HCH CONTAMINATION IN THE SABIÑANIGOS´S ... - IHPA

1177-9 September 2011, Gabala, Republic of Azerbaijan

The manufacture of lindane between the years1975 to 1988 in the city of Sabiñanigo,Aragonian Pyrenees (Spain), left away severalsites contaminated by the dumping of solidwastes. About 80,000 tonnes of HCH mixtureremain located at three main sites that lack of anadequate liner system.

At these sites, a DNAPL groundwater plume hasbeen found, containing benzene, chlorobenzenesand chlorophenols and a mixture of HCHisomers. With a density of 1.5 cps and 950 g/kgof contaminants it constitute a serious risk due tothe vicinity of the Gallego river and the complexaquifer system consisting in alternating verticalssandstones and marls.

The Regional Government and the SpanishMinistry of the Environment are taking action,focusing in the DNAPL treatment and, due to thehigh quantities involved, in the temporalconfinement of the solid waste until properdisposal operations were develop.

Lindane containing solid waste in Sabiñanigo

Sabiñanigo is a small industrial city located inthe Aragonian Pyrenees (Spain). At thebeginning of the twentieth century bulkchemical industries were installed. In theseventies the factory of the firm INQUINOSAbegan to produce lindane.

HCH CONTAMINATION IN THE SABIÑANIGOS´S ENVIRONMENT(SPAIN)Fernández, J.1, Arjol, M.A.2, Cacho, C.1, Regol, Y.1

1Department of the environment, Aragón Government, Saragossa, Spain2 SODEMASA, Saragossa, Spain

Geographical location of the lindanecontaminated sites

In the XX century, and until the closure ofINQUINOSA at the end of the 80´s, badenvironmental practices associated with thedumping of the solid waste generated in the cityand his industries left away several contaminatedsites.

The firm INQUINOSA produced lindane from1975 to 1988, and formulate lindane productsuntil 1992. Waste generation data differs uponthe information source used: about 6,800

MT/year of solid waste and 300-500 MT/year ofliquid waste (1,500 MT/year for other sources)were estimated.

Without taking account of small dumps sites, foursites remain contaminated: the Sardas and Bailindumping sites, the industrial ruins ofINQUINOSA, and the dam of Sabiñanigo. In thefirst three sites the Regional Government ofAragon is executing remediation works, whilethe dam is supervised by a national authority.

Fernández, J., Arjol, M.A., Cacho, C., Regol, Y.

Table 1. Concentration of HCH and other chlorinated compounds in soil and groundwater in theINQUINOSA ruins

11th International HCH and Pesticides Forum118

The dumping site of Sardas:

The Sardas site is located over Eocene marls, andlacks of a liner system in its basin. It containsabout 350,000 m3 of all kinds of solid wastes. Thedisposal of wastes generated at a chlorineproduction facility causes a lixiviates pH of 13.The wastes also contain high amounts ofhydrocarbons, metals and lindane isomers. It isestimated that over 30.000 and 80.000 MT ofdust HCH wastes and 2.000 Mt in, liquid formwere disposed in this site.

In 2009, a DNAPL was detected in the surface.Immediately collection works and studies of thehydro-geological behavior of the site were

initiated, as a work previous to consider viableconfinement and treatment alternatives for itslater implementation. This site is treated in othercommunication at this congress, and details aregiven there.

Inquinosa’s industrial ruin

The production facility of INQUINOSA closedin 1994, removing operative equipment andremained abandoned. Now, after obtainingjudicial access, soil and groundwatercharacterization and an inventory of the wastesfound in the site, have been undertaken.

HCH CONTAMINATION IN THE SABIÑANIGOS´S ENVIRONMENT (SPAIN)

Table 2. DNAPL properties and composition.

Landfill sites at the Bailin creek.

The liquid form waste is a dense mixture ofbenzene, chlorobenzenes and chlorophenols, and

HCH isomers, with a density of 1.5 cps and 950g/kg of contaminants, behaving as dense non-aqueous phase liquid (DNAPL).

7-9 September 2011, Gabala, Republic of Azerbaijan 119

About 100 MT of HCH, 6 MT of o,o-dimethylphosphorodithioic acid that was used in themanufacture of Phosmet insecticide, and otherchemicals still remains in the industrial ruins.

Short-term interventions include legal declarationas a contaminated soil, characterization of the siteand the solid wastes remaining, which in partwere treated by an authorized agent, and in partwere translated to a conditioned landfill in Bailín.Remediation of the site is conditioned by thejudicial position of the property and in lastinstance by budget provisions at regional level.

The Bailin’s dumping site

Between the 1984-1992 a site near de urbannucleus of Sabiñanigo was used for the disposalof industrial and municipal solid wastes. It islocated over and alternating vertical series ofsandstone and limolite strata, without liners in hisbasement. A final cover with a HDPE liner wasmade in 1996. The total volume of the landfill is180,000 m3, containing about 30,000 – 80,000MT of HCH solid waste and 2,000 MT in liquidform.

Fernández, J., Arjol, M.A., Cacho, C., Regol, Y.


This dense liquid has percolated from thedumping site towards the Gallego river, 800meters away, through a fracture net in the rocksubstrate. The liquid flows through four verticalstrata of sandstone connected by horizontalfractures in the limestones alternates.

The DNAPL plume location depends on de strataand his grade of fracture, with a maximum of 150m length and 20-40 m deep. The aqueous plumehas reached the Gallego River and peaks of 1 µg/lof HCH has been measured 0.5 km down theriver, with average concentration of 0.57 µg/l.These levels drop under the detection limit 2.5Km down the river, due to flow incremental fromand Hydro power plant channel. Occasionally alevel of 0.1 µg /l has been recorded. According tothe Council Directive 2008/105/CE the HCHaverage limits is established in 0.02 µg/l, and0.04 µg/l for maximum peaks.

The treatment strategy in this site is conditionedby the DNAPL presence. Detected in 2006, thepriority has been to stop its flow and controlcontaminant levels in the aqueous phase. As aresult of this early work, a flow control protocolhas been established. The efforts are nowfocused in study how the aquifers behave. First,we have developed a conceptual model and thena mathematical one assimilating a lowpermeability porous multilayer fractured media(based in Modflow code). The model, that fitswell with experimental data, was used to knowthe hydrogeological balance and to design pilottest.

The control of the aquifer is done with 150piezometer and a pumping and wastewatertreatment system. The DNAPL is extracted fromthe aquifer by a programmed pumped system thatavoids the flow of the plume, while the wastesthat remain in the dumping site as the source ofpollution, were disposed. 17,000 liters have beenextracted since 2006. At the same time, being theplume under control, two additional workinglines have been executed: removal of thepollution source and the study and test of aquiferremediation techniques.

Several remediation techniques (MERK, ISCO,

ISTD, SEAR, ISGS, zero-valent iron) have beentested at laboratory scale. In site pilot test withsurfactants (SEAR) are in progress. The resultsof this his studies will be published in the future,but preliminary results show the difficulty oftreatment associated to this complex soil-aquifermatrix.

In 2007, the Project of dismantling and transferof the Bailin dumpling site was redacted. A nearsite, in the same valley, was the chosen site. Dueto social and security matters other sites far awaywith better hydrogeological conditions wererejected.

The disposal of the solid wastes was also rejectedfor several reasons:

• The need to remove the source of pollution inshort terms as a first step in order to proceedat the aquifer remediation.

• The limited yields of disposal techniques,being necessary several years to complete thetreatment and also make necessary thetransfer or storage of the wastes.

• The high quantities involved requireproprietary pretreatment and disposalfacilities, with associated high cost.

The Works began in 2010 with the constructionof infrastructures to facilitate the dismantling.

Due to the inadequate geological characteristicsof the site, the new cell has been constructed withisolating measures additional to the legalrequirements. The landfill basin has a set ofdrainage trench 5 meter deep, excavating in therock, to depress the water table. The waterscollected were taken to a tank and his qualitymonitored prior to its released.

Over the rock, a compacted clay layer, a geo-drain and a gravel layer connected to a drainagesystem that divide the base and takes the flowsto a control tank, isolate the landfill.

Two sets of geomembranes liners of HDPE (1.5mm), bentonite (5,500 g/m2), and HDPE (1.5mm) impermeabilize the base. The sets areseparated by a geo-drain in order to controlpossible leakages.

HCH CONTAMINATION IN THE SABIÑANIGOS´S ENVIRONMENT (SPAIN)


Infrastructures needed to dismantle the Bailindumping site. Details of the transfer station.Chutes and dust suppression system. Newlandfill for the HCH solid wastes. Drainagesystem and final aspect of the new landfill cell.

A final gravel layer with drainage tubes collectthe lixiviates, that are taken to a tank connectedto the wastewater treatment plant.

The cap will consist in a gas collection system,a set of geomembrane liners of HDPE (1.5 mm),bentonite (5,500 g/m2), and HDPE (1.5 mm), ageotextile, a geo-drain and soil.

The transfer station is designed to make thepretreatment of the solid wastes, depending onthe size, the moisture content and the HCHconcentration. It has four chutes, a packingsystem, a solidification-stabilization unit for highmoisture content wastes, a centrifuge unit, aseparator unit and a loading bay. A dustdepressing system minimize the dust whileoperated.

The dismantling is planned for May-October2012, coinciding with the low precipitationperiod. It will be executed advancing towards thelaterals in layers of 2 meters deep. The operatingarea will be cover with a HDPE sheet with a dustdepressing system in.

A grid of 30x30 m drilling test, sampling 2 mdeep, will serve to characterize the solid wastesand to establish the pretreatment at the transferstation.

To minimize the risks associated to the transfer ofthe solid waste a meteorological system isavailable. The works will be suspended thosedays with rain and wind conditions.

The transfer to the new constructed landfill is nota definitive solution, but it will allow to takeactions against the contaminated aquifer and itwill provide a secure storage infrastructure untilthe development of adequate remediationtechniques, maintaining costs and times at areasonable level.

Introduction Polyfluoroalkyl compounds (PFCs) are verypersistent, and several are toxic pollutants1a,b. InMay 2009 PFOS and related substances were addedto the Stockholm Convention POPs list2. Therefore,according to article 6 of the Convention PFOScontaminated sites should be identified3.PFCs are used extensively in numerous consumergoods (e.g. impregnated paper, textiles, leather,furniture), and eventually end up in landfills viadisposal of these products. Due to their highwater solubility, PFCs are subject to mobilizationand release from landfills4. PFOS, PFOA, andother perfluorinated acids may be present in waterin ionic and highly soluble forms, and waterresources are a primary final sink due to thepresence of PFCs in domestic wastewaters aswell as certain industrial discharges.

The 3M Company was the primary globalproducer of PFOS- related PFCs, producingmillions of pounds annually at its plants in theUnited States and Europe5. 3M produced PFOAat its Cottage Grove, MN/USA plant until the endof 2002 when it stopped production of PFOA andPFOS- related compounds. The production or useof other PFC- related compounds (“4 carbonPFCs”) continues today6. Significant amounts ofwastes, residuals, and sludges were generated inthe production of PFCs and associated products.An assessment by the Minnesota PollutionControl Agency revealed that large amounts ofPFC wastes from the 3M production plant inCottage Grove, Minnesota, USA had beendeposited in landfills and under the 3Mproduction plant property7.

PFC production also occurs in Europe withsimilar contamination. In this paper we brieflyexamine a European and a US contaminationscenario related to PFC production: The 3M

plant in Minnesota which resulted incontamination of the wider environment(groundwater, sediments, surface water, andfish)7, and the contamination of agricultural landin Germany by application of PFOS/PFOAcontaminated sludge imported from a EuropeanPFC production plant. This use of PFCcontaminated sludge in Germany resulted incontamination of drinking water supplies toabout 5 million people13,14. The cases bothhighlight the importance of the proper control,management and destruction of organofluorineproduction wastes.

Materials and MethodsSamples (soil, sediment, landfill leachates andgas condensate, ground water, sewage sludgeand, fish) were collected by MPCA staff.7 Soilcores were obtained by soil borings at the landfillsite. PFC analysis (up to 14 different PFCsincluding PFOS and PFOA)7 was performed bya commercial laboratory using approved standardmethodologies. Analysis and quantification ofPFC was performed by LC-MS/MS.In the German case, analyses were carried out onan Agilent 1100 HPLC System interfaced to anAPI 2000 triple-quadrupole mass spectrometr.Analytical details are reported elsewhere8.

Results and Discussion1) The Minnesota CaseThe Minnesota investigation of selected 3M PFCproduction sites and associated environmentalcontamination included.

Washington County Closed Landfill The Washington County landfill (WCLF) is a 35acre unlined closed landfill with no leachatemanagement. After elevated VOC levels werefound in groundwater below the site in 1981, a‘pump and treat’ system was installed including

CONTAMINATION OF DRINKING WATER AND THEENVIRONMENT BY THE PRODUCTION AND USE OF PFOS ANDOTHER PERFLUOROALKYL COMPOUNDS (PFCs)Oliaei F1,2, Weber R3; Kriens D2,4; Watson A5

1Cambridge Environmental Consulting, MA, USA; 2Former Staff, Minnesota Pollution ControlAgency (MPCA), MN, USA; 3POPs Environmental Consulting, Göppingen, Germany;4Harvard University, Boston,MA,USA;5 Public Interest Consultants, Swansea, Wales


CONTAMINATION OF DRINKING WATER AND THE ENVIRONMENT BY THE PRODUCTIONAND USE OF PFOS AND OTHER PERFLUOROALKYL COMPOUNDS (PFCs)


a spray stripper system where contaminatedgroundwater was sprayed into the atmosphere tovolatilize/remove VOCs. This system operatedfor about 25 years.

3M disposed of PFC production wastes to thelandfill from 1969–1975. The study found highPFC contamination in the groundwater under andclose to the landfill. PFCs migratingdowngradient from the site caused extensivecontamination of private drinking water wells.PFOA and PFOS concentrations in groundwater,at up to 42 ppb and 2.7 ppb respectively,exceeded the then drinking water criteria of 7.0ppb and 1.0 ppb; the standards were subsequentlyreduced to 0.5 and 0.3 ppb, respectively8.

“Ponded” stripper water was found to contain upto 1.7 ppb PFOS, 15 ppb PFOA, and 352 ppbPFBA. PFCs were found deep within the soilprofile at the site – probably due to the spraystripping system and continuous PFC migrationover 25 years of stripper operation. PFBA, aswell as PFOA, was found to be highly mobile,moving many kilometers down-gradient in thegroundwater. PFBA was found present ingroundwater up to 1170 ppb. A drinking watercriteria was later established for PFBA at 7.0 ppb,and the same value of 7.0 ppb is proposed forPFBS. Widespread PFC contamination indrinking water wells resulted in a program thatin their replacement by alternate water suppliesor the fitting of individual activated carbon watertreatment systems. The Washington CountyClosed Landfill is currently being remediatedwith the installation of a composite- liner systemwith leachate collection.

Pine Bend Landfill (PBLF) The Pine Bend Landfill PBLF receivedwastewater treatment plant sludges from the 3Mproduction plant7. The PBLF has both lined andunlined areas. Leachates from the PBLFcontained PFOA, PFOS, and PFHxA in leachateup to 82 ppb, 31 ppb, and 29 ppb, respectively,with total PFCs up to 178 ppb. PFCs were alsodetected in groundwater, with higher levels indowngradient wells (PFOS and PFOA at 0.11and 1.6 ppb,respectively), indicating migrationof PFCs from the landfill to groundwater.

