vergleichbaren und vollständigen Emissionsinventaren. UWSF – Z Umweltchem.Ökotox. 13 (2) 88-94 Detzel, A.; et al. ”Investigation of emissions and abatement measures for persistent organic pollutants in the Federal Republic of Germany“, 1998 UBA - Texte 75/98 2) Internal evaluation by the Federal Environmental Agency, Germany 3) Target value for sinter plants by 2007: 20 g TEQ / a TEQ values are based on NATO/CCMS and do not include coplanar PCB. Table 7. The time trend for French emission estimates for 1990 to 2002 expressed as g I-TEQ Substances 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 Dioxins (g I-TEQ) 1859 1933 1958 2023 2014 1809 1592 1105 957 658 560 468 405 PCBs (kg) 61 68 67 67 64 60 60 49 49 45 43 43 41
Substances 1990-2002
Dioxins (g I-TEQ) 74,8 PCBs (kg) 30,1
Source : CITEPA / CORALIE format SECTEN – Février 2003 Principal industries responsible for dioxin and PCBs release to air: Dioxins (2001): Waste incineration, metallurgy & residential combustion of wood. PCBs (2001): residential (39%) & waste processing (23%). 2.3.3 Specific Examples
A case study will illustrate how integrated monitoring techniques can be used to estimate the human exposure to PCDD/F from a known source and enable the responsible authorities to take measures for reduction and control/document their successful implementation. The case study deals with the identification of local effects of dioxin emissions from a copper reclamation plant on the environment and the local population in an inner alpine region, the establishment of environment and health protecting measures (especially to avoid further emissions) and the permanent monitoring of the success of the measures set by environmental politicians by carrying out control investigations especially by monitoring a whole food chain important for human nutrition. A copper reclamation plant working for some decades (copper ore smelter before that for centuries) produced strong heavy metal pollution in its vicinity. It is situated in a village in an inner alpine valley in Tyrol/Austria with mainly grassland farming and milk production. When it became evident in the late 1980s that metal reclamation plants could produce high amounts of PCDD/F, environmental investigations were carried out. A monitoring scheme has been elaborated to cover the whole food chain comprising PCDD/F analyses of soil
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 27
fodder grass, human blood, breast milk and cow’s milk. Additionally PCDD/F analyses in stack gas of the copper plant and of ambient air were carried out. Fig. 6 shows the PCDD/F load in different environmental compartments and in the food chain fodder grass - cow’s milk in the year 1988, prior to the implementation of environmental protection measures.
Fig. 6. Dioxin levels (in International Toxic Equivalents) in different environmental compartments and in a human food chain in the main wind direction prior to implementation of environmental protection measures (Riss et al., 1990, modified). The most important immediate measures were drastic emission control at the copper plant, feeding cows with fodder grass from other regions and withdrawing milk from the market for a period until tolerable concentrations in milk were reached. After reconstruction measures at the copper plant to reduce air emissions drastically, the effect on the environment was monitored with simple bioindicator methods. By periodically analysing some fodder grass and cow’s milk samples the development of the contamination could be monitored over the following seasons. Additionally spruce needles were used as bioindicator, giving an estimate for the ambient air pollution originating from the reclamation plant. The development of the PCDD/F contamination of ambient air, fodder grass and cow’s milk from the “bioindicator farm” from the starting point of the investigations, after setting emission reduction measures and during the current environmental monitoring reflects the effectiveness of environmental protection measures. All results show a strong decrease of contamination during the first years, and a stabilisation for many years on a level close to background levels, as can be seen in the following figure.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 28
0
10
20
30
40
50
60
70
80
90
100
89 90 91 92 93 94 94 96 97 98 99
sampling year
ng T
EQ/k
g d.
w. (
need
les)
0
10
20
30
40
50
60
88 89 90 91 92 93 94 95 96 97 98 99 00 01
sampling year (cow's milk)
ng T
EQ/k
g fa
t (m
ilk) r
esp.
d.w
. (gr
ass)
spruce needles cow’s milk
grass
Fig. 7. Dioxin concentrations in spruce needles and in cow’s milk from a“bioindication farm” Currently, the local state of the environment is monitored by an annual investigation of three fodder grass samples, one cow’s milk sample and one sample of spruce needles. The validity and conclusiveness of the results of the investigations finally enabled the necessary steps to be taken by the permission authority for the industrial plant and the technical retrofitting to minimise further emissions from the enterprise. 2.3.4 EU-Policy - soil The European Commission published a Communication “Towards a Thematic Strategy for Soil Protection” on 16 April 2002 (EU COM 2002). The purpose of this Communication is to build on the political commitment to soil protection in order that it be achieved more fully and systematically in coming years. In addition, working with Member States, Candidate Countries and relevant stakeholders, the Commission will prepare the ground for a proposal for soil monitoring legislation to be made in 2004. Furthermore, and also working with relevant partners, it will prepare a communication dealing with erosion, the decline in soil organic matter and soil contamination including recommendations for actions to overcome them. In 1999, following a joint initiative of the Commission and some Member States (Bonn Memorandum on Soil Protection Policies in Europe, 1998) the European Soil Forum (ESF) was created. Its membership includes EU, EFTA and Accession Countries, the Commission and the EEA. Its role is to provide a better understanding of soil protection issues and to promote the exchange of information among participating countries. Soil has been also one of the thematic areas within the EEA. The main activity of the European Topic Centre of the EEA on Terrestrial Environment (ETC-TE) related to soils is to follow up the development of indicators as the main tool to provide policy-relevant information. The 6th Environmental Action Programme published by the Commission in 2001 established the objective to protect soils against erosion and pollution while the Sustainable Development Strategy, also published in 2001, noted that soil loss and declining fertility are eroding the viability of agricultural land.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 29
2.4 Previous information of the state of the Baltic Sea Sediments. Analysis of material from different depths in benthic sediments can give us an idea of how pollutant levels in the Baltic environment have varied over a period of many decades. The level of dioxins peaked in the 1970s after which a decrease can be observed (Fig. 8). Based on the sampling in 1988, Broman and coworkers (1991) estimated that the annual sedimentation of PCDD/Fs in the whole open Baltic Sea (near-coastal areas excluded) was 290 g N-TEQ/a (37 kg/a total PCDD/Fs). Highest concentrations in water samples, including particulate and dissolved fractions, were reported in the Bothnian Sea (Southern part of the Gulf of Bothnia). Areas where some contamination of the sediments has been identified in the Bothnian Sea and Bothnian Bay (Northern part of the Gulf of Bothnia) include the Hedesunda Bay (estuary of Dala river, multiple sources), and the vicinity of the Iggesund pulp mill, both located north of Stockholm. In Hedesunda Bay, the levels of 2,3,7,8-chlorinated PCDD/Fs reached 190 ng/g (1.8 ng N-TEQ/g) (Kjeller et al. 1990). 4 km away from the Iggesund pulp mill PCDD/F sum concentration was approximately 2.4 ng/g d.w. (Rappe et al. 1989). The concentration of 2,3,7,8-chlorinated PCDD/Fs in a sediment slice that was sampled from the area between Gotland and the Swedish coast in 1985 was low, 0.65 ng/g. The presence of alkyl-PCDFs, however, indicated releases from pulp mills (Kjeller & Rappe 1995). Influence of the Norrsundet pulp mill (southern part of the Gulf of Bothnia) was shown in the PCDD/F congener patterns in perch (Rappe et al. 1989). In 1988-1990, pulp bleaching was estimated to produce a total of 1.5-5 g N-TEQ/a to the water systems in Sweden (European Dioxin Inventory). Past emissions from Swedish chlorine production to water were estimated to be 229-1338 g N-TEQ (European Dioxin Inventory). In the Southern Baltic Sea, PCDD/F levels of up to 19.8 ng TEQ/g d.w. (PCDD/F sum 5 800 ng/g d.w.) have been analysed in surface sediments that were sampled from the estuary of Warnow River, in front of Rostock. Mean concentration (± sd) in 16 sediment samples from the estuary of Warnow River, Bodden area, Mecklenburg Bight, Oder Bight and Arkona Basin was 8.53 ± 5.40 ng TEQ/g d.w. Levels of PCDDs were typically much higher than those of PCDFs, and the predominating congener was OCDD (Wit et al. 1997). Dannenberg & Lerz (1999) found much lower levels of PCDDs (0.013-2.99 ng/g d.w.) and PCDFs (0.0025-0.82 ng/g d.w.) in sediment samples collected from approximately the same areas – they admitted, however, that the sampling points were not located in the most important sedimentation areas for PCDD/Fs. The highest PCDD/F concentration analysed in the harbour of Hamburg sediments was 74.6 ng/g d.w., and a concentration as high as 400 ng/g d.w. was reported in the sediments that had been disposed at the Georgswerder landfill site. The homologue profile of the harbour sediments resembled the pentachlorophenol profile, with OCDD and HpCDD as the most abundant homologues. There are several possible sources of PCDD/Fs next to the River Elbe, including manufacture of organochlorine pesticides and pulp and paper industry (Götz et al. 1990).
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 30
Fig. 8. A map showing time trends of PCDD/Fs (I-TEQ, pg/g dry weight) in sediment profiles at different locations in the Baltic (data from Kjeller and Rappe 1995, Verta et al. 1999, Isosaari et al. 2002, SYKE unpublished results). Note the different scale in some hot spots near Kymijoki river, the Gulf of Finland. Kymijoki River is probably the worst point source to the Gulf of Finland. Chlorophenols, in form of a commercial preparation called "Ky-5", were produced in Kuusankoski for about 40 years, and it has been estimated that this production led to a release of several kilograms PCDD/F (as I-TEq) into the Gulf of Finland (Verta et al., 1999, 2003). Sediment studies have revealed that horizontal distribution extends to about 75 km out from the river inlet. The surface sediments contained 24-66% of the maximum concentrations present in the 1960s and 1970s (Isosaari et al., 2002). PCB compounds were uniformly distributed over the Gulf,
0 250 500 Km
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Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 31
but the time course from sediments was fairly similar to that of PCDD/F. The surface concentrations were 13-69 % of the maximum concentrations (Isosaari et al., 2002).
Fig. 9. Areal distribution of PCDD/Fs in surface sediments in the Baltic Sea
An areal distribution of PCDD/Fs in surface sediments taken from Jensen (2003) suggests that local hot spots have been identified from several locations in Finnish and Swedish coast but not from the southern Baltic (Fig. 9). More studies in Sweden and Finland have been initiated. No data is available from the coastal areas of Poland, Lithuania and Latvia. Soil. In Estonia PCDD/Fs concentrations were analysed near South-Eastern Laguja landfill. PCDD/F concentrations 100 meter from the landfill in the agricultural soil were at background levels ( 0.11-0.29 pg/g fresh weight (as WHO-TEQ) and 0.64-1.53 pg/g dry weight ( Roots et al., 2003). Air. There are data available only from few countries of air concentrations or deposition of PCDD/F over the Baltic (Table 8).
↑350 ng/kg
Norway Sweden
Bothnian Sea
12 º E 20 º E
↑ 1850 ng/kg
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 32
Table 8. Summary of the different PCB concentrations (total PCB calculated from 51 identified peaks) at the Baltic Sea stations (from Agrell et al 2001). Latitude Station Air (pg/m3) Precipitation (ng/L) Deposition (ng/m2 d) 54°00’ Dziwnow 55 (n=5) 1.4 (n=2) 2.3 (n=2) 54°15’ Swibno 69 (n=6) 4.4 (n=4) 5.0 (n=4) 55°25’ Ventes R. 61 (n=10) 2.0 (n=15) 3.7 (n=15) 56°14’ Öland 76 (n=21) 8.3 (n=15) 3.5 (n=15) 56°17’ Breanäs 79 (n=21) 2.8 (n=12) 2.8 (n=12) 56°50’ Salaspils 454 (n=20) 10.7 (n=15) 17.9 (n=15) 58°20’ Vilsandi 79 (n=9) 1.5 (n=9) 2.2 (n=9) 58°21’ Gotska s. 60 (n=24) 2.0 (n=15) 3.0 (n=15) 59°17’ Stockholms s. 80 (n=21) 1.3 (n=10) 2.4 (n=10) 59°30’ Lahemaa 49 (n=16) 0.8 (n=12) 1.8 (n=12) 63°02’ Vasa 32 (n=27) 0.9 (n=12) 1.2 (n=12) 63°03’ Docksta 50 (n=24) 1.8 (n=15) 2.6 (n=15) 63°32’ Norrbyn 48 (n=24) 1.8 (n=17) 3.2 (n=14) 63°36’ Holmögadd 57 (n=23) 4.9 (n=12) 5.7 (n=12) 64°31’ Bjuröklubb 38 (n=24) 2.9 (n=13) 2.2 (n=13) 65°44’ Kalix 47 (n=24) 2.4 (n=14) 1.5 (n=14) All stations 57 (n=299) 2.3 (n=192) 2.7 (n=192) Further data on POPs in Estonian, Latvian and Swedish air is published in the - State of Environment in Estonia on the threshold of XXI century (EEIC 2002). Most data is from Germany (Government/Laender Working Group on Dioxins 2003) (http://www.umweltbundesamt.de/uba-info-daten-e/index.htm>) and from Denmark (Vikelsre et al.2003) and they do not cover the Baltic Sea area. Summertime deposition data is also available from Finland from recent years (Korhonen et al. 2002). An example of PCDD/F deposition trend from early 1990's to 2002 in different location in Germany (urban, rural, backround) is given in Fig. 10, which shows a clear decrease in all locations during early 1990's and minor decrease or levelling off during recent years.
0
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1990 1995 2000 2005
Year
Dep
os. (
pg I-
TEQ
m-2
d-1)
FrankfurtHünfelden Crumstadt
Fig. 10. Time trends of PCDD/F deposition in three locations in Germany (Frankfurt-urban, Crumstadt-rural, Hünfelden-backround). Deposition in Frankfurt in 1990-1991 was over 100
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 33
pg I-TEQ m2 d-1 (Data from UBA - source Hessisches Landesamt für Umwelt und Geologie).
A clear seasonal trend in air and to minor extent in deposition has been observed both in German and Danish data (Fig. 11).
Fig. 11. Seasonal variation in bulk deposition in Crumstadt, Germany (a) and in air, bulk deposition and throughfall in North Zealand, Denmark b) ( German data as in fig. 10, Danish data Vikelsre et al. 2003).
There are recent data on PCB-congeners (e.g. Brorström-Lunden et al., 2003). Atmospheric transport of PCB has been shown to exist. Using PCB-180 as a marker for the present situation indicates that the air levels have not decreased during the last 5 years. These findings are in accordance with the data from fish that no further decrease in PCDD/F is observed. Unlike PCDD/Fs seasonal variation shows highest concentrations during the summer months (Fig. 12).
020406080
100120140
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Sum 7 PCBpg/m3
IUPAC: 28,52,101,118,153, 138, 180
Fig. 12. A time trend of certain CB-congeners in air in Rörvik, Southern Sweden (Brorström-Lunden et al. 2003).
0
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Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 34
Biota. There are several different time series for the levels of PCB in fish from the Baltic – e.g. herring, cod, perch, and blue mussel, as well as guillemot eggs. The fish analysed were 2-5 years of age. A sample from the muscle without skin was used for analysis (except for cod where the liver is used). The concentration of PCB is decreasing at a rate of approximately 4 - 10% per year in herring (Fig. 13) and cod from the Baltic as well as from the Kattegat and in guillemot eggs (Fig. 14) and perch from the Baltic since the end of the seventies. During the last 10 years however, the decreasing trends seem to have levelled out at Landsort and Utlängan (autumn).
Figure 13. Time series of the sum of PCBs in herring muscle (microg/g in lipid) Samples of 2-3-year-old female Baltic herring were caught during the years 1995-2002 from the two areas in the Gulf of Finland (Tallinn and Kunda) and from the north-eastern part of the Gulf of Riga (Pärnu Bay) (EEIC 2002). The aim of these investigations was to measure levels of POPs in the fish at specific locations over time in order to detect whether levels are changing in response to the changes in inputs of contaminants to the Baltic Sea.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 35
0.0
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1.0
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1.4
1994 1995 1996 1997 1998 1999 2000 2001 2002 2003
mg/
kg li
pids
sPCB sDDT
Fig. 14. Contents of sDDT and sPCB (mg/kg lipids ) in the muscle tissue of Baltic herring from different parts of the Estonian coastal sea (Roots and Simm 2003). This particular survey proceeds from the results obtained within the framework of the Estonian National Monitoring Program and several other research programs. Figure 14 shows that the concentrations sDDT and sPCB in the tissue of Baltic herring have decreased during years 1995-1998, but there is a certain rise after 1998. However, the reasons for this rise are not clear. Peak of dioxin concentrations in sediments with subsequent decrease is in agreement with what has been found in guillemot eggs. Four time series are available for TCDD/TDCF, one in guillemot eggs (Fig. 15; Stora Karlsö, Gotland) and three from herring. The fish analysed were 2-5 years of age. A sample from the muscle without skin was used for analysis. Significant decreasing trends are observed for TCDD, TCDF and TCDD-equivalents. The development over time is quite different for TCDD and TCDF, see Fig. 16. The decrease of TCDD-equivalents has not continued to decrease significantly during the recent 10 years. The number of years required to detect an annual change of 5% varied between 8 and 13 years for the last ten years.
Fig. 15. Time series of PCDD/F concentrations in guillemot eggs
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 36
Fig. 16. Time series of PCDD/Fs in herring muscle (pg/g WHO-TEq in lipid) [or I-TEq??] The Russian data confirmed a rather high level of pollution in the Baltic seafood by PCDD/Fs. Highest PCDD/Fs concentrations were analysed in Baltic herring (Clupea harengus membras) – 11.46 pg/g (as I-TEq in fresh weight)(Shelepchikov et al., 2003).
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age, years
pgTE
Q/g
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wei
ght
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Figure 17. Dioxin concentration (pg/g wet weight in TEq) in Estonian (Roots, et al., 2003) and Finnish (Isosaari et al., 2003; Kiviranta et al., 2003) Baltic Sea herring muscle tissue.
TCDD-eqv., pg/g lipid w., herring muscleHarufjarden
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n(tot)=83,n(yrs)=10m=24.8 (20.4,30.1)slope=-.62%(-7.5,6.3)SD(lr)=.29,11%,16 yrr2=.01, NS
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n(tot)=128,n(yrs)=11m=26.6 (21.5,32.9)slope=-3.6%(-9.3,2.1)SD(lr)=.30,9.4%,16 yrr2=.18, NS
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n(tot)=84,n(yrs)=11m=8.67 (7.32,10.3)slope=-.36%(-6.1,5.4)SD(lr)=.27,8.3%,15 yrr2=.00, NS
pia - 03.10.10 12:17, dxqcat
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 37
2.5 Food 2.5.1 Background and outline The Environment and Health Strategy has a clear and specific focus on children health. The present TWG, “ Integrated monitoring of dioxin & PCBs in the Baltic Region ”, is thus aimed at monitoring of dioxins and PCBs to improve the causal links between environment and health, specifically children health. Subsequently, central in this context is children exposure to dioxins and PCBs. Critical (adverse) exposure windows of children are both prenatal (foetus) and postnatal (breast-feed infants), periods when children are directly exposed to the accumulated maternal body burdens. It is estimated that more than 90 % of the human dioxin/PCB exposure derives from food and that food of animal origin contributes to about 80 % of the overall exposure. Thus, by concluding that food is the major source of human exposure, the effort should be concentrated on foodstuffs relevant to human exposure.
This will be achieved by getting comparable data from the Baltic region to estimate levels of dioxins and PCBs in food and compare regions, countries and time trends. The three initial steps to reach the goal of better human exposure estimates would therefore be: 1) Integrated monitoring of dioxin and PCBs in food 2) Integrated human dietary questionnaires 3) Integrated human intake estimations of dioxins and PCBs
The countries representing the “Baltic Region” are Finland, Estonia, Latvia, Lithuania, Russia, Poland, Germany, Denmark and Sweden. However, today the present knowledge for the Baltic region, and the rest of the European union, as a whole is far from complete and accordingly, such integrated measurements need to be undertaken as a first step. Once this integration (harmonisation of methods and co-ordination of programmes) is achieved and the human exposure (i.e. intake) is documented, further actions regarding specific food items and sources can be taken to reduce the human exposure for dioxins and PCBs. 2.5.2 Identification of the need for “Integrated monitoring of dioxins & PCBs” in
foodstuffs
For food, the commission recommendation “on the monitoring of background levels of dioxins and dioxin-like PCBs in foodstuffs” (SANCO/4546/01 – rev.3) will (during autumn 2003) be published in the official Journal of the European Communities. Its recommendations are country wise and are specified to a number of analyses per food group (e.g. beef, pig, fish and fishery products, dairy, animal fats, fruits etc.). The numbers are based on the production in each country (Annex 1, SANCO/4546/01 – rev.3). The total number of samples that will be analysed within the Baltic region in this programme is 312 samples. For all foodstuffs of animal origin in the monitoring programme that have a “farmed origin”, the proposed methods for sampling are at present acceptable and can be viewed as harmonised (SANCO 2002/69/EG). The reasons for this are basically two; 1) the tissue analysed is specified to fat (or egg), 2) the variation of fat content in domesticated animals and the final products thereof, are relatively low. Thus, concerning monitoring of these foodstuffs, the already existing principles (analysis and sampling methods) are basically adequate and can be used in the integrated monitoring. Once the acceding countries become members, also those countries will get national data that are comparable with the rest
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 38
of the EU. What are lacking are an overall co-ordination of the sampling design and a longer time series of an increased number of analyses. However, the most inhomogeneous food group is fish and fish products for which the situation is markedly different. This is due to a large number of different species and the extremely large difference in fat content between lean species (e.g. cod 0.7 %) and fatty fish (e.g. eel 30 %), geographical differences in the level of contamination in (e.g. Baltic Sea vs. e.g. Atlantic Ocean) and large variations (national and within a nation) in what is considered edible portion. This in combination with large differences in national dietary intake habits for fish and fish products result in large variation in fish and fish product consumption (e.g. SCOOP Report Task 3.2.5, 2000) Table 1. Subsequently, the sources and levels of human dioxin and PCB exposure from fish have large national variability. The following compilation is not intended to cover all historically performed dioxin and PCBs fish surveys undertaken in the Baltic region. It will sooner try to give the reader a current picture of the dioxin and PCB content in the Baltic region, with special emphasis on fish, using the most recent data available. It will also illustrate the big complexity that characterise sampling and analysis of wild fish intended for food consumption in a large and heterogeneous water body such as the Baltic Sea. The Baltic Region is used as an area to exemplify what problems an integrated monitoring of dioxins and PCBs would have with the present non co-ordinated survey activities/monitoring. It will also try to highlight the advantages with such integration and what is needed to take into account when designing such activities at EU-level. 2.5.3 Fish contribution to human dioxin/PCB TEq-exposure Baltic region. In Sweden, fish stands for as much as 33-38 % of the human PCDD/DF-TEQ-exposure (Lind et al. 2002) and in Finland 63-83 % (for Finnish results, depending on the calculation methods; upper bound and lower bound method, respectively) is estimated to derive from fish consumption (Kiviranta et al. 2001). The corresponding numbers in other countries in the Baltic Region with a historic/traditional influence from the Baltic Sea, such as Estonia, Latvia, Lithuania and Poland, are not known at present. However, since these countries do catch fish from the same stocks of fish as Sweden and Finland, the contribution can be suspected to be within the same range. In Finland, herring alone contributes with 52 % and in Sweden fatty fish from the Baltic Sea region with 19-22 % to the daily human PCDD/DF intake. Countries outside the Baltic region. Also in countries outside the Baltic Sea region, fish contribute significantly to the daily human PCDD/DF exposure, e.g. Italy (Venice region) 42-50 %, Norway 28-43 %, UK 8%, Germany 17%, Spain 15 % and Holland 10 % (Zanotto et al. 1999; Becher et al. 1998; Harrison et al. 1998; Vieth et al. 2000; Malisch 1998; Domingo et al. 1999; Freijer et al. 2001). 2.5.3.1 Present levels in fish from the Baltic region Since 2000 to 2003, different Baltic region countries have undertaken more or less extensive dioxin/PCB surveys on fish. To our knowledge, Finland, Estonia, Latvia, Germany and Sweden have reported on data from Baltic fish. Since the dioxin/PCB in most animals accumulate in the lipid fraction of the animal, the adequate focus of dioxin/PCB in the Baltic region has been analyses of a number of fatty fish species with high commercial interest as well as impact (i.e. consumption) on the public health. The species in question are herring (Clupea harengus L.), sprat (Sprattus sprattus) and salmon (Salmo salar). However, due to different methodologies in sampling and analyses of PCDD/Fs in fish from the Baltic Region
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 39
an assessment and comparison of the studies is difficult. Therefore, a table summarising all the results from different surveys would not fulfil any comparable purpose. Instead, we report some of the results that are comparable and illustrative regarding the regional and age related differences that prevail. 2.5.3.2 Herring The data presented in Fig. 18 represent levels of PCDD/DF in herring with skin, caught in spring or the autumn from Finland (Kiviranta et al 2003 and personal communication), Estonia (Otts and simm, 2003), Latvia (Maris Balodis, personal communication) and Sweden (Bjerselius et al. 2003). According to ICES, the Baltic Proper stock also covers the herring in the Gulf of Finland and the Gulf of Riga. The different figures illustrate the most recent PCDD/DF herring analysis from the different stocks in the Baltic Sea region. The results clearly show that the concentrations are highly and significantly correlated with age of the fish. It is noteworthy that in all four stocks, the age classes 1-4 seem to have average PCDD/DF levels below the maximum limit, while the rest are above. For the dioxin-like PCBs, data from the results in Fig 18 are available only from the Finnish and Swedish surveys. The results show that the percentage contribution from the dioxin-like PCBs to the total TEQ are 34% in the Bothnian Bay and Bothnian Sea stocks (Finnish data), 47 % in the Baltic Proper stock (Swedish data), the Gulf of Finland region has 43% contribution (Finnish data), and Rugen stock has 52% contribution (Finnish and Swedish data). A German study from 1999 of dioxin and dioxin-like PCB in herring show results that are in accordance with this (personal information, Karl and Ruoff, Federal Research Centre for Fisheries and Federal Dairy Research Centre). From four locations in the southern Baltic Proper area (see “G” in Fig. 18) the average percentage dioxin-like PCB contribution to total TEQ was approximately 44 % (range 34-56 %). The corresponding number from three samples from the Rugen stock is 60 % (range 56-65 %). However, in their sample preparation the skin was removed (but not the subcutaneous fat layer) before analysis and no age determination was made and therefore the results are not comparable regarding levels with the results in Fig. 18. However, the contribution from the dioxin-like PCBs is substantial and seems to increase the further south (and west of Bornholm) in the Baltic region the samples are collected.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 40
Fig. 18.
S
Norway
Sweden
Bothnian Sea
Bothnian Bay
Finland
Skagerak
Kattegat
BalticProper
Gulf of Finland
12 º E 20ºE 28ºE
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Herring Bothnian Bay - PCDD/DF
y = 2,6693x - 4,3793R2 = 0,767
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Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 41
2.5.3.3 Time series to follow trends Today, only three time series are available for dioxins and dioxin-like PCBs in herring (see environmental monitoring section). To be able to conclude that levels in different fish species are going up or down, time series from different parts and species of the region has to be established within the integrated monitoring project. 2.5.3.4 Other fatty fish species Other fatty fish species such as eel (Anguilla anguilla), brown trout (Salmo trutta) and whitefish (Coregonus lavaretus) are of less commercial interest, but are popular species for recreational fishing. Thus, it is important not to neglect these species in an integrated monitoring since the recreational fishing activities in some Baltic countries are substantial. Estimates in Sweden, based on a postal questionnaire in 1999/2000 sent out to 7000 randomly selected 15-75 years old permanent residents, revealed that about 3.4 million, or 55 %, of the selected population, showed an interest in recreational fishing (Finfo, 2000:1). The total catch amounted to 58.2 million kg, with an average catch of 18 kg per person. This should be compared with the estimated annual Swedish consumption of fish and shellfish, which is approximately 14 kg (Report 26 – 2002, Swedish National Food Administration). In Finland it was estimated in 2000 that there was about 2 million recreational fishermen. The total catch in both sea and inland lake areas was 41 million kg, with an average catch of 20.7 kg per person (Finnish Fisheries Statistics, 2002). The important point to make with this is that the group “ recreational fishermen”, including their families with children and pregnant women, consists of potential high consumers of fish and subsequently belong to the identified risk groups for dioxin and PCB exposure. However, this large population group is not covered by maximum limits, neither national nor EU-based. Here, information activities with dietary recommendations are a possible tool to improve the children health. 2.5.3.5 Final products In Sweden, public, industry and authorities are more and more often asking for levels of POPs in final fish products. It is indeed an adequate question since the final product often is processed in a way that might change the level of dioxins and PCBs (e.g. final product of herring without skin has a reduction of approx. 50 % of the dioxins and PCBs). Fish and fish products are special in this respect since many products are eaten without the skin, smoked, grilled or processed in ways that might change the fat content, and thereby also the dioxin and PCB content. To be able to perform correct intake estimations of the European population, such analyses should be made and taken into consideration when intake estimations are performed within the Environment and Health strategy.
2.5.4 Contribution and intake from major food groups in Europe Table 9 gives an overview of the food groups in Europe that contribute most to the human intake of dioxins. Please note that the dioxin-like PCBs are not included and all data here is as upper bound data.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 42
Table 9: Average percent contribution of dioxins (I-TEQ) from major food groups. Adults or total population. Table from SCOOP report Task 3.2.5 (Dioxins). % contribution from
Country Food consumption data
Occurrence data
Total intake pg/d
Dairy products
Meat, poultry
Eggs Fish Other foods*
FI Finsurvey 1997 1991-99 61 16 6 4 63 11 FR National survey 1998-
99 1998-99 97 33 13 2 26 26
DE 1985-89 1995-98 51 39 30 11 11 9 IT INN-CA 1995 45 26 32 7 35 - NL National survey 1987-
88 1990-91 82 39 20 4 2 35
NO NORKOST 1997 1989-96 29 22 14 12 46 6 SE Riksmaten 1997-98 1996-99 68 19 31 2 34 14 UK Adult survey 1986-87 1992 88 25 20 4 6 45 Range 1989-99 29-97 16-39 6-32 2-12 2-63 6-45 *other foods = cereals and cereal products, vegetables, fruit, vegetable fats and oils Of the 8 countries included in the SCOOP report, the four groups “dairy products”, “meat and poultry”, “fish” and “other products” contribute on average with almost equal amounts of dioxin-TEQ units (27, 21, 28 and 21 % respectively), representing 97 % of the total intake of dioxin-TEQ. Thus, for the “average country” in Europe, approximately ¾ of the dioxin exposure come from food groups other than fish. In a “Baltic Region” versus “other European” country comparison, the major differences are that the groups “dairy products” and “other foods”, each contribute with approximately 12 % less for Finland and Sweden and that the “fish group” contribute with approximately 28 % more in those countries compared to the others. This indicates that fish would have a stronger impact on the dioxin intake in the Baltic Region countries compared to other member states. Subsequently, a better knowledge of the fish intakes would help to reduce the body burden for populations with a significant intake of Baltic region fish products. In a similar fashion, the foodstuffs that contribute most to the dioxin and PCB exposure in other member states should be identified in manners similar to the present report and an integrated monitoring for dioxins and PCBs constructed. More recent estimations of the average percent contribution of dioxins and PCBs from fish have shown that the Netherlands has 16 % (Freijer et al. 2001), and the UK 20-30 % (lower bound and upper bound data, FSA report 38/03), respectively. The SCOOP-report indicates that also for countries outside the Baltic region fish contribute significantly to the dioxin exposure (21 %) but that the Baltic countries have a relatively bigger contribution from fish (49 %) (numbers calculated from Table 9). The report also highlights the fact that in many cases, results from the dioxin-like PCBs were not available at the time of the report (2000). Further, the big variances between countries regarding the dioxin contribution might illustrate actual differences in consumption habits but can also indicate different methods of collecting the raw data (e.g. tissue analysed, dietary questionnaires, intake estimations etc.). Thus, relevant for all food groups and countries is a need for an harmonised monitoring for dioxins and PCBs to be able to make correct human intake estimates.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 43
2.5.5 Human intake of dioxins and dioxin-like PCBs The last compilation of intake of dioxin and PCBs was done 2000 and resulted in the SCOOP report Task 3.2.5 (Assessment of dietary intake of dioxins and related PCBs by the population of EU Member States; 7 June 2000). Here, we will briefly cut out the most recent results from this comprehensive report, to illustrate the status at the time of the report, 2000. Since the data on dioxin-like PCBs were very scarce in the report, only PCDD/F levels are considered in this paragraph if not otherwise mentioned. Numbers in parenthesis represent intake per kg bw and day. Germany and UK provided PCDD/F data from infants with an intake from breast milk at 4 months of age (fully breastfed), of 370 (57) and 531 pg TEQ/d, respectively. UK also provided intake data for PCBs at 283 pg TEQ/d for 4 months old infants indicating a dioxin/dioxin-like PCB ratio of 1.9. For children and adolescents (1.2-18 years old), UK, Germany and France reported data of 49 (3.38), 22 (1.61) and 72-78 (2.28-1.31) pg/d (I-TEq), respectively. Thus, the data showed that the intakes ranged from 22 pg/d among German toddlers to 78 pg/d among British school children and French adolescents. UK also provided intake data of infants for PCBs at 31 (2.17) pg/d indicating a dioxin/dioxin-like PCB ratio of 1.6. The following levels of PCDD/F were reported for the adult populations in: Finland 61 (1.01), France 97 (1.45), Germany 49 (0.72), Italy 45 (0.74), Netherlands 41 (0.59), Norway 29.0 (0.39), Sweden 79 (1.07) and UK 88 (1.26). Finland, Norway, Sweden and UK also provided intake data for PCBs at 50.5 (0.84), 110.2 (1.5), 58 (0.0.79) and 56 (0.81) pg/d, respectively. Recent data from Germany (Mathar, 2003) report 90.5 (1.3) pg/d. The ratios for dioxin/dioxin-like PCB ranged from 0.26 in Norway to 1.6 among British adults. The results show that the daily PCDD/DF intake per kg body weight and day, range from a breastfed infant value of 57, children and adolescents between 1.3-3.4 to adults with values between 0.49-1.4. This indicates a 40-100 fold higher exposure of infants compared to adults and a 2.5-fold higher exposure of children/adolescents compared to adults. Further, the large range in ratios of dioxin/dioxin-like PCB 0.26 –1.6 indicate big differences of sources of contamination and/or different consumption habits between countries. The total daily intakes for dioxins and PCBs in the SCOOP report were between 111-145 pg TEQ/d or 1.85-2.07 pg TEQ/kg bw/d (data only from Finland, Norway, Sweden and UK). This indicate that the countries in the report had a relatively even total-TEQ exposure of the adult population but that the average daily intakes are close to the SCF TDI value of 2 pg TEQ/kg bw /day. 2.5.5.1 Updated intake information Since the SCOOP report was released in 2000, The Netherlands (Freijer et al. 2001), UK (FSA report 38/03), Sweden (Lind et al. 2002) and Germany (Mathar 2003) have collected and reported updated intake estimates that are somewhat different from the SCOOP report. The Netherlands has provided data from 3 different age groups calculated by the statistical exposure model (STEM). The age classes were 2, 10 and 40 years old median intake per kg body weight and day, respectively: dioxins=1.5, 0.75, 0.56; dioxin-like PCBs=1.30, 0.68, 0.50 pg/kg (WHO-TEq). The population average total daily intakes for dioxins and PCBs
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 44
were 1.3 pg/kg bw/d or 90 pg/d. The contribution from fish was estimated to be 16 %, compared to only 3 % in the SCOOP-report. The UK has provided data from many different age-classes. To be able to compare with the Dutch data, the age classes closest to the Dutch data (2, 10 and 40) are listed according to 1.5-2.5 years, 7-10 years and adults, respectively: dioxins=1.1, 0.7, 0.4; dioxin-like PCBs=1.1, 0.7, 0.5 pg/kg bw/d. The population average (1-70 years old) total daily intakes for dioxins and PCBs was 0.7 pg/kg bw/d. The new Swedish estimate reported an adult (17-74 years) median intake for dioxins = 0.62; dioxin-like PCBs = 0.44. The median total daily intakes for dioxins and PCBs was 1.1 pg/kg bw/d. Corresponding numbers for Germany are: dioxin = 0.7; dioxin-like PCBs = 1.3 and the total daily intakes for dioxins and PCBs was 2.0 pg/kg bw/d. The new results provide data showing that the intake seems to decrease in those countries. However, still the total-TEQ exposures of the adult population are close to the SCF TDI value of 2 pg/kg bw /day. 2.5.5.2 Intakes of some European populations in relation to the tolerable daily intake
(TDI) To protect the general population against the adverse health effects of dioxins and dioxin-like PCBs, health safety objectives such as the TDI have been derived (SCF). Thus, of special interest is to compare the percentage of a population that is estimated to be above the SCF TDI of 2 pg/kg bw/day. This has been done for The Netherlands (2001), UK (2003) and Sweden (2002). UK=1.1 % (adults); 10 % (children); 37 % (toddlers). The Netherlands: 8 % (the whole population, 1-70 years old). Sweden: 12 % (17-79 years old). Interestingly, despite the indications of significant decreased levels in foodstuffs and subsequent intake, such high numbers as 8 and 12 % of populations in some member states in the European union are still estimated to exceed the tolerable intake of dioxins and dioxin-like PCBs. Because the risk assessment is based on developmental effects using maternal body burden as the exposure metric, it would be important to know the dioxin and PCB intake in the female population before the first pregnancy. 2.5.5.3 Time trends regarding exposure from food of the general population in Europe The SCOOP report concluded that the data reported from some countries (Finland, Germany, Netherlands, Sweden and the UK) was sufficient to reveal that the exposure of the general population was declining. A similar trend was seen also for concentrations in breast milk. 2.6 Feed As dioxins and PCBs enter the human body mainly through food and as food from animal origin is the main contributor to the intake, it is very important to monitor feed, although compound feedingstuffs are not the only source of intake for the animals. Free-range animals are subject to intake of dioxins and PCBs from soil and dust on plants they eat, or from soil animals they eat (free range chicken can eat earth worms). Contaminated fodder (silage) can be a source in areas with high levels of air deposition of dioxins/PCBs. Compound feedingstuffs can be contaminated because of air deposition on plants, because of the inclusion of fish oil of meal from contaminated waters or because of the inclusion of animal fat. This is partly unavoidable, but e.g. fish oil can be refined to reduce contamination.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 45
A list of special cases was identified such as incorrect drying procedures, naturally contaminated mineral additives, and illegal disposal of PCBs, etc. Feed monitoring is very important to identify unexpected sources, which can have a major impact on intake of consumers. Feed monitoring has the advantage that measures can possibly be taken in time to prevent the consumer to eat unusually high-contaminated foodstuffs. A good summary on the issue of dioxins in feed can be found in the opinion of SCAN (http://europa.eu.int/comm/food/fs/sc/scan/out55_en.pdf ). European harmonised maximum levels for PCDD/F are fixed in directive 2002/32/EC, as modified by directive 2003/57/EC. Monitoring activities in the member states are reported in the frame of Directive 95/53/EC. E.g. in Table 10 an extract of the Belgian report for 2002 is given. Each year a recommendation for a coordinated control programme for feed is issued. Recommendation 2002/214/EC for the year 2002 and Recommendation 2003/91/EC for the year 2003 include dioxins. Results on dioxins, dioxin-like PCBs and non-dioxin-like PCBs are also sent for each sample for all congeners in excel format to the EU Commission dioxin/PCB database, similar as for food, in order to have a scientific basis to include the dioxin-like PCBs in the legislation with maximum levels in the future, and to evaluate whether the maximum levels can be reduced in the future. Deadlines for such evaluation are included in the directive and are similar as for foodstuffs. Table 10. Extract of the 2002 report of the Belgian Federal Agency for the Safety of the Food Chain, in the frame of directive 95/53/EC.
Number of analyses Aliments composés Feed
materials Additives Pre-mixes cattle sheep pigs poultr
y rabbits horses other Total
Type of analysis T NC T NC T NC T NC T N
C T N
C T N
C T NC T N
C T NC T NC
PCB 284 1 3 0 390 0 3433 1 145 0 5003 1 1073 1 137 0 447 0 253 1 11168 5 Dioxin 22 0 80 0 - - 269 1 10 0 344 1 84 1 10 1 26 0 14 0 787 4
Dio
xine
an
d P
CB
Total 306 1 83 0 390 0 3702 2 155 0 5347 1 1157 2 147 1 473 0 267 1 11955 9
(T=total ; NC=not conform) PCB = non dioxin like PCBs (ICES 7) Dioxin = PCDD/F Methods for sampling and analysis are described in directive 2002/70/EC. Recommendation 2002/201/EC is another example of integration of food and feed monitoring. It contains the principle of action levels when tracing to the source of contamination and measures to eliminate or reduce the source are requested, in cooperation with environmental authorities. On the level of Codex Alimentarius, document CX/FAC 03/32 “Position paper on dioxin and dioxin-like PCBs” summarizes the situation of occurrence in food and feed, dietary intake, risk assessment, time trends, concentrations in human milk, current regulations on dioxins in food and feed and methods of analysis. Each year, an update is issued and possibilities for risk management are discussed during the annual meetings of the Codex Committee on Food additives and contaminants (including feed). Another document, CX/FAC 03/33 is the draft code of practice for source directed measures to reduce dioxin and dioxin-like PCB contamination of foods. This document will be redrafted under the leadership of Germany.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 46
2.7 Food monitoring activities commenced due to EU recommendations Denmark was obliged by SANCO 4546/1 to analyse the following 128 food samples: beef, sheep, poultry, and liver, each 3 samples, pigs 5 samples, wild fish 39 samples, aquaculture fish 5 samples, and milk, butter, eggs, free-range eggs, animal fats, vegetable oils, vegetables, fruit and cereals, 3 samples each, and fish oils 42 samples. Finland was obliged by SANCO 4546/1 to analyse the following 52 food samples: beef, pig, sheep, poultry and liver, each 3 samples, wild fish 4 samples, aquaculture fish 3 samples, and milk, butter, eggs, free-range eggs, animal oils, vegetable oils, fish oils, vegetables, fruit and cereals, 3 samples each. Because Baltic fish was considered the main problem, concentrations in all other foodstuff in Finland being very low, the decision was made to analyse ample coverage of Baltic herring, sprat and salmon. Other items were planned to meet the requirements, although some additional items have been added such as reindeer and elk. On various items results obtained by the end of 2002 were already reported (32 samples). In beef (0.23 pg/g, I-TEq in fat, n=5), pork (0.051, n=6), eggs (0.52, n=5), milk (0.12, n=5), and in all items of plant origin the PCDD/F levels (I-TEq) were clearly below the limit values. Another three samples of beef liver, pig liver, sheep, reindeer, elk, poultry, eggs, vegetable oils, berries, and mushrooms will be analysed in 2003 (in all 33 samples). Among fish, already reported samples indicate that in old Baltic herring and in wild salmon the limit values are exceeded, but in other fish the levels are below the limit with the exception of an occasional large and old fish. Some of these results were also published (Isosaari et al, Org Comp 62:41, 2003). In herring there is a correlation in both PCB and PCDD/F concentrations to age and somewhat lower correlation to length. Geographic differences are best described by herring samples, which show that in the Gulf of Bothnia the dioxin, but not necessarily PCB concentrations are higher than in the Gulf of Finland. This may be due to different food habits (possibilities) or due to different exposure sources. Altogether 240 samples have been analysed representing 1036 individual fishes and 145 pools of 3-10 fishes each, and 90 individual Baltic herring. Analysis plan for 2003 includes 26 additional analyses encompassing 148 individual fishes. Germany was obliged by SANCO/4546/01-rev 3 to analyse 147 food samples: beef and pigs each 13 samples, sheep 3 samples, poultry 6 samples, liver 7 samples, fish 7 samples, aquaculture products 5 samples (2 mussels, 2 trout, 1 carp), milk and milk products each 14 samples, eggs 10 and free range eggs 11 samples, animal oil and fat 12 samples, vegetable oil 14 samples, oil and fats from fish and food supplements 4 samples, vegetables 4 samples, fruit and cereals each 2 samples Germany reported the result of 92 food samples analysed from 1999 to 2002 to the commission (dioxin, furan, dioxin-like PCB): 11 samples of meat and meat products (beef 5, pig 4, poultry 1, game 1, 13 samples of fish (herring 12, farmed salmon 1), 60 samples of milk and milk products (including 50 milk and 10 butter samples), 9 samples of eggs (including 3 eggs from free range hens).
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 47
Sweden was obliged by SANCO 4546/1 –rev.3 to analyse 54 food samples: beef, pigs and poultry each 3 samples, sheep and liver each 2 samples, wild fish 10 samples and aquaculture fish 3 samples. Milk, milk products, conventional eggs and free range eggs 3 samples each. Animal oils 2 samples, vegetable oils 3 samples, fish/food supplement 4 samples. Vegetables 3 samples and fruit and cereals 2 samples each. In addition to the above 2 more egg samples from free-range eggs and 6 additional fish samples (herring and sprat) will be analysed. Overview of all countries combined: Basically the results indicate quite clearly that there are problems with Baltic herring and salmon. In herring the concentration is age-dependent as shown in Fig. 18. Site-dependence requires more work. Several points to be considered in future have been presented in the chapter Problems and difficulties. 2.8 Human exposure studies within the catchment area of the Baltic Sea Dioxins and PCBs have a long half-life in humans (e.g. TCDD 7 to 8 years). This causes a lifelong cumulation of these substances, and indeed in a recent Finnish study on appendicitis patients thought to represent a random selection of the population, concentrations in 20-year old people were 5-20 ng/kg (WHO-TEq in fat) while in 60-year old population the levels were 20-100 ng/kg (Fig. 19). The steep increase may be partially caused by carry-over from earlier decades in the older generations.
Fig. 19. PCDD/F concentrations in Finnish population ng/kg (WHO-TEq in lipid). There is no significant difference between males and females nor between appendicitis patients (controls) and soft-tissue sarcoma patients (Tuomisto et al., 2003). Results of an exposure and effect monitoring program for children showed slight differences in PCDD/F body burdens between boys and girls, breastfed and not breastfed children. This monitoring of 9 to 11 year old children in the federal state Baden Württemberg was initiated in 1992. The 4 locations are representative of rural, urban and urban-industrial areas. The investigations are carried out every other year. In addition to exposure to chemicals (e.g. heavy metals, chlorinated organic compounds), health effects (e.g. respiratory diseases,
0
20
40
60
80
100
120
140
160
0 20 40 60 80 100
Age, years
WH
O-T
Eq,
ng/
kg
CasesControls
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 48
allergies) are documented. For PCDD/F analysis 16 pooled blood samples, each consisting of 5 to 30 single samples (boys, girls, breastfed and not breastfed), are used. In 2000/2001 the analysis also included dioxin like PCBs (Landesgesundheitsamt Baden-Württemberg, 2002).
PCDD/F concentration in blood
0
2
4
6
8
10
12
1992 1994 1996 1998 2000 2002
pg I-
TEQ
/g fa
t
Mannheim
Stuttgart
Kehl
Aulendorf
Fig 20. Trends in blood PCDD/F levels of children aged 9 - 11 Table 11. Blood PCDD/F levels - boys and girls, breastfed and not breastfed, pg/g (WHO-TEQ in fat), pooled blood samples. Data from 2001/2002 (not detected congeners included with half the detection limit).