Gas condensate generated from the landfill,normally collected and treated at the Twin CitiesMinnesota main Metro wastewater treatmentplant, was analyzed. This is the first study weare aware of where PFCs have been analyzed inlandfill gas condensates. PFOA, PFOS, andPFHxA in gas condensate were found atunexpectedly high levels of 84 ppb, 30 ppb, and38 ppb, respectively, with total PFCs up to 194ppb. PFC levels in gas condensate suggests thatPFCs could be released to the atmospherethrough emission of landfill gases.

3M Wastewater Treatment Plant (WWTP) 3M has discharged treated PFC productionwastewaters to the Mississippi River since about1950. These wastewaters are treated using aconventional activated sludge system and anactivated carbon filtration system was added tothe system in 2004. 3M data for PFCconcentrations in the wastewater discharge priorto the termination of PFC production in 2002 wasused by MPCA staff who calculated that 33,000kg per year of PFCs could have been dischargedto the Mississippi River12.

In 2005 it was found that the total concentrationof the 13 PFCs in the 3M WWTP final effluent tothe river was 291,300 ppt. PFOS and PFOAlevels were 19,200 and 62,400 ppt, respectively.The highest PFC concentrations in the effluentwere PFBA and PFBS at 80,600 and 104,000 ppt,respectively. PFOS and PFOA increased inconcentration through the WWTP activatedsludge system, probably due to the biologicaldegradation of PFOS and PFOA precursors.Preliminary analysis indicated that the activatedcarbon system was relatively efficient andremoved about 95% of PFOS but only 79% ofcarboxylic PFCs and 42% of PFBA. Whilstdischarge data prior to the stopping of PFOA andPFOS-related production in 2002 is limited thereare indications that much greater levels of PFOShave been discharged to the river in the past. InJan-Mar 2001 and Sept-Oct 2001 the averagePFOS discharged was about 1,403,000 ppt and262,000 ppt, respectively, and 550,000 ppt inDec. 20029. The 3M plant non-contact cooling water alsocontained PFCs totaling 30,460 ppt. Cooling

water is comprised of groundwater pumped froma barrier well system at another closed unlinedlandfill nearby (3M Woodbury Landfill) wherePFC production wastes were disposed in the past.

Mississippi River Water, Sediment, and Fish PFCs were analyzed in Mississippi river water,sediment, and fish near and downstream of the3M plant and wastewater treatment plantdischarges. PFOS was detected at 6 and 15 pptin the river downstream of the plant. PFOA wasfound at 35 ppt downstream. The surface waterfrom a cove area that immediately receives thePFC plant wastewater discharge containedPFOS, PFOA, PFHxS, and PFBS up to 18,200ppt, 3,600 ppt, 9,700 ppt, and 89,800 ppt,respectively. PFCs in the top 10 cm of sediment cores of theriver and cove were also analyzed. PFOS levelswere at 1.6 ng/g in a sediment core upstream ofthe plant, and 27.9, 8.3, and 1.7 ng/g in coresdownstream of the plant. PFOS in the covesediment core was 99 ng/g with total PFCs at 188ng/g. A significant mass of PFOS in the covesediment may pose a reservoir for PFOS exposureto benthic organisms and fish. Fish tissue (fillets), blood, and livers wereanalyzed to determine whether fish PFC levelsrepresented a source of risk for humanconsumption. Fish were collected from two areasin the Mississippi River near and downstream of3M plant in August 2004, and October 2005.Elevated levels of PFOS were found in fish, with40 of 42 fish (fillets) exceeding a MinnesotaDepartment of Health (MDH) guideline thattriggered a fish consumption advisory at 40 ng/g.Elevated PFOS levels were found in liver andfish blood. The PFOS level in the blood of one,year old, White Bass was 29,600 ng/g. Webelieve this to be the highest PFOS level found inany animal worldwide. PFOS in fish collectedfarther downstream of the PFC plant containedlower levels of PFOS, but still exceeded fishconsumption guidelines.

2) A German Experience In 2006 Skutlarek et al.13 reported onperfluorinated surfactant contamination of theGerman river Ruhr (up to 446 ng/l), the tributary

river Möhne (up to 4385 ng/l) and in tributarycreeks (up to 43,000 ng/l). PFOA was/ is themain contaminant accounting in most cases forca 80% of the PFC. The drinking water in thisarea, which serves approx. 5 million people, wascontaminated with PFS up to 598 ng/l (PFOA519 ng/l) in the most affected area.13,14 Someagricultural fields on the upper reaches of theMöhne river were identified as a main emissionsource.13,14

The PFOS/PFOA contaminated sites on theagricultural fields resulted from themismanagement of PFC containing sludge whichwas imported by a German company from TheNetherlands in accordance with the EU WasteShipment Regulation for hazardous waste (EEC259/93). In a criminal act the company declaredthe sludge as bio-waste and sold it to farmers. InSeptember 2006 the BUND (FoE Germany)accused the company and also the local authoritySoest14. The company proclaimed bankruptcyafter the contamination was revealed and theformer owner and CEO of the company went toprison. The comparison of PFC surface anddrinking water contamination showed that thePFC were not reduced sufficiently by most waterworks (Table 1). Higher levels of reduction couldbe seen only for a few water works with highground water dilution levels or by using newactivated carbon (Table 1). The observedcorrelation of the PFC concentrations in surfacewater and drinking waters indicate that evenwater treatment works in industrialized countriesdo not effectively eliminate PFCs, althoughapproximately 50% of the waterworks wereequipped with activated carbon filters. Thepopulation in the area with the highest drinkingwater contamination (approx. 500 ng/l PFOA inMarch 2006, table 1) increased their PFOA levelsin blood plasma by five to eight times comparedwith German background cohorts15 after only ca.3 years exposure (children 4.5-fold (median 22.1µg/l), men 4.7-fold (median 27.4 µg/l) andmother 8.4-fold (24.9 µg/l)). The maximumvalues, in two children were 383 and 218µg/l.Considering of the bioaccumulation potential ofPFC and the alarming health effects reportedincluding reduced birth weight of infants and

124 11th International HCH and Pesticides Forum

Oliaei F., Weber R., Kriens D., Watson A.

reduced sperm quality16, these human levelsindicate that the proposed German drinkingwater guidelines are too high.

Several water treatment works in the region wereupgraded at a cost of approximately 100 millionEURO. The agricultural use of PF contaminatedareas is now controlled and recommendationshave been given for the human consumption ofcontaminated fish.

Conclusions This study illustrates that PFCs deposited andreleased at landfills or from contaminatedagricultural areas are highly mobile andcontaminated the wider environment. Substanceflows from landfill leachates to wastewaterplants and rivers, from landfills to groundwater,from landfill gases to atmosphere, and fromcontaminated ground water sprayed to theatmosphere, reveal multiple pathways for PFCsat landfills and disposal sites to end up in surfacewaters and fish. Human exposure and risk

assessments around such contaminated sitesincluding all exposure pathways such as fishconsumption, drinking water intake, soilingestion, fruit and vegetable consumption, andpossibly even intake via inhalation of air andlandfill gas emissions near those sites, should beperformed to assure adequate safeguards.

The German case demonstrates thatmismanagement of waste streams from PFC- producers can contaminate the drinking water ofmillions of people. In addition to the immediatecontamination of sites around PFC productionplants, waste streams of these industries canbecome a significant hazard to humans.Therefore, the mass flow and waste managementof PFC producing and using industries should betightly regulated by national authorities.

The German and the US case show that evenrelatively well regulated countries withestablished hazardous waste managementregimes have considerable difficulty incontrolling these contaminants. Considerationshould be given to how developing and transitioncountries can ever effectively regulate and controlPFC production and use or the disposal ofcontaminated products. Countries need to beaware of PFC wastes and waste streamsincluding those in consumer products and theneed to manage and destroyed them in anenvironmentally sound manner. Compliance withthe obligations of the Stockholm Convention isessential if countries are to effectively addressPFC contamination.


CONTAMINATION OF DRINKING WATER AND THE ENVIRONMENT BY THE PRODUCTIONAND USE OF PFOS AND OTHER PERFLUOROALKYL COMPOUNDS (PFCs)

Table 1. PFC concentration in surface waters andrelated drinking waters of some cities inthe Ruhr area

City: Surfacewater

Drinkingwater

Surfacewater

Drinkingwater

PFOA [ng/L] Sum of PS [ng/L]

MülhelmEssenBochumWittenHagenSchwertNeheim

4860587591178646

3158535065146520

949791147152280765

631049691118234609

References

Disclaimer –The Minnesota data used in thisstudy/report was acquired during MPCA studieswhile two of the authors were MPCA staff. The

MPCA was not involved with preparing thispaper.

Oliaei F., Weber R., Kriens D., Watson A.


1a. Brooke, D.,Footitt, A.,Nwaogu, T.A B.R.E.Ltd & R.A.P.A.Ltd. (2004). Environmentalrisk evaluation report:perfluorooctanesulphonate (PFOS) for theEnvironment Agency.

1b. Oliaei F (2010), Update on PFCInvestigation and Health Risks http://www.w-e-i.org/update-pfcinvestigation-and-health-risks-fardin-oliaei-2010

2. Stockholm Convention, E. (2009). Report ofthe Conference of the Parties of theStockholm Convention on Persistent OrganicPollutants on the work of its fourth meeting.UNEP/POPS/ COP.4/38. 8 May 2009.

3. Stockholm Convention (2004) www.pops.int.4a. Busch, J.,Ahrens, L.,Sturm, R. Ebinghaus, R.,

(2010). Polyfluoroalkyl compounds inlandfill leachates. Environmental Pollution158 (5): 1467-1471.

4b. Weber R, Watson A, Forter M, Oliaei F.Persistent Organic Pollutants and Landfills -A Review of Past Experiences and FutureChallenges. Waste Management & Research29 (1) 107-121 (2011).

5. Oliaei F, Kriens D L, The MinnesotaPollution Control Agency (MPCA) PFCInvestigation Workplan, June 30, 2005.

6. Organisation for Economic Cooperation andDevelopment (OECD) (2002). Cooperationon Existing Chemicals, Hazard Assessmentof Perfluorooctane Sulfonate (PFOS) and itsSalts report.

7. Oliaei F, Kriens DL, Kessler K. (2006)Investigation of PerfluorochemicalContamination in Minnesota Phase One,Report to Minnesota Senate EnvironmentCommittee, February 2002.

8. ATSDR, U.S. Department of Health andHuman Services, (2009) Draft ToxicologicalProfile for Perfluoroalkyls, Public HealthService Agency for Toxic Substances andDisease Registry, May 2009.

9. Minnesota Department of Health (MDH)(2009) Perfluorochemicals and Health, May2009.

10. MPCA (2008) PFCs in MN’s AmbientEnvironment: 2008 Progress Report, MPCA.

11. MPCA (2010) Mississippi River Pool 2Intensive Study of Perfluorochemicals inFish and Water: 2009, MPCA, March 8,2010.

12. Calculation by Don Kriens, P.E., MPCAworking document, 2007.

13. Skutlarek D, Exner M, Färber H. EnvironSci Pollut Res 2006; 13: 299.

14. Kröfges P, Skutlarek D, Färber H, Baitinger C,Gödeke I, Weber R. PFOS/PFOAContaminated Megasites in GermanyPolluting the Drinking water Supply ofMillions of People. Organohalogen Compd.69, 877-880 (2007).

15. Hölzer J, Wilhelm M (2007)Querschnittsstudie zur Untersuchung derinneren Belastung von Mutter-Kind- Paarenund Männern in Gebieten erhöhterTrinkwasserbelastung mit perfluoriertenVerbindungen („PFT“) http://www.umwelt.nrw.de/ministerium/presse/presse_extra/pdf/pft_abschlussbericht.pdf

16. Joensen UN, Bossi R, Leffers H, JensenA.A, Skakkebæk NE, Jørgensen N. 2009.Do Perfluoroalkyl Compounds ImpairHuman Semen Quality? Environ HealthPerspec 117(6): 923-27.

AbstractThe data about production, use and storage ofpesticides in Azerbaijan for the last 60 years arereported. Azerbaijan had a developed agriculturein the Soviet era. Up to 60 thousands tonnes ofpesticides per year were used in pest control ofthe agriculture. A part of these pesticides wasproduced in Sumgait chemical complex and apart was imported from outside. During 1951-1978, the Sumgait factory ofSurface-active-substances produced 480,549tonnes of 5 % DDT. For this purpose, 25thousands tonnes of pure DDT was importedfrom Russia. The data about production andusage of DDT in Azerbaijan in 1958-1980 areprovided in this paper. It has been recorded that283,827 tonnes of DDT was used in the cotton-growing areas of 24 regions of Azerbaijan. Dataabout production of hexachloran in 1951-1978and lindane in 1986-1988 are also provided.Information about “hot spots” and environmentalimpact of obsolete pesticide are also provided.After 2004 the Government of Azerbaijan tooksteps to deal with the obsolete pesticides in thecountry. The results of the first inventory andmonitoring of the obsolete pesticides within theframework of the projects of the EcologicalSociety “Ruzgar”, financed by the InternationalPOPs elimination Network (IPEN) and CaspianEnvironmental program are reported in thispaper.

Key words: Pesticides, production, use, “hotspots”, capacity, NGO.

IntroductionAccording to FAO every year 34 % of the worldpotential crops – with estimated cost of 75 bln USdollars - are destroyed by insect pests and weeds.The 50% of these losses are happening in thecountries, which tend to lag behind the economicdevelopment. It is impossible to receive high andstable crops in the agriculture without the

application of pesticides. These chemicals areapplied to protect the plants from insect pests anddiseases, and also to fight against weeds. Theexcessive use of pesticides without considerationof application instructions applicationinstructions lead to environmental contaminationand negative health impact. During FormerSoviet Union (FSU), the centralised managementsystem of agriculture used to overlook the use ofpesticides above permissible amounts, thatresulted in the vast pollution of soil, water andair. It is necessary to note that the majority ofpesticides used were persistent and stable in theenvironment. In the 1970s and 1980s, 1.4 million tonnes ofgrain, up to 700-800 thousand tonnes of cotton,over 1 million tonnes of grapes, more than 1.2million tonnes of vegetables, 400 thousandtonnes of fruit and other agricultural productswere produced in Azerbaijan. At the same time,the climate of Azerbaijan was very conducive tothe distribution of various diseases by insectsand pests of agricultral products. After the breakup of the Former Soviet Union (FSU) the use ofpesticides has decreased 20-fold. However, theaccumulated unused and banned pesticides stillrepresent threat to the environment and health ofthe population.

1. Production of pesticides in AzerbaijanDuring 1984-1994, nearly 20 thousand tonnes ofsurface-active substances were produced inSumgait factory. The factory was established in1958 to produce DDT with a capacity of 60thousand tonnes a year. The productionproceeded until 1980. Within 22 years ofproduction, the technical dust containing 4.5-5%of DDT had reached 482539 tonnes. It is worth tomention that production of DDT was banned inthe FSU in 1970. In 1951 the factory of surface-active substances began to produce technicalhexachloran containing gamma-isomerhexachlorcyclohexane (lindane), and within 27

EXPERIENCES WITH OBSOLETE PESTICIDES ANDPOPS IN AZERBAIJAN

MANAGEMENT OF OBSOLETE PESTICIDES IN AZERBAIJANIslam MustafayevEcological Society «Ruzgar»

SESSION 3.


Islam Mustafayev

Table 1. Quantity (tone) of pesticides and poisonous chemicals used in Azerbaijan in 1989categorised by their type

Table 2. Use of DDT (tone) in cotton planting in the regions of Azerbaijan for 1965-1982

The distribution of DDT by regions in the cotton planting of Azerbaijan are listed in Table 2.


years produced 30,449 tonnes ofhexachlorcyclohexane. The process was built onthe basis of photochemical chlorination ofbenzene. In 1986-1989 the same factoryproduced 181 tonnes pure gamma-isomerhexachlorcyclohexane - lindane, that was sent toNovomoskovsk (Russia). Today “Preparation -30” is the only plant protection product produced

in Azerbaijan. This pesticide is used as a wintertreatment in the orchards and vineyards.