Location Area Boys Girls Breast-fed
Not breast-fed
Mannheim Urban/industrial 6.4 4.7 5.1 5.7 Stuttgart Urban/industrial 7.6 4.4 9.4 5.6 Kehl Urban/rural 7.4 6.4 7.7 3.6 Aulendorf Rural 8.4 6.2 8.3 5.3
As shown in Table 11, blood dioxin levels in boys are higher than in girls. Also in 3 of the 4 locations breastfed children have higher blood dioxin levels. Table 12. Weighted average for non-ortho and mono-ortho PCBs in pooled blood samples, data from 2001/2002, pg/g (WHO-TEQ in fat)
Location Numbers Non-ortho PCB Mono-ortho PCB Mannheim 96 2.00 2.70 Stuttgart 79 3.45 3.43 Kehl 74 3.95 4.24 Aulendorf 84 4.00 3.75
Table 12 shows the results for dioxin like PCBs. The PCB WHO-TEQ in German children is roughly as high as the WHO TEQ of the PCDD/F. All data are available via the Internet: www.landesgesundheitsamt.de in German. Influence of fish consumption on human exposure has been clearly demonstrated (Fig. 21). In fishermen consuming high amounts of fish, PCDD/F concentrations were 220 (range 51-520) ng/kg (WHO-TEq in fat), i.e. within the range of TCDD concentrations in Seveso B-area or higher (Kiviranta et al, EHP 110:355, 2002). Even more conspicuous in the study was that in fishermen consuming predominantly one fish species, the PCDD/F spectrum
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 49
resembled clearly that of the consumed fish, e.g. herring eaters could be differentiated from pike or bream eaters. From other food items than fish, exposure in Finland is very low, total intake was calculated in 2000 to be 0.8 pg/kg/day on an average. If also PCBs are included, intake in Finland is 1.45 pg/kg/day. Fig. 21. PCDD/F concentrations in fishermen vs. average population. How has the exposure of humans to dioxins and PCB changed over time and how is it affected by fish consumption? In 1991, blood samples were drawn from 43 males from the south of Sweden, with a wide variation in consumption of fatty fish from the Baltic Sea, for analysis of a number of persistent organic compounds including PCB:s and dioxins. In 2001 a new study on the persons in the same study group that were still alive was performed. Data for CB-153 levels are available. (Dioxin data will be available later in October 2003.) The data indicate that there has been a continuous decrease in serum levels of PCB during the 1990´s. The mean levels for the total group decreased from 363 ng/g lipid to 241 ng/g lipid. There was a 3% increase in body mass index, which may explain some of the decrease (Wallin et.al., 2003). It should be noted, however, that the individuals were 10 years older at the later time point, and at a constant intake level the expectation would be a cumulative increase of body burden with age (see Fig. 19). Therefore the result implies a clear decrease in intake level. For the general Swedish population the main route of exposure to dioxins and PCB is via food consumption. The median intake has however decreased compared to 10 years ago. About 10-12% of the general Swedish population can be assumed to have an intake above TDI (tolerable daily intake).
In Finland at the end of 1990's, fishermen versus average population
0
100
200
300
400
500
0 10 20 30 40 50 60 70 80 90age
WH
OPC
DD
/F-T
EQ, f
at
average menaverage womenfishermen
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 50
Table 13. Estimated intakes of dioxins and PCBs in Sweden. Substance Estimated intake Reference ΣPCB 1988-1993 3.2 µg/day Wicklund-Glynn et.al. (1996) ΣPCB 1998-1999 0.76-0.87 µg/day Lind et al. (2002) Dioxin 1990 246-287 pg/day (WHO-TEq) De Wit and Strandell (1999) Dioxin 1988-1993 255-300 pg/day (WHO-TEq) Wicklund-Glynn et.al. (1996) Dioxin 1998-1999 69-81 pg/day (WHO-TEq) Lind et.al. (2002) Breast milk Various organochlorine compounds have been measured in breast milk in Stockholm region from 1967 (Norén and Meironyte, 2000). Total PCBs have decreased from 1972 to 1997 by about 70 %. The 50 % decrease rate for different congeners was from 11 to 17 years. PCDD/Fs decreased from about 90 pg/g to below 30 pg/g (WHO-TEq in lipid) from 1972 to 1997. The levels of PCB in mothers' milk have decreased by 30% since 1996. This decrease is significant. It has been corrected for the age of the mother. A significant decrease is also observed for the levels of total TEq (sum of PCB and dioxins) (Glynn et.al. 2003).
Figure 22. Levels of CB-153 and total TEQ in mothers' milk from mothers from the Uppsala area in Sweden. Table 14. Summary of data on levels of PCB in blood from populations with presumed “background” levels (ng/g lipid or ng/l plasma) Area Mean levels of PCB Range Reference
136 women from the area around SAKAB, Karlskoga and Lillkyrka
358± 135 lipid
0.88± 0.37 plasma
64-718
0.15-2.06
Swedish Environmental Prot. Agency (1995)
Women living in Kiruna
353 PCB lipid 171-537 Lagerkvist, B. (1996)
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 51
Young Swedish males from Skåne (18-21 years)
68 lipid (CB-153) 23-250 Richthoff et.al. (2003)
Breast milk monitoring of primiparae mothers has been going on in several European countries in collaborative manner since 1987. A protocol of these studies is in Annex 3, and it illustrates a well-done international standardisation. In 1987 concentrations in many countries were around 30-40 ng/kg (I-TEq in fat), in some countries even higher. In Finland the concentrations were 30.8 ng/kg (PCDD/F-WHO-TEq in fat) in Helsinki (next to the Baltic Sea and typical Baltic herring consumption area) and 23.6 ng/kg in Kuopio area (where mostly lake fish, typically vendace is consumed) (Vartiainen et al, 1998). Since 1987 the PCDD/F concentrations have linearly decreased, and the most recent levels in 2000 were 9.52 and 9.35 ng/kg in Helsinki and Kuopio, respectively (Figure 23, Vartiainen et al, 1997, Kiviranta et al, 1999, van Leeuwen et al 2002). Hence the concentrations have decreased to one third in 13 years. The concentrations in different countries in 2001 are presented in Table 15. Figure 23. Decrease of PCDD/F in breast milk of primiparae mothers in Finland 1987-2000. Table 15. Levels of PCDD/Fs and dioxin-like PCBs in human milk in different countries (van Leeuwen 2002) Country
PCDDs/PCDFs WHO-TEQ
pg/g fat median range
PCBs WHO-TEQ
pg/g fat median range
Number of pools
Australia 5.65 5.50 - 5.79 3.09 2.48 - 3.69 2 Brazil 3.93 2.73 - 5.34 1.81 1.30 - 12.30 9 Bulgaria 6.14 5.08 - 7.11 4.21 3.74 - 4.70 3 Croatia 6.40 5.99 - 6.80 7.17 6.82 - 7.52 2 Czech Republic 7.78 7.44 - 10.73 15.24 14.32 - 28.48 3
Finland, mothers milk 1987-2000, primiparae mothers WHOPCDD/F-TEq
9.4
15.516.2
19.1
27.6
0
5
10
15
20
25
30
1985
1986
1987
1988
1989
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
Year
pg/g
fat
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 52
Egypt 22.79 17.16 - 51.50 6.01 4.43 - 8.26 7 Finland 9.44 9.35 - 9.52 5.85 5.66 - 6.03 2 Hungary 6.79 5.26 - 7.46 2.87 2.38 - 4.24 3 Ireland 6.91 6.19 - 8.54 4.66 2.72 - 5.19 3 Italy 12.66 9.40 - 14.83 16.29 11.02 - 19.33 4 New Zealand 6.86 6.08 - 7.00 3.92 3.50 - 4.71 3 Norway 7.30 7.16 - 7.43 8.08 6.56 - 9.61 2 Romania 8.86 8.37 - 12.00 8.06 8.05 - 8.11 3 Russia 8.88 7.46 - 12.93 15.68 13.38 - 22.95 4 Slovak Republic 9.07 7.84 - 9.87 12.60 10.72 - 19.49 4 Spain 11.90 10.41 - 18.32 11.65 9.96 - 16.97 3 Sweden 9.58 - 9.71 - 1 The Netherlands 18.27 17.09 - 21.29 11.57 10.90 - 13.08 3 Ukraine 10.04 8.38 - 10.16 19.95 14.10 - 22.00 3 Dioxin concentrations in breast milk in Russia have been relatively low implying generally low population exposure regardless of some hot spots of very high emissions (such as Ufa). In Bashkortostan 50 samples of breast milk were analysed from urban and rural areas (12 cities and 10 districts, Table 16). Table 16. PCDD/Fs in breast milk, pg/g I-TEq in lipid (Amirova, et al., 1999) PCDD/Fs Mean of cities, n=8 Mean of rural areas, n=9 Region, total TEQ 15.9± 11.2 12.8 ±11.9 14.4± 12.2 Number of donors 43 23 66 Also in other areas of the Russian Federation the results in human tissues have varied 1998-2000 from about 15 pg/g to over 30 pg/g in more polluted areas: Angarsk 14.8; Sayansk 27.7; Irkutsk 24.0, and Ufa 37.8 (Amirova and Kruglov,2001; Amirova, et al., 2003). Blood samples from urban and rural areas of Bashkortostan (12 cities and 10 districts) agree with breast milk samples (Table 17). Table 17. PCDD/Fs in blood, pg/g I-TEq in lipid (Amirova, et al.,1999) PCDD/Fs Industrial
centres Small towns Rural areas Region, total
TEQ 39.8± 10.2 25.0± 15.3 24.8± 7.5 29.9± 13.9 Number of donors
124 138 102 364
PCDD/Fs in blood samples were compared in Ufa residents and immigrants, and some difference was found (Table 18). This also implies regional variation in exposure. There are few results near the Baltic Sea, but those available from St. Petersburg also suggest relatively low levels in breast milk (van Leeuwen et al, 2002, Vartiainen, personal communication).
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 53
Table 18. PCDD/F concentrations in Ufa area. Year Group PCDD/F (pg/g WHO-TEq in lipid)1997 Residents (age 22±2) 22.8 Newcomers from Uzbekistan (age 21±3) 18.2 2000 Residents (age 38±2) 27.6 Newcomers from Kazakhstan (age 40±1) 16.0 In Poland the organochlorine compounds in food, including infant formula and breast milk were measured in mid 1990s. To assess environmental exposure to organochlorine insecticides, PCBs and HCB, samples were collected from 18 voivodships in Poland. Mean concentrations of PCBs in breast milk form 7 locations in Poland in the first half of 1990s are presented below (Goralczyk et al., 1996). In the study of several chloro-organic derivatives (PBC, HCH isomers, HCB, and DDT and its metabolites), assayed in 62 milk samples collected from 15 human milk donors from Warsaw and surroundings, PCB concentration was the highest when compared with the other compounds (mean 0.0241 mg/dl of milk or 0.723 mg/kg of fat). Substantial differences in halogenated hydrocarbons excretion with human milk were noted during lactation. No correlation between the amounts of excreted fat and these compounds levels in the milk was seen, neither the tendency to the decrease in excretion of assayed compounds with milk during lactation (Czaja K., et al., 1993). Exposure of the inhabitants of Katowice Voivodeship to PCBs was assessed within the Program of Monitoring of Environmental Health Hazards, coordinated by the Institute of Occupational Medicine and Environmental Health. Between 1992 and 1993, 200 milk samples (within three days after delivery) from the representative group of mothers (aged 15 – 43 years), living in the urban center of the Voivodeship were collected. PCBs were analyzed in the Voivodeship Sanitary Epidemiological Station in Katowice. Geometric mean concentration was 0.00761 mg/l; among four tested cities geometric mean levels ranged from 0.0044 to 0.009 (Grabecki J. et al., 1993; report of the Institute of Occupational Medicine and Environmental Health). 2.9 Health effect studies Health studies on PCBs were recently reviewed and several although not all studies suggest a subtle adverse effect of prenatal PCBs exposure on child neurodevelopment (Feeley & Brouwer 2000, Ribas-Fito et al., 2001). Postnatal exposure to PCBs through breast-feeding was not clearly related to neurological development. Recent studies from Faroe Islands, where exposure levels are 3-4-fold higher than in most other locations (Longnecker et al., 2003), demonstrated slight association of decreased weight gain with breast-feeding (Grandjean et al., 2003a. In the analysis between methyl mercury and PCBs, association to methyl mercury was clearer (Grandjean et al., 2003b). High accidental exposures of PCBs (with contaminant PCDFs) have been clearly shown to cause different health effects, notably developmental effects due to foetal exposure (e.g. Yusho and Yu-Cheng accidents, Rogan et al., 1988, Masuda 1996). Therefore the pertinent question is the level of exposure that still can cause effects. More subtle effects including
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 54
lower birth weights, alterations of thyroid hormones and lymphocyte subpopulations and detriments in neurological development have been seen in several studies. The best known of such studies are the Michigan and North Carolina cohorts and the Dutch cohort (cf. Feeley & Brouwer,2000). In the latter cohort an association was observed between human milk TEqs and plasma thyroid hormone levels. Dioxins are known from animal studies to have effects on thyroid hormone metabolism, and hypothyroidism is known to cause developmental retardation. Therefore although all of the effects found in the cohorts were very subtle, they give another reason to identify and control the environmental contamination. In the Baltic region several studies have been performed to compare the high consumers of Baltic vs. North Sea fish, especially in the families of Swedish east coast and west coast fishermen. Both cohort and case-control techniques were used to study the birth weights of babies born to fishermen's wives and sisters. These study groups can be presumed to have a high fish intake, but the concentrations were not actually measured in most studies. Several statistically significant associations between the birth weight and fish consumption were observed, the most notable being that the frequency of children born with a low birth weight (<3000 g) was doubled on the east coast for mothers with a serum CB-153 of at least 300-400 ng/g lipid (Rylander et.al. 1995, 1996, 1998). Among positive outcomes, a significantly decreased death rate from coronary heart disease among Swedish fishermen can be mentioned as compared with the general population. It can be presumed that it is related to higher fish consumption. (Svensson et.al., 1995). Also positive effect on pregnancy outcomes has been reported in fish-consuming individuals (Olsen & Secher, 2002). Birth weighs have also been studied in Finland (Vartiainen et al, 1998), and in this case exposure was measured by analysing breast milk samples after the delivery. PCBs and PCDD/Fs were analysed in 167 random milk samples, and a number of environmental and dietary parameters asked by questionnaire. The birth weights were slightly lower in correlation with higher dioxin but not PCB levels. However, when only primiparae were assessed, there was no correlation. It is very important to note this source of error, because the second child is on average heavier than the first child, and due to excretion of PCDD/Fs to breast milk, the second child is also exposed to less dioxins than the first. If the birth number of the child is not appreciated as a source of bias, higher dioxin concentrations erroneously seem to correlate with lower birth weight when in fact both of them depend on a third factor. The time to pregnancy (as a measure of fertility) for women with high fish consumption was also investigated. There was little consistent support for the hypothesis of a negative association between organochlorine exposure and fertility (Axmon et.al., 2000, 2001, 2002). Also no significant increased risk of miscarriages and stillbirths associated with high fish consumption could be observed (Axmon et al., 2000 AOEH 73:204). There is evidence from animal studies that persistent organic compounds can affect the male reproductive function. Studies were therefore carried out in men randomly recruited from the Swedish population (Richthoff et al., 1993, 2003) and in a presumably higher exposed fishermen group (Rignell-Hydbom et al., 1993) to investigate whether there is a correlation between serum levels of CB-153 and semen function parameters. The results imply that there is a tentative weak negative correlation between serum levels of CB-153 and free testosterone level and sperm motility, and that the group with the highest CB-153 level (327-
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 55
1459 ng/g lipid) had impaired sperm motility compared with the group in the lowest CB-153 quintile (<112 ng/g lipid). Animal studies have shown bone and tooth effects correlating to POPs both in field studies in e.g. seals (Bergman et al., 1992) and in laboratory studies in rats (Alaluusua et al, 1993). Peak of enamel mineralisation defects in children born around 1970 as compared with those born either before or after that time period (Koch et al, 1987) prompted studies of correlating defects to POP exposure. This was made possible by breast milk measurements in 1987, and it was shown that mineralisation defects of the first molar teeth in the children at 7 years' age were more common in those with the highest calculated exposure to dioxins from breast milk (Alaluusua et al., 1996). Adding PCBs to the analysis did not improve the correlations (Alaluusua et al., 1999). The crowns of the first molar teeth develop during the first two years of life. Increased risk of mineralisation defects was no more found in children born in 1994 (Hölttä et al, 2001), and one possible explanation is the decreasing dioxin level in breast milk. Recently tooth mineralisation defects have been confirmed in Seveso accident victims who were younger than 9 yeas at the time of the accident (Alaluusua et al, 2003, submitted). Supporting these clinical findings, developmental effects of teeth have been shown to be among the most sensitive developmental effects ever reported in rats (Kattainen et al., 2001). Recently a remarkable lowering of boy/girl ratio was reported in families of Seveso victims who had been prepubertal boys at the time of the accident (Mocarelli et al., 2000). In several studies it has been hypothesized that a decreasing trend in boy/girl ratios seen in Europe during the last decades is associated with environmental chemicals (Möller et al, 1996, Davis et al, 1998). In a 250-year retrospective analysis of Finnish population remarkable fluctuation in boy/girl ratio was found over the times, but the present decrease in the ratio started too early (around 1920) to be logically associated with pesticide use or any other synthetic chemical exposure (Vartiainen et al., 1999). In Finland a large case-control study on soft-tissue sarcoma was performed 1996-2000 (Tuomisto et al, 2003). PCDD/F concentrations were measured in 110 soft-tissue sarcoma patients undergoing surgery, and 227 age and area matched controls undergoing appendicitis operation. The range of PCDD/F concentrations was 4.4 to 145 ng/kg (WHO-TEq in fat). Surprisingly, no positive correlation of risk to PCDD/F concentration was seen, but the risk was highest in the lowest quintile (Fig. 24). This implies that the present concentrations of the normal population are not associated with increased soft tissue sarcoma risk. It is noteworthy that in no previous cancer study individual dioxin concentrations were measured, but exposure assessment was based on work history; in some studies dioxin concentrations were measured in a sub-sample of workers. Studies on high-exposure groups (e.g. fishermen) continue. There are some 8000 fishermen in Finland and more than 10 000 in Sweden available for epidemiological studies. This size of a cohort should reveal if there is any true cancer risk from high dioxin exposure.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 56
Figure 24. Risk of soft-tissue sarcoma as a function of PCDD/F concentrations in body fat (ng/kg as WHO TEq).
00.20.40.60.8
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Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 57
3 Problems and deficits For a European Environment and Health Strategy with its focus on children health, it is especially important to be able to produce accurate intake estimations regarding dioxins and PCBs, based on correct and comparable levels in foodstuffs. The same line of evidence is needed to be able to use the measured levels in foodstuffs to link to, and identify, sources in the environment. As exemplified above, the problems identified regarding present fish surveys/monitoring are numerous and refer to the complex biological situation in such a large water body as the Baltic Region.
• In general, the variables that have to be taken into account can be concentrated around a species-specific age-region-size axis.
• Depending on the species in question, different strategies must be used to get a
correct and comparable picture of the dioxin/PCB concentrations that should be used for human intake estimations.
• In addition to this, an estimation of the fish caught from the different species and
stocks intended for human consumption should be made. This is already available from the ICES statistical records.
Based on the current report, detailed instructions and recommendations for fish in the Baltic Region will follow in the next report ‘Recommendations for the Commission's Action Plan 2004-2010’, considering species of fish, stocks and regions, age, analysed tissue, congener pattern, time series, final products and annual catches. 3.1 Unfamiliarity of the requirements of other disciplines The most important obstacle of integrated studies is worldwide lack of communication between environmental and health researchers and authorities (cf. e.g. Seegal & Bowers, 2002). They rarely know enough of each other's activities to be able to utilise the data properly, and often also lack understanding of the strengths and weaknesses of the data on the other side of the border. Typically environmental data for health studies is taken from different databanks without true collaboration with people who collected the data. This also leads to ignorance of the needs of health studies when planning the data collection in the environmental side. So integrated monitoring has not developed properly. In environmental epidemiology the exposure data is often collected by questionnaires or other indirect methods dependent on memory and understanding of the study population, or on vaguely determined exposure parameters such as distance from the pollution source. This has lead to a general notion that the weakest link in environmental health studies is poor exposure assessment. On the other hand, in some diseases such as cancer, the time interval between the exposure and the disease is such that it cannot be covered in a single study
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 58
except in very long-lasting cohorts such as over 40-year follow-ups used in studying effects of tobacco smoking. This could be helped by adequate historical environmental information. There is not much information on the situation in some accession countries. An integrated monitoring program could help in assessing this in a way comparable to other European countries. 3.2 Problems of sampling techniques There are technical problems both in technical standardisation of methods of analysis (see Requirements of integrated monitoring) and in sampling and sample preparation. For this standardised protocols may exist in other areas and there should be fact finding to identify any such protocols. For instance HELCOM and OSPAR programs have had guidelines for sampling for a long time. The problem is that these are optimised for environmental measurements and not for monitoring human exposure. An example is use of small fish that are not used for human consumption. The basic problem with the recent control monitoring program (SANCO/4546/01 – rev.3) is the lack of an overall co-ordination of the sampling design (e.g. no co-ordination between age of the collected animals, if the animals are beef cattle or dairy cattle) and a longer time series of an increased number of analyses. However, it should be clearly stated that the (by the Commission) already existing principles (analysis, sampling reporting methods) are well written and adequate and should be used in the integrated monitoring. Once the acceding countries become members, also those countries will get national data that are comparable with the rest of the EU. Further, today there is no attempt to co-ordinate the corresponding control monitoring program for feedingstuffs with the one for foodstuffs. Since the link between the feed and the food is so close, such a co-ordination might be effective in tracking sources etc. However, of bigger concern are the national foodstuff surveys that are performed in individual countries with different time intervals. The foodstuff surveys are one of the cornerstones in the human exposure estimations and are at present considered to contribute with a large part of the uncertainties in the exposure estimations. Since there are no harmonised guidelines for these surveys, big discrepancies exist such as differences in which food products are collected to represent a food group. This variation produces results that are not comparable between different European countries with subsequent difficulties to track sources of dioxins/PCBs at a European level. 3.3 Fish as food – a complex matrix A case study from Sweden. To illustrate the significant and huge difference that prevails regarding dioxin levels in herring in the Baltic region, a “best case scenario” and “worst case scenario” can be used. A one-year herring caught in the Bothnian Bay had a dioxin/furan (PCDD/F) level of 0.86 pg/g fresh weight in the muscle+skin tissue matrix (Bjerselius et al. 2003). If only the muscle tissue is to be considered and reported as the “herring level”, the PCDD/F would be reduced to approximately half, 0.43 pg/g fresh weight (Aune et al. 2003). If we instead analyse a 7-9 years old herring from the Bothnian Sea, with the skin included, we get a PCDD/F level of 23 pg/g fresh weight. The difference in the example is 53-fold!
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 59
The enormous difference in PCDD/F level between the same species caught in the same Sea (Baltic Sea) depend on tissue analysed, age of the fish and location where it was caught. Analysed tissue. Since the daily human PCDD/F contribution from fish is significant in many European countries there is an obvious need to have accurate data to execute correct intake estimations and subsequent risk assessments. Today, different countries analyse different parts of the fish, which result in significantly different reported PCDD/F levels. For example, Sweden, Finland, Estonia and Latvia analyse herring with the skin included since this is the edible part in some of the final products in these countries. A recent German survey did not include the skin in their analyses of herring and the results from their studies cannot be compared with the former results. The significance of this has been shown in a study by Aune et al. (2003) where as much as 50 % of the dioxins/PCBs is removed if the skin with the subcutaneous fat layer is removed before analysis (Fig. 25). In addition, results from a study on salmon indicate that it is important with specific method descriptions also for sampling of larger fish for dioxin/PCB analyses. The same study showed that there
Figure 25 a, b. a) The mean WHO-PCDD/F-TEQ (pg/g fresh weight) and mean WHO-PCB-TEQ (pg/g fresh weight) is shown for two pooled samples of herring analysed as muscle tissue or muscle tissue including skin. The herrings were caught south west of Bornholm in 2002. Numbers at arrows represent the decrease in percent. b) Different parts of two salmons from the Bothnian Bay and Baltic Proper were analysed for PCB congeners. The sum PCB mean levels (µg/kg fresh weight) for the analysed parts as well as the percentage differences between the parts are shown. could be as big as a 4.5 fold difference in the analysed PCB level depending on if the anterior or posterior part of the fish body is taken out for analysis (Aune et al. 2003). In both cases, the results are explained by corresponding changes in fat content in the analysed part of the fish. In addition, also for salmon different countries have used different tissues in their studies of PCDD/F concentrations (i.e. only muscle tissue vs. muscle tissue + skin), results that cant be directly compared. Age differences. As in humans, also in fish there is a very strong and positive correlation between the age and the concentrations of dioxins and dioxin-like PCBs. The best-studied species in this respect in the Baltic region is the herring (Kiviranta et al., 2003, Roots et al., 2003). It is the species of highest commercial value in the region and it can become as old as up to 15-20 years old and is therefore suitable for such studies. Kiviranta et al. (2003) analysed 7 different age classes of herring from the Gulf of Finland. The study consisted of
SW Bornholm herring 2002
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Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 60
fish in 7 pooled samples with a range from 2-7 years and one pool of fish ageing 8-15 years (total of 7 age classes ). The results showed that there is a highly significant positive correlation between age of the fish and level of PCDD/F (Fig. 26) and a “rule of thumb” could be created for this stock of herring in the Gulf of Finland; every year of a herring’s life led to a rise of one PCDD/F-TEQ unit on fresh weight basis. It should however be pointed out that different regions, with separate stocks of herring, could have different slopes in such first-degree equations, illustrating the bioaccumulation of contaminants with increasing age. Sweden, Estonia and Latvia (Bjerselius et al. 2003; Roots et al. 2003, M. Balodis personal communication) have indicated similar results for herring as indicated by Fig. 26.