2. Use of pesticides in Azerbaijan81 pesticides and chemicals were introduced tothe Azerbaijani agriculture to protect the crops.As an example data from 1989 are listed in Table1 below:

MANAGEMENT OF OBSOLETE PESTICIDES IN AZERBAIJAN


It should be noted that during 1984-2004 thequantity of used pesticides in the countrydecreased from 6705 t/year to 2720 t/ year. In1991-2004 the registration and inventory ofobsolete pesticides in Azerbaijan was not kept.The data on storage warehouses and usage ofthese obsolete pesticides were not available.There were the cases when population accessedpesticide containers and used obsolete pesticidesin private farming.

3. ”Hot spots” of obsolete pesticides inAzerbaijan

IPEN framework projects created to makepublic-environmental inventory show that ”hotspots” can be divided into the following groups:

3.1. Places of pesticide production Of concern in Azerbaijan is Sumgait factory ofsurface-active substances, which still containsDDT waste and other pesticides.

3.2. Polygons for storage of obsolete pesticidesThe first inventory of obsolete and bannedpesticides stored in polygon took place in 2004.The construction of polygon at distance of 53 kmfrom Baku in Gobustan region began in 1963 andcompleted in 1990. As shown in the official data,nearly 8 thousands tonnes of obsolete and bannedpesticides, mainly DDT, hexachlorcyclohexane,calcium-cyanamid, calcium-arsenad, weredelivered in polygons in the years 1989-1991.Until 2006 the local population started to use thepesticides in their own agricultural facilities orfor sale. After 2007 the polygon wasreconstructed and protected in accordance withthe sanitary-technical norms. From that timeonwards, obsolete pesticides from other hotspothad been brought and stored at the polygon.There is also a Polygon for hazardous waste,where the obsolete pesticides from Dayikend aredelivered.

3.3. Interregional bases of maintenance withchemical compoundsUntil its abolition in 1996, the interregionalchemicals storage warehouses were controlled byorganization “Аzselkhozkhimiya”. Afterwardsthe Open Joint-stock company“Аzerkendkhimiya” took over the warehouses.

They were privatized, and all the pesticidescontained there were discarded. Some pesticidesstill contain obsolete pesticides that create risk tothe environment. In total, there were 11warehouses and 50 distribution points inAzerbaijan, some of which are cloase to railwaystations.

3.4. Former storehouses in former collectivefarms and field campsIt is true to say that pesticide warehouses existedin almost all cotton-growing collective farms andstate farms. After privatization of the land, thesepoints were liquidated and the rest of pesticidesdisseminated in the environment.However, the number, characteristics and theexact site of all the storehouses have not beenidentified yet.

4. Distribution of DDT and Lindane in thesoil and water environment of Azerbaijan

4.1. DDT and lindane in the soil of AzerbaijanSince 1983, the Ministry of Ecology and NaturalResources of Azerbaijan has conductedmonitoring of the level of DDT and hexachloranein the soil from more than 10 stations. Within aperiod 22 years, a huge analytical material hasbeen collected, which made it possible to make aconclusion about changes of distribution andpesticide levels in the regions of Azerbaijan. The territory of Azerbaijan can be nominallydivided into 4 distinct areas such as:

1. Relatively clean areas where DDT andhexachlorane concentration is < 1 µg/kg

2. Areas with 1 µg/kg <DDT <10 µg/kg3. Contaminated areas where DDT and

lindane concentration used to be 15-20times higher than the permissibleconcentration, and where the DDT andhexachlorane concentration today is 10times lower than the permissibleconcentration

4. “Hot spots” where DDT and hexachloraneconcentration can reach several percent.

However, this division of territory should be usedwith caution as regular and consequtive analyseson all territory have not been done yet.

Islam Mustafayev


4.2. DDT and lindane in potable water ofAzerbaijanAbout 70 % of the Azerbaijani population use theresources of the transboundary rivers of Kur andAraz for drinking water and irrigation. Thereforethe measurement of the concentration of pesticidelevels of Kura waters has been of greatimportance. The Company “Azekolab” hasmeasured the content of DDT and lindane in 4points of the rivers Kura and Araz. Theconcentration of DDT and lindane in Kura andAraz waters and in suspense particles, was muchbelow the permissible norm and, in many cases,even below the sensitivity limit. The reason isthe sedimentation of firm particles in cascadewater reservoirs of the Shamkir-Yenikend-Mingechevir-Varvara, but it is also possible thatthe measurements are low due to the smallprobability of penetration of pesticides insuperficial waters at the distance Mingechevir-Shirvan.

5. Capacity of the Republic of Azerbaijan onmanagement of pesticides

5.1. Capacity at the systemic levelAzerbaijan has signed the Basel and StockholmConventions and carries out correspondingobligations. National Legislative basis ofmanagement of pesticides consists of the law ofthe Republic of Azerbaijan on “Phytosanitarycontrol” from 2006 and the legal acts onrealization of the main law. For the last 10 years,the Government had adopted various Nationaland State Programs, which include problem ofmanagement of obsolete pesticides:The State Program on Poverty Reduction andSustainable Development (2008-2015); TheNational Program for Ecologically SustainableSocial-economic Development (2003); The StateStrategy of the Azerbaijan Republic onManagement of Dangerous Wastes (2004); TheProgram on Social and Economic Developmentof Regions (2004); The Program of Developmentof Agrarian Sector (2008), etc.

5.2. Capacity at the Institutional levelThe main Stakeholders at the institutional level:The Ministry of Ecology and Natural resources,The Ministry of Agriculture, The Ministry of

Health, The Ministry of Emergency, TheMinistry of Justice, Milli Medjlis (Parliament),The Customs Committee, The StatisticsCommittee, the local executive authorities andmunicipalities, NGOs, and Mass-media.

5.3. The international organizationsVarious programs of the United Nations(UNIDO, UNDP, UNOPS), FAO, WB, IREN,CEP) finance the international projects on POPsmanagement in Azerbaijan, which are carried outby the Governmental Agencies and NGOs.

With support from the UNIDO program, in 2005-2006, The Ministry of Ecology and NaturalResources carried out the project entitled as“Development of the National ImplementationPlan on Stockholm Convention”. The process ofcreating the National Implementation Plan (NIP)involves all stakeholders. At present, the MENR,Ministry Agriculture and Ministry Health areworking on projects covering various aspects ofmanagement of POPs and pesticides.

5.4. Participation of the NGOs in themanagement of the obsolete pesticidesThe Ecological Society “Ruzgar”, financed andmethodically supported by IPEP, the Center of“Ecoaccord” and the Caspian EcologicalProgram have developed about 10 projects oninventory of the obsolete pesticides, monitoringof these substances in the environment andpublic awareness of this problem. “Ruzgar” isalso involved in a project initiated by the WorldBank on inventory of POPs in Azerbaijan andCaspian POPs Workshop in Baku on 2009.Further, the Ecological Information AgencyECORES also implement projects onmanagement of pesticides, and public awareness.

5.5. Private CompaniesThere are more than 12 private companies, whichdeliver pesticides and chemicals for use in theagriculture in Azerbaijan.

6. NGO-proposals on improvement of processto manage pesticides

By their performance of obligations under theStockholm Convention in Azerbaijan the NGOscame up with the following suggestions:

• Improve the National legislative and

MANAGEMENT OF OBSOLETE PESTICIDES IN AZERBAIJAN


normative documents according to theEuropean Directives

• Create a special Center for management ofthe obsolete pesticides in Azerbaijan, whichcan organize and coordinate activitiesbetween various Agencies

• Deepen the activities on inventory of theobsolete pesticides in the country;

• Allocate special bunkers in the polygon for

separate classes of the POPs • Package and repackage obsolete pesticides

and transport them to the polygon• Conduct large-scale information campaign

on the management of obsolete pesticides • Develop and provide awareness of

population for re-collection of DDT,hexachlorane and other dangerouspesticides from population.

1. Study and survey project to determine thefluxes of major contaminants from the Kurato Caspian Sea (Mingechaur reservoir to Kurariver delta).CEP. (Ruzgar- Azekolab)-2005

2. Azerbaijan National Implementation Plan onthe Stockholm Convention. UNIDO Baku-2006

3. I.Mustafayev, E.Gurbanov, Z.Ramazanova.Pesticides and Environment. IPEP. Baku-2005

4. I.Mustafayev. POPs: Situation in Azerbaijan.IPEP. Baku-2006

5. Report on Caspian POPs Workshop. WB.Baku-2009

References


The paper reports on the results of quantum-chemical calculations of electronic structure of22 isomers of tetrachloro-dibezo-para-dioxinusing Wolfsberg-Helmholtz method (W-Hmethod).

Continuing our research on calculation of atomiccharges in the molecules of mono-, di-, and threechlorinated dibenzo-para-dioxins, [1,2] toestablish correlation between the number and thelocation of chlorine atoms in phenyl rings and thetoxicity of the molecule [3], in this work we

study the electronic structure of 22 isomers iftetra-chlorine-substituted molecules of dioxinusing Wolfsberg-Helmholtz method (W-Hmethod).

The molecule of dioxin C12HxO2 consists of 22atoms as shown in Figure 1. The tetrachlorinated isomers are derived by simultaneoussubstitution of 4 atoms of hydrogen to 4 atomsof chlrorine. It’s known, that in this waytetrachloro-dibezo-para-dioxin produce 22isomers.

QUANTUM CHEMICAL CALCULATION OF ELECTRONSTRUCTURE OF THE TETRACHLORINATED DIBENZO-PARA-DIOXIN ON THE BASIS OF SLATER-TYPE ATOMIC ORBITALSМ.S. Salahov, N.D. Ashurova, Т.М. Mursalov, F.H. PashayevInstitute of Polymer Materials of National Academy of Sciences of AzerbaijanBaku State University, Azerbaijan

The Wolfsberg-Helmholtz method is one of thesemi-empirical ways of Molecular Orbital (MO)theory of Linear Combination of Atomic Orbitals(MO LCAO). The molecular orbitals describethe status of electrons in a molecule, and arerepresented as a linear combination of atomicorbitals in the molecule of interest:

where, Xq is a basis atom orbital.

For basic functions, we use real Slater-typeatomic orbitals (SAO) [4]:

(1)

(2)

where is real spherical harmonics.

(3)

(4)

For determination of exponential parameter ξ weuse the followings formula [5]:

where N= number of electrons in the atom.The quantum mechanical calculations ofelectronic structure of a molecule are restrictedto the valence electrons of atoms, and the

molecular orbitals are represented as a linearcombinations of SAO of the valency electrons.For each of carbon and oxygen atom valanceSAO are 2s-, 2px-, 2py- and 2pz-, for hydrogen

atoms 1s- and for chlorine atoms 3s-, 3px-, 3py-and 3pz - Slater functions, respectively. Hence,in quantum mechanical calculations of tetrachlorinated molecules of dioxin (C12H4Cl4O2)as basis atomic orbitals we used 76(12x4+4x1+4x4+2x4=76) Slater functions

of atoms of carbon, hydrogen, chlorineand oxygen. Applying formulas (2), (3) and (4)we determined analytical expressions of SAO.

In (1), Cqi – unknown coefficients, which aredetermined by solution of the followings systemof equations of simple order of MO LCAO:

Quantities of Hpq represent the matrix elementsof effective operator of Hamilton for oneelectron, moving in a certain effective field,independent from other electrons; quantities Spqare integrals of overlap between SAO Xp and Xq.Therefore, for the solution of the system ofequations (6). i.e. for determination of orbitalenergies εi and of corresponding set of coefficientsCqi, it is necessary to know the numerical valuesof Hpq and Spq.However, quantities Hpq cannot be accuratelycalculated, because real expression of Ĥ isunknown. Therefore, Hpq can be calculated in avariety of ways, one of which is a quantum-mechanical semi-empirical method ofWolfsberg-Helmholtz. According to this method,each diagonal matrix element Hqq is assumedequal to ionisation potential of the correspondingvalence state of the particular atom, and notdiagonal matrix elements are determined basedon equation [6,7]:

where the value of the coefficient is determinedtheoretically or from a comparison with theexperimental data.Its noteworthy, that for the quantum mechanicalcalculations of molecules in accordance with W-

H method, it is required to find out the exactnumerical values of integrals of overlapping (8)in the total coordinate system of the molecule.For this purpose, we use the analyticalexpressions obtained in [8-10]. Forcomputational quantifications based on theseequations, the Cartesian coordinates of the atomsin a molecule coordinate system are used. In our calculations, we consider the dioxinmolecule is planar, and in each case the centre ofthe Cartesian coordinate system is assumed to bethe centre of the molecule mass. Z-axis isperpendicular to the projection of the molecule.For determination of the atom coordinates ineach molecule, we used the followinggeometrical parameters (bond lengths and bondangles) [11]:dc-c= 1.4 A, dc-0= 1.44 A, dc-h= 1.09 A, dc-cl= 1.7 A<ccc= 120º, <cco= 123º, <coc= 114º, <cch= 120º, <cccl = 120º

Using these data, we have calculated theCartesian coordinates of atoms for each isomerof C12H4Cl4O2. For determination of diagonalmatrix elements Hqq of operator Ĥ we used thefollowing values of ionization potential ofvalence state of the atoms of H, C, O and Cl [12]

(1s |H| 1s) = - 0.499786(2s |C| 2s) = - 0.772096(2p |C| 2p) = - 0.419161(2s |O| 2s) = - 1.325536(2p |O| 2p) = - 0.680952(3s |Cl| 3s) = - 0.552337(3p |Cl 3p) = - 0.882774

The effective charge of the atom A in molecule isdetermined according to MO LCAO formula [13]

where noA is the positive nuclear charge of the

atom A (for carbon noC= 4, for hydrogen no

H =1, for chlorine no

Cl=7, and for oxygen noO =6),

ni is the number of electrons on i-molecularorbital. Summarising I is done using molecularorbitals occupied by electrons. The program we developed for computercalculations using W-H method on the basis of


QUANTUM CHEMICAL CALCULATION OF ELECTRON STRUCTURE OF THE TETRACHLORINATEDDIBENZO-PARA-DIOXIN ON THE BASIS OF SLATER-TYPE ATOMIC ORBITALS

(5)

(6)

(7)

where, the followings are included

(8)

(9)

1. Minkin V.I., Simkin B.YA., R. M. Minyaev.Theory of the structure of molecules, M., Vs,1979, Page 407.

2. Shembelov G.A., Ustinuk YU., Mamaev V. M.,Ishchenko S.Y., Glorizov I.P., Luzhkov V.B.,Orlov V.V., Simkin V.Y., Pupishev V.I.,Burmistrov V. N., Quantum Chemicalmethods of calculation of molecules, M.:,Chemistry, 1980, page 255.

3. Gastilovich E.A., Klimenko V. G., KorolkovaN. V., Nurmukhametov R.N.// Successes ofchemistry, 2000, VOL. 69, Issue 12, pages1128-1147.

4. Fedorov L. A., Myasoyedov B. F. //Successes of chemistry. 1990, T. 59, Vol. 11,P. 1818-1866.

5. Dewar M. Theory of molecular orbitals in

organic chemistry, M.:, Mir, 1972, P. 590.6. Guseinov I.I., Mursalov T.M., Pashayev F.G.,

Mamedov B.A., Allahverdiev N.A. // WELL.Chemistry Structure, 1989,Vol.30, P. 183-185.