Fig. 26 a, b. a) Correlation between WHOPCDD/DF-TEQ and Baltic herring age in the Gulf of Finland. Data from Kiviranta et al. 2003. B) Correlation between WHOPCDD/DF-TEQ and Swedish Baltic salmon age in the Baltic Region. Data from Bjerselius et al. 2003. In both figures the, correlation are statistically significant. Also for salmon and sprat, there seem to be a positive age correlation with levels of PCDD/DF-TEQ units per fresh weight (Vuorinen et al. 2002; Bjerselius et al. 2003, Roots et al. 2003; M. Balodis personal communication). The Baltic salmon and Baltic sprat stocks consist of one stock each. Both these stocks have their major feeding areas in the Baltic Proper region and are therefore exposed to the same level of contamination. The salmon data presented in Fig. 26 b represent pooled salmon samples (only muscle tissue) from Swedish surveys 2000-2002 (Bjerselius et al. 2003). Regional differences. Again, herring is the best fish species to illustrate the big regional differences that persist in the Baltic Sea region. The region is thought to be populated by at least 4 different herring stocks. These 4 stocks are not mixing with each other to a larger extent and can therefore be treated as separate stocks from which directed fishing can be performed. The stocks are divided into different parts of the Baltic Sea region according to the map in Fig 18. The stocks in question are Bothnian Bay stock, Bothnian Sea stock, Baltic proper stock and the Rugen stock (south of Bornholm). Subsequently, large differences in PCDD/DF concentrations have been shown to exist between different stocks. Kiviranta et al. (2003) showed that stock differences exist between herring caught in the Gulf of Finland (belonging to the Baltic proper stock) and herring caught in the Bothnian Sea/Bay (i.e. higher in the Bothnian Sea/Bay). Similar results have been indicated by Bjerselius et al. (2003) showing different PCDD/F concentrations for herring of year classes 3.5-5.5 from Bothnian Sea, Baltic Proper and the Rugen stock decreasing levels from north to south. . Roots et al. (2003) showed different PCDD/F concentrations for herring 2.0-6.7 and for Baltic sprat 1.9-
Baltic Salmon - PCDD/DFy = 1,2523x + 2,1251
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Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 61
3.8 years from Gulfs of Riga and of Finland and from Central Baltic Sea. Karl and Munkner (2002) have also shown differences between the Baltic Proper stock and the Rugen herring stock. The explanations for the varying levels are complex. However, since the stocks/areas are oriented in a North-South direction, there are large differences in temperature and feed availability with subsequent large differences in growth. A pooled herring sample with average age 2.5 years in the Bothnian Bay weigh approximately 25 g and a 2.4 year old herring belonging to the Rugen stock weigh 57 g (Bjerselius et al. 2003). In addition, different feeding characteristics as well as levels of ambient contamination of the different regions might affect the levels of dioxins and dioxin like PCBs in fish (Kiviranta et al. 2003; Bjerselius et al. 2003). Annual catch of herring in relation to levels in different sizes of fish. To be able to make the desired intake estimations it is of interest to know the annual catches from the respective area are, and how much of those catches that is supposed to be consumed by humans. Because of the strong correlation between age (and size) and PCDD/F level, and the documented large differences in levels, the annual catch of different sizes of herring should be included in the exposure estimations. For example, when a statistical evaluation of age classes 1-4 years is made, no difference in PCDD/F level is seen and the averages from the different stocks are all below the maximum limit of 4 pg/g fw (Fig. 27). These age classes (1-4) constitute 69 % of the Baltic Proper catch of herring in weight, in 2001 (ICES). However, a similar comparison of the older year classes 5-7 and 8- reveals a difference between the stocks, where the Baltic Proper stock has significantly lower PCDD/F level compared to the Baltic Sea and Baltic Bay stocks. These year classes show all averages well above the maximum limit. A similar comparison regarding the age distribution within the different year classes and stocks showed no significant differences. This indicates that the differences observed in the PCDD/F levels are due to different levels in different stocks, and not to different ages of the fish in the analysed material (Fig. 27).
Fig 27. The most recent herring PCDD/F data from Finland, Estonia, Latvia and Sweden. The data are represented by pooled samples that have their average a) PCDD/F concentration (pg/g fw) and b) age determined. Statistical evaluation with non-parametric ANOVA (Kruskal-Wallis) followed by Dunns multiple comparison test. P<0.05 (*); p<0.01 (**); NS = non significant. Congener differences. A preliminary principal component analysis (PCA) analysis of the congener pattern in herring from different stocks has indicated that the patterns differ
Herring PCDD/DF
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Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 62
significantly between the stock in the Bothnian Sea compared to both the stocks north (Bothnian Bay stock) and south (Baltic proper stock) thereof (Katrin Lunstedt-Enkel, Environmental Toxicology, Uppsala University, Sweden, personal communication). More thorough analysis of the congener patter should be done and used in the assessment of tracking sources of dioxins and PCBs. In addition, the distribution pattern of PCDD/Fs and dioxin-like PCBs have been shown to vary largely between different species in the Baltic Sea region. In a study on herring, salmon and yellow eel, caught from the Baltic proper area in 2000 the average contribution from dioxin-like PCBs was 46, 64 and 82 %, respectively (Bjerselius et al. 2002). The result indicates that the contribution of the PCDD/F is less than half of the total TEQ when the dioxin-like PCBs are incorporated in the total TEQ measured. In four Estonian coastal areas PCA analysis in grey seals suggested that the PCB patterns differ between juveniles and adults, but not between genders or areas (Roots and Zitko, 2002). 3.4 Problems with sediment profiles Significant number of papers have been published which use sediment profiles in order to interpret concentrations or accumulation rates as signs of past changes in pollutant load to lakes or sea areas. Generally for most POPs (DDT, PCB, PAHs and dioxins, which are poorly water soluble and attached to organic material) sediments are considered as a good matrix to study spatial and temporal trends. There are many prerequisites and methodological possibilities that have to consider in order to properly sample, analyse and interpret the sediment data. Shortly, following aspects has to be taken into account: Site selection.
• bathymetry, stratification, point source contamination, coastal/offshore, predicted sedimentation rate high/low, previous paleolimnological studies etc.
Field methods • Obtaining undisturbed sediment profiles and adequate sediment for analysis, coring
techniques etc. Analyses of sediments
• dating (210Pb, 137Cs, 241Am, varved/laminated sediments, other markers), POP/dioxin analysis, quality assurance etc.
Interpretation of the data • data representation (concentrations/accumulation rates), interpretations
(temporal/spatial trends, magnitude of change, diffusion (for some POPs), bioturbation, resuspension and spatial transport of previously sedimented material etc.
Questions and indications of problems that have been raised specifically to the Baltic in relation to POPs in sediments include eg. (see AMBIO 29, Vol 4-5):
• changes of permanent/occasional anoxia (Echéll et al.2000) • erosion/resuspension dynamics, winds (Jonsson et al. 2000, Eckhéll et al.2000) • transport coastal/offshore or offshore/archipelago (Jonsson et al. 2000, Meili et al.
2000) • eutrophication induced biodilution and scavenging (Skei et al. 2000, Larsson et
al.2000) • trends in sediments/trends in biota (Olsson et al. 2000)
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 63
• properties of different congeners in determining the distribution in sediments (Jönsson and Carman 2000)
Clearly, there is only little questioning whether major changes in pollution load would not be reflected in sediment profiles. Many site-specific or environmental characteristic problems however make it difficult or hinder the interpretation of minor changes in sediment profiles. 3.5 Air/deposition This Baltic Sea is very polluted, leading to a high level of dioxin and other POPs (such as PBDEs) in fish and other marine organisms (such as mussels). The high dioxin concentration in fish poses a paradox, since most dioxin is generated on land and emitted to the atmosphere (for instance by combustion processes). According to the European Dioxin Inventory published by the EU Commission, the atmospheric emission amounts to about 95 % of the total emission, whereas only about 2 % are ascribed to direct water emission. The dioxins are almost exclusively generated on land, and carried to the mainly sea by atmospheric transport. Therefore deposition of dioxin over the Baltic Sea is at present an important input route, although waterborne sources e.g. rivers inputs also contribute to the dioxin input. Considerable atmospheric transport of PCBs and PCDD/Fs takes place both in the gas and particle phases. The partitioning between the phases is different for each congener and will affect the removal mechanism (deposition, photodegradation, chemical degradation) of these substances from the atmosphere. The main removal mechanism for most compounds is deposition (wet scavenging of the gaseous phase/ dry deposition). The tetra- to octachlorinated PCDD/Fs have lower lower vapor pressures and Henry's law constant than PCBs and are therefore not expected to undergo long-range transport to the same extent. Gas exchange between soil/atmosphere and sea surface/atmosphere takes place and again is more important for PCBs than PCDD/Fs. Significant reemission of PCBs may occur as indicated e.g. by the higher concentrations in air during summer months (see earlier) (Wania and Mackay 1995). In terrestrial systems uptake by plants from gas and particulate phases has also been indicated (Brorström-Lunden 1995). Due to the low concentrations (fg/m3- pg/m3) in air large volumes must be collected with long sampling times and/or a sampler with large flow capacity. These prerequisites create risks for changes both in the qualitative and quantitative content of the compounds in the sample compared to the original air mass. Compared to air measurements, deposition sampling provides a more direct estimate of the flux of PCBs and PCDD/Fs to soils or sea surface. Deposition sampling has been carried out with various kinds of samplers with surrogate surfaces, which will affect the deposition in different way to that occurring in the environment. The northern climate with a long period when wet deposition occurs through snow scavenging, causes additional problems with sampling. e.g. while heating of samplers has probably no or minor effect on PCDD/F deposition estimates (Vikelsøe et al. 2003), it may affect more volatile PCB congeners. The choice of the type of sampler depends on the substance and the purpose of the measurements (wet only, bulk/throughfall). In contrast to emission measurements, which focus mainly on single industrial known sources, deposition measurements can be used to elucidate the impact of regional combined sources, non-industrial sources, diffuse sources and emissions from re-evaporation. Finally
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 64
the existence of unknown sources can be established and eventually pointed out by deposition and air measurements. The reduction of emissions by remediation or closure of sources is the only war to reduce the input to the sea. In spite of this situation, studies of deposition over the Baltic Sea are lacking. This is regrettable since knowledge on the deposition is mandatory in order to track sources, and to study transport and fate of dioxin. More far-reaching goals will be to make an inventory of sources, and to calculate a dioxin mass balance for the Baltic Sea total. 3.6 Soil Soil is a basis of life and a habitat for people, animals, plants and soil organisms. It performs essential functions as a medium for decomposition, balance and restoration as a result of its filtering, buffering and substance-converting properties, and especially groundwater protection. Furthermore it is used as land for settlement, traffic, industry and recreation and land for agricultural and silvicultural use.
Dioxin inputs into soil result mainly from land uses, agricultural activities and atmospheric deposition. Pathways through which dioxins in soil may adversely affect human health are soil-man (e.g. playground), soil-useful plant (e.g. pasture) and soil-groundwater (for drinking water). It can be assumed that direct transfer of dioxins from soil to plants is very low, so that the contamination of plants is mainly via adsorption from soil particles.
Dioxins in soil are measured mostly near emission sources. For the assessment of the results it is important to determine reference values, which indicate the concentrations to be expected at a site in the absence of anthropogenic contamination. In order to derive reference values it is useful to compile an inventory of dioxin concentrations in soil. Such an inventory also makes it possible to identify sites that are contaminated and to recommend future uses that minimize dioxin inputs into the food chain.
As dioxins have very long half lives, dioxin concentrations in soil change very slowly. Due to the dioxins’ low mobility, such changes are mostly a result of dispersal, e.g. during soil cultivation. Therefore monitoring of the development over time makes sense only if it takes place over a longer time horizon.
In addition to quality assurance in analysis, standardised sampling is an essential requirement in soil monitoring, as in all monitoring programmes, in order to ensure the comparability of samples. In Germany standardised sampling and analytical methods are regulated by the Federal Soil Protection and Contaminated Sites Ordinance (BBodSchV) dated 16 July 1999. This could be a very good model for EU regulations. As soil composition and type of land use are major determinants not only for the availability of pollutants but also for the assessment and the recommended future use, information on this should ways be documented. 3.7 Problems of time series information Time series are absolutely necessary to be able to predict the future and to some extent also to define the sources. To get as much information as possible out of the series available they should be comparable and be carried out at essential areas and in essential media. This discussion focuses on what is available for the Baltic area.
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Are series available? Some series are available, but not for all congeners and not for all media. The conclusion that can be drawn from this is that more series are needed. An in depth analysis of available data can point out where and in what measurements should be carried out on a regular basis. The most important task is to have time series for different media. Do they cover essential media? The series available cover air, deposition, fish, and mother’s milk. In sediment the depth profile gives an indication of the changes over the years. So the series available do not cover all essential media if one wants to follow the whole path from emissions to health effects. Do they cover essential areas? There are gaps, which will increase the uncertainty when looking at geographical differences. Are the results comparable? So far there are relatively few series available. When several series in one media are carried out by the same country these are comparable. There is, however, not the same comparability between countries. Has timing been performed? Timing has to our knowledge not been performed. Since there are seasonal variations this will also increase the variation and decrease the possibility of comparing results. 3.8 Problems of the TEF concept TEF (toxic equivalency factor) concept has been in use since 1980s (Ahlborg et al, 1994). Originally TEF was based on short-term toxicity or only on in vitro data (such as binding affinity to AH receptor or potency in CYP enzyme induction). In this stage it was practically the same as the later concept of relative potency. TEF concept has been shown to be a relatively good measure of in vivo toxicity in the rat among various polychlorinated dibenzo-p-dioxin congeners, which have roughly similar kinetic characteristics (Viluksela et al, TAP 151:57, 1998, Simanainen et al, TAP 181:38, 2002). Correlation between in vitro potency and in vivo effects may not be so good among polychlorinated dibenzofurans, some of which may have pharmacokinetic properties different from those of TCDD, e.g. poor absorption or faster elimination (Ahlborg et al, EJP 228:179, 1992). Subsequently in vivo toxicity data have been prioritized according to the ranking scheme: chronic>subchronic>subacute>acute (van den Berg, 2000). This corrects to some extent for pharmacokinetic differences. Uncertainties are increased when moving to PCB-compounds, especially those which are not among the most potent (e.g. mono-ortho compounds). It has been noted that even in a simple laboratory setting the sum effect of a "natural mixture" of dioxins and PCBs tends to be less than expected on the basis of TEq (Hamm et al, 2003). These uncertainties have obvious implications for monitoring activities. Emissions of PCDD/Fs have a certain spectrum of congeners, but due to their variable fate in the environment or different pharmacokinetic properties, this spectrum is not maintained all the way to the target organism, e.g. human body. Some compounds are eliminated more rapidly in the environment than others, some are not accumulated as effectively to biota as others, some are metabolised by micro-organisms or fish. Therefore some congeners present in the original emissions are concentrated more than average, some may not appear at all towards the end of the food chain. In other words the intake fractions (iF) of different compounds are different.
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The deviations mean that in fact there is no universal way of defining TEq. For emissions there should be one set of TEF-values, for fish feed another set, for consumed food a third one, and finally, for human risk assessment on the basis of concentrations in human body, still another set of TEFs. TEF-concept and TEq values were created to simplify the assessment of sum risks of all dioxins in complex mixtures, but one should obviously be very careful and transparent in applying these tools for risk assessment and monitoring. If the sum concentration expressed as TEqs has a different meaning in different media along the environmental routes, then also the use of biological assay systems (such as DR-CALUX) is problematic except for the simplest screening activities. The only reliable way of expressing the concentrations in specific media at the moment is congener-specific mass spectrometric analysis. Because TEF-values have changed over time, time series of TEq have to be performed with care. In environmental samples OCDD and OCDF may be quite dominant, and their I-TEF values were 0.001 but the more recent WHO-TEF values only 0.0001. This may change the TEq quite drastically. Similar errors come from the increase of the TEF of 1,2,3,7,8-PeCDD from 0.5 to 1. 3.9 Problems with specificity of analysis and congener spectra Comparison of PCB exposures in different studies is notoriously difficult, because measuring and reporting have differed (Longnecker et al., 2003). The earlier analyses were based on “total” PCBs analysed by using packed columns in gas chromatographs, and later separation of different congeners allowed various number of “marker PCBs” to be analysed. Only recently with high-performance GS-MS analytic systems a complete congener-specific analysis has become possible including the analysis of “dioxin-like” PCBs individually. Different fish species have different spectrum of various PCDD/F congeners apparently due to their different feeding habits. This may change due to local pollution to some extent. In the estuary area of the River Kymijoki, fish exhibit some features of the spectrum of Ky-5-preparation, a chlorophenol synthesised at large amounts in Kuusankoski town on the Kymijoki. The total concentrations of PCDD/Fs in fish are not significantly elevated, even if the congener spectrum is different. Hence the impact of even extreme pollution on fish is limited, if the chemicals are bound to the sediment. The congeners typical of Baltic herring in all parts of the Baltic Sea are (contributing most to TEq) 2,3,4,7,8-PeCDF, and to some extent 2,3,7,8-TCDD, 2,3,7,8-TCDF and 1,2,3,7,8-PeCDD (Kiviranta et al, 2002) (Fig. 28). This deviates clearly from the spectrum of Ky-5 which contains most 1,2,3,4,6,7,8-HpCDF, and to lesser amounts other (e.g. hexa-) furans (Vartiainen et al, 1995). (cited as AKL in Fig. 28).
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Figure 28. Congener patterns of different environmental media within the Baltic. (data from UBA, NERI, SYKE and Finnish NHI) On the other hand, the typical herring spectrum is close to the spectrum present in Central European milk and meat products, which are mainly derived from airborne emissions. The main congeners contributing to TEq (2,3,4,7,8-PeCDF, 1,2,3,7,8-PeCDD and TCDF) are also among the main congeners in most air emission, air and deposition samples (e.g. Vulykh and Shatalov 2001). This raises the possibility that for some fish species the airborne pollution might be more important than the heavy load of PCDD/Fs and PCBs in the sea and especially that in sediments. Because of these discrepancies it is highly important to study the transport of dioxins in the atmosphere and in plankton, to understand the sources and hence to be able to effectively monitor the routes to fish. It is also highly important to understand the sources to be able to predict future: abatement of airborne pollution might be possible within relatively short time frame, whereas PCDD/Fs and PCBs in the sediments will not disappear in foreseeable future. Only further burying under new sediments will gradually decrease their biological significance, and in fact the surface sediments show a decrease of over 50% in the Gulf of Finland as compared with the worst levels in 1960s to 1970s (Isosaari et al, 2002). 3.10 New emerging threats There are millions of registered chemicals in our society. Among these approximately 100 000 are used in different products. Sufficient knowledge on possible environmental and health effects is often lacking. It is therefore likely that we will occasionally find substances to cause environmental or health effects that we do not know about today. Two examples of substance groups that have caused increased concern are the polybrominated diphenyl ethers and the perfluorinated substances. In this respect this integrated monitoring system that is being worked out for PCB and dioxins may serve as model for how we should monitor other chemicals that may be of concern. Recently, preliminary Swedish intake estimations of different flame-retardants (PBDE, HBCD) indicate that fish products are one of the main sources to adult human exposure (up to 60 %).
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3.11 Exposure assessment Except the need for accurate and comparable data regarding levels in foodstuffs, there is also a need for harmonisation and co-ordination of dietary questionnaires that will result in reliable intake estimations for the European population. Indeed, in the SCOOP report “Executive summary”, the authors state that “there were large differences in the amount, detail and quality of the data from the participating countries”. This induces uncertainties in the evaluation of the results, which was very clear when referring to the report. Thus, the major problems and deficits with the present available data (i.e. SCOOP 2000) concern: 1) the dietary questionnaires that differed and included consumption records studies (2-28 days) as well as 24-h recall, household budget and food frequency studies. The questionnaires were generally directed to adults (teenagers to elderly) but also to age groups such as infants, toddlers, children and adults. 2) the intake estimations that were “based on a limited amount of data and there are uncertainties related to the methods used to estimate dietary intakes”. The usefulness of data would improve significantly if there were agreed guidelines on how to calculate the human intake (e.g. what products to include, upper/median/lower LOQ (limit of quantitation), same year classes etc.). It would be useful to repeat the exposure assessment exercise done in 1999 (SCOOP), as there is much new information and evidence for a time trend changing the exposure of the consumer. It could be suggested to conduct such exercise during the year 2004, five years later than the first project. As Regulation (EC) N° 466/2001, amended by regulation (EC) N° 2375/2001, contains a clause that before 31 December 2006, the maximum levels should be reviewed, the results of the risk assessment should be available as scientific basis for the discussion on the review of the maximum levels before the end of 2005. As a sufficiently low exposure of the consumer is the main target for all safety measures, including emission reduction, measures on feed etcetera, the results would be useful for an integrated strategy. 3.12 Problems with health effect studies It is difficult to find a meaningful way to monitor health indicators in order to find health effects caused by environmental factors, because health endpoints such as cancers, developmental effects, allergies, infectious diseases, and cardiovascular diseases depend on multiple causes and risk factors, such as dietary factors and other lifestyle factors (smoking, alcohol consumption, sexual habits, and even social factors). Because of these complexities, only a carefully planned and controlled health study can give reliable answers on possible environmental causative factors, and rarely, if other factors are stable or can be controlled, repeated well-performed studies can be used for monitoring purposes. Studies between different geographical locations are notoriously unreliable in giving answers to health differences. The cause of error is called ecological fallacy. An example is testis cancer, which is much more common in Denmark than in Finland, and it has been hypothesised that this could be caused by higher chemical pollution in Denmark. Testis cancer may, however, be initiated already prenatally, and tobacco smoking of women started about one generation earlier in Denmark than in Finland. If the potential difference in maternal smoking during pregnancy or other lifestyle factors cannot be excluded as the cause of cancer difference, no conclusions can be made of the roles of chemicals. Therefore integrated monitoring can provide material for specific health studies, but usually not directly
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monitor health consequences of environmental pollution, and this limitation should be clearly understood and appreciated. In many environmental health studies exposure assessment is based on questionnaires or other semiquantitative measures. Actually measured exposures would improve the reliability remarkably. Proxy measures such as fish consumption have led to uncertainties of interpretation, and integrated monitoring might be hoped to improve quantification of exposures. In diseases with a long delay from initiation to actual disease such as cancer, the problems of correct exposure analysis are formidable. Good health registers (e.g. cancer registries, birth defect registries) are a good source of information when adequately used. Small area statistics and other GIS-based methods are needed to link together environmental information and health register information. 3.13 Problems with risk assessment and risk management Precautionary principle states that one should not expect a full scientific certainty of harm to initiate actions to abate the noxious agent or activity. This principle has always been incorporated in prevention of harms of chemicals, and this should be continued especially when new chemicals are introduced. When applied to old activities or chemicals and especially on chemicals in our environment, the situation is more problematic. Because they cannot usually be easily removed, abatement requires thorough understanding of not only the risks of the particular activity or chemical to be regulated, but also of countervailing risks. These may be caused by replacement of the activity or chemical with something else, the risk of which may be less well known. There may also be countervailing risks caused by indirect consequences of the abatement activity. Also understanding the risk/benefit assessment in the particular case is needed, so that abatement activities do not result in losing health and other benefits that would be greater than the potential harm. Furthermore, also understanding of uncertainties of both the risks and benefits is required. This is especially important when not dealing with the original source of the emission, but some later step in the chain to human exposure such as food. In dioxin question the most obvious example is breast-feeding. So far all scientific advisory bodies have agreed that regardless of considerable exposure to dioxins of breast-fed babies, the countervailing risks of alternative food and the nutritional and immunological benefits of mother's milk are such that breast-feeding should not be jeopardised. In some countries the length of breast-feeding has been discussed and in some cases advised to be limited to four or six months. In general the actions recommended to minimise these risks are reductions of emissions, not limitations in feeding behaviour. However, there is no actual research on how beneficial breast-feeding is in these conditions, how long breast feeding should continue to keep the benefits larger than the risks, and so on. Another obvious similar item is fish with potential chemical risks of dioxins and with potential health benefits of vitamins and minerals (especially vitamin D and selenium), nutritionally valuable proteins, and nutritionally preferable fatty acids. Even if there are still some disputes on the significance of polyunsaturated n-3-fatty acids for health, most dietary authorities consider benefits of fish consumption well founded and scientifically sound (Kromhout, 2000, Erkkilä et al., 2003). In some studies fish consumption has been calculated to decrease mortality and morbidity much more than even maximally estimated POP exposure from fish could increase them. In this comparison one should also appreciate that
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health benefits of fatty acids are based on human epidemiology and intervention studies while the risks are based on extrapolations from animal experiments, and therefore include a safety factor. There is no clear answer yet to the question what would be the optimal consumption of fatty fish to take maximal use of the benefits while not yet causing a significant risk, but it is likely that a fairly frequent consumption of fish is still beneficial if several types of fish are consumed rather than large amounts of a single species. Use of several species also reduces exposure to other potentially toxic compounds such as methyl mercury and arsenic. A thorough understanding of these considerations should accompany the monitoring activities and their interpretation in the spirit of precautionary principle. Still another aspect to precautionary thinking is consideration of generally decreasing concentrations of POPs in fish and decreasing dioxin and PCB intakes from all sources combined. The concentrations in primiparae mothers are already one third of the levels in 1987 and probably 20 % of those in late 1970s. The most sensitive potential health effect noted in humans, tooth defect, was not any more detectable in mid-1990s. There is no decrease in TEqs in herring during 1990s, but compared from 1978 to 2002 there is 60-80 % decrease, this agrees with long-term emission history seen in sediments. Predicting to future, this tends to decrease the weight of risks while the benefits are likely to remain the same or to be confirmed. Therefore a wise precaution should perhaps be seen in this wider framework In conclusion, research should be promoted in the EU to advance understanding in risk comparison and risk benefit assessment to be able to make more informed and better decisions in important environmental health issues.