7. Guseinov I.I.,Hanzayev M.G., Veliyev R.M.,Sadykhov F.S.,Mursalov T.M.// Ukr. Nat.,sib., 1991, V.36, P. 679-681.

8. Guseinov I.I., Hamzayev M.G., Mursalov T.M.,Veliyev RM., Mamedov B.A., Pashayev F.G.//WELL. Chemistry Structure, 1991, Т.32, P.135-139.

9. Hinze J. Jaffe H.H.// Cornal of the AmericanChemikal Socierty, 1962, Vol.84, P. 540-546.

10. Dmitriev I.S. The electron through the eyesof a chemist, L.:, Chemistry, 1986, P. 225.

References

М.S. Salahov, N.D. Ashurova, Т.М. Mursalov, F.H. Pashayev


SAO allows to calculate the values of electronenergy (E), the ionization potential (J), thecoefficients in (1), and the effective charges (qA)

of atoms. However, in Table 1, for the studiedmolecules, we report only the numeric values ofeffective charges of atoms.

ABSTRACTVarious analytical approaches that utilize FourierTransform Ion Cyclotron (FT-ICR) massspectrometry and data reduction schemes foranalysis of complex sample mixtures arediscussed. Specifically, the advantages of highmass resolving power (MRP), mass measurementaccuracy (MMA), and gas-phase ion-moleculereactions for highly confident identification ofpesticides in complex sample mixtures such ascontaminated soils, or water are demonstrated.High performance mass spectrometers (e.g., FT-ICR MS or FTMS) combined with data reductionapproaches allow rapid identification ofchlorinated compounds including persistentorganic pollutants (POP) and obsolete pesticidesin complex environmental sample mixtures at thehighest level of confidence currently achievable.This methodology avoids the need for a pre-separation step (e.g., gas chromatography (GC)or high pressure liquid chromatography (HPLC))and at the same time offers one of the mostsuitable approaches for highly reliable and rapididentification of contaminated areas at lowconcentrations (below femtomole range) andsubsequent monitoring of the potential soil orwater remediation processes.

INTRODUCTIONOur research is focused on various areas of “x-omics” and addressing issues related to samplecomplexities in biomedical and environmentalresearch areas.1-3 The term “x-omics” refers to acomprehensive study of various complexsystems such as the components of a livingorganism (e.g., genomics, metabolomics,proteomics, etc), an environmental sample,and/or a non-living system (e.g., petroleumics).3

In all of these research areas, we must resolve thedifferent components of a mixture, determineindividual molecular identities, acquire relativeabundance or concentration information, andunravel potential interactions among the variousconstituents of the sample at a high level ofconfidence.

Ideally, for comprehensive characterization of acomplex ensemble, we need to know (a) types,(b) concentrations, and (c) nature of theinteractions of all individual components of themixture under the investigation. For example, fordetection of a potential pesticide in a heavilycontaminated area, we must address a-c. One ofthe most important initial steps in designing animplementation plan for remediation of apotentially contaminated soil or waterecosystem is comprehensive characterization ofthe environment at the molecular level. Highlyconfident evaluation of the ecosystem under thestudy demands high accuracy and high precisionand ideally identification of all molecularcomponents that are present in these complexmixtures. Often it is not a difficult analytical taskto inspect and characterize samples that containonly a few chemicals and at sufficiently highconcentrations (depending on the detectorresponse factor). However, with “real world”samples, such as contaminated soil or water,detection of analytes at low concentrations canpresent a formidable analytical challenge.

Conventionally, gas chromatography (GC) orother types of separation techniques (e.g., highpressure liquid chromatography (HPLC)) areused in tandem with mass spectrometry toseparate various analytes and subsequentlydetect each individual component present in the

ULTRAHIGH RESOLUTION AND MULTIDIMENSIONAL ANALYSISOF PESTICIDES AND COMPLEX SAMPLE MIXTURES WITHFOURIER TRANSFORM MASS SPECTROMETERS: ENHANCEDIDENTIFICATION POINTST.Solouki*1,2, B.Zekavat1, A. J.Ramirez2, D.A.Olaitan1,2, M.Miladi1,2,V.M.O.Farzaliyev3, P.S.Mammadova3, E.R.Babayev3

1Department of Chemistry, 5706 Aubert Hall, University of Maine, Orono, ME – USA2Department of Chemistry and Biochemistry, Baylor University, Waco, TX – USA3Institute of Chemistry of Additives/Azerbaijan National Academy of Sciences, Baku - AZ


T.Solouki, B.Zekavat, A.J.Ramirez, D.A.Olaitan, M.Miladi, V.M.O.Farzaliyev,P.S.Mammadova, E.R.Babayev


mixture. Although chromatography has been anexcellent work horse to address samplecomplexities, the separation process requiresadditional time and often sample preparationsteps. Here we discuss an analytical approach fordetection of chlorinated contaminants (e.g.,persistent organic pollutants (POP), obsoletepesticides) present in complex environmentalsample mixtures that avoids the need for priorsample separation.

Two dimensional (2D) graphical visualizationtechniques such as Kendrick plots can be used tosimplify the interpretation and classification ofdifferent class compounds.4 Highly confidentcharacterization of pesticides in complex samplemixtures, such as soils contaminated with crudeoil, requires multiple analyses and often highperformance mass spectrometry (MS). Forexample, electrospray ionization (ESI) Fouriertransform ion cyclotron resonance (FT-ICR)mass spectra of crude oil samples contain severalpeaks at each nominal mass and thousands ofpeaks in the entire mass spectrum.5 Hence,characterization or classification of pesticides insuch complex sample mixtures by conventionalmethods can be quite challenging or impossible.

For detection of dioxins and furans, a methodthat employs a GC in tandem with a highresolution sector mass spectrometer(e.g.,combined electrical and magneticanalyzers) can be used. We have shown that GCcombined with high resolution MS can be used todifferentiate gasoline samples from different gasstations for unambiguous source identification6

as well as isomer differentiations.7 Althoughthese approaches provide invaluable information,they are not suitable for direct analysis ofcomplex mixtures. Fernandez-Lima et alshowed that the combined use of ultrahighresolution MS and ion mobility spectrometry(IMS) provides unique fingerprinting ability inpetroleumics.8 Here, we discuss theoretical andexperimental results for direct, rapid, andunambiguous identification of chlorinatedcompounds present in highly complex mixtures.

We utilize Kendrick plots and proton affinity(PA) differences (as an additional chemicaldimension to Kendrick plots)9 as well as

multistage MS for analysis of complex mixturesat low concentrations. It is particularly importantto note that “effective” concentrations of many ofthe chlorinated environmental contaminants canbe increased via bioaccumulation and thereforean ideal detector must be sensitive enough toaddress these challenges. FT-ICR MS providesultra high MRP and MMA and multidimensionalanalyses can be conducted using ion-moleculereactions. We could demonstrate that pesticidecontent of highly contaminated samples can bedetected and visualized through data reductionand use of ultra high MRP and MMA. Weselected oil samples from Naftalan (Azerbaijan)and deliberately inserted theoretical massspectral peaks (corresponding to mass-to-charge(m/z) values of eleven chlorinated contaminants)in the acquired mass spectra. Here, we also useasphaltenes samples as examples of complexmixtures and show that pesticides andchlorinated chemicals can be differentiatedvisually and without a need for a separation step.Moreover, we discuss the merits of usingadditional identification points such as ultrahighmass measurement accuracy (MMA) and ion-molecule reactions to enhance selectivity andreduce the probability of error.

EXPERIMENTALAll of the chemical reagents and solvents werepurchased from Sigma (Sigma, St. Louis, MO).An FT-ICR mass spectrometer equipped with anopen-ended cylindrical Penning trap (IonSpecCorp., Irvine, CA) and a 9.4 teslasuperconducting magnet (Cryomagnetics Inc.,Oak Ridge, TN) was used to carry out gas-phaseion-molecule reactions and acquire massspectra.7 Ions were generated externally using anAnalytica electrospray source (Analytica ofBranford Inc., Branford, CT) equipped with anin-house built spraying setup. 1 Ubiquitin andsubstance P were used for external calibration ofthe mass spectra (Sigma, St. Louis, MO). Alsoan Orbitrap FTMS was used to acquire massspectra of Asphaltenes extracts (toluene extracts)and samples that were deliberately spiked withchlorinated compounds. The list of halogenatedcompounds that were used for computersimulations (along with their chemical

composition and molecular weights, columns twoand three, respectively) are included in Table 1.

RESULTS AND DISCUSSIONFigure 1 shows how identification points earnedby MS can be increased by performing additionalmass spectra (e.g., acquiring tandem or highresolution mass spectra – please note that thisFigure reiterates the original concept that was inintroduced by Thurman et al earlier 10). We haveadded mass measurement accuracy and ion-molecule reactions to indicate that theseprocesses would increase earned identificationpoints.11 For example, we have shown that ion-molecule reactions and multidimensional MS canbe used for isomer differentiation 12 andidentification of halogenated disinfection

byproducts (DBP).9, 13 Ion-molecule reactionscan also be used to reduce data complexity. Toillustrate, in Figure 2, we show the Kendric plotsfor a portion of the m/z range for an oil samplefrom Nafthalan with diisopropylethylamine(DIPEA) (as a proton transfer reagent). Figure 2

shows almost complete depletion of singly-charged ions from a typical crude oil sample(after 150 s reaction time at P(DIPEA) = 2.0 ×10-6 torr). Detailed comparison of narrow massrange of Kendrick plots before and after reaction(for 150 s) with DIPEA shows selective depletionof chemical compounds with different chemicalcompositions. For example, among C31H61O2S3(m/z 561.3828), C40H65O (m/z 561.5030),C36H56O2N3 (m/z 562.4367), C34H66O2N4 (m/z =562.5180), C37H58O3N (m/z 564.4411), andC37H72OS (m/z 564.4298), only C31H61O2S3,C34H66O2N4, and C37H72OS survive. These resultssuggest that the interpretation of Kendrick plotscan be complemented by including PA as anadditional dimension. Figure 2 shows that thecomplexity of data can be reduced by usingappropriate proton transfer reagents. Suchadditional analysis dimensions can increaseidentification points which is a crucial parameterto consider for potential certification purposes(e.g., agricultural products, petrochemicalindustry, xenobiotics analyses, etc).Similar approaches can be used for identificationof halogenated compounds in complex mixtures.Figure 3 contains a computer simulated (crudeoil type) mass spectrum and its Kendrick plot onthe left hand top and right hand top, respectively.In the bottom portion of Figure 3, computersimulated (crude oil type) mass spectrum and its

ULTRAHIGH RESOLUTION AND MULTIDIMENSIONAL ANALYSIS OF PESTICIDES AND COMPLEX SAMPLEMIXTURES WITH FOURIER TRANSFORM MASS SPECTROMETERS: ENHANCED IDENTIFICATION POINTS


Table 1. Halogenated Chemical CompoundsUsed for Simulations

Figure 2. Proton Transfer Reaction

Figure 3. Kendrick Plots: “Rapid” Pollutant Identification in Complex Mixtures



Kendrick plot of a spiked sample (with elevenhalogenated compounds) are shown. Because ofthe mass deficiency for Cl atoms, a quick visualinspection allows rapid identification of allhalogenated compounds (viz., as expected, thehalogenated compound with six Cl atoms orlindane (C6 H6Cl6) shows the highest deviationin the simulated Kendric plot and is the easiestto spot from hundreds of interfering compoundsin bottom right corner of Figure 3. Our experimental results show similar trendswhere halogenated compounds stand out and canbe visually identified. For example, Figure 4depicts a FTMS mass spectrum (left hand side)and its Kendrick plot for toluene extract of anasphaltenes sample spiked with 1 ppb ofmiconazole (corresponding to less than picomole

mass analyzed) after toluene extraction. Inset inFigure 4 show an expanded region for the m/zrange 414.8 to 415.6 where more than fifteenpeaks are present around the nominal mass of415, with the halogenated species, miconazole,in the farthest left hand side with the lower m/zvalue (i.e., peak corresponding to ions with thehighest mass deficiency). A quick inspection ofthe Kendrick plots provides the same informationand allows for rapid identification of all Clisotopomers of the halogenated species.Novel Aspects: Graphical visualization ofultrahigh resolving power ESI/FT-ICR MS alongwith proton affinity differences and othermultistage MS can be used for highly confidentdetection/characterization of pesticides incomplex sample mixtures.

ULTRAHIGH RESOLUTION AND MULTIDIMENSIONAL ANALYSIS OF PESTICIDES AND COMPLEX SAMPLEMIXTURES WITH FOURIER TRANSFORM MASS SPECTROMETERS: ENHANCED IDENTIFICATION POINTS

Figure 4. Asphalt-Toluene Extract (Spiked at ~1ppb of Miconazole)

REFERENCES


1. Fattahi, A.; Zekavat, B.; Solouki, T., H/Dexchange kinetics: experimental evidencefor formation of different b fragment ionconformers/isomers during the gas-phasepeptide sequencing. Journal of TheAmerican Society for Mass Spectrometry2010, 21, (2), 358-369.

2. Szulejko, J. E.; McCulloch, M.; Jackson, J.;McKee, D. L.; Walker, J. C.; Solouki, T.,Evidence for cancer biomarkers in exhaledbreath. Sensors Journal, IEEE 2010, 10, (1),185-210.

3. Solouki, T.; Miladi, M.; Zekavat, B.;Khalvati., M. A., “Plant Proteomics”, in“Organic Xenobiotics and Plants: FromMode of Action to Ecophysiology”, Editedby Peter Schroeder, Springer-Verlag BerlinHeidelberg New York. In 2011.

4. Kendrick, E., A Mass Scale Based on CH,=14.0000 for High Resolution MassSpectrometry of Organic Compounds.Analytical Chemistry 1963, 35, (13), 2146-2154.

5. Marshall, A. G.; Rodgers, R. P., Petroleomics:the next grand challenge for chemicalanalysis. Accounts of Chemical Research

2004, 37, (1), 53-59.6. Szulejko, J. E.; Solouki, T., Potential

analytical applications of interfacing a GCto an FT-ICR MS: fingerprinting complexsample matrixes. Analytical Chemistry 2002,74, (14), 3434-3442.

7. Solouki, T.; Szulejko, J. E.; Bennett, J. B.;Graham, L. B., A preconcentrator coupled toa GC/FTMS: advantages of self-chemicalionization, mass measurement accuracy, andhigh mass resolving power for GC applications.Journal of The American Society for MassSpectrometry 2004, 15, (8), 1191-1200.

8. Fernandez-Lima, F. A.; Becker, C.;McKenna, A. M.; Rodgers, R. P.; Marshall,A. G.; Russell, D. H., Petroleum crude oilcharacterization by IMS-MS and FTICRMS. Analytical Chemistry 2009, 81, (24),9941-9947.

9. Luo, Z.; Heffner, C.; Solouki, T.,Multidimensional GC-Fourier transform ioncyclotron resonance MS analyses: utilizinggas-phase basicities to characterizemulticomponent gasoline samples. Journalof Chromatographic Science 2009, 47, (1),75-82.



10. Thurman, E. M., et al. Anal. Chem. 2006,Oct. 1st, 6702-6708.

11. Szulejko, J. E.; Luo, Z.; Solouki, T.,Simultaneous determination of analyteconcentrations, gas-phase basicities, andproton transfer kinetics using GasChromatography/Fourier Transform IonCyclotron Resonance Mass Spectrometry(GC/FT-ICR MS). International Journal ofMass Spectrometry 2006, 257, (1-3), 16-26.

12. Solouki, T.; Szulejko, J. E., Bimolecular and

unimolecular contributions to the disparateself-chemical ionizations of alpha-pineneand camphene isomers. Journal of TheAmerican Society for Mass Spectrometry2007, 18, (11), 2026-2039.

13. Heffner, C.; Silwal, I.; Peckenham, J. M.;Solouki, T., Emerging technologies foridentification of disinfection byproducts:GC/FT-ICR MS characterization of solventartifacts. Environmental Science &Technology 2007, 41, (15), 5419-5425.

The length of Kur-river is 1515 km, 980 km ofwhich run through the territory of Azerbaijan. Itsthe biggest river in Azerbaijan providing 70% ofwater supply of the country. In April 2010 thewater level in Kura started rising hourly and flowspeed increased from 500 m3 sec-1 to 2,500 m3 sec-

1, what created an emergency situation in theprovinces of Azerbaijan. According to officialstatistics report, 110 thous. hectares of land wentunder the water, of which 60 thous. hectarescomprised fertile arable lands. These lands hadlong been used for agricultural developmentsduring the former Soviet Union. According toStatistics Committee of Azerbaijan, in 1990, thetotal usage of pesticides in the agricultural areascomprised 87 kg per hectare. In 1985, the usagerate was 166 kg per hectare.

The recent flood washed away large obsoletepesticide stocks in the former chemicalwarehouses adjacent to agricultural areas inSalyan, Neftchala, Sabirabad, Saatli and otherregions. Five villages in Sabirabad regioncompletely stayed under the water for a lengthyperiod, the reason why people flee these villages.The official statistics in Azerbaijan indicate that3,741 thous. hectares of arable lands underwentserious degradation due to the flooding. Thismakes 41% of the total arable land area.

Along Kur-river, in Aghstafa-Qazakh and centrallowland regions of Azerbaijan there are ~38-40thous. tonnes of obsolete pesticides either buriedor stored in old warehouses. Flood washed awayand disseminated to vaster areas the remaindersof these obsolete pesticides in Sabirabad,Neftchala, Salyan, Imishli and other regionslocated in Kur-river lowland. This eventuallyresulted in the decrease of the biosenosys ofthese areas by 60-70%. According to theestimated reports between 1995-2010, the area

of degraded land increased by ~20 thous.hectares.

Kur-river also destroyed storages of mineralfertilizers, that caused salinization of these areas.

Every time, flood covers area of about 500meters at both sides of Kur river. That makes~2,000 hectares of fertile land. In Salyan andNeftchala regions, where the largest obsoletepesticide stocks exist, the lands along Kur-riverare of no use any more and require highinvestment for restoration. Population living inthese area, especially children, exposed to highhuman health risks.

The 105 thous. hectares of land on both sides ofKur-river used to be covered by riverine tugayforests. In some areas, these forests used toextend to over 10 km along the river. Tuqayforests maintained fertility of lands and served asa barrier to flooding. Later on, the large area offorest had been destroyed to open space forconstruction of dam, and this resulted in decreaseof tugay forest area along Kur-river.

During floods, the water covers whole villagesfor a lengthy period and this impacts not only theinfrastructure. It stays in the pits, destroyingarable lands and forests, causing serious damageto natural ecosystems. Thus, heavily pesticidepolluted water stayed for almost four monthsaround Sarisu lake –Sabirabad, Askerbayli, closeto Qasimbayli village. Then it was pumped backto Kur without any treatment, regardless Kur-river river being a source of drinking water fortens of thousands of people.

The situation in Sabirabad is very similar to otherareas, where flood water stays for up to fourmonths, creating bogs and causing damage tofertility of soil in the affected areas.

THE IMPACT OF KURA RIVER FLOODS ON SPREADING OFOBSOLETE PESTICIDES IN THE ENVIRONMENT OF AZERBAIJANSadiq HasanovHealthy Life Non-Government Organisation, Baku, Azerbaijan


Sadiq Hasanov


Recommended actions to be taken in the nearfuture are as follows:

1. Raise public awareness, particularly inthe areas regularly affected by floods.

2. Quantify the volume of obsoletepesticides and fertlisers near-by Kur-river and prioritise them for clean-up anddisposal (this step is in the process by theGovernment)

3. Improve pesticide management system4. Clean oozy river bed and to define works

for moving small ships there. Moving ofships is one of the methods forpreventing river delta from oozing.

5. Strengthen dams along the Kur-river. Oursurvey field trips recorded that the widthof the dams makes 4-5 meters and this isnot strong enough.

6. Restore of Tuqay forests along the Kur-river. In 1950, Tuqay forests occupiedarea of 105 thous. hectares. Nowadaysthe area decreased to 50 thousandhectares according to official data.

7. Initiate som cleaning and restorationworks in the areas covered by floods, bogand prioritize small lakelets.

The Green Revolution in agriculture, whichswept much of the developing world during the1960s, saved an estimated one billion peoplefrom famine. Thanks to high-yielding cropvarieties, irrigation, agrochemicals and modernmanagement techniques, farmers in developingcountries increased food production from 800million tonnes to more than 2.2 billion tonnesbetween 1961 and 2000. Intensive cropproduction helped to reduce the number ofundernourished, drive rural development andprevent the destruction of natural ecosystems tomake way for extensive farming. Thoseachievements came at a cost. In many countries,decades of intensive cropping have degradedfertile land and depleted groundwater, provokedpest upsurges, eroded biodiversity, and pollutedair, soil and water. As the world population rises toa projected 9.2 billion in 2050, we have no optionbut to further intensify crop production. But theyield growth rate of major cereals is declining, andfarmers face a series of unprecedented, intersectingchallenges: increasing competition for land andwater, rising fuel and fertilizer prices, and theimpact of climate change.

The present paradigm of intensive cropproduction cannot meet the challenges of thenew millennium. In order to grow, agriculturemust learn to save. Consider, for example, thehidden cost of repeated ploughing. By disruptingsoil structure, intensive tillage leads to loss ofnutrients, moisture and productivity. Morefarmers could save natural resources, time andmoney if they adopted conservation agriculture(CA), which minimizes tillage, protects the soilsurface, and alternates cereals with soil-enrichinglegumes. Those simple practices help to reducecrops’ water needs by 30 percent and the energycosts of production by up to 60 percent. In trialsin southern Africa, they increased maize yieldssix-fold. Combining CA with precision irrigationproduces more crops from fewer drops. Farmers

can reduce the need for fertilizers by adopting“precision placement”, which doubles theamount of nutrients absorbed by plants. By usinginsecticides wisely, they can save pest predatorsand disrupt the cycle of pest resistance.Economizing on agrochemicals and buildinghealthy agro-ecosystems would enable low-income farm families in developing countries –some 2.5 billion people – to maximize yields andinvest the savings in their health and education. This new paradigm of agriculture is sustainablecrop production intensification (SCPI), whichcan be summed up in the words “save and grow”.Sustainable intensification means a productiveagriculture that conserves and enhances naturalresources. It uses an ecosystem approach thatdraws on nature’s contribution to crop growth –soil organic matter, water flow regulation,pollination and natural predation of pests – andapplies appropriate external inputs at the righttime, in the right amount. “Save and grow”farming systems offer proven productivity,economic and environmental benefits. A reviewof agricultural development in 57 low-incomecountries found that ecosystem farming led toaverage yield increases of almost 80 percent.Conservation agriculture, which is practised onmore than 100 million hectares worldwide,contributes to climate change mitigation bysequestering in soil millions of tonnes of carbona year. SCPI represents a major shift from thehomogeneous model of crop production toknowledge-intensive, often location-specific,farming systems. Its application will requiresignificant support to farmers in testing newpractices and adapting technologies.Governments will need to strengthen nationalprogrammes for plant genetic resourcesconservation, plant breeding and seeddistribution in order to deploy improved cropvarieties that are resilient to climate change and

APPROACHES FOR SUSTAINABLE PESTICIDEMANAGEMENT

SAVE AND GROW: FAO’S NEW PARADIGM FOR SUSTAINABLECROP PRODUCTION INTENSIFICATIONRichard Thompson (AGP) and Walter de Oliviera (AGS)UN Food and Agriculture Organisation

SESSION 4.


Richard Thompson (AGP) and Walter de Oliviera (AGS)


use nutrients, water and external inputs moreefficiently. Fundamental changes are alsorequired in agricultural development strategies.Policymakers must provide incentives foradoption of SCPI, such as rewarding goodmanagement of agro-ecosystems. Developedcountries should support sustainableintensification by increasing considerably the flowof external assistance to, and investment in,agriculture in the developing world. Sustainable intensification of smallholder cropproduction is one of FAO’s strategic objectives.Our aim over the next 15 years is to assistdeveloping countries in adopting “save and grow”policies and approaches. FAO has published thebook “Save and Grow” as a toolkit of adaptablefarming systems, technologies and practices, andexplores the policies and the institutionalarrangements that will support the large-scaleimplementation of SCPI.

The “Save and Grow” book together with theaccompanying fact sheets is available to be readon-line in Arabic, Chinese, English, French,Russian and Spanish at http://www.fao.org/ag/save-and-growAn overview of the main chapters of Save andGrow is included as Annex A.

1. The challengeTo feed a growing world population, we have nooption but to intensify crop production. Butfarmers face unprecedented constraints. In orderto grow, agriculture must learn to save.

The Green Revolution led to a quantum leap infood production and bolstered world foodsecurity. In many countries, however, intensivecrop production has depleted agriculture’snatural resource base, jeopardizing futureproductivity. In order to meet projected demandover the next 40 years, farmers in the developingworld must double food production, a challengemade even more daunting by the combinedeffects of climate change and growingcompetition for land, water and energy. Thisbook presents a new paradigm: sustainable cropproduction intensification (SCPI), whichproduces more from the same area of land whileconserving resources, reducing negative impacts

on the environment and enhancing natural capitaland the flow of ecosystem services.

2. Farming systemsCrop production intensification will be built onfarming systems that offer a range of productivity,socio-economic and environmental benefits toproducers and to society at large.The ecosystem approach to crop productionregenerates and sustains the health of farmland.Farming systems for SCPI will be based onconservation agriculture practices, the use ofgood seed of high-yielding adapted varieties,integrated pest management, plant nutritionbased on healthy soils, efficient watermanagement, and the integration of crops,pastures, trees and livestock. The very nature ofsustainable production systems is dynamic: theyshould offer farmers many possible combinationsof practices to choose from and adapt, accordingto their local production conditions andconstraints. Such systems are knowledge-intensive. Policies for SCPI should build capacitythrough extension approaches such as farmerfield schools, and facilitate local production ofspecialized farm tools.

3. Soil healthAgriculture must, literally, return to its roots byrediscovering the importance of healthy soil,drawing on natural sources of plant nutrition, andusing mineral fertilizer wisely.Soils rich in biota and organic matter are thefoundation of increased crop productivity. Thebest yields are achieved when nutrients comefrom a mix of mineral fertilizers and naturalsources, such as manure and nitrogen-fixingcrops and trees. Judicious use of mineralfertilizers saves money and ensures that nutrientsreach the plant and do not pollute air, soil andwaterways. Policies to promote soil health shouldencourage conservation agriculture and mixedcrop-livestock and agroforestry systems thatenhance soil fertility. They should removeincentives that encourage mechanical tillage andthe wasteful use of fertilizers, and transfer tofarmers precision approaches such as urea deepplacement and site-specific nutrientmanagement.

SAVE AND GROW: FAO’S NEW PARADIGM FOR SUSTAINABLE CROP PRODUCTIONINTENSIFICATION


4. Crops and varietiesFarmers will need a genetically diverse portfolioof improved crop varieties that are suited to arange of agro-ecosystems and farming practices,and resilient to climate change.Genetically improved cereal varieties accountedfor some 50 percent of the increase in yields overthe past few decades. Plant breeders mustachieve similar results in the future. However,timely delivery to farmers of high-yieldingvarieties requires big improvements in the systemthat connects plant germplasm collections, plantbreeding and seed delivery. Over the past century,about 75 percent of plant genetic resources (PGR)has been lost and a third of today’s diversity coulddisappear by 2050. Increased support to PGRcollection, conservation and utilization is crucial.Funding is also needed to revitalize public plantbreeding programmes. Policies should help to linkformal and farmer-saved seed systems, and fosterthe emergence of local seed enterprises.

5. Water managementSustainable intensification requires smarter,precision technologies for irrigation and farmingpractices that use ecosystem approaches toconserve water.Cities and industries are competing intenselywith agriculture for the use of water. Despite itshigh productivity, irrigation is under growingpressure to reduce its environmental impact,including soil salinization and nitratecontamination of aquifers. Knowledge-basedprecision irrigation that provides reliable andflexible water application, along with deficitirrigation and wastewater-reuse, will be a majorplatform for sustainable intensification. Policieswill need to eliminate perverse subsidies thatencourage farmers to waste water. In rainfedareas, climate change threatens millions of smallfarms. Increasing rainfed productivity willdepend on the use of improved, drought-tolerantvarieties and management practices that savewater.

6. Plant protectionPesticides kill pests, but also pests’ naturalenemies, and their overuse can harm farmers,

consumers and the environment. The first line ofdefence is a healthy agro-ecosystem.In well managed farming systems, crop losses toinsects can often be kept to an acceptableminimum by deploying resistant varieties,conserving predators and managing crop nutrientlevels to reduce insect reproduction.Recommended measures against diseases includeuse of clean planting material, crop rotations tosuppress pathogens, and eliminating infectedhost plants. Effective weed management entailstimely manual weeding, minimized tillage andthe use of surface residues. When necessary,lower risk synthetic pesticides should be used fortargeted control, in the right quantity and at theright time. Integrated pest management can bepromoted through farmer field schools, localproduction of biocontrol agents, strict pesticideregulations, and removal of pesticide subsidies.

7. Policies and institutionsTo encourage smallholders to adopt sustainablecrop production intensification, fundamentalchanges are needed in agricultural developmentpolicies and institutions.First, farming needs to be profitable:smallholders must be able to afford inputs and besure of earning a reasonable price for their crops.Some countries protect income by fixingminimum prices for commodities; others areexploring “smart subsidies” on inputs, targetedto low-income producers. Policymakers alsoneed to devise incentives for small-scale farmersto use natural resources wisely – for example,through payments for environmental services andland tenure that entitles them to benefit fromincreases in the value of natural capital – andreduce the transaction costs of access to credit,which is urgently needed for investment. In manycountries, regulations are needed to protectfarmers from unscrupulous dealers selling bogusseed and other inputs. Major investment will beneeded to rebuild research and technologytransfer capacity in developing countries in orderto provide farmers with appropriate technologiesand to enhance their skills through farmer fieldschools.

The project goals are to reduce reliance onpersistent insecticides, including DDT, withoutincreasing the occurrence and spread of malariaand other VBDs; to promote appropriate vectorcontrol management practices by strengtheningcapacities and capabilities of countries toimplement environmentally sound, effective andsustainable vector control alternatives; and toreduce the availability of DDT stocks to thepopulation through safeguarding of relevantstocks. The Project is focused on Georgia,Kyrgyzstan and Tajikistan.

The project is divided into two parts. Health part– WHO (1-2) which is implementing by WHOrepresentatives in countries and second theenvironmental part implementing byMilieukontakt International (3).

Project duration is 5 years. - GEF/UNEP - 2010-2015.

In the frame of the Project, MilieukontaktAmsterdam has been contracted by Green CrossSwitzerland to undertake the following actions:

DEMONSTRATION AND SCALING UP SUSTAINABLEALTERNATIVES TO DDT FOR CONTROL VECTOR BORNDISEASES IN SOUTHERN CAUCASUS AND CENTRAL ASIAKhatuna AkhalaiaMilieukontakt International, Georgia


DEMONSTRATION AND SCALING UP SUSTAINABLE ALTERNATIVES TO DDT FOR CONTROLVECTOR BORN DISEASES IN SOUTHERN CAUCASUS AND CENTRAL ASIA


• undertake an integrated managementapproach for the participatory safeguardingof (on average) 60 tonnes of prioritisedPOPs stockpiles per country and thedevelopment of participatory disposalconcepts (mainly DDT) as example forsimilar projects in other countries in theregion;

• present measures to safeguard stockpiles;and

• communicate on the hazards of DDT tospecific target groups.