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4 Advantages of an integrated monitoring system Today resources for risk management are often wasted both in underprotection, when an established but environmentally risky product is protected by administrative and market inertia, and not replaced; and in overprotection, when unnecessary restrictions, based on theoretical worst case assessments, deny the benefits of a product. The fragmented risk assessment process is driven by experts specialised to their own fields. This easily leads to risk management, which is not based on balanced and comparable characterisations of the competing risks, or even consideration of the competing risks at all. Integrated monitoring is needed to help risk assessment to assess the chemical/product in its realistic exposure scenario(s), in the presence of exposure and effect modifying factors. The objective is to express the risk within the target population or ecosystem as a best available estimate. This includes the expected value of the risk, the uncertainty about the value, the variability within the population, and the most important factors driving the outcome estimate. Protocols and methods have to be developed for combining ecological and human risk assessments. The approach with wider possibilities for aspects enables inclusion of societal values, produces wiser management, and results in better resource allocation and competitiveness. Harmonisation of the different methods and a co-ordination of the programmes on an inter-European level will produce more accurate and comparable data. This will significantly improve our understanding of levels and sources of dioxins/PCBs and subsequently help us to reduce the children exposure. An integrated strategy, including harmonisation and co-ordination of the methods for dietary questionnaires and intake estimations, would result in improved knowledge for the European countries. Below are some important advantages to be seen with such a strategy. - Compare dioxin and PCB levels in foodstuffs in different countries - Country wise comparison of human exposure levels of dioxins and PCBs - Compare if countries with different strategies (e.g. information, prohibition etc.) to
reduce the human dioxin and PCB exposure have different intake/body burdens - Compare intakes in countries with and without strategies to reduce the human dioxin and
PCB exposure Time trends within countries as well as between countries
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5 Requirements for an integrated monitoring system
As in all exercises using scientific approach, only scientifically proven methods and arguments should be used. Especially dioxins, but to some extent also PCB compounds, are burdened by non-scientific argumentation and both substantiated and unsubstantiated fears among the public and decision-makers. It is especially important to take into consideration difficulties and possibilities for misinterpretation when two culturally different sciences, such as medicine and environmental sciences meet. The most important requirement for integrated monitoring is an honest discourse over the borders between scientific disciplines and administrative structures. This is poorly done in many countries or even at international level. This requires sincere collaboration and appreciation of the other partners’ work and expertise. Done in a proper way such interdisciplinary and intersectoral work may be highly rewarding and produce innovative ideas. Integrated monitoring is aimed at being helpful in risk assessment. In risk assessment the crucial determinants of risk are the dose-response of the potential adverse effect, and the relevant exposure. A mere existence of a noxious agent is no importance, if it will not lead to exposure which is relevant taking into account the information on dose-response. This also means that from the health point of view it is only meaningful to monitor such parameters that help in assessing human exposure. If, for instance, certain dioxin congeners do not pass the whole food chain to human being, their monitoring may be important for environmental reasons but not for health reasons. This also means that soil or sediment contaminations as such are not actual health concerns unless there is a route to human food chain. Meaningful monitoring within EU framework is only worthwhile, if methodology can be ascertained so that results from different parts of Europe are comparable. A good example of a highly useful international intercalibration exercise is dioxin measurements in mother's milk in different European countries. Protocols and methods have to be developed for combining monitoring aiming both assessment of ecological and human risk. The approach with wider possibilities for aspects enables inclusion of societal values, produces wiser management, and results in better resource allocation and competitiveness. Integration in the monitoring of various POPs can also be viewed from the perspective of various chemical groups. New groups of chemicals are emerging, such as brominated diphenylethers and other brominated compounds. With some modifications, monitoring of these compounds can be included in dioxin and PCB monitoring programs. Simultaneous monitoring of many physicochemically similar chemicals is cost-effective. Also old samples originally collected for a whatever purposes could be screened for the possibility of measuring compounds with newly raised concerns. Because time-course information is often important for assessing the risks of persistent chemicals, archived samples such as eggs or fish may be important, and also benthic sediments can be used for time course assessments and prediction of future.
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5.1 Requirements of time series monitoring In general it can be said that time series offer the advantage to follow the environmental load with the investigated pollutans and allow the control of the success of emission reduction measures. A careful planning and documentation of the sites, samples (incl. all relevant information in this context that may be crucial for the detected concentration), procedures of sample preparation and chemical analysis are prerequisites to study time series. Any comparison of data requires consistency in these working steps and in the studied samples. To a certain extent a retrospective analysis of time series is possible, even for organic compounds like PCB and PCDD/F which may be subject to degradation, chemical breakdown and losses. Such retrospective time series in the literature are frequently based on sediment cores, bog profiles or ice cores from the glaciers. A further example is the analysis of archived samples, for instance samples from an environmental specimen bank as it exists in some countries. Such archives or any retrospective analysed samples should have been stored at least under the following conditions to allow a retrospctive analysis for PCDD/F and PCB: airtight sealed in glass or metal jars, protected from UV light and at -20 °C. 5.2 Requirements of air monitoring Ambient concentrations of POPs fluctuate widely in space and time. An important challenge is therefore to consider how to address this variability in the sampling. Because POPs compounds encompass a wide range of vapour pressures, gas-particle partitioning behaviours and concentrations, there are substantial difficulties in designing a multi-purpose sampling strategy and some compromises over sample time/volumes are almost inevitable (cf. Jones & Barber 2003). 5.2.1 Active air sampling
The techniques for air sampling of POPs are well established.Typically, high volume (Hi-Vol) air samplers are used, with a head adapted to sample POPs from the particulate and gas phases (with a filter and sorbent trap, respectively). The air volume sampled before breakthrough occurs varies for different POPs and with temperature. Such ‘active’ air sampling requires a power supply, trained operators, dedicated sites and the financial resources to buy the Hi-Vol samplers. Careful consideration also needs to be given to the use of field blanks, pre-cleaning and preparation of the sampling media. However, detailed knowledge of the performance and requirements for such sampling exists, so that protocols can be developed. Active air samplers are most usefully installed at meteorological stations, where supporting information of temperature, wind directions, precipitation etc. are obtained to support data interpretation. 5.2.2 Passive air sampling Such techniques provide a cheap and powerful tool for obtaining detailed spatially resolved and time trend data relatively cheaply and efficiently. The utility of passive samplers has been demonstrated for local, national and regional scale monitoring. The general concepts behind passive air sampling have been discussed elsewhere (Ockenden et al., 2001). A sorbent/solid phase sampler is used, to which gas phase POPs can partition (ad-/absorb). The
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mass of chemical on the sampler will increase with exposure time (kinetic uptake phase), and approach equilibrium. The time to equilibrium will vary, depending on the ‘capacity’ of the sampler. The rate of supply may be influenced by wind speed, deployment conditions and compound. The advantages/opportunities of passive air samplers are as follows:
• Low cost • Excellent opportunities for high spatial and temporal sampling resolution data • No power supply needed, easy deployment and little operator training required
Their disadvantages/constraints are:
• Current techniques are still ‘semi-quantitative’, requiring knowledge of thesampling rate (m 3 air sampled/day) and the effects of temperature
• Optimisation of sampling requires further study, of the effects of wind speed,temperature
• Sampling is efficient for the gas phase component, but generally poorer for theparticulate phase
• The time to reach gas phase-sampler equilibrium varies widely between POPs The development of passive air samplers for POPs is an active area of research. Different designs are being tested/used. There is no consensus yet as to what is the ‘best design’; indeed, it is probable that different samplers will be useful for different purposes (i.e. different time scales; different compounds).
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6 Possibilities and missing links 6.1 Links to other TWGs Without having access to the other TWGs, we assume that there will be many questions that should be answered within the same study groups (cohorts). For example, both the “bio monitoring of children” cohort and the “neurodevelopment disorders” groups should be contacted to be able to design cohorts where the intake/exposure should be assessed in parallel with studies of different health effects. In addition, one obvious link to the already ongoing establishment of “bio monitoring of children” cohort would be to include those parents in the coming intake studies to be performed. 6.2 Links to existing programs Existing programs such as HELCOM should use health expertise to add some parameters that would be helpful in assessment of health risks, e.g. relevant types of fish that are most important for consumer viewpoint and so measure the human intake. There is still an incomplete understanding on the chain of events leading from industrial and other emissions to food, especially Baltic fish, and possibilities to clarify these steps should be emphasised. This would give better possibilities for emission abatement. Integration of official control monitoring and risk management can be done by communication and cooperation, as is asked for in Recommendation 2002/201/EC for dioxins and PCBs discovered in the food chain. In such cases tracing and information to environmental authorities is assured, who should react and communicate about their measures taken. Commission database on concentrations of dioxins, dioxin-like PCBs and non-dioxin-like PCBs in food and feed should be utilised in integrated manner to predict safety of food. Food consumption information available would be an important link to actually understanding intakes in special population groups such as women and children. Possibilities to integrate health registries (such as cancer registries, birth defect registries) with environmental information should be studied both nationally and internationally. Integration (harmonisation of methods and co-ordination of programmes) could be very useful in further actions to reduce the emissions from sources and resulting contamination of feed and food, and human exposure for dioxins and PCBs. Thus the integrated strategy will result in improved knowledge on how to reduce children's exposure for dioxins and PCBs and reduce risks in the European union as a whole. The results and examples in this Base line report will be used to formulate the strategies in the next report, ‘Recommendations for the Commission's Action Plan 2004-2010’.
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7 References References for the main text only, country annexes have their own reference lists
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Ahlborg UG, Brouwer A, Fingerhut MA, Jacobson JL, Jacobson SW, Kennedy SW et al. Impact of polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyls on human and environmental health, with special emphasis on application of the toxic equivalency factor concept. Eur J Pharmacol 1992; 228(4):179-199.
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Amirova Z. PCDD/Fs pollution in Russian regions (Urals, Volga region, far East and Siberia). Review of research made by Environmental Research & Protection Center, Ufa, Russia. TOCOEN Report 2003, No.244, 29p.
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Assmuth T, Vartiainen T. Concentrations of 2,3,7,8-chlorinated dibenzo-p-dioxins and dibenzofurans at landfills and disposal sites for chlorophenolic wood preservative wastes. Chemosphere 1994; 25:971-979.
Aune, M., Bjerselius, R., Atuma, S., Larsson, L., Bergh, A., Darnerud, P.O., Andersson, A., Arrhenius, A., Bergek, S., Tysklind, M., and Glynn, A. Large differences in dioxin and PCB levels in herring and salmon depending on tissue analysed. Organohalogen Compounds 2003;64:378-381.
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Axmon A, Rylander L, Strömberg U, Hagmar L. Miscarriages and stillbirths in women with a high intake of fish contaminated with persistent organochlorine compounds. Int Arch Occup Environ Health 2000; 73:204-208.
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Annex 1. Mandate of the sub-group
DRAFT Mandate : “Integrated monitoring of dioxins & PCBs in the Baltic Region”
1. Introduction Dioxins, furans and PCBs (polychlorinated biphenyls) are a group of toxic and persistent chemicals whose effects on human health and on the environment include dermal toxicity, immunotoxicity, reproductive effects and teratogenicity, endocrine disrupting effects and carcinogenicity. The toxic properties seem to have been underestimated and new epidemiological, toxicological and mechanistic data have emerged in particular with respect to neurodevelopmental, reproductive and endocrine effects, which indicate that dioxins and some PCBs have a broader impact on health than previously assumed, even in very low doses and in particular on the most vulnerable groups like breast-fed infants and the foetus, which is directly exposed to the accumulated maternal body burdens.
2. Problems identified Dioxin & PCB monitoring activities in the different environmental compartments (air, water, sediment, marine,…), feed, food, human health (blood, fat, breast milk, …) are not harmonised and therefore not comparable. An integrated dioxin & PCB monitoring system is needed in order to understand the link between dioxins & PCBs released into the environment, their transport through different environmental compartments, their accumulation in the environment, ecosystem, food and their effects on health. This integrated information is needed for further policy development.
3. Objectives An EU integrated dioxin & PCB monitoring system would provide the necessary information to understand the link between dioxins & PCBs and their adverse health effects, to develop further policy and to develop a methodology for integrated environment and health monitoring. It is an important step in the direction of the ultimate goal of the “Environment & Health Strategy”, notably: to develop an environment and health “cause-effect framework” that will provide the necessary information for the development of Community policy dealing with sources and impact pathways of health stressors.
4. Tasks of the Working Group Step 1 : definition of the baseline The Working Group will first define a baseline including :
• an overview of the existing dioxin & PCB monitoring activities & programmes in the Baltic Countries. This should include monitoring of the different environmental compartments (air, water, sediment, marine, bio-indicators (pine needles……), fish, human health (blood, fat, breast milk and also results from epidemiological studies).
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 88
• problems and deficits of existing monitoring systems e.g. related to the co-ordination and comparability of monitoring activities due to specific problems such as different measurement methods, different congeners analysed, different sample types, only local measurements, overlap of monitoring activities, etc. Such problems and deficits make it difficult to obtain a clear overview on the dioxin & PCB situation based on reliable and European-wide temporal and spatial trends.
• advantages of an integrated environment and health dioxin & PCB monitoring including the advantages at local, regional, national and Community level such as use of synergies, consistent and reliable data base, comparable data, avoidance of double work, saving of resources, etc. [note: The recognition of advantages is an important aspect to encourage and motivate all experts and stakeholders involved, also within the technical working group]
• requirements for an “integrated” environment and health dioxin & PCB monitoring e.g. determination of links between environment and health data, the establishment of an appropriate data base, harmonised sampling, comparable measurement and reporting methods, geographical co-ordination of monitoring activities, etc. [note: The determination of requirements is essential for the next task].
• an assessment of the possibility to integrate the existing activities & programmes and identify the missing links in order to develop an integrated environment and health dioxin & PCB monitoring
The result of this first step is the « Baseline Report » to be presented by the end of December 2003.
Step 2 : establishment of options for action & recommendations On the basis of the outcome of the first step, the Working Group will then :
• Establish options for action and recommendations for the Commission’s “AP 2004-2010”. In particular :
– Proposals for an EU integrated dioxin & PCB monitoring system (including proposals for revisions of existing legislation)
– Proposals on how to use the results and experiences generated by this pilot project in the development of the “overall EU Integrated E&H Monitoring & Response System”
– Proposals for actions to rectify any information defiates and gaps identified. These may include research where greater understanding of environmental and health interactions may be required.
– Proposals for preventive actions such as further legislation, regulation, enforcement of monitoring/emissions compliance, education and information programmes.
• Each recommendation or option presented will be accompanied by a justification of the choices, the practicability, the estimated impacts and costs involved, the time lines and the interlinkages with other measures or policies.
The result of this second step is the draft « Recommendations for the Commission’s Action Plan 2004-2010 » to be presented by the end of March 2004
Links with other TWGs should be ensured in step 1 as well as in step 2 (e.g. TWGs on neurodevelopmental disorders, endocrine disrupters, …)
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5. Chairs The Working Group will be chaired by Prof. Jouko Tuomisto and co-chaired by Dr Allan
Astrup Jenssen 6. Members Final list of members is to be established after the Prelimininary Meeting of the Consultative Group on 10/9. 7. Co-ordination, work methods, planning and deliverables Guidelines and requirements common to all groups are specified in the Framework Mandate and in the Co-ordination Mandate. Detailed planning is to be established by the chair and co-chair, in consultation with the Commission services.
***
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Annex 2. Country information 7.1 Countries in catchment area of the Baltic Sea 7.1.1 Denmark
1. Jensen AA, Grove A, Hoffmann L. Kilder til dioxinforurening og forekomst af dioxin i miljøet. Arbejdsrapport nr. 81. København: Miljøstyrelsen, 1995. 2. Jensen AA. Dioxins. Sources, Exposures and Levels in Denmark. Working Report No. 50. Copenhagen: DEPA, 1997. 3. Hansen E, Skaarup S, Jensen AA. Substance Flow Analysis for Dioxins in Denmark. DEPA, Environmental Project No. 570, 2000. 4. Hansen E, Hansen CL. Substance Flow Analysis for Dioxin 2002. DEPA, Environmental Project No. 811, 2003. 5. Jensen AA. Kortlægning af dioxinforurening samt kilder til dioxinforurening i Østersøen. Miljøprojekt 796. København: Miljøstyrelsen, 2003. 6. Jensen AA, Kyramarios M. Draft OSPAR Background document on chlorinated dibenzo-p-dioxins and chlorinated dibenzofurans (”Dioxins”). December 2001. 7. Vikelsøe J, Johansen E. Estimation of Dioxin Emission from Fires in Chemicals. Chemosphere 2000; 40:165-175. 8. Schleicher O, Jensen AA, Blinksbjerg P. Måling af dioxinemissionen fra udvalgte sekundære kilder. DEPA Miljøprojekt nr. 649, 2001. 9. Vikelsøe J, Madsen H, Hansen K. Emission of Dioxins from Danish Wood-stoves. Chemosphere 1994; 29(9-11): 2019-2027. 10. Vikelsøe J, Johansen E. Analyse af dioxin og pentachlorphenol i nye textiler. Danmarks Miljøundersøgelser. - Faglig rapport fra DMU 166, 1996. 11. Vikelsøe J, Blinksbjerg P, Jensen AA. Emissions of dioxins from co-incineration of health-care risk waste and municipal solid waste. Organohalogen Compounds 2000; 46: 232-235. 12. Oxbøl A, Schleicher O, Fuglsang K, Jensen AA, Jensen KB, Schilling B. Dioxin deposition around a Danish municipal incinerator. Organohalogen Compounds 2002; 57:369-373. 13. Schleicher O, Jensen AA, Blinksbjerg P, Thomsen E, Schilling B. Dioxin emissions from biomass fired energy plants and other sources in Denmark. Organohalogen Compounds 2002; 56: 147-150. 14. Schleicher O, Blinksbjerg P, Jensen AA, Wade P, Schilling B. Air emissions and dioxin in soil and vegetation around a metal reclaiming plant in Denmark. Organohalogen Compounds 2003; 61: 510-513. 15. Jensen AA, Blinksbjerg P. Baggrundsdokument for fastsættelse af luftemissions-grænseværdi for dioxin. MST RefLab1999. 16. Vikelsøe J. Dioxin måleprogram. Statusrapport April 2003. DMU. 17. Vikelsøe J, Hovmand M, Andersen HV. PCDD/F deposition, spruce throughfall and air in Denmark. Organohalogen Compounds 2003; 61: 454-457. 18. Vikelsøe J: Dioxins in Danish Soil. Organohalogen Compounds 2002; 57: 373-376.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 91
19. Vikelsøe J, Thomsen M, Carlsen L, Johansen E. Persistent Organic Pollutants in Soil, Sludge and Sediment. A Multianalytical Field Study of Selected Organic Chlorinated and Brominated Compounds. National Environmental Research Institute. NERI Technical Report 402, 2002. 20. Vikelsøe J. Dioxins and Organic Pollutants in Danish Sewage Sludge and Harbour Sludge. Organohalogen Compounds 2001; 50: 488-491. 21. Rapport over Dioxinhandlingsplan 2001. Fødevaredirektoratet/Plantedirektoratet, maj 2002. 22. Cederberg T, Laier P, Vinggaard AM. Screening of food samples for dioxin levels – comparison of GC/MS determination with Calux bioassay. Organohalogen Compounds 2002;58:409-412. 23. Dioxiner I modermælk. Hygiejnemeddelelser: 7. Sundhedsstyrelsen, 1987. 24. Indhold af dioxiner, PCB, visse chlorholdige pesticider, kviksølv og selen I modermælk hos danske kvinder 1993-94. Sundhedsstyrelsen/Fødevaredirektoratet, 1999. 25. Jensen AA, Schleicher O, Blinksbjerg P. Baggrundsdokument for emissionsgrænseværdi for PCB. MST RefLab 2002. 26. Maag J, Lassen C. PCB i apparater i Danmark. Arbejdsrapport fra Miljøstyrelsen 15, 2000. 27. Henriksen P, Andersen J, Carstensen J, Christiansen T, Conley D, Dahl K, Dahllöf I, Hansen JLS, Josefson A, Larsen MM, Lundsgaard C, Markager S, Nielsen TG, Pedersen B, Rasmussen B, Strand J, Ærtebjerg G, Fossing H, Krause-Jensen D, Middelboe A-L, Risgaard-Petersen N, Ellermann T, Hertel O, Ambelas Skjøth C, Ovesen NB, Glasius M, Pritzl G, Gustafson BG. Marine områder 2000 - Miljøtilstand og udvikling. NOVA 2003. Faglig rapport fra DMU 375. Danmarks Miljøundersøgelser, 2003. 28. Storr-Hansen E, Spliid H. Coplanar polychlorinated biphenyl congener levels and patterns and the identification of separate populations of harbor seals (Phoca Vitulina) in Denmark. Arch Environ Contam Toxicol 1993; 24: 44-58. 29. Storr-Hansen E, Spliid H. Distribution patterns of polychlorinated biphenyl congeners in harbor seal (Phoca vitulina) tissues: Statistical analysis. Arch Environ Contam Toxicol 1993; 25: 328-345. 30. Granby K, Kinze CC. Organochlorines in Danish and West Greenland harbour porpoises. Mar Pollut Bull 1991; 22: 458-462. 31. Mason CF, Madsen AB. Organochlorine Pesticide Residues and PCBs in Danish Otters (Lutra lutra). Sci Total Environ 1993; 133: 73-81. 32. Fromberg A, Cederberg T, Hilbert G. Determination of toxaphene congeners in fish samples from Danish waters. Organohalogen Compounds 1998; 35: 259-262. 33. Fromberg A, Cederberg T, Hilbert G, Büchert A. Levels of toxaphene congeners in fish from Danish waters. Chemosphere 2000; 40: 1227-1232. 34. Cederberg T, Fromberg A, Mosegaard H. Bioaccumulation of persistent halogenated organic compounds in herring (Clupea harengus). Organohalogen Compounds 2000; 49: 17-20. 35. Fromberg A. Determination of PCB congeners and organochlorine pesticides in fish oil food supplements. Abstract Dioxin2001. 36. Overvågningssystem for levnedsmidler 1988-1992. Publikation nr. 232. Levnedmiddelstyrelsen, 1995. 37. Overvågningssystem for levnedsmidler 1993-1997. Del 2. Kemiske forureninger. Fødevaredirektoratet, 1999. 38. Fromberg A, Højgård A, Østergaard L. Organochlorine pesticides in Danish milk. Organohalogen Compounds 2003; 64: 79-82. 39. Forurening af modermælk med visse chlorerede pesticider og PCB. Hygiejnemeddelelser:3. København: Sundhedsstyrelsen, 1983. 40. Statusredegørelse for indsatsen mod dioxiner. Ministeriet for Fødevarer, Landbrug og Fiskeri & Miljøministeriet, 15. maj 2003. 41. Hilbert G, Cederberg T, Büchert A, Andersen LS. Time trend studies of chlorinated pesticides, PCBs and dioxins in Danish human milk. Organohalogen Compounds 1996;30:123-126.
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7.1.2 Estonia Data 1978-1991 ( Baltic Sea - water, plankton, algae, fish, mussels, seal, etc): 1. O. Roots. Polychlorinated biphenyls and chlororganic pesticides in the ecosystem of the Baltic Sea - Tallinn Technical University, 1992, 181 p. (in Russian, tables and figures translated to English). 2. O. Roots. Toxic chlororganic compounds in the ecosystem of the Baltic Sea - Tallinn, Estonian Environment Information Centre, 1996, 144 p. (ISBN 9985-9072-0-5)(helios.nlib.ee). Air, precipitation and deposition. 3. O. Roots. Organochlorine pesticides and polychlorinated biphenyls in the ecosystem of the Baltic Sea. – Chemosphere, 1995, v. 31, No. 9, pp. 4085 – 4097. 4. G. Agrell, P. Larsson, L. Okla, G. Bremle, N. Johansson, M. Klavins, O. Roots, O. and A. Zelechowska. Atmospheric and River Input of PCBs, DDTs and HCHs to the Baltic Sea. In.: A System Analysis of the Baltic Sea ( Eds. F. Wulff, L. Rahm and P. Larsson ).Ecological Studies, ( Springer Verlag ), 2001, v. 148, pp. 149-175 ( ISSN 0070-8356; ISBN 3-540-67769-0 ). Soil 5. O. Roots, T. Jürma, I. Ojamäe and M. Laatsit. Kagu-Eesti prügilapinnase dioksiini- ja furaanisisaldus.- Keskkonnatehnika, 2003, No. 5, pp.33-35 ( in Estonian) 6. Kagu-Eesti prügila uuring. Eesti Keskkonnauuringute Keskus (Leping nr.15/2003 (E. Otsa ja O. Roots),2003, 10 lk (in Estonian). Fish (PCB): 7. O.Roots and M. Simm.. Persistent organic pollutants monitoring in the Estonian coastal waters – Baltic Sea Science Congress 2003 Helsinki. Abstract Publication, Finland, August 24-28, 2003, 229-230.
8. O. Roots, I. Holoubek and V. Zitko. Polychlorinated biphenyls and chlororganic pesticides patterns in perch ( Perca fluviatilis ). Fresenius Environmental Bulletin, PSP, 2003, v.12, No.8, 883-900. 9. O. Roots. Halogenated contaminants in female perch from the Matsalu Bay ( Baltic Sea ). Chemistry and Ecology. Taylor & Francis, 2003, v.19, No.1, 1-3. 10. O. Roots. Halogenated environmental contaminants in fish from Estonian coastal areas , Chemosphere (Elsevier Science Ltd.) , 2001 , v.43 , No. 4-7 , pp. 623-632. Fish (PCDD/Fs) (without skin) 11. O.Roots, R. Lahne, E. Otsa, M. Simm and Schramm, K.W. . Dioxin in the Baltic sea herring (Estonian data). Abstract Book. 7th Int. Symp. On Fish Physiology, Toxicology and Water Quality, Tallinn,2003, 44-45 12.E. Otsa, O. Roots and M. Simm. Determination of dioxins in the fish (Public procurement ref. Number:003664), Estonian Environmental Research Centre, 2002,12p. PCDD/Fs(with skin) 13. O. Roots, V. Zitko and I. Holoubek. Chlorinated dibenzo-p-dioxins and dibenzofurans patterns in the Baltic herring and sprat. Organohalogen Compounds, v. 62, 140-143 (DIOXIN 2003,USA August 24-29). 14. O. Roots, R. Lahne, M. Simm and K.W. Schramm. Dioxins in the Baltic herring and sprat in Estonian coastal waters. Organohalogen Compounds, v. 62, 201-203 (DIOXIN 2003, USA August 24-29). 15. E. Otsa, O. Roots and M. Simm. Dioxine content in Baltic herring and sprat in autumn 2002. Estonian Environmental Research Centre, Report ( Contract ) No. 397, Tallinn, 2003, 34p.( http://www.agri.ee/eng ) PCDD/Fs+dioxin like PCBs (with skin): 16. Dioksiinide ja dioksiinide sarnaste PCB sisaldused Eesti rannikumere kalades 2003 aastal, Leping 133, Eesti Keskkonnauuringute Keskus (E. Otsa, O. Roots ja M. Simm), 2003, 36 lk (in Estonian).
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Seal 17. O. Roots and A. Talvari. Bioaccumulation of toxic organic compounds and their isomers into the organism of Baltic grey seal. – Chemosphere ( Elsevier Science Ltd. ), 1997, v. 35, No. 5, pp. 979 – 985. 18. O. Roots and A. Talvari. Bioaccumulation of toxic organic compounds and their isomers into the organism of seals in West-Estonian Archipelago Biosphere Reserve. - Environmental Monitoring and Assessment (Kluwer Academic Publishers) (The Netherlands), 1999, v. 54, No. 3, pp. 301-312. 19. O. Roots. Did natural changes save the grey seal of the Baltic Sea? Hypothesis or reality. Toxicological and Environmental Chemistry (Gordon and Breach Science ) (Germany)), 1999, v. 69,No. 1-2, pp. 119-131. 20. O. Roots and V. Zitko. Polychlorinated Biphenyls Patterns in Grey Seals ( Halichoerus Grypus ). Ecological Chemistry, St. Petersburg ( Thesa ), 2002, v. 11, No. 1, 68 – 71( ISSN 0869-3498 )(www.thesa.ru). Sources (PCB): 21. I. Holoubek, A. Kocan, I. Holoubkova, K. Hilscherova, J. Kohoutek, J. Falandysz and O. Roots. Persistent, Bio-accumulative and Toxic compounds in the Central and Eastern European countries. –The-State-of-the-Art Report – hot spots. – Arch. Industr. Hyg. Toxicol., 2001, v.52, 239 – 251. 22. Holoubek I., R. Alcock, E. Brorström-Lundén, A. Kočan, V. Petrosjan, O. Roots, V. Shatalov, Z. Amirova, A. Bergman, A. Beyer, L. Bláha, P. Bureaul, P. Coleman, P. Čupr, S. Dutchak, J. Duyzer, J. Falandysz, C. Fuell, E. Heinisch, I. Holoubková, K. Jones, A. Kettrup, J. Kohoutek, S. Koroleyva, M. Krzyzanowski, R. Kubiak, G. Lammel, A. Lecloux, M. Machala, A. Malanichev, M. McLachlan, J. Lulek, A. Palm, A. Sweetman, D. van de Meent, M. van den Berg, J. Vanderbroght, J. Vijgen, P. Weiss, S. Wenzel: Regionally Based Assessment of Persistent Toxic Substance - European Regional Report. UNEP Chemicals. Number of project: GF/CP/4030-00-20, Number of subproject: GF/XG/4030-00-86, November 2002, 147 p. 23. Holoubek, I., A. Kocan , I. Holoubkova , K. Hilscherova , J. Kohoutek , J. and O. Roots Persistent , Bioaccumulative and Toxic Chemicals in Central and Eastern European Countries State-of-the-Art Report ( 2nd Version ).TOCOEN Report 150 a , Brno , CR , May 2000 , 253 p.( http://recetox.muni.cz ). Source (PCDD/Fs): 24. Project.Survey of anthropogenic sources of dioxins in the Baltic Region. Dioxin measurements in Estonia. DANCEE (J. No. M124/000-0139). 2003. Food: 25. Ilmoja, K and Reinik, M. 2000. Determination of PCBs in food samples. – Health Protection 1999. – Ministry of Social Affairs, Health Protection Inspectorate, Tallinn, 67-68.
26.O. Roots. POPs in the Estonian food – butter. J. Estonian Physician, 2003, No.2, 98-101 (in Estonian, summary in English).
Health: 27. O. Roots. The effect of environmental pollution on human health in the Baltic States (Assessment and regional differences). Tallinn 1999, 120 p. (ISBN 9985-881-13-3)(helios.nlib.ee). 28. O. Roots. Environmental levels of PTS in Estonia. Background document for the 1st Technical Workshop of UNEP/GEF Project Regional Based Assessment of Persis-tent Toxic Substances – Region III – Europe. TOCOEN Report No. 243, Brno, January 2003, 10p ( http://recetox.muni.cz ). Cancer: 29. O. Roots. Health concerns in the Baltic countries and environmental quality. – Ecological Chemistry, St. Petersburg, ( Thesa ), St. Petersburg, 2000, v. 9, No.1 , 54 – 62 ( ISSN 0869-3498 ). ADI and NOEL: 10. O. Roots. Halogenated environmental contaminants in fish from Estonian coastal areas , Chemosphere (Elsevier Science Ltd.) , 2001 , v.43 , No. 4-7 , pp. 623-632. 30. O. Roots. Polychlorinated biphenyls and chlororganic pesticides. Assessment of health risk associated with the consumption of seafood. – Proc. Estonian Acad. Sci. Ecol., 1996, v. 6, No. ¾, pp. 124 - 135.
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Breast milk. 31. I. Holoubek, A. Kocan, I. Holoubkova, K. Hilscherova, J. Kohoutek, J. Falandysz and O. Roots. Persistent, Bio-accumulative and Toxic compounds in the Central and Eastern European countries. – The State-of-the-Art Report- human exposure. – Arch. Industr. Hyg. Toxicol., 2001, v.52, 181 – 215. 32. O. Roots. 2002. Persistent organic pollutants levels in human milk and food ( Chemistry Preprint Server (CPS:envchem/0207001- http://www.chemweb.com).
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7.1.3 Finland (1) Korhonen, M., Kiviranta, A. and Ketola, R. (1998). Bulk deposition of PAHs, PCBs and HCHs in Finland in summer seasons 1993-1996. Tox. and Env. Chemistry, Vol. 66, pp. 37-45. (2) Korhonen, M., Verta, M., Salo, S., Kankaanpää, H. and Vartiainen, T. (2002). The deposition and sedimentation of PCDD/Fs in the Gulf of Finland. Organohalogen Compounds, Vol. 57: 317-320. (3) Borström-Lunden, E., Palm, A., Strömberg, K., Junedahl, E. and Leppänen, S. (2003). Atmospheric concentrations and deposition fluxes of persistent organic pollutants (POPs) at the Swedish West Coast and in Northern Fennoscandia. Status Reprt, IVL-U716. (4) HELCOM 2003. Manual for Marine Monitoring in the COMBINE programme of HELCOM. Part D. Programme for monitoring of contaminants and the effects of contaminants. (http://www.helcom.fi/Monas/CombineManual2/CombineHome.htm) (5) Korhonen, M., Verta, M. and Backström, V. (2001). 10 Harmful substances, pp. 94-104. In: The state of Finnish coastal waters in the 1990s. Kauppila, P. and Bäck, S. (eds). The Finnish Environment, 472. (6) Nakari, T., Suortti, A-M. and Järvinen, O. (2002). Monitoring of toxic compounds in fresh and coastal waters in 1997-1999. (in Finnish). Finnish Environment Institute, Mimeographed report 271/ 2002. (7) Korhonen, M., Verta, M., Lehtoranta, J., Kiviranta, H. and Vartiainen, T. (2001). Concentrations of polychlorinated dibenzo-p-dioxins and furans in fish downstream from Ky-5 manufacturing. Chemosphere, 43 (2001), 567-593. (8) Olsson, M., Bignert, A., Aune, M., Haarich, M., Harms, U., Korhonen, M., Poutanen, E-L., Roots, O. and Sapota, G. (2002). 6.3.2. Organic contaminants, pp. 133-140. In: Environment of Baltic Sea area 1994-1998. Baltic Sea Environment Proceedings No. 82B. Helsinki Commission, 2002. (9) Vuorinen P.J., Paasivirta J., Keinänen M., Koistinen J., Rantio T., Hyötyläinen T. & Welling L. 1997. The M74 syndrome of Baltic salmon (Salmo salar) and organochlorine concentrations in the muscle of female salmon. Chemosphere 34: 1151-1166.
(10) Vuorinen P.J., Parmanne R., Vartiainen T., Keinänen M., Kiviranta H., Kotovuori O. & Halling F. 2002. PCDD, PCDF, PCB and thiamine in Baltic herring (Clupea harengus L.) and sprat (Sprattus sprattus (L.)) as a background to the M74 syndrome of Baltic salmon (Salmo salar L.). ICES J. Mar. Sci. 59:480-496. (11) Verta, M., Lehtoranta, J., Salo, S., Korhonen, M. and Kiviranta, H. (1999). High concentrations of PCDDs, and PCDFs in river Kymijoki sediments, South-Eastern Finland, caused by wood preservative Ky-5. Organohalogen Compounds Vol. 43:261-263..
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(12) Isosaari, P., Kankaanpää, H., Mattila, J., Kiviranta, H., Verta, M., Salo, S. and Vartiainen, T. (2002). Spatial distribution and temporal accumulation of polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in the Gulf of Finland. Environ. Sci. Technol. 36:2560-2565. (13) HELCOM 2002. Environment of the Baltic Sea area 1994-1998. Baltic Sea Environment Proceedings No. 82 B. Helsinki Commission. Baltic Marine Environment Protection Commission 2002. (14) Finnish Environment Institute (SYKE), monitoring database 2000.
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7.1.4 Germany
As Germany is a country with a federal structure, most monitoring activities in Germany are carried out by the Länder (Federal States). PCDD/PCDF levels have been measured in many different monitoring programs for years. At their 34th Conference in 1990, the Federal and Länder Ministers for the Environment decided to set up a joint working group on dioxins. The working group was commissioned inter alia to initiate and coordinate measuring programs and to documenting and evaluate the data generated. Substances to be included were polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), polychlorinated biphenyls (PCB) and other chlorinated organic compounds; the results were to be entered into a central database. This German DIOXIN Database is maintained by the Federal Environmental Agency (UBA) for environmental matrices including emissions and by the former Federal Institute for Consumer Safety and Veterinary Medicine (now reorganized in the Federal Institute for Risk Assessment and the Federal Office for Consumer Protection and Food Safety) for food and concentrations in humans.
The Federal Government/Länder DIOXIN working group elaborated data collection forms for documentation of the analysis results and specific metadata for the various compartments (inter alia sampling procedure, analytic method). Most data have been reported on a congener-specific basis, which allows calculation of toxic equivalents either according to the International or the WHO schemes. Further, TEQs are calculated using different approaches for the limit of detection or quantification (upperbound, halfbound and lowerbound). Most data were provided by the Länder and forwarded to the central database.
In 1994 the Federal Government/Länder DIOXIN working group started a dioxin reference measuring program. This multi-annual program allows conclusions to be drawn about long-term trends.
The German environmental specimen bank (ESB) is part of the ecological monitoring program in Germany, financed by the federal government. The ESB draws, processes and stores biotic samples from marine ecosystems (bladder wrack [Fucus vesiculosus], common mussel [Mytilus edulis], eelpout [Zoarces viviparous], herring gull egg [Larus argentatu], limnetic ecosystems (zebra mussels [Dreissena polymorpha], bream [Abramis brama]) and terrestric ecosystems as well as human samples (blood, urine, hair). The greatest potential of the ESB is the possibility to conduct retrospective monitoring.
For marine ecosystems there are two sampling sites in the North Sea and one in the Baltic Sea. The sampling area in the Baltic Sea is located seawards off the peninsula Zingst and Darss near the island of Ruegen. The samples are routinely monitored for heavy metals, polycyclic aromatic hydrocarbons and a fixed set of organochlorine compounds including PCB (the indicator congeners 28, 52, 101, 138, 153, 180).
1. BMU - Bundesministerium für Umwelt, Naturschutz und Reaktorsicherheit 2003: DIOXINS Data from Germany – Data on environmental pollution by dioxins – 3rd report of the Federal Government/ Länder working group on dioxins, http://www.umweltbundesamt.de/uba-info-daten-e/index.htm The focus of this report was the evaluation of the 117 measuring programs contained in the DIOXIN database with a total of about 10,000 datasets. It contains data for soil, air, deposition, biota, chemicals (products/mixtures) and sewage sludge.
2. BMU - Bundesministerium für Umwelt, Naturschutz und Reaktorsicherheit 2003: DIOXINS Data from Germany – Dioxin reference measuring program - 4th report of
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the Government/Länder working group on dioxins, http://www.umweltbundesamt.de/uba-info-daten-e/index.htm. The results of the Dioxin reference measuring program are published in this report, including data for soil, sediments, air, bioindicators, cow milk as well as human data.
3. Information about the German environmental specimen bank including extensive data retrieval is available on the Internet: www.umweltprobenbank.de. All procedures (sampling, sample preparation, analyses, storage) are performed according to Standard Operating Procedures and documented in the data management and information system of the ESB. These documents will soon be available via the Internet in German and English.
4. Bayrisches Landesamt für Umweltschutz (2003): Dioxinähnliche PCB in der Umwelt – Quellen, Verbleib, Exposition und gesundheitliche Bewertung. Fachtagung 13./14 Jan 2003, Augsburg 2003. http://www.bayern.de/lfu
5. Kerst, M. et al. (2003): Dioxin-like PCB in environmental samples in southern Germany. Fres. Environ Bull. 12 (6) 2003, 511-516
6. R & D project in Bavaria in 2003 – 2005, Untersuchung und Bewertung von Proben aus verschiedenen Umweltkompartimenten auf PCDD/F sowie PCB unter Berücksichtigung der neuen WHO-Toxizitätsfaktoren [Investigation and evaluation of samples from different environmental compartments with respect to PCDD/F and dioxin like PCB having regard to the new WHO TEF]
7. Sewage sludge: Concentrations of PCDD/F and Indicator PCBs in sewage sludge are determined on a regular basis. All operators of sewage treatment plants which spread sludge on agricultural or horticultural soils have to analyse the sludge biannually (about 800 samples annually). These data are collected by the competent Länder authorities and reported regularly to the European Commission (article 16 of Directive 91/271/EEC)
8. Detzel, A. et al. (1998): Investigation of emissions and abatement measures for persistent organic pollutants in the Federal Republic of Germany, 1998 UBA - Texte 75/98
9. Johnke B., Menke D.; Böske J.(2003): “WHO Revision of the Toxic Equivalency Factors for Dioxins and Furans and its impact on the emissions of waste incineration plants in Germany. Newsletter, NR. 31, WHO Collaborating Centre for Air Quality Management and Air Pollution Control, Berlin, 5-12 6/2003
10. Ambient air and deposition: Time series with comparable data are being compiled in some Länder. They started in different years, the longest dating back to 1989. The sites are located in characteristic areas (industrial, urban, rural) and mostly have no specific source nearby to also cover the trend in background pollution. The measurements are carried out all year round in order to cover seasonal variations. The first series with dioxin like PCB started in 2000.
11. R & D project in Bavaria in 2002 – 2004: Ermittlung der Immission von PCDD und PCDF und dioxinähnlichen PCB in Bayern. [Determination of ambient air levels of PCDD, PCDF and dioxin like PCBs in Bavaria]
12. Environmental specimen bank: Retrospective monitoring of eelpout muscles samples from 1994 to 2003 at 2 locations (North Sea, Baltic Sea-Darß) – 14 samples;
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herring gull eggs samples from 1988 to 2003 (2 locations North Sea) and from 1993 to 2003 (1 location Baltic Sea-Heuwiese) bream muscle samples from 1995 and 2000 from 14 locations (River Saar, Rhein, Elbe, Saale, Mulde, Belauer See) All samples will be analysed for PCDD/F and dioxin like PCBs. Measurement of indicator PCBs is part of the standard program.
13. R & D project in Bavaria 2001, 2003: Wissenschaftliche Grundlagen für den Vollzug der Bodenschutzgesetze. In 2001 analysis of 100 samples only for PCDD/F, in 2003 analysis of 200 samples for PCDD/F and dioxin like PCB
14. Schöppe G.,et al. (1996): Untersuchung zum Eintrag von PCDD und PCDF über Tierkraftfutter in die menschliche Nahrungskette [Pathways of PCDD and PCDF input into food . Umweltbundesamt F+E Vorhaben UBA-FB Nr. 97-102
15. R & D project : A national project is planned to investigate feedingstuffs and food of animal origin. Until 2006 1000 samples (feedingstuffs, milk and milk products, meat and meat products, eggs, fish and fish products) will be collected all over Germany and analysed for dioxins, furans, dioxin-like PCBs and non dioxin-like PCBs.
16. Children monitoring: The monitoring program is described in the 4th report (2). The monitoring programme includes fourth-grade children at 4 locations. For PCDD/F analysis16 pooled blood samples, each consisting of 5 to 30 single samples (boys, girls, breastfed and not breastfed), were used, . In 2000/2001 analysis also included dioxin like PCBs. More details and recent results (congeners) are available in German via the Internet: http://www.landesgesundheitsamt.de - Epidemiologie, Gesundheitsberichte.
17. Environmental specimen bank: Retrospective monitoring of human blood samples. 20 samples annually from 1977 to 1999, analysed for PCDD/F, 5 dioxin like PCBs, 6 indicator PCBs
18. Human milk: Results from the human milk program in Lower Saxony are available via the Internet: http://www.nlga.niedersachsen.de/umwelt/mumi.htm (in German)
19. Food and feedingstuffs: Results from Lower Saxony are available via the internet: http://www.laves.niedersachsen.de/master/0,,C1526122_N1225_L20_D0_I826,00.html Jahresbericht – in German
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7.1.5 Poland 1-7. Bykowski, P.J et all. Reports from national state monitoring soil, plants, agriculture and
food products, Min. Of Agriculture, Warszawa 1996, 1997, 1998, 1999, 2000, 2001, 2002. [in Polish]
8. Falandysz, J.,1975, Presence of polychlorinated biphenyls (PCBs) in food. Roczniki Państwowego Zakładu Higieny, 26, 197-204. [in Polish]
9. Falandysz, J.,1987, Occurrence of polychlorinated biphenyl (PCB) residues in seafoodresources and an attempt to assess daily intake of this compounds in Poland in 1970-1982. Studia i Materiały, Seria D, No. 16. [in Polish]
10. Falandysz, J., 1994, Polychlorinated biphenyl concentrations in cod-liver oil: evidence of steady-state condition of these compounds in the Balitic oils and levels noted in Atlantic oils. Archieves of Environmental Contamination and Toxicology,27, 266-271.
11. Falandysz, J.,1999, Polychlorinated biphenyls (PCBs) in the environment: chemistry, toxicity, concetrations and risk assessment. Fundacja Rozwoju Uniwersytetu (Gdańskiego, Gdańsk). [in Polish]
12. Falandysz, J., Dembowska, A., Stranberg, L., Stranberg, B., and Rappe, C., 1998, Spatial distribution of PCBs in threespined stickleback from the beach zone in the Gulf of Gdańsk, Baltic Sea. Organohalogen Compounds, 39, 229-233.