Steps implemented b 2010-2011 in Tajikistan,Kyrgyzstan and Georgia Tajikistan and Kyrgyzstan:Training inventory was already done in the frameof FAO/Turkey project, and inventory groupswere established for both countries. In spring2012, both countries will start inventory

activities according to the FAO standard, and alldata will be available in PSMS database aftercompleting the inventory for the whole country. DDT project will proceed with the repackaging of60t of DDT or DDT containing obsolete pesticidesand associated wastes. Final disposal of repackedpesticides will be implemented with planedproject FAO- EC.Most important part is that in both countries it ispossible to make one complete model fromInventory till destruction with local workinggroup.Georgia In the frame of EECCA FAO project, there willbe 18 inventory sites. Repackaging of DDT orassociated waste will be completed in the frameof the DDT UNEP/WHO project. The finaldestruction of UNDP GEF project is ongoing.MKI - Planning for 2012

In the future, it is planned to include Azerbaijanin the future activities as new project will beinitiated in December 2011.

Potential outcomes of the project are as follows:

Outcome 1: Demonstrated viability and cost-effectiveness of alternatives vector controlinterventions to persistent insecticides that areappropriate to the major eco-epidemiological,environmental and socio-cultural settings

• To design research protocols for eachparticipating country with assistanceprovided by an international expert andWHO: international expert recruited andexpert advice rendered (February-March2011): COMPLETED

• To implement and monitor project activitiesincluding support for procurement of itemsin demonstration sites: international expertand NPC/project staff recruited and expertadvice being rendered, country-leveltrainings completed, project progress beingreported and relevant procurements done(April 2011-October 2014): ONGOING

• To evaluate project activities: expert advicebeing provided, project data beingprocessed and analyzed, and progressreports being prepared (October 2011-November 2014): ONGOING

Outcome 2: Enhanced national capacity forplanning and implementation of IVM To formulate and draft regional IVM policy andstrategy: international expert recruited, a firstdraft developed and being discussed: ONGOING

• To design regional technical guidelines andtraining/learning materials on IVM:international expert recruited and theircontent discussed and agreed: ONGOING

Outcome 4: Existing regionally coordinatedmechanisms for effective dissemination andsharing of specific project/country experiencessupported

• To develop and agree on specificcommunication activity plans for healthsector: local/international expertsrecruited, expert advice rendered andcommunication activity plans for healthsector developed (2012-2015): NOTINITIATED YET

MAIN ACTIVITIES FOR HEALTHSECTOR, 2012

• To finalize regional IVM policy andstrategy and communication activity planfor health sector: International expert willbe recruited in close collaboration withWHO/Europe in February 2012

• To design and finalize regional technicalguidelines and training/learning materialson IVM: International expert will berecruited in close collaboration withWHO/Europe in April-May 2012

• To conduct a regional consensus workshopon regional IVM policy and strategy andon development of national IVM policyframework: A regional workshop will beconducted in September-October 2012

• To implement and monitor project

Khatuna Akhalaia


DEMONSTRATION AND SCALING UP SUSTAINABLE ALTERNATIVES TO DDT FOR CONTROLVECTOR BORN DISEASES IN SOUTHERN CAUCASUS AND CENTRAL ASIA


activities in demonstration sites: Expertadvice rendered and progress with projectimplementation being monitored andreported (January – December 2012)

• To evaluate project activities: Expertadvice rendered, project data processedand analyzed, and progress reports beingprepared (January - December 2012)

A number of sites, where obsolete pesticides areeither kept in storage or buried were investigatedfor this technical study. This project wasimplemented in the following five stages: training,inventory, characterization and prioritization ofobsolete pesticide containing sites, risk assessmentin priority burial sites, identification and feasibilityassessment of safeguarding, transport andelimination/disposal options of identified stocksand other contaminated wastes, feasibility of insitu site remediation/containment alternatives forhighly contaminated burial sites.

The national working group (NWG) of theproject noted the professional work of experts ofTauw Consortium and expressed deep gratitudefor a professional research work. By The “AnIntegrated Recovery” is the optimal solution tothe problems of obsolete pesticides (OP), incomparison with known experience on solvingproblems in the CIS countries (Ukraine,Moldova). Therefore, this “Option of IntegratedRecovery” was preferred by the State Agency onEnvironment Protection and Forestry under theGovernment of the Kyrgyz Republic for futureproject in Jalal-Abad district.

NWG expressed the following views, whichshould be taken into the account whendeveloping the future project:

1. To exclude activities on transportation 500 m³ /250 tonnes of OP to former Jalal-AbadAgrochemical Store and to the Central Store(CS) in local administration Sarai village(Osh) due to number of significant reasons:

• Jalal-Abad Store is private, and definitelythe owner will not agree with storage ofrepacked OP from the whole oblast, even itis temporarily.

• It will also save significant funds – it willbe not necessary to repair the facilities offormer Agrochemical Store in Jalal-Abadtown.

• For obtaining agreement for transportationand storage of additional volumes of OP inSC in local administration of Sarai village,it is necessary to obtain such agreementfrom local authorities. But it is clear, thatthey would not agree with this. Theparticipants of the meeting insisted on theincluding 90 tonnes of OP from CentralStore of local administration of Sarai village(Osh) to the vitrification process.

2. All collected and repacked OP from Jalal-Abad district and Central Store in localadministration of Sarai village should betransported immediately to the site Suzak A.At the same time it is necessary to build lightsheds with light construction for temporary(1 year) storage of repacked OP up to theirdisposal by method of vitrification.

3. For bioremediation, it should be allowed to usethe methods of selection of strains along withtechnology of oxidation and reduction.

4. To carry out tests for selection of local plantsfor phytoremediation.

5. To include to the plan of project activitiescreating information system (web-site) forcollection information on work being done onOP in KG.

TC - Tauw ConsortiumNWG - national working groupOP – Obsolete pesticides

Storage sites at Jalal Abad districtThe Jalal Abad district encompasses numerousbadly maintained former pesticide storage siteswith obsolete pesticides, waste and persistentorganic pollutant pesticides (referred to as OPs).25 of these storage sites were indentified andvisited by TC and trainees to make an inventoryand risk assessment in relation to the OPs andtheir environmental threat. Buried OPs andheavily contaminated topsoil are problems at

OBSOLETE PESTICIDES TECHNICAL STUDYIN KYRGYZ REPUBLIC (WORLD BANK PROJECT 100020592)Indira ZhakipovaPublic Fund “Ekois”, KyrgyzstanRepresentative of Milieukontakt-International Kyrgyzstan


OBSOLETE PESTICIDES TECHNICAL STUDY IN KYRGYZ REPUBLIC (WORLD BANK PROJECT100020592)


many of these sites, most of which are privateproperty. Risk assessments reveal that ten of the25 sites are high-priority sites. In total, these siteshave 250 tonnes of OPs and 145 m3 of heavilycontaminated soil. Measures to eliminate acuterisks in the short term are required at these sites,including measures such as repackaging,removal and safe storage of OPs, soilremediation and, finally, destruction of the OPs.Before a cleanup campaign can be executed, thequantities of OPs, buried pesticides and heavilycontaminated topsoil need to be updated becausethe situation at privately owned sites can changeovernight.

In addition to the ten high-priority storage sites,there are nine low-priority sites that do not haveOPs but probably do have contaminated topsoil.At least two have buried pesticides. The TCproposes to further assess the topsoil and the pitsto determine the quantity of contaminated soiland the quantity of buried pesticides at thesesites. If these surveys reveal that the sites haveburied OPs and contaminated soil and that thereare environmental risks, the cleanup of these sitescan be incorporated into the Jalal Abad oblastcleanup campaign.

Burial site Suzak AThe original design of the Suzak A burial site isgood, but pesticides at the site are now exposedand have been spread through the area by ‘illegalwaste miners’. DDT, in particular, is removedfrom the site to be sold on local markets. Thetotal estimated exposed pesticide quantity isapproximately 1,000 tonnes; the amount stillburied in the trenches is estimated atapproximately 2,000 tonnes (October 2009). OPshave contaminated the topsoil and the rainwatercollected in pits and potholes is contaminated.Over the years, pesticides have seeped intoapproximately 15,000 m2 of soil. The estimatedvolume of heavily contaminated soil is 8,250 m3,the volume of contaminated soil is 5,000 m3 andthe volume of slightly contaminated soil is 4,500m3.

The situation at the burial site poses a direct andunacceptable threat to public health and theenvironment and urgent measures must be taken.

35 cattle and 12 sheep died after drinkingstanding rainwater contaminated with OPs at theSuzak A burial site in March 2010. The ownersof the lifestock quickly sold the contaminatedmeat, resulting in the hospitalization of20 consumers. This sad incident underlines theseriousness and urgency of this issue and theneed to address it as soon as possible.

Selection of most appropriate rehabilitationalternative In order to come up with a group of wellbalanced measures to mitigate or eliminate therisks at the burial site and storage sites, TCassessed the relative merits of four rehabilitationalternatives in terms of risk reduction,environmental benefits and costs. In the shortterm, the TC proposes elimination of the acuterisks at the storage sites and the Suzak A burialsite in an integrated approach (Phase 1). For themedium-term, the TC proposes elimination of theremaining risks related to the contained OPs atthe Suzak A burial site based on destruction ofthese OPs (Phase 2). For the long term, the TCproposes addressing the risk related to thecontaminated soil at the Suzak A burial site(Phase 3).

Phase 1 - short-term measures to be taken toeliminate the acute risksThe following short-term actions are proposed toreduce the acute risks of the storage sites and theSuzak A burial site:

• At the 10 high-priority storage sites, executesurveys to update the amounts of buriedobsolete pesticides and contaminated soil.Repack the 250 tonnes of OPs and excavatethe 145 m3 of heavily contaminated topsoil.Transport the contaminated soil to theSuzak A burial site for containment, alongwith the pesticides and contaminated soilalready present at this site

• Appoint capable managers to the Suzak Aburial site. Fence the site and hire guards tokeep trespassers and lifestock off the siteand further reduce risk. Repair and updatethe old surface drainage system andimplement erosion control measures

• Collect 1,000 tonnes of OPs exposed to the

Indira Zhakipova


open air at the Suzak A burial site and placethese them in trenches. Then cap thetrenches with available soil. Contain these1,000 tonnes with the 2,000 tonnes of OPsthat are stilled buried at the site until on-sitedestruction is arranged

• Carry out an on-site and/or in-situ OPsdestruction pilot. The available projectbudget (EUR 3 million) should cover the in-situ destruction by vitrification of 1,700tonnes of OPs and 3,400 tonnes of heavilycontaminated soil

On-site and/or in-situ treatment techniques (e.g.vitrification, thermal desorption, andSupercritical Water Oxidation (SCWO) withBase Catalyzed Decomposition (BCD)) seem tobe the most suitable and robust techniques.Vitrification is a particularly interestingtechnique because it combines soil remediationand destruction of OPs. To vitrify one-third ofOPs, two-thirds of (contaminated) soil is neededas a matrix.

Phase 2 - medium-term measures Based on the experience done up in in-situ pilotand on-site destruction efforts, the remaining1,550 tons of OPs and 3,100 tons of heavilycontaminated soil can be destroyed with the sametechnique once the Kyrgyz authorities havegathered sufficient funding. If the Kyrgyzauthority is able to gather sufficient funding tocover the costs of in-situ and/or on-site

destruction, the costs of the final, sustainablesolution are limited to management, containmentand destruction costs. With in-situ and/or on-sitedestruction, there are no extra costs forrepackaging and (international) transport off-site.The money saved can be spent on in-situ and/oron-site destruction. Once the technique isoperational, it should be considered for use in thedestruction of OPs from other burial sites, suchas the Suzak B and Naryn burial sites, as well asfor the destruction of the 200 tons of OPs storedin the Intermediate Collection Centre in Osh.

Phase 3 - long-term measures In this phase, all of the risks related to thepresence of contaminated topsoil at the burial siteare addressed. To avoid expensive transport costsfor large quantities of soil, on-site treatment ofall contaminated soil is recommended. Theremaining (heavily) contaminated soil can beremediated with the oxidation, reductiontechnique. Phytoremediation is a viable optionfor the remediation of slightly contaminated soil.The soil remediation techniques and the volumesof soil to be treated are:

• Oxidation and reduction techniques- 4,800 m3 (8,400 m3 minus 3,600 m3) of

heavily contaminated soil

- 4,000 m3 contaminated soil

• Phytoremediation- 3,500 m3 slightly contaminated soil

AbstractMalaria is still a threat in Bangladesh as in manycountries although a concerted effort was initi-ated for the eradication of its mosquito vector byapplying DDT during the 60’s. At one point,eradication of malaria was acclaimed but later onit reappeared along with other virulent fevers likeKaalazar and Dengue. Use of DDT is no morelegally allowed in Bangladesh, which has beenofficially replaced by a number organophos-phates and/or synthetic pyrethroids and theircombinations in addition to the Integrated Vec-tor Management (IVM) package. IVM being alabour-intensive community approach is still togo a long way to be mass popular. Adulticides,larvicides, residual sprays, mosquito coil, insec-ticide-impregnated curtain, aerosol etc. still serveas the major weapons of mosquito control. Thusmosquito control still mostly depends on chemi-cal insecticides. Although use of DDT is bannedin Bangladesh, there are reports on their illegaluse in different forms. Moreover, there is tons ofleft-over DDT in Bangladesh, which is likely tocause several diseases. As per one report, about500 MTs of DDT stockpiles are lying in the Med-ical Sub-Depot at Chittagong for over a periodof 26 years. DDT is a persistent organic pollutant(POP) pesticide, which can cause diseases likecancer, endocrine disorder, disruption of immunesystem, embryonic abnormality, reproductivedisorder, etc. Other chemical insecticides, whichare replacing DDT, are also not free from haz-ardous impacts. IVM thus appears to be a wiseapproach requiring concerted efforts for the man-agement of mosquito to control malaria. Such anIVM comprises use of Bacillus thuringiensisBerliner var. israelensis (B.t.i.), methoprene, bio-control agents, cleaning of breeding sites,pyrethroid-impregnated curtain etc. Therefore, awise effort should be to completely stop the useof DDT, elimination of its stockpiles wherever theyare in Bangladesh and to popularize the IVMthroughout the country.

Key words: Persistent Organic Pollutant, DDT,Mosquito coil, aerosol, Integrated VectorManagement

IntroductionMalaria caused by 4 organisms such asPlasmodium vivax, P. ovale, P. malariae and P.falciparum still is a serious threat in many partsof Bangladesh. These are transmitted by 7species of mosquitoes of which 4 are mostimportant. These are: Anopheles dirus, a wildspecies found both in out-door and in-dooroccurs in hilly forested and foot hill areas, A.minimus occurs in hilly forested and foot hillareas – a primary vector, which waseliminatedthrough Malaria Eradication Program(MEP) using DDT, is recently reappearing, A.philippinensisoccurs inflood plain deltaic regionwas also eliminated through MEP is scarcelyfound now, and A. sundaicusoccurs in coastalareas was virtually eliminated through MEP butis recently reappearing. Other than these, A.annularis usually found in large numbers, is animportant vector in some places, A. aconitus notcommon is secondary vector in some places andA. vagus fairly common all over Bangladesh hasbeen recently incriminated as vector. Besides, 79Culicine species are recorded of which Culexquinquefasciatusis a vector of Filariasis disease,and Aedes aegypti and Ae. albopictusaresuspected as vectors of dengue. DDT because ofits health hazardous effects has been banned in1998 in Bangladesh in compliance with theStockholm Convention and a number ofchemicals in different forms are now used assubstitutes of DDT. Now the question is: Arethese chemical substitutes free from any healthhazardous effects? To find out answers to thisquestion a review has been made and compiled inthis article.