13. Falandysz, J., Kawano, M., Kannan, K., and Rappe, C., 2000, Relative contribution of chlorinated naphthalens, -biphenyls, -dibenzofurans and -dibenzo-p-dioxins to toxic equivalent in biota from the southern coast of the Baltic Sea, Organohalogen Compounds, 47, 9-12.
14. Falandysz, J., Tanabe, S., and Tatsukawa, R., 1994a, Most toxic and highly bioacumulative PCB congeners in cod-liver oil of Baltic origin processed in Poland during 1970s and1980s, their TEO-values and possible intake. Science of Total Environment, 145, 207-212.
15. Falandysz, J., Yanashita, N., Tanabe, S., and Tatsukawa, R., 1994b, Congener specific data of polychlorinated biphenyl residues in human adipose tissue in Polan. Science of Total Environment, 149, 113-119,
16. Falandysz, J., Wyrzykowska, B., Puzyn, T., Strandberg, L., and Rappe, C., Polychlorinated biphenyls (PCBs) and their congener-specific accumulation in edible fish from the Gulf of Gdańsk, Baltic Sea, Food Additives and Contaminants, 2002, Vol. 19, No. 8.
17. Falandysz J., Brudnowska B., Iwata H., Tanabe S.: Organochlorine pesticides and PCBs in ambient air in city of Gdansk. Roczniki PZH 1999; 50:39-47.
18. Kawano M., Brudnowska B., Falandysz J., Wakimoto T.: Polichlorinated biphenyls and orgnaochlorine pesticides in soils in Poland. Roczniki PZH 2000; 51: 15-28.
19. Grochowalski, A., Chrząszcz, R., The Result of the Large Scale Determination of PCDDs, PCDFs and Coplanar PCBs in Polish Food Product Samples using GC-MS/MS Technique. Organohalogen Compounds 47, 306-310, 2000.
20. Grochowalski, A., Ambient air concentration and emissions of dioxins in Poland. JRC Workshop on the Determination of dioxins in Industrial Emission. Brno,Czech republic, 16-19.04.2002. EUR 20538 EN p.87-98. ISBN 92-894-4862-8.
21. Góralczyk K., Czaja K., Ludwicki J.K.: Biological and environmental monitoring of exposure to chlorinated aromatic hydrocarbons. Roczniki PZH 1996; 47: 25-32 (in Polish).
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22. Ludwicki J.K., Czaja K., Struciński P.: An attempt on health risk assessment for the environmental exposure to chlorinated aromatic hydrocarbons. Roczniki PZH, 1996; 47: 33-39 (in Polish).
23. Czaja K., Ludwicki J.K., Góralczyk K., Struciński P.: Organochlorine pesticides, HCB and PCBs in human milk in Poland. Bull. Environ. Contam. Toxicol. 1997, 58, 769-775.
24. Czaja K., Ludwicki J.K., Góralczyk K., Struciński P.: Effect of Age and Number of Deliveries on Mean Concentration of Organochlorine Compounds in Human Breast Milk in Poland. Bull. Environ. Contam. Toxicol. 1997, 59, 407-413.
25. Czaja K., Ludwicki J.K., Góralczyk K., Struciński P.: Effect of Changes in Excretion of Persistent Organochlorine Compounds with Human Breast milk on Related Exposure of Breast-Fed Infants. Arch. Environ. Contam. Toxicol. 1999, 36, 498-503.
26. Struciński P., Ludwicki J.K., Góralczyk K., Czaja K., Olszewski W., Barańska J., Robson M., Buckley B.: Organochlorine Pesticides Residues in Human Breast Adipose Tissue in Poland. 6th Meeting of the Central and Eastern European Section of SECOTOX (International Society of Ecotoxicology and Environmental Safety) - Organochlorine Pollution in Central and Eastern Europe - Hazard and Risk for Humans and the Environment, Balatonföldvár, Hgary, September 19-23, 1999, 88.
In Poland, Institute of Environmental Protection implements the Project: "Enabling activities to facilitate early action on the implementation of the Stockholm convention on persistent organic pollutants (POPs)" with the main objective to prepare inventories of threats from use in Poland of hazardous substances, subject of the Stockholm Convention and to develop the National Implementation Plan. The main outcomes of the project activities are: National POP profile, and Poland’s Implementation Plan for the Stockholm Convention (to be completed by the end of 2003). The national profile includes comprehensive inventory part, covering several aspects of POPs in Poland, e.g. legal status, health issues, export, import, emission to air, releases to other media, monitoring, research, etc. In May 2003, a workshop was held to present Poland’s inventory. Reports (in Polish) are available at: http://ks.ios.edu.pl. Monitoring data on PCBs in river water (from basic and bench mark monitoring) are available in the annual reports of the State Environmental Protection (Status of the river, lake and marine waters in Poland). Data on PCBs in the bottom sediment in the Oder river are available from the “International Oder Project” carried out between 1998-2000.
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7.1.6 Sweden Monitoring programme for marine fish The Swedish national monitoring programme (Swedish EPA). Data can be accessed at the datahost at http://www.ivl.se/miljo/db/. A summary of results can also be obtained at http://www.nrm.se/mg/monitor.html.en. Monitoring in background air The Swedish national monitoring programme (Swedish EPA). Data can be accessed at the datahost at http://www.ivl.se/miljo/db/. Monitoring programme for food The National Food Administration. More information can be obtained at http://www.slv.se/engdefault.asp. Monitoring programmes for PCB and dioxins in animal feed The Swedish Board of Agriculture. More information can be obtained at http://www.jordbruksverket.se/net/SJV/Home. Monitoring in breast milk and human tissues The Swedish national monitoring programme (Swedish EPA). Data can be accessed at the datahost at http://www.imm.ki.se/national/datavard/introsidan.asp. Monitoring programme for the water environment The Swedish national monitoring programme (Swedish EPA). Data can be accessed at the datahost at http://www.ivl.se/miljo/db/. A summary of some results can also be obtained at http://www.nrm.se/mg/monitor.html.en. Emissions of PCB and dioxins from different sources to the environment Project run by the Swedish EPA under 2004. Contact person Niklas Johansson (e-mail: [email protected]). 7.2 Countries not in the immediate vicinity of the Baltic Sea
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7.2.1 Austria In the following a brief overview of existing dioxin and PCB monitoring activites in Austria will be given. A more comprehensive staus report of the Austrian Environment, also with regard to POPs, can be found in the Report State of the Environment in Austria which is prepared and updated by the Umweltbundesamt on a regular basis. The current report is Volume 6 (2002). Sources: Emissions of waste incinerations and large combustion plants are regulated and
controlled according to Ec-directives 2000/76/EC and 2001/80/EC respectively. Measurement data are in most cases not open to the public due to legal regulations. According to UNECE Convention on CLRTAP Austria already reports emission data for PCDD/F and PCB on a yearly basis.
Air: Since 1997 Austria carries out an ambient air measrument programme for PCCDD/F, dioxin-like PCB and indicator PCB. The programme comprises 8 sampling sites of different types (urban, rural, industrial, remote) with mesuring campaigns during winter and summer.
Water: In 2000 measurements of indicator PCB in river water at more than 60 sampling sites in the framwork of the Austrian Water Monitoring Database (WGEV) have been carreid out.
Soil: Indicator PCBs have been analysed in the provinces Carinthia and Upper Austria according to a systematic grid. Several other studies have been carried out at local level. The Umweltbundesamt operates the Soil Information System BORIS, which currently holds soil information (site-, profile data and measured values) from more than 10.000 sites. In the framework of several studies measurements of PCDD/F and PCB in remote forest soils and spruce needles have been carried out.
Feed: Monitoring of PCDD/F, dioxin-like PCB and indicator PCB according to
commission directive 2002/32/EC, app. 70 samples of feed and feed components per year.
Food: Milkmonitoring of PCDD/F, dioxin-like PCB and indicator PCB in app. 30 raw milk samples per year. Monitoring of PCDD/F, dioxin-like PCB and indicator PCB in food according to commission directive (will come into force by end of 2003) will start 2004, comprising app. 45 samples of dirfferent matrices.
Literature A. Riss: Impact of PCDD/F emissions of a copper reclamation plant: five years of experience with environmental monitoring. Organohalogen Compounds, Vol. 14. Vienna, pp. 23-26 (1993). G.Thanner, W.Moche; Dioxine in der Luft von Ballungsräumen Teil 1; UBA-Monographien Band 50 (1994). G.Lorbeer, W.Moche, G.Thanner; Dioxine in der Luft bei Inversionswetterlagen: Ergebnisse von fünf Meßstellen in Linz; UBA-Bericht 045 (1995).
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G.Thanner, W.Moche; Dioxine in der Luft bei Inversionswetterlagen: Ergebnisse von vier Meßstellen in Graz; UBA-Report 113 (1995). W.Moche, G.Thanner; Dioxinimmissionsmessungen in Ulmerfeld/Amstetten; UBA-Bericht 031 (1995). W.Moche, G.Thanner; Ambient Air Concentrations of Dioxins during Stable Weather Conditions; Organohalogen Compounds Vol. 28, 291-294 (1996) . W.Moche, G.Thanner; Ambient Air Concentrations of Dioxins in Austrian Conurbations; Organohalogen Compounds Vol. 28, 286-290 (1996). G.Thanner, W.Moche; Dioxinimmissionen in Leoben-Donawitz; UBA-Bericht 066 (1996) G.Thanner, W.Moche; Dioxine in der Luft von Ballungsräumen Teil 2; UBA-Monographien Band 76 (1996). P.Weiss, W.Moche, G.Thanner; PCDD/F in Spruce Needles and Soils of Background Forest Sites in Austria; Organohalogen Compounds Vol. 32, 112-117 (1997). P.Weiss, W.Moche, G.Thanner; Changes of PCDD/F Homologue Profiles from Forest Canopy to Forest Soil; Organohalogen Compounds Vol. 33, 205-208 (1997). W. Moche, G.Thanner; Modification of a MAT 90 for Use with two Gaschromatographs Organohalogen Compounds Vol. 31, 136-138 (1997). W.Moche, G.Thanner; Ambient Air Patterns and Concentrations of PCDD/F in the Vicinity of Steelworks in Austria; Organohalogen Compounds Vol. 32, 380-383 (1997). U. Quaß, M. Fermann; Identification of Relevant INdustrial Sources of Dioxins and Furans in Europe, Materialien N. 43, Landesumweltamt Nordrhein Westfalen (1997). G.Thanner, W.Moche; Dioxinimmissionsmessungen in Graz, Ostern 1997; UBA-Bericht 109 (1998). W. Moche, G.Thanner; PCDD/F-Emissions from Coal Combustions in Small Residential Plants; Organohalogen Compounds Vol. 36, 329-333 (1998).
Öberösterreichische Bodenzustandsinventur, Amt der OÖ LR 1993, Bodenzustandinventur Kärnten, Amt der Kärntner LR (1999).
W. Moche, G.Thanner; PCDD/F-Emissions from Domestic Heating with Wood, Coal and Coke; Organohalogen Compounds Vol. 46, 295-297 (2000).
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W. Moche, G.Thanner; PCDD/F-Emissions from Road Traffic abtained by Tunnel Experiments; Organohalogen Compounds Vol. 46, 284-286 (2000). W. Moche, G.Thanner; One Year Continuous Monitoring of PCDD/F and PCB Ambient Air Concentrations in the Vicinity of Steelworks in Austria; Organohalogen Compounds Vol. 51, 81-83 (2001). U. Quaß, M. Fermann. G.Bröker; The European Dioxin Emission Inventory Stage II; Materialien N. 59, Landesumweltamt Nordrhein Westfalen (2001). W. Moche, G.Thanner; Ambient Air Monitoring of PCDD/F and PCB in Austria; Organohalogen Compounds Vol. 57, 5-6 (2002). G.Thanner, W.Moche; Emissionen von Dioxinen, PCBs und PAHs aus Kleinfeuerungen; UBA-Monographien Band 153 (2002). State of the Environment in Austria, Vol. 6; Umweltbundesamt, Vienna, (2002).
K. Kienzl, A. Riss, W. Vogel, J. Hackl, B. Götz,. Bioindicators and biomonitors for policy, legislation and administration. In: Bioinidicators and Biomonitors, 2003 Elsevier Science Ltd. (2003). B. Gugele, K. Huttunen, M. Ritter; Annual European Community CLRTAP emission inventory 1990-2001; Technical Report (in preparation), European Environment Agency (2003). M. Anderl et al., 2003, Luftschadstoff-Trends in Österreich 1980-2001 ; Report (in prearation)Umweltbundesamt Austria (2003). 7.2.2 Belgium
Sources Belgian estimated total dioxin emissions in 2001: 163.58 g I-TEq. EC Report on dioxin emissions “EPER” in September 2003 for the first time. Flanders (Northern part of Belgium): emission in the year 2000: 98415 mg I-TEQ, of which 73% from the population (open fires and heating of buildings), 13% from trade and services (e.g. waste incineration), 14% from industry (especially ferric and non-feric industry and industrial heating devices). Air Emissions are measured routinely for all incinerators and industry at risk, often in continous sampling systems of PCDD/F. Reporting for the South of Belgium: http://environnement.wallonie.be/data/air/dioxines/index.htm for continuous sampling
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(incinerators) and at http://mrw.wallonie.Be/dgrne/data/air/valorisation/index.htm for punctual sampling of emission at sources. Reporting for the North of Belgium: “Milieuhandhavingsrapport van de Afdeling Milieu-inspectie” Depostion measurements: targeted and random. Dioxin deposition measurements since 1995. Deposition of PCB126 is being analysed since two years. Many samples a year, more than once a year. http://www2.vmm.be/servlet/be.coi.gw.servlet.MainServlet/standard?toDo=open&id=1993&& http://www2.vmm.be/servlet/be.coi.gw.servlet.MainServlet/standard?toDo=open&id=1993&& Aquatic environment OSPAR: Routine monitoring of bioindicators at the coast (shellfish, …) of the North Sea. This is different from food monitoring. Ongoing research project on marine bioindicators and marine sediments. The final report is being written. Project Effects of pollutants on benthic populations and communities of North Sea organisms. Cristina Beans, Virginie Debacker, Thierry Jauniaux, Anne-Cécile Massart, Gauthier Eppe, Jean-Marie Bouquegneau and Edwin De Pauw. 2003. Dioxins, furans and dioxin-like PCBs in juvenile harbour porpoises (Phocoena phocoena) from the North Sea. Organohalogen Compounds, vol 62, 240-243. V. Debacker, G. Eppe, A.-C. Massart, C. Xhrouet, T. Jauniaux, P. Huart, P. Hauteclair, J-M Bouquegneau and E. De Pauw. 2003. Polychlorinated dibenzo-p-dioxins and dibenzofurans in livers of an Atlantic seabird, the common guillemot Uria aalge: influence of the general body condition. Organohalogen compounds, vol. 64, 443-446. Fresh water fish: analysis of PCBs in eel in rivers in Flanders (North of Belgium): http://www.ibw.vlaanderen.be/ This is not food, as it is not allowed to eat this fish. A monitoring programme for dioxin, furan and PCBs was launched in 2001 in Walloon rivers and finished in April 2003 (eel and chub as bioindicators). Water environment and Wallonia (South of Belgium): in 2003, ICES 7 PCBs are analysed in 21 locations in surface water and sediments several times of the year. Reporting by DGRNE. Plans are made for 2004 to increase the number of samples if possible. Soil and terrestrial environment See also food and feed. In case there is a problem with food or feed contamination and environmental problems are suspected, sometimes samples of soil are analysed as a follow up according to Recommendation 2002/201/EC.
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No routine monitoring of soils. Some measurements on request. Some punctual studies of PCBs in soil: “Comparison of analyses for 29 soils collected from representative areas in Walloon Region (industrial sites, incinerators, agricultural zones, paper making industry traffic axes, zone “blanche”)” Some work on analytical methods. Interlaboratory study on soils/sediments and particles. Fish Fish, included in the regular food monitoring for PCBs (ICES7) and dioxins (PCDD/F) and dioxin like PCBs, including imported fish and domestic fish, aquaculture and sea fish. Remark: for the analysis of PCBs in fish (ICES 7), the skin itself is removed as it gives problems during homogenisation, but all the fat near the skin is included by removing all the fat layers from the skin and include this in the homogenate. See also bioindicators for aquatic environment. Feeding stuffs Since the year 2000, the number of routine samples for control of PCBs (ICES7) and dioxins (PCDD/F) is very high. In 2002, for PCB’s analyses are made on 284 samples feed materials, 3 samples additives, 390 samples premixes and on 10491 samples composed feedingstuffs (for cattle, sheep, pigs, poultry, rabbit, horse, and other animals). Only 5 samples exceeded the limits. For dioxins in 2002 22 samples of feed materials were analysed, 80 samples of additives, and 757 samples of composed feedingstuffs. These samples are official samples in addition of the obligatory autocontrol of critical ingredients. Sampling for Recommendation 2003/91/EC. Reporting according to directive 95/53/EC. See also www.favv.be Research project ongoing on modelling and transfer factors from soil to feed to food. “Chain model for the impact analysis of contaminants in primary food products”. Food Belgium has national maximum levels for indicator PCBs (ICES 7) in the royal decree of 19 May 2000, amended by the royal decree of 6.3.2002. The number of samples for the analyses of PCBs (ICES 7) and dioxin-like PCBs and dioxins (PCDD/F) has been increased in recent years and the kind of foodstuffs include since 2002 all of recommendation 2002/201/EC: the major kinds of meat and poultry, fish, milk (farm milk targeted and random and pooled milk samples)and dairy products (cheese and butter, including imported products), eggs (including free range eggs), fish (liver) oil, animal fats, vegetable oil, fruits, vegetables and cereals. The number of samples for dioxins is about 200 a year, exceeding the number of samples in the EU draft recommendation SANCO/4546/01-rev.3. For ICES7 PCBs in foodstuffs, in 2001 the Food Agency had 982 samples of meat analysed and 627 samples of other foodstuffs. See also www.favv.be . Monitoring of dioxins in milk is going on already since 1990. Analyses of dioxin-like PCBs since 2000. Clear time trend of lowering concentrations. Sampling method according to EU legislation (directive 2002/69 or 96/23). Reporting partially in the frame of directive 96/23/EC. Since recently reporting in electronic form
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(excell) including congener information according to the format of the Commission (SANCO/4546/01-rev.3). In addition: Levels of PCDDs, PCDFs and PCBs in Belgian and international fast food samples, Chemosphere, Volume 54, Issue 1, January 2004, Pages 137-142 Survey of commercial pasteurised cows' milk in Wallonia (Belgium) for the occurrence of polychlorinated dibenzo-p-dioxins, dibenzofurans and coplanar polychlorinated biphenyls, Chemosphere, Volume 52, Issue 4, July 2003, Pages 725-733 Levels and congener distributions of PCDDs, PCDFs and non-ortho PCBs in Belgian foodstuffs: Assessment of dietary intake, Chemosphere, Volume 48, Issue 2, July 2002, Pages 167-179 Exposure estimates of dioxins (and dioxin like PCBs): During 1999-2000: participation in SCOOP Task 3.2.5 (DGSANCO): Assessment of dietary intake of dioxins and related PCBs by the population of EU Member States. In Belgium, cheese was identified as the most important contributor of intake of milk fat. B. Vrijens, S. De Henauw, K. Dewettinck, W. Talloen, L. Goeyens, G. De Backer and J.L. Willems. Food additives and Contaminants, 2002, vol.19, No.7, 687-700. Probabilistic intake assessment and body burden estimation of dioxin-like substances in background conditions and during a short food contamination period. Advice 2002/35 of the Scientific Committee of the Food Agency about eggs of free range chickens in private gardens. http://www.favv-afsca.fgov.be/portal/page?_pageid=34,65286&_dad=portal&_schema=PORTAL Broeckaert and Bernard. 2000. Polychlorinated biphenyls (PCBs) and dioxins (PCDD/Fs) in the contaminated food chain in Belgium: sources, profiles and correlations. Breast milk During the year 2000, two pooled samples (from 6-10 mothers) of breast milk were collected in only one city according to the WHO protocol and analysed in a German laboratory of WHO. Results will be published soon. Calux assay for dioxins on the same two pooled samples give 30.7 and 26.1 pg TEQ/g fat, respectively. Levels and profiles of PCDDs, PCDFs and cPCBs in Belgian breast milk: Estimation of infant intake. Chemosphere, Volume 48, issue 8, september 2002, pages 763-770. Catherine Pirard, Edwin De Pauw and Jean-François Focant. 2003. Levels of selected PBDEs and PCBs in Belgian human milk. Organohalogen compounds, vol. 61, 263-266. Human tissues Dioxin accumulation in residents around incinerators. Journal of toxicology and environmental health, Part A, 66:1287-1293 (2003). S. Fierens, H. Mairesse, A. Bernard. 2002. “Evaluation de l’exposition environnementale aux dioxines et polluants associés en Region wallone” Dioxine-like PCBs were analysed in blood. People living near sources (incinerators etcetera) were compared to people from an area without sources. Only in the neighbourhoud of one source, significant higher levels were found in blood. In people eating more than 150 g of fat from products of poultry and cattle from the neighbourhoud of the source, the body burden
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 109
was doubled. The emissions of the incinerator were high until the nineties and now comply with the legislation. FLEHS: In 1999 the project “Flanders Environmental and Health Study” was set up to measure a series of exposure and health effect biomarkers. Concerning dioxins and PCBs, the following publications were made: 1) Gudrun Koppen, Adrian Covaci, Rudy Van Cleuvenbergen, Paul Schepens, Gerhard Winneke, Vera Nelen, Greet Schoeters. Comparison of CALUX-TEQ values with PCB and PCDD/F measurements in human serum of the Flanders Environmental and Health Study (FLEHS) Toxicology Letters 123 (2001) 59-67. 2) Gudrun Koppen, N. van Larebeke, Vera Nelen, H. Van Loon, and Greet Schoeters. Contribution of host factors and environmental factors to Calux-TEQ values in serum of 50-65 years old women. Organohalogen Compounds, vol. 58 (2002) 325-328. 3) G. Koppen, A. Covaci, R. Van Cleuvenbergen, P. Schepens, G. Winneke, V. Nelen, N. van Larebeke, R. Vlietinck, G. Schoeters. Persistent organochlorine pollutants in human serum of 50-65 years old women in the Flanders Environmental and Health Study (FLEHS). Part 1: concentrations and regional differences. Chemosphere 48 (2002) 811-825. 4) Adrian Covaci, Gudrun Koppen, Rudy Van Cleuvenbergen, Paul Schepens, Gerhard Winneke, Nicolas van Larebeke, Vera Nelen, Robert Vlietinck, Greet Schoeters. Persistent organochlorine pollutants in human serum of 50-65 years old women in the Flanders Environmental and Health Study (FLEHS). Part 2: correlations among PCBs, PCDD/PCDFs and the use of predictive markers. Chemosphere 48 (2002) 827-832. Ongoing Project “Biological monitoring of the exposure to PCBs and dioxins in the population living in Belgium before and after the PCB/Dioxins incident”: 2001-2004. Objective of the project : To assess qualitatively and quantitatively the impact of the PCB/dioxin event on the body burden of these compounds in a particular group of the general population through the measurement of biological markers in plasma of blood donors, collected before and after the PCB/Dioxins event. In the present project, the concentration of 7 PCB congeners used in the screening of food contamination during the dioxin event, AhR antagonism activity measured by the Calux assay and the concentration of the different congeners of PCDDs and PCDFs are used as biological markers of the PCB/dioxins body burden. In addition, the feasibility and the utility of the indicators as screening tools in the related public health problems will be evaluated. Human serum projects: Fierens S., Mairesse H., Focant J.-F., Eppe G., De Pauw E., and Bernard A. (2002) PCDD/F and non-ortho PCB body burden of the general population in Wallonia, Belgium : Impact of different sources of environmental pollution. Organohalogen Compd. 55, 243-245. Fierens S., Mairesse H., Hermans C., Bernard A., Eppe G., Focant J.F., and De Pauw E. (2003) Dioxin accumulation in residents around incinerators. Journal of Toxicology and Environmental Health-Part A 66, 1287-1293. Fierens S., Mairesse H., Hermans C., Broeckaert F., Focant J.-F., De Pauw E., and Bernard A. (2001) Dioxin body burden of population living in the vicinity of two municipal solide waste incinerators (MSWI) in Belgium. Organohalogen Compd. 52, 334-336. Fierens S., Mairesse H., Heilier J.-F. and Bernard A. (2003) PCB body burden in the vicinity of different sources of environmental pollution in Belgium. Organohalogen Compd. 63, 445-448.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 110
Summary Centre of Environment and Health (2002-2006 projects): offer as much information as possible on the impact of the environment on the health of the Flemish society. Includes literature search, information desk, multidisciplinary research projects (biomonitoring, screening of cohorts of persons representative). The first entity focuses on the application of microarrys in studying alterations in the levels of gene expression, and in studying susceptibility by simultaneous analysis of multiple genetic polymorphisms. The second entity focuses on the presence of endocrine disrupters in environmental matrices and in food. A last entity concentrates upon the presence of asthma and allergy in relation to the exposure of environmental pollution. Another aim refers to the development of methodologies which can be divided in two entities. The objective of the first, more general line, is to outline methodological concepts and to develop tools and instruments that will be of use within the context of environmental health monitoring. The object of the second line is to design the optimal set of biomarkers which is to be applied in ongoing and future environmental health studies. Among many other items, the following will be studied: 1600 newborns and their mothers (dioxin activity in cord blood), 1600 adolescents (14-15 y, serum marker PCBs), 1600 adults (50-65 y, serum, marker PCBs and dioxin activity). Effects See also FLEHS already mentioned under “human tissues” and the following publication: Rosette L. Van Den Heuvel, Gudrun Koppen, Jan A. Staessen, Elly Den Hond, Geert Verheyen, Tim S. Nawrot, Harry A. Roels, Robert Vlietinck and Greet E.R. Schoeters. Immunologic biomarkers in relation to exposure markers of PCBs and dioxins in Flemish adolescents (Belgium). Environmental Health Perspectives, vol. 110 (6) June 2002; 595-600. A correlation has been detected. Research project ongoing on immunosuppression in lymphocytes in vitro. Biomarker identification. Fierens S., Mairesse H., Heilier J.-F., Eppe G., Focant J.F., De Pauw E., and Bernard A. (2003) Dioxin/PCB body burden, diabetes and endometriosis: findings in a population-based study in Belgium. Biomarkers ; (in press) Fierens S., Mairesse H., Heilier J.-F., Eppe G., Focant J.-F., De Pauw E., and Bernard A. (2003) Increased dioxin/PCB body burden in diabetics: findings in a population-based study in Belgium. Organohalogen Compd. 63, 449-452.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 111
Annex 3. WHO Protocol for human milk studies
World Health Organization European Centre for Environment and Health
Levels of PCBs, PCDDs and PCDFs
in human milk
Protocol for third round of exposure studies
March 2000
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 1
Contents 1. Introduction 2 2. Aims of study 5 3. General principles 5 4. Organization of study 6
4.1 Type of samples 6 4.2 Number of samples/sampling locations 6 4.3 Selection of donors 6 4.4 Questionnaire 7 4.5 Collecting and storing of samples 7 4.6 Pooling 7 4.7 Transporting of samples 7 4.8 Analysis 8
5. Ethics 8
6. Costs 8
7. Publication of Results 8
8. Coordination of study 9
ANNEX 1: Instructions for sampling, storing and transporting of samples 10 ANNEX 2: Questionnaire to mothers donating breast milk for analysis of PCBs 12 PCDDs and PCDFs ANNEX 3: List of individual congeners of PCBs, PCDDs and PCDFs to be analysed 18 analysis of PCBs, PCDDs and PCDFs ANNEX 4: List of laboratories which met the criteria for analysis of PCBs, PCDDs 19 and PCDFs in human milk during the fourth round of WHO/ECEH interlaboratory quality assessment studies
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 2
1. Introduction Chlorinated hydrocarbons such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are globally distributed in the environment and people are exposed inadvertently to them from numerous sources, of which foodstuffs are the most important. These compounds are lipid-soluble, poorly eliminated and are therefore accumulated and stored in human adipose tissues. They can pass through the placenta causing exposure of the foetus, and their existence in human milk exposes infants during the lactating period. The previous WHO exposure study showed declining trend of levels of PCDDs/PCDFs and PCBs on breast milk with largest declines in countries with the highest initial levels. In industrialised countries mean levels ranges from 10-35 pg TEQ/g, and in developing countries mean levels were less than 10 pg TEQ/g milk fat. A decline of exposure is also observed from recent studies in industrialised countries on the daily intake of PCDDs, PCDFs and PCBs. But when compared to adults, the daily intake of PCDDs, PCDFs and PCBs for breast fed babies is still 1-2 order of magnitude higher on a per body weight basis. (Assessment of the health risk of dioxins; Re-evaluation of the tolerable daily intake (TDI) 25-29 May 1998, Geneva, Switzerland)
Breast milk contains many lipid soluble compounds that are also present in mother’s adipose tissue. It can be assumed that the levels of PCDDs, PCDFs and PCBs in breast milk are representative for those in plasma, serum lipid and adipose tissue. The advantage of studying human milk instead of serum lipid is based upon of a non-invasive characteristic of the method and the high content of fat, what makes technical concentration methods easier and the precision of measurements higher. Therefore the analysis of pooled breast milk samples is a useful mean to estimate the overall exposure of a local population (In Conclusions of the Second round of WHO-coordinated exposure study on Levels of PCBs, PCDDs and PCDFs in human milk Environmental Health in Europe no. 3, 1996)
Since the first findings of these chemicals in human milk were published, WHO Regional Office for Europe – and since 1995 the WHO European Centre for Environment and Health, Bilthoven Division (ECEH) - has been coordinating a programme in collaboration with other international organizations and national institutions aimed to evaluate the possible health risks especially in infants and to control and prevent environmental exposure. In 1987, based on available research data on exposure levels and on toxicity and health effects, an expert group invited by WHO/EURO made an assessment of the health risks in infants associated with contamination of human milk. They concluded that at the levels generally found in human milk, a safety margin existed, although rather limited, and taking into account the many proven and universally accepted advantages of breastfeeding for the developing infant, it was strongly
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 3
recommended to encourage and promote breast-feeding under all circumstances.
Since the database utilized for this first health risk assessment in infants was rather limited, several projects have been developed to produce more reliable data as a basis to improve this assessment. These include the exposure studies on levels of these chemicals in human milk, the first round of which took place in 1987-88. The second round was completed in 1992-93 with participation of 19 countries, most from the European region but some also outside Europe. Results showed declining trends on exposure to PCDDs and PCDFs in many participating countries. However, rather high exposure levels to PCBs were identified in certain areas in Europe.
In order to improve the reliability and comparability of analytical data from different laboratories, WHO/EURO has also been coordinating interlaboratory quality control studies. The second round of the studies, which included analysis of human milk and blood, was completed in 1989 with participation of 19 laboratories, and a consultation to evaluate the results and qualify the laboratories was held in 1990. This was the first time laboratories have been qualified to perform these analyses. The third round of the interlaboratory quality control studies took place in 1991-92 and it was expanded to include cows' milk and fish in addition to human milk and blood. This study included three categories of chemicals: PCDDs/PCDFs, dioxin-like PCBs and other so-called marker PCBs. Thirty laboratories were involved in this study and results were evaluated by a consultation in 1992.
Based on conclusions and recommendations of this consultation the fourth round of intercalibration study was organized in 1996-97 by coordination of WHO-ECEH. The included matrices were human milk and blood plasma. Altogether 24 laboratories submitted analytical data and a consultation held in November 1997 evaluated the results. Laboratories, which met the accepted criteria for analyses of PCDDs and PCDFs, dioxin-like PCBs and marker PCBs in human milk, are listed in Annex 4. Results obtained by those laboratories were accepted by WHO for this third round exposure studies.
The third round of the exposure studies, for which the present protocol has been prepared is jointly organized by WHO-ECH, the International Programme on Chemical Safety (IPCS) and the WHO Global Environment Monitoring System/Food Contamination Monitoring and Assessment Programme (GEMS/Food). The study will collect exposure data on levels of the PCDDs/ PCDFs, dioxin-like PCBs and marker PCBs, and is being planned and coordinated by a committee established by WHO. It will be extended beyond the European Region in order to support and strengthen national
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 4
capabilities for the monitoring and sound management of hazardous chemicals on a global scale.
WHO urges all countries to participate in the third round of exposure studies in order to produce more reliable exposure data for risk assessment, to obtain a good overview of exposure levels and trends in different areas of the Region, and to identify any specific populations for further follow-up.
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 5
2. Aims of study The planned study has the following main aims:
• to produce more reliable and comparable data on levels of PCBs, PCDDs and PCDFs in human milk for further improvement of health risk assessment in infants
• to determine trends in exposure levels in the countries and
areas already studied during the first and second round of the studies during the period 1986-88 and 1992-1993, respectively
• to provide an overview of exposure levels in various
countries and geographical areas
• to identify highly exposed local populations in relation to their daily intake for guidance on risk management actions, including epidemiological follow-up studies
• to promote, if necessary, additional national studies to be
closely linked with the present studies through use of the same protocol.
3. General principles The guidelines set out in this protocol should be followed by each
country participating in the study. The protocol used in the previous rounds of the studies has been slightly modified by the coordinating committee. However, as few changes as possible have been introduced to ensure that the data collected can be compared with those from the previous rounds, thus providing information on trends in the various areas.
Only data submitted through the national coordinators will be accepted by WHO for inclusion in the study.
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4. Organization of study 4.1 Type of samples Since this protocol has been developed to give comparable results
with those from the previous rounds of the studies, pooled milk samples should again be used. If individual samples were used in the previous rounds, such samples may again be used and the average of the individual results should be reported.
4.2 Number of samples/ sampling locations Milk from well-defined groups of mothers
living in at least two areas with different exposure levels should be collected and levels should be collected and pooled. At least two different groups from each country (preferably more if possible) should be included in the study, e.g. expected high exposure group and low exposure group (highly polluted/unpolluted areas).
Such highly polluted areas could be found in the vicinity of incinerators, pulp and paper industries and metal industries, as well as areas where the population has a high fish consumption and where pesticides are openly or regularly used in agriculture. A careful description of the selected areas, e.g. regarding habitation, pollution sites, and industry, is very important. Those countries which participated in the second round of the studies must collect samples from exactly the same locations as in the previous round for purposes of comparison. Each milk pool should contain milk from at least 10 mothers.
4.3 Selection of donors ● Donors should be primiparae.
• Both mother and child should be apparently healthy, and the pregnancy should have been normal.
• The mother should be breastfeeding one child only (i.e. no twins).
• Mothers who have resided outside the area for more than 6 months
during the last 5 years should be excluded. • Only mothers who are exclusively breastfeeding should be
included. In order to be able to determine trends in exposure levels, it is very important that the profile of the donating mothers issimilar to the group of mothers from the second round of the studies. To ensure this, the national coordinators should examine the questionnaires from the second round and base the selection of mothers for the present study on those results. In the case that such questionnaires are not available since this is the first time that the study is being carried out in the country, the mothers can
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 7
be selected randomly with the above reservations. In all cases, however, the attached questionnaire should be used.
4.4 Questionnaire The attached questionnaire (Annex 2) should be used as the basis
for the interview with the donating mother (see 4.2 and 4.3 above) and its completion is compulsory The completed individual questionnaires should be sent to WHO-ECEH, Bilthoven Division for possible additional use within this study. They will also be important in identification of similar groups for an eventual fourth round of the studies, to ensure reliable results for determination of exposure trends.
4.5 Collecting and storing of samples Breastfeeding mothers living in areas of different
expected levels of exposure should be recruited at or from contact places (maternal and/ or child clinics). They should be included only after having received both verbal and written information and given written consent. Individual interviews should be carried out using the attached questionnaire (see 4.4). Mothers should be given a carefully decontaminated bottle for the milk sample and instructed on how to collect the milk. They should also be given a copy of the attached detailed instructions for sampling, storing and transporting of milk samples (Annex 1). Sampling should be carried out between 2 weeks and 2 months after delivery.
When pooled samples are used, at least 50 ml of milk must be collected from each mother. When individual milk samples are used in the studies, the collected amount depends on the demands of the analytical procedure, but a minimum of 350 ml per individual sample is recommended. The portions collected during each feeding should be added to the collecting bottle and stored in the home freezer until the total volume has been collected (in a thick-walled 100 ml glass bottle with a teflon-lined screw cap). Subsamples should be homogenized (shaking for 10 min.) before pooling.
4.6 Pooling Pooling should be done on volume basis by using 50 ml of
collected milk from each mother. The minimum number of individual samples is 10, making a total of 500 ml of pooled milk available for analysis.
4.7 Transporting of samples Shipping of the samples to the selected analytical
laboratory should be carried out strictly in accordance with the attached instructions (see Annex 1) in order not to damage the samples. Samples should be identified with an unique code and an appropriate
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 8
description. The receiving laboratory should be notified when the package will be sent. The laboratory will confirm receipt of the samples. Remaining milk samples should be stored deep-frozen for further analysis.
4.8 Analysis The pooled milk samples should be analysed for three groups of
compounds, i.e. normal PCBs, dioxin-like PCBs, and PCDDs/PCDFs. Annex 3 lists the individual congeners of each group of chemicals, which should be analysed for and reported as a minimum requirement. Reporting forms are sent separately to the national coordinators.
Only those laboratories which have been qualified through the fourth round of the WHO-ECEH interlaboratory quality control studies may be used to perform the analyses of the collected milk samples. The list of laboratories qualified through the fourth round of studies is attached as Annex 4 .
To assist those countries which need qualified analytical service, WHO-ECEH will negotiate with those qualified laboratories included on the attached list, in order to select, for each group of compounds, a laboratory which will carry out analyses of samples from those countries.
5. Ethics The results of this study are expected to strengthen the factual
basis for the health risk assessment in infants and to promote measures to reduce input of these chemicals into the environment, as the only effective way to limit exposure of the general population to dioxins and related compounds.
6. Costs Each country is responsible for the costs of sample collection,
shipping and analysis, and makes payments for analysis directly to the analysing laboratory. The costs of further statistical analysis of the exposure data and data gathered through the questionnaire, the costs of meetings of the coordinating committee and the consultation to evaluate the results, as well as publication costs, will be covered from other sources.
7. Publication of results Results from participating countries will be collected and
evaluated by WHO-ECEH in accordance with the decisions of the coordinating committee. Any WHO publication will be cleared by the national coordinators, however, each country is free to publish its own results.
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8. Coordination of study WHO will coordinate this study and has for this purpose established a coordinating committee with the following membership:
Professor Martin van den Berg, RITOX Institute, University of Utrecht, The Netherlands (toxicologist)
Professor Rainer Malisch, State Institute for Chemical Analysisof Food, Freiburg, Germany (analytical chemist)
Dr Erkki Yrjänheikki, Ministry of Social Affairs and Health, Tampere, Finland
Dr Marie H. Sweeney, National Institute for Occupational Safety and Health, Education and Information Division, Cincinatti, USA
Professor Dr Michael Moore, National Research Center for Environmental Toxicology (NRCET), Brisbane, Australia
Secretariat: Dr F.X.Rolaf van Leeuwen, WHO European Centre for Environment and Health, Bilthoven, The Netherlands (study coordinator) Mrs Agnes Soares, WHO European Centre for Environment and Health, Bilthoven, The Netherlands Dr Maged Younes, WHO Programme on Chemical Safety, Geneva, Switzerland
Dr Gerry Moy, WHO GEMS/FOOD, Geneva, Switzerland
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 10
Annex 1 Instructions for sampling, storing and transporting of samples • The breast pump needs to be provided free of contamination. The mothers themselves
should do no more than rinse the pump container with water and, if desired, boil it to avoid contamination from soap. However, since this can lead to bacterial contamination, care must be taken that the mothers do not use these pumps for private use, collecting milk for consumption by the baby without the pump first having been washed and sterilized.
• The collecting bottle needs to be provided free of contamination. It needs to be thoroughly
washed, rinsed and given a final acetone rinse before delivery to each mother. The mothers are not to do anything to these bottles.
• The bottle should preferably be made of Pyrex glass; the cap should either have Teflon
lining or be made of polyethylene. • The bottle with collected milk should be kept in the home freezer until the total amount
from the mother has been collected, i.e. the portions collected during each feeding should be added to that bottle. Once frozen the milk should not be allowed to thaw.
• No other vessel is to be used for collecting milk. Mothers must not use cups or other
bottles they may have at home. Should they prefer to use manual lactation, the milk needs to be collected directly into the furnished bottle or in the collecting container that comes with the pumps.
• The breast and hands should be kept as clean as possible, yet soap should be avoided as
much as possible. When necessary to use soap, the breasts and hands should be thoroughly rinsed.
• Should it be necessary to use ointments on the nipples because of soreness or tenderness,
this should be done outside of sampling time and the ointment removed prior to sampling. • The ideal method to reduce problems of contamination from both soap and ointments is to
provide the mothers with soap for personal hygiene and for dishwashing that has already been tested for possible contamination and found to be free thereof. The same holds true for ointments that can be used on the breast.
When sending the samples for analysis:
• Add tablets containing K2Cr2O7 as preservative at an amount of 0.1% (w/w) (active ingredient) to each of the samples before shipment (3 tablets per 100 ml of milk) [International Association of Official Analytical Chemists procedure for the analysis of organic contaminants in milk].
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• Identify each of the samples with a unique code. • The package should be marked clearly "human milk samples" with the notation “STORE
BELOW –20OC” and the name and address of the laboratory. • The samples should be placed firmly in a thermoinsulated (tempex) box with a sufficient
amount of DRY ICE (-79oC). Prevent the bottles from moving inside the box during transportation.
• The receiving institution should be notified giving precise details of delivery (e.g. number
of samples, sample codes, airwaybill no., airline no., date and time of arrival). This information will be used to contact the airport/custom to make sure that samples will arrive at the laboratory in good condition. Also for the use of the laboratory to confirm the receipt of the samples.
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Annex 2a
Questionnaire
to mothers donating breast milk for analysis World Health Organization of PCBs, PCDDs and PCDFs Regional Office for Europe CONFIDENTIAL! 1. Country:
2. Area (city or region of the country):
3. Pool identification code:
4. Sample identification
code:
5. Samples collected
From: DD/MM/YY to: DD/MM/YY
6. Date completed:
DD/MM/YY
7. Mother’s age in years:
8. Mother’s height in cm:
9. Mother’s weight before pregnancy in kgs:
10. Mother’s weight just prior to delivery in kgs:
11. Area of residence during last 5 years: urban suburban rural 12. Previous area of residence: Years urban suburban rural and before: Years urban suburban rural 13. Child’s age in weeks at start of sampling
14. Child’s sex: boy girl
15. Child’s weight at birth in grammes:
16. Child’s weight at time of sampling (g) First day: Last day:
17. Mother’s dietary habits: mixed diet vegetarian, but with milk strictly vegetarian and eggs other give details: _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
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18. Has the mother changed dietary habits no yes markedly since the start of pregnancy? if yes, state how: _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 19. How often, on average, does she eat fish never less than once once a
or other seafood? a week week twice a week more than twice a week if twice a week or more, state the species she consumes most often: _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 20. How often does she, on average, twice or less consume milk and milk products? never a week more than twice a week, every day but not every day high-fat Fat content: low-fat medium-fat (3.0% or (0.5-1.9%) (2.0-2.9%) more) Consumption per day: less than 250 250-499 500 ml or ml a day ml a day more a day 21. How often, on average, twice of less does she consume cheese? never a week more than twice a week, every day but not every day Fat content: low-fat high-fat 22. How often, on average never less than once once a does she eat beef? a week week twice a week more than twice a week
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 15
23. Current smoking habits: Non-smoker Ex-smoker Smoker if smoker, what does she Cigarettes Cigars/ceruttes Pipe smoke? if cigarettes, how many per day? if cigars/ceruttes, how many per day? 24. Is the mother working?
No Yes
24.1 If yes, present type of work (describe function, activities, contact with hazardous substances etc): ___________________________________________________________________ code ___________________________________________________________________ ___________________________________________________________________ ___________________________________________________________________
25. Present workplace: urban suburban rural
26. Duration in years:
27. Previous types of work: a)________________________ b)________________________ has never worked
28. Previous workplaces: urban suburban rural urban suburban rural
29. Duration in years:
30. Kinds of medicine, time and dosage taken during sampling period: (include vitamins and mineral supplements)
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 31. Questionnaire completed by: (TYPE NAME)
Date:
Signature:
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 16
Annex 2b
WORLD HEALTH ORGANIZATION Regional Office for Europe
Summary for each pool of questionnaires to mothers donating breast milk for analysis of PCBs, PCDDs and PCDFs
1. Pool identification
code
2. Country:
3. Area:
4. Number of mothers in the pool:
5. Age of the mothers Mean: Range:
6. Mother’s height in cm: Mean: Range:
7. Gain of weight during pregnancy:
Mean Range:
8. Area of residence during last 5 years: (%) urban suburban rural (percentage of the total mothers of the pool) 9. Previous area of residence:Years urban suburban rural and before: Years urban suburban rural 10. Child’s age in weeks
at start of sampling
Mean:
Range:
11. % of children’s sex in the pool:
boys girlrs
12. Children’s weight at birth (g):
Mean:
Range:
13. Children’s gain of weight during time of sampling (g):
Mean:
Range:
14. Mother’s dietary habits (em % of mothers in the pool):
mixed diet vegetarian, but with milk strictly vegetarian others and/or eggs 15. % of mothers in the pool who changed dietary habits markedly since the start of pregnancy: 16. Mothers’ fish and other see food consumption (% in the pool):
never less than once an week once a week twice a week more than twice a week
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17. Mothers’ consumption of milk and milk products: (% in the pool)
never less than once an week once a week twice a week
more than twice a week but not every day every day 18. Fat content: (% in the pool that consume)
low-fat medium-fat high fat (0.5-1.9%) (2.0-2.9%) (3.0% or more)
19. Consumption per day: less than 250 250-499 500 ml or ml per day ml per day more per day 20. Mothers’ cheese consumption (% in the pool):
never less than once an week once a week twice a week
more than twice a week but not every day every day 21. Fat content: (% in the pool that consume)
low-fat high fat (0.5-1.9%) (3.0% or more)
22. Mothers’s beef consumption: (% in the pool)
never less than once an week once a week twice a week
more than twice a week but not every day every day 23. Mothers’smoking habits during collecting period (% in the pool):
Non-smoker ex-smoker light smoker heavy smoker
Cigarettes Cigars/ceruttes Pipe
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 18
24. Mothers working
during pregnancy and or lactancy period in the pool:
No. %
25. % of mothers that work by last/actual workplace:
urban suburban rural
26. Years in the last/actual work:
Mean: Range:
27. No. and % of mothers in the pool with potential risk of occupational exposure to organic chemicals: No. %
28. No. and % of mothers in the pool that was taking any kind of medicine during sampling period: None Antibiotics No. Vitamines or other supplements: No. % % 29. Hormones: No. For pain relief: No. Others No. % % % NAME
Date: Signature:
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 19
Annex 3 List of individual congeners of PCBs, PCDDs and PCDFs to be analysed Marker PCBs Mono-ortho PCBs IUPAC No. 28 IUPAC No. 105 IUPAC No. 52 IUPAC No. 114 IUPAC No. 101 IUPAC No. 118 IUPAC No. 138 IUPAC No. 123 IUPAC No. 153 IUPAC No. 156 IUPAC No. 180 IUPAC No. 157 IUPAC No. 167 Non-ortho PCBs IUPAC No. 189 IUPAC No. 77 IUPAC No. 81 IUPAC No. 126 IUPAC No. 169 PCDDs PCDFs 2,3,7,8-TCDD 2,3,7,8-TCDF 1,2,3,7,8-PeCDD 1,2,3,7,8-PeCDF 1,2,3,6,7,8-HxCDD 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDF 1,2,3,7,8,9-HxCDD 1,2,3,4,7,8-HxCDF 1,2,3,4,6,7,8-HpCDD 1,2,3,7,8,9-HxCDF 1,2,3,4,6,7,8,9-OCDD 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF 1,2,3,4,6,7,8,9-OCDF
Baseline Report on Integrated monitoring of dioxins and PCBs in the Baltic Region 20
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