FindingsMalaria Eradication Program (MEP) was

UNWISE ALTERNATIVE EFFORTS TO CONTROL MOSQUITO MAYBE CAUSES OF SEVERAL DISEASESMd. Mahbubar RahmanDepartment of Entomology, BSMRAU, Gazipur, Bangladesh


Md. Mahbubar Rahman

Pf: Plasmodium falciparumSPR: Slide Positivity Rate (Positive case per 100 slides examined)SFR: Slide falciparum rate (Pf infection per 100 slides examined)

No epidemic was reported in 2008.However,Chittagong, Netrakona and Cox’s Bazar wereaffected by malaria epidemics in 2004 whereasNetrakona alone was affected by the epidemicsin 2005. The discontinuation of DDT as well as import ofsubstandard DDT caused obsolete DDTstockpiles in different locations of Bangladesh.A total of 602.389 MTs comprising 482.904 MTsof substandard DDTin 4 Medical Sub-Depots inChittagong out of 500 MTs imported by theHealth Directorate through ADB finance in 1984,101.69 MTs of DDT technical at BangladeshChemical Industries Corporation (BCIC),Chittagong, 12.795 MTs of DDT 75 WP atdistrict godowns of Directorate of Health (DOH)

and 0.005 MTs of DDT 75 WP at districtgodowns of Department of AgriculturalExtension (DAE) have been stockpiled inBangladesh. The very poor storage conditions areresulting in seepage, pilferage, weathering andmisuse of DDT, which are contaminating theenvironment and are suspected to cause serioushealth hazards such as cancers and tumors(Particularly breast cancer in women),neurobehavioural impairment including learningdisorders, endocrine system disruption,reproductive deficits and sex-linked disorders(Birth-defects/premature birth of baby), and ashortened period of lactation in nursing mothersand increased rate of diabetes to the surroundingaffected human residents.


successfully carried-out with residual spray ofDDT supplied by WHO during 1960 – 1977(Eradication Era) resulting in completeeradication of malaria/mosquito in 1977. But themalaria again started reappearing. The use ofDDT was continued for mosquito control during1971-1992 (Control Phase) with DDT producedinside the country along with donor-suppliedDDT. Subsequently Revised Malaria ControlStrategy (1993-2002) was adopted that included

restricted use of DDT and other control measuresincluding insecticide treated nets (ITNs) andLong Lasting Insecticidal Nets (LLIN). The DDTwas subsequently banned in 1998 followingwhich the use of DDT was highly restricted. Theresurgence of malaria continued (Roll BackMalaria) and still malaria is observed in manyparts of Bangladesh. DDT is no more producedin the country and is also not imported.

UNWISE ALTERNATIVE EFFORTS TO CONTROL MOSQUITO MAY BE CAUSES OF SEVERALDISEASE


Currently peoples are using different alternativesfor getting rid of mosquito biting, nuisance, highpitched buzzing, dengue fever, filariasis andmalaria. These alternatives include mosquitocoils, mats, aerosols and vaporizers preparedwith synthetic pyrethroids (SP) andorganophosphate (OP) insecticides (Table 1)along with other adjuvants and fillers. Reviewofpublished articles reveals that most of theseproducts have adverse effects, which may causeseveral diseases in the affected human beings.

Probable Health Risks of Mosquito Coils/MatsSPs are major a.i. accounting for about 0.3-0.4%of coil mass, the lowest lethal oral dose of whichis 750 mg/kg for children and 1,000 mg/kg foradults. Pyrethrins are of low chronic toxicity tohumans and low reproductive toxicity in animals,although headache, nausea, and dizziness areobserved in male sprayers. But the remainingcomponents of mosquito coil are organic fillers,binders, dyes, and other additives. Theircombustion generates large amounts ofsubmicrometer particles [(particulate matter <2.5 [micro]m in diameter; P[M.sub.2.5])] andgaseous pollutants. Burning one mosquito coilgenerates P[M.sub.2.5] = burning 75-137cigarettes. Coil smoke contains a suite of volatileorganic compounds (VOCs), including humancarcinogens and suspected carcinogens.Submicrometer particles can reach lowerrespiratory tract and may be coated with a widerange of organic compounds, some of which arecarcinogens or suspected carcinogens[(polycyclic aromatic hydrocarbons (PAHs)].Gas phase of coil smoke contains some carbonylcompounds (e.g. formaldehyde andacetaldehyde- as much as 55%) with propertiesthat can produce strong irritating effects on upperrespiratory tract. The emission of formaldehydefrom burning one coil is equal to burning 51cigarettes. Long-term exposure to coil smokeinducesasthma and persistent wheeze in children.Benz[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, dibenz[a,h]anthracene, and indeno[1,2,3-ca] pyrene areclassified by the U.S. EPA as probable human

carcinogens. Acrolein,glyoxal and methyl-glyoxal known for their high reactivity, strongirritation effects and suspected carcinogeniceffects are emitted from coil burning. SeveralVOCs including benzene, toluene, ethylbenzene,p,m,o-xylene, and styrene, are identified in coilsmoke. All are known to cause adverse healtheffects. When mosquito coils containing S-2(Octachlorodipropyl Ether) are burned, theyrelease a potent lung carcinogen calledbischloromethyl ether (BCME).

Probable Health Risks of AerosolAn aerosol spray often consists of very smalldroplets of solvent, propellant and AI. Major AIsare SP, which are relatively safer. But mostindustrial aerosols contain organic solvents,which give off vapours that are dangerous ifbreathed for too long or in too highconcentrations. Excessive intake can causeheadache, giddiness, mental confusion, blurredvision, nausea, weakness and fatigue, numbnessof limbs and, in extreme cases, loss ofconsciousness. Solvents in contact with skincause irritation and defatting of the skin. Long-term effects of solvent exposure include damageto the heart, liver, kidneys and central nervoussystem. Most common propellant, butane, is ofrelatively low toxicity, but is extremelyflammable. But others are potentially hazardousin addition to flammability. Some of very smalldroplets of solvent, propellant and AI are ideallysuited for breathing deep into lungs. Largerdroplets are trapped in the nose, throat and upperpart of the lung.

Probable Health Risks of VaporizerAIs of most vaporizers are SP, which arerelatively safer. However, human biomonitoringdata revealed urine concentrations of themetabolite (E)-trans-chrysanthemum dicarboxylicacid ((E)-trans-CDCA) between 1.7 microg/l and7.1 microg/l after 5 minutes of exposure to thedifferent sprays. Also the use of electro-vaporizersled to (E)-trans-CDCA concentrations in theurine in the range of 1.0 microg/l to 6.2 microg/l(1-3 hours exposure period).

Md. Mahbubar Rahman

Table 1. Substitutes of DDT, Their Formulations and Hazard Classifications


Recommendations for Safeway of MosquitoManagementIn the above context, the wise alternative to DDTfor mosquito/malaria control may only refer toadoption of the Integrated Vector (Mosquito)Management (IVM). This may include to preventbreeding of mosquito removal/cleaning of allbreeding sites e.g., bird baths, rain barrels, oldautomobile tires, ditches, unusedswimming/water pools, tree holes, flower pots,roof gutters to avoid stagnant water/ breeding ofmosquitoes; to control larvae, the most logicalapproach, examining each week the presence oflarvae, using one or more of the insecticides suchas Bacillus thuringiensis Berliner var. israelensis(B.t.i.), Methoprene, an insect growth regulator

(Altosid or any available formulation) to 2nd, 3rd

and 4th instar larvae in water, Petrolium distillateoil, Temephos or to control adults by usingAdulticides such as Ultra-low volumeapplication (Malathion/ Chlorpyrifos/Chlorpyrifos+ permethrin), thermal fogging withMalathion/ Chlorpyrifos/Chlorpyrifos+ permethrinas a space treatment against adult mosquitoes atnight or early morning when the air is calm (lessthan 5 mph) or applying Insecticide ResidualSpray (IRS) as barrier treatments to tall grasses,weeds, shrubs, fences, and other harboragessurrounding parks, playgrounds, residences tohelp reduce adult mosquito populations, and toavoid Contact of Adult Mosquitoes by usingLong-lasting Insecticide Treated Bednets(LLINs)/Insecticides Treated Bednets (ITNs).

UNWISE ALTERNATIVE EFFORTS TO CONTROL MOSQUITO MAY BE CAUSES OF SEVERALDISEASE

1. Agency for Toxic Substances and DiseaseRegistry (ATSDR). 2002. ToxicologicalProfile for DDT, DDE, and DDD. Update.Atlanta, GA: U.S. Department of Health andHuman Services, Public Health Service.

2. Ali, M., Wagatsuma, Y., Emch, M., andBreiman, R.F. 2003. Geographic InformationSystem for defining spatial risk for denguetransmission in Bangladesh: Role for Aedesalbopictus in an urban outbreak. Am. J. Trop.Med. Hyg., 2002. 69(6), pp. 634-640.Copyright © 2003 by The American Societyof Tropical Medicine and Hygiene

3. Berger-Preiss E, Koch W, Gerling S, KockH, Appel KE. 2009. Use of biocidal products(insect sprays and electro-vaporizer) in indoorareas – Exposure scenarios and exposuremodeling. Fraunhofer Institute for Toxicologyand Experimental Medicine, Nikolai-Fuchs-Str. 1, 30625 Hannover, [email protected]

4. Hamida, K. and Rashidul, H.Relationshipbetween sand fly fauna and kala-azarendemicity in BangladeshInternational Centerfor Diarrhoeal Disease Research Bangladesh,68 Shaheed Tajuddin Ahmed Sharani,Mohakhali, Dhaka 1212, Bangladesh.

5. Harry J. Ettinger, Charles I. Fairchild,Lawrence W. Ortiz, and Marvin I. Tillery.1973. Aerosol research and development

related to health hazard analysis. AerosolStudies Section. Industrial Hygiene Group.National Institute for Occupational Safetyand Health, Cincinnati, Ohio. Project R072.USA.

6. <http://www.epa.gov/pesticides/health/mosquitoes/pyrethroids4mosquitoes.htm>

7. J. Schoessow. 2002/2010. Insect Repellent.Texas AgriLife Extension Service, Texas A&M System, College Station, Texas.

8. Krieger RI, Dinoff TM, Zhang X. 2003.Octachlorodipropyl Ether (S-2) MosquitoCoils Are Inadequately Studied forResidential Use in Asia and Illegal in theUnited States. Environ Health Perspect111:1439-1442. doi:10.1289/ehp.6177.

9. Rahman, M. M. 2007. Mirroring obsoletepesticides issues of Bangladesh throughinternational standards. In John Vijgen,Valentine Plesca, Ion Barbarasa and LarisaCupecea (eds) Forum Book on the 9thInternational HCH and Pesticides Forum forCentral and Eastern European, Caucasus andCentral Asian Countries held during 20-22September, 2007 at Chisinau, Republic ofMoldova, Europe. http://www.hchforum.com/presentations/pdf/III-21_Rahman_Mahbubar.pdf

10. Travel Health Advisory. 2003. Website. [On-line]. Available: http://www.un-bd.org/unwa/

References


** Health hazards are most probable throughemissions due to ingredients other thanActive Ingredients;

* Health hazards are probable through highconcentrations and long exposure due toorganic solvents and propellant other thanbutane;

“No evidence” means literatures searched did notindicate significant health hazards under properuse.WHO Class II means moderately hazardous(non-carcinogenic, non-teratogenic etc.)WHO Class III means slightly hazardous WHO Class U means unclassified.

HomePage/ Travel%20Advisory/ dengue.html.Accessed: Feb. 2, 2005.

11. Walters J.K., Boswell, L.E., Green, M.K.,Heumann, M.A., Karam, L.E., Morrissey,B.F., and Waltz, J.E. 2009. Pyrethrin andPyrethroid Illnesses in the Pacific Northwest:A Five-Year Review. Public Health Reports /January-February 2009 / Volume 124. ©2009Association of Schools of Public Health.Oregon Department of Human Services,Public Health Division, Toxicology,Assessment, & Tracking Services, 800 NE

Oregon St., Ste. 640, Portland, OR 97232.12. WHO South East Asia Regional Office. The

Revised Malaria Control Strategy. 2006-2010.

13. WHO. 2005. Safety of pyrethroids for publichealth use. WHO/CDS/WHOPES/GCDPP/2005.10,WHO/PCS/RA/2005.1

14. WHO-Mekong Malaria Programme. 2009.A Mekong Malaria Programme PartnershipInitiative Working Document.

Md. Mahbubar Rahman


Abstract

The year-round cultivation of many crops isprovided by the weather and climatic conditionsof Uzbekistan with its characteristic hightemperatures. But, as in any southern region,these natural resources can be considered only byovercoming strong competition from pests,diseases and weeds. Uzbekistan has a longhistory of using beneficial insects for the pestcontrol. Plant Protection Committee becameoperational in the first half of the twentiethcentury. In the early 70’s, the regulations aimedat the development of biological and integratedmethods of plant protection were adpoted. InUzbekistan, the Integrated Pest Management iswidely used. The essence of the system is torecommend, in phytosanitarian conditions theuse of one or another method of pest controlwhich would provide full protection fromharmful cultural effects and promote agro-ecosystems. Integrated Pesticide Management isconsisting also in agro-chemical, agro-technicalmeasures and biological methods. The role of thechemical method is not excluded, in some casesit may be only way to protect plants from pests.

Key words: entomophagous insects,biofactories, biological and integrated methodsof plant protection, IPM

IntroductionUzbekistan is the second largest country inCentral Asia and the first by the number of itspopulation. Agriculture has always been a majorcomponent of the Uzbek economy. Cotton andwheat are the most important farming cultures inUzbekistan, followed by gardens, vineyards,vegetables, melons, potatoes, beans, rice andmaize. In the past, the pest control in Uzbekistan,as well as elsewhere, was carried out by chemicalmethods. However, the widespread use ofpesticides has caused irrepairable damage to theenvironment which are as follows:

- contamination of water basins,- dramatic reduction of useful

entomophagous insects and other animalsand plants

- environmental degradation in rural areas - incidence rate among the population.

In the early 70’s, the first biofactories for theproduction of biological material for agriculturalpurposes had started (Fig.1-2). The Republican Central Laboratory “Biosifat”(Bioquality”) and its subsidiaries, available in allregions of the country, have been created in orderto exercise control over the quality of productsmanufactured in laboratories and comply withthe requirements of the production ofentomophagous insects in biolaboratories.

In Uzbekistan, the Integrated Pest Managementis widely used. The essence of the system is torecommend, in phytosanitary circumstances, theuse of one or another method of pest controlwhich would provides full protection fromharmful cultural effects and promote agro-ecosystems.

Advantages of an integrated system (IPM)consist in the fact that it does not completelydestroy the harmful organisms and bring them toa safe number for the crop. In other words, theaim of the mentioned system is to provide thecost-harmless amount of injurious insects as foodfor the entomophags and acarifags inagrocoenosis. IPM is the plant protection systemby natural insects which can exterminate thepests.

However, the Integrated Pesticide Managementalso consist in agro-chemical, agro-technicalmeasures and biological methods. The role of thechemical method is not excluded; in some cases,it may be only way to protect plants from pests.

A special role of the Integrated PesticideManagement is performed by the biological

AN INTEGRATED PEST MANAGEMENT IN THE REPUBLIC OFUZBEKISTANAhror Sagdullaev, Zulfiya SuleymanovaNational Scientific Research Institute of Plant Protection, Tashkent, UzbekistanState Committee for Nature Protection of the Republic of UzbekistanState Inspection of Analytical Control, Tashkent, Uzbekistan


Ahror Sagdullaev, Zulfiya Suleymanova


methods, as the most environmentally safe andcost-effective. For example, the cost of chemicaltreatment is US$ 9-15 per hectare, whereas thecost of biological methods ~US$ 5 per hectare.

One of the positive aspects of biological method,according to specialists, is the lack of pestresistance to entomophags. As we know, manypests have acquired resistance against thepesticides.

The pheromonitoring insect developmentmethods are also widely used in the country. Oncotton plant the pheromone traps are successfullyused to indicate the timing of the generations(hence, the timing of the entomophag issuance)and the density of pests. The use of pheromonetraps in cotton can reduce the cost of protectingplants from pests by 30-40%.

Advantage of IPMThe application of developed technology forintegrated agricultural protection reduce usa ofcrop protection chemicals and save a significantannual investment made by the country for thepest control (Fig.3-4).

The spread of biological pest control methods inrecent years has reduced the volume of chemicalsused per hectare.

The incidences of chronic poisoning of farmers,during application of crop protection chemicals,have also been reduced. According to theMinistry of Health of the Republic ofUzbekistan, since 1995, there have been almostno cases of acute poisoning or deaths among theemployees using chemicals for the cropprotection. Over the last five years, there havebeen only 14 - 30 cases of acute poisoningreported in the country.

AN INTEGRATED PEST MANAGEMENT IN THE REPUBLIC OF UZBEKISTAN

Important role in reducing pesticide treatment isperformed by resistant crop varieties whichconstitute one of the core elements of theintegrated plant protection. Populations of pestson the resistant crop are 30-100 times lower thanon the susceptible one and the use of pesticides isrespectively less.

ConclusionThe nurture of the healthy plants, the use of highquality seed material, timeliness of sowing,harvesting, and seasonal work on the processingof crops - all of these methods of agro technology

deliver from the need for excessive chemicaltreatments of crops.According to the experts of the NationalScientific Research Institute of Plant Protection,sometimes the losses of the crop, caused by thepests, have represented a quarter of cropproduction. The use of the Integrated PestManagement has allowed saving the crop.The Government of the Republic of Uzbekistanis taking all feasible measures to develop theIntegrated Pest Management in the country. Inorder to improve the quality of agricultural cropprotection, the plant protection service, the


In the samples analyzed at the sanitary-epidemiological laboratory of the Ministry ofHealth, there has been found only one percent of

the substances which exceeded the limit ofpesticides. In the food, this figure is representedby about 0,3% - 0,7%.

Ahror Sagdullaev, Zulfiya Suleymanova


efficiency of protective measures, severaldocuments were adopted by the President and theGovernment of the Republic of Uzbekistan.

Public administration and control of plantprotection is carried out by the State Committee

for Plant Protection and Agricultural Chemistryunder the Ministry of Agriculture and WaterResources, the State Sanitary andEpidemiological Service of the Ministry ofHealth and the State Committee for NatureProtection of the Republic of Uzbekistan.

AbstractPesticides are important tools that help increaseagricultural production, improve food quality andsafety,contribute to the public health and protectthe environment. Effective and fully operationalsystems that ensure safe handling, use andmanagement of these products are often scarceor weak in most developing countries. Misuse,mishandling and mismanagements of theseproducts continue being significant challenges tothese countries andeasy access to the market bybanned, unregistered and old pesticidesexacerbates the problem. Pesticide consumptionin these countries is estimated less than a quarterof the global pesticide production, but more thanhalf of the poisonings and close to three quartersof fatalities associated with pesticide misuseworldwide occur here. This is a clearmanifestation of the weaknesses of the pesticidedelivery systems partly attributed to lack ofadequate knowledge and appropriate skills andscarcity of resources. Limited human andmaterial resources and lack of strong andenforceable regulatory policies and proceduresundermine the situation. In countries whereenabling work environments and policy

directives are absent or rudimentary, societalmotivations and creativity are rare andcommunications among partners are stagnant.To address these chronic problems effectively, astrategy that espouses stewardship throughbroader participations and collaborations amongvarious stakeholders was developed and tried intwo sub-regions. The strategy was focused onstrengthening the existing national pesticidedelivery systemby promoting, encouraging, andadvocating for enabling environments andfacilitating broader engagements amongstakeholders, including the ultimatebeneficiaries.

IntroductionAgriculture employs half of the world’s laborforce. Nearly a third of the 1.3 billion men,women and children that work in agriculture arepaid laborers (PAL)(FAO-ILO-IUF 2005)..Agriculture is the number one consumer andabuser of pesticides and is the most dangerousjobafter construction and mining. PALs in DCsoften carry out agricultural activities, includinghandlingof toxic pesticides, without appropriateprotection.

THE ROLE OF STEWARDSHIP IN PESTICIDE RISKREDUCTION – A SYNOPSIS OF TWO SUB-REGIONAL WORK-SHOPSYeneneh T. Belayneh Senior Technical Advisor and Project Manager, USAID/DCHA/OFDA; Director Universityof Maryland Eastern Shore, USA* Opinions expressed in this article are entirely those of the author

(photo: courtesy of Mr. Zebdewos Salato).


In DCs large quantities of obsolete and toxicpesticides are present (most of which have beenbanned in developed countries or have limited andrestricted uses). In these countries, pesticidesbecome obsolete for many reasons: lack of wellplanned importation, overstocking for fear ofuncertainties among end users, aggressivemarketing, forced offers from government sourcesor associated business partners, poorly assesseddonations by benevolent foreign entities and manymore.These old stocks cost national governmentsand donors millions of dollars in clean up anddisposal.

While all of these factors play a role in causingpesticide related problems, the solutions to theproblems do not seem to match the problems.Strengthening and improving the existingpesticide delivery system (PDS) at the nationaland regional levels, building capacityand raisingawareness among stakeholders and partners canbring some relief to the problem. To address thischronic problem in a more coordinated manner,a strategy that espouses stewardship throughactive collaborations among various stakeholderswas developed under the rubric of pesticide[stewardship] program (PSP)and launched in twosub-regions. The strategy was aimed atstrengthening the existing national pesticidedelivery systems (PDS) by promoting,encouraging, and advocating for enabling policiesand environment and facilitating broaderengagements among stakeholders. It emphasizeson sharing knowledge, information and skillamong partners, including beneficiaries as well asencouraging mutual benefits of the outcome of theinitiatives.

The effort is to get end users from the left phototo right photo (Photo: courtesy of Mr. Salato)

Goals and ObjectiveThe primary objective of the pesticidestewardship networking program (PSNP) is todevelop and execute PSP strategies that willimprove pesticide delivery systems (PDS) andultimately achieve the overarching goals of theprogram, i.e., to minimize human health risks,reduce environmental contaminations, contributeto the national economy and improve well-beingof the citizens.

Pesticide Stewardship Networking Program:An overviewIntroduction of PSNP as a strategy to improvePDS is one of the strategies widely perceived asan important tool to address thebroader issues ofpesticide related problems. The PSN programrequires a strong conviction in behavior changesacross a spectrum of stakeholders to help reducepesticide risks to humans and the environment.Fundamental changes in behavior amongpesticide handlers, users, regulators, providers,petty vendors and others are necessary inimproving PDS and enhancing the execution ofcorruption-free and effective enforcement ofregulatory procedures and policies.

The PSNP strategy emphasizes the creation ofsynergy among plant protection staff, healthofficers, environmental practitioners andregulatory bodies and others and strives to lay thefoundation for a safer and sustainable use of pestcontrol tools and agricultural and public healthpesticides. To attain these, the program advocatesfor active engagements by partners in

Yeneneh T. Belayneh


THE ROLE OF STEWARDSHIP IN PESTICIDE RISK REDUCTION – A SYNOPSIS OF TWOSUB-REGIONAL WORKSHOPS


disseminating knowledge and skills through allavailable means. The strategy underscores theimportance of launching structured and target-oriented awareness raising and advocacyinitiatives for the success of the program.

The PSNP can serve as a process for coordinatingand supporting proper disposal of obsolete anddangerous pesticides by exploring andintroducing effective and safer alternative pestcontrol tools that can minimize unnecessary useand accumulation of obsolete stocks whileguaranteeing effective control and prevention oftarget pests.

PSN: implementation frameworkEffective implementation of the overarchingobjectives of the stewardship initiative wouldrequire a coalition of stakeholders and a public-private sector synergy. Such strategy can beimplemented through a well defined andexecuted program.

The PSN approach stimulates and encouragespesticide experts, regulatory authorities, non-governmental organizations, private sector,researchers, academia, end-users and others toengage in a continued dialogue. It believes thatengaging in effective dialogue can significantlyimprove information flow between and amongall partners as well as narrow down the gapsbetween the source of know-how and skills andthe needs among beneficiaries. More importantly,it will help reduce and mitigate pesticide relatedhealth risks as well as poisonings and fatalitiesby enhancing awareness in safety and well-beingof producers, consumers, handlers and others.The process will also contribute to protecting theenvironment and conserving the much needednatural resources. In addition, PSN can helpavoid duplication of efforts by optimizingresource utilization, employing integratedproduction systems and there by contributing tothe overall food security and the nationaleconomy.

The PSN strategy and its programmatic elementsare implemented through the existing structurein the agriculture, public health, and other sectorsrelevant to its core messages and overarchinggoals and objectives. Engaging public and

private sectors will not only help improve thestewardship education and training programs forthe various sectors, but also creates a viablesynergy between and among the key stakeholdersthat play a crucial role in forging ahead a strongand viable PDS at the national, sub-regional aswell as regional levels.

The Three Step ApproachFollowing the above mentioned strategies and

tactics, two sub-regional workshops werelaunched in 2008 and 2009 in East Africa and theHorn of Africa, respectively. The workshops ledto the creation of the nuclei of two PSNassociations in the sub-regions, leading up to anofficial registration of a not-for-profit professionalassociation with a regional undertone in one ofthe sub-regions (Belayneh, 2008, DLCO-EA,2009).In both the East Africa and the Horn of Africainitiatives, the creation of the PSN nucleiinvolved a series of events through “the ThreeStep Approach (TTA)”. This approach began bylaunching a series of exploratory consultationswith key stakeholders. The consultationprocesses were focused on needs assessmentsand interests of host-organizations and otherpartners. Each step was executed methodicallyand chronologically. The exploratoryconsultations took place through a series of directdialogue with the national authorities that play agreater role in the national pesticide deliverysystem. The consultations paved the way for anintensive pre-workshop seminar.

Elements of stewardship processesKey elements of the stewardship process were

elaborated and thoroughly discussed andrigorous exploratory activities were undertakenat the pre-workshop seminar. Needs assessmentsand resource identification at the local, regionaland international levels were executed at theseminar. Dates and time for the final workshopwere discussed and determinations were made.

The pre-workshop seminar was tailored to givekey participants the opportunity to exchangeideas, opinions, and questions which helpeddefine the role of the stewardship within thetargeted sub-regional context. It also served as an

Yeneneh T. Belayneh


ideal venue for identifying means and ways tohelp improve the existing PDS. Areas relevant toand crucial for the implementation of thestewardship were outlined, examined, discussedand defined.

While the execution of all these events wasessential, the launching of the sub-regionalworkshop was the culmination of the processesdefining the establishment of the corner stone forthe stewardship system. As the prelude to theworkshop, individuals and offices were assignedto further elaborate the findings of the seminar.Intensive consultations were undertaken topursue the coordination and organizationalaspects of the stewardship workshop. During thistime, significant efforts were made to bringtogether key players to dialogue and contributeto the findings of the consultation processes andthe analysis of the seminar to determine thelaunching of the workshop.

Operational Themes and ProcessesAs mentioned earlier, the launching of thestewardship workshop revolved around threeprimary operational themes using the TTA(DLCOEA, 2009):

1. Developing practical and implementablePSN program,

2. Analyzing needs assessments through thefirst two steps of “the Three Step Approach”and custom tailoring mechanisms forknowledge and skills transfer at all levels

3. Launching enhanced and improvedcommunication systems that traversenon-traditional domains

The thematic operational teams were formedduring the initial period of the workshop andimmediately engaged in the analysis andcritiquing of the existing PDS. Each thematicgroup was tasked with discrete responsibilities tofurther develop its voluntarily mandated sectorand contribute to the implementation of the PSNstrategy. Each group was instructed to roll out itsoperational plan for intense discussions by thepanel. This process was deemed necessary andproven effective and useful in refining the workplans and making the plans ready for adoption atthe national and sub-regional levels.

As per the agreed up on procedures, the programdevelopment group focused on formulatingprocedures and guidelines, drafting by-laws forthe stewardship program and defining code ofconduct for its operational policies. Likewise, theknowledge and skills transfer group concentratedon formulating relevant means and ways ofdeveloping tools and methodologies forknowledge imparting processes and procedures.This group was charged with exploring ways andmeans of developing training materials,awareness raising and ways and means ofensuring readiness and delivery of these tools.

The communications system and outreach groupwas charged with developing methodologies,standard procedures and mechanisms forpromoting and introducing PSNP to the broaderaudience and also encouraging stakeholders tojoin the program or be associated with it. Raisingawareness and advocating for safer pesticidehandling and use to ensure human health safetyand environmental protection were also tasked tothe communications system. All of these werecarried out within the framework of stewardshipprocess with a clear message of improving andenhancing PDS at the national, sub-regional andregional levels and establishing the descendinghierarchy within these structures.

Chronology of observational readout on theTTA mode

I. The First Workshop on PesticideStewardship Networking - The East AfricaSub-Regional ExperienceThe first ever pesticide stewardship workshopwas launched in Tanzania in May, 2008 as theEast African sub-region [stewardship]initiative. As discussed elsewhere, a dialoguewas initiated on PSN with potential partners in2001 and a pre-workshop seminar was launchedin 2005 in Tanzania. Thereafter, the first everworkshop on PSN in East African was conductedin 2008. The sub-regional workshop culminatedat the creation of the nucleus of the PSNTanzania through a 3-step approach (Belayneh2008).The workshop greatly benefitted from



collaborative efforts among U.S. Office ofForeign Disaster Assistance’s (USAID/OFDA),emergency pests and pesticide program(AELGA), U.S. Department of Agriculture(USDA), various national ministries in Tanzania,Kenya and Uganda, NGO’s, academia andothers. Full participation by Kenya, Uganda andof course, the hosting nation, Tanzania gave theworkshop a great sense of sub-regionalendeavor. Added to this, the former TropicalPesticide Research Institute (TPRI) that once hada jurisdiction over all pesticide related activitiesin the then East African community played acrucial role and was one of the major attractionsfor the launching of PSN in Arusha, thehometown of TPRI in Tanzania. Although theestablishment [TPRI] has since retained itsacronym, it had gone through a name change toreflect its national ownership, hence, TanzaniaPesticide Regulatory Institute (Belayneh, 2008). The East African sub-region pilot program wasable to create the nucleus of the first ever PSN inTanzania and the region. As a result of theexecution of the three-step processes, namelyextensive exploratory consultations, intensivedialogue and pre-workshop seminar and the all-inclusive sub-regional workshop, there is a greatexpectation for rolling out of dozens of networksof trained PS persons equipped with experiencedtraining skills and knowledge. In addition,production of robust and custom tailored trainingmaterials is expected. Countries that wererepresented at the Tanzania PSN workshop havebeen encouraged and expressed interests to forgeahead with the creation of national level PSNprograms and sow the seeds for similar initiativesin their respective regions. Relevant National ministries, international andregional institutions such as the InternationalCenter for Insect Physiology and Ecology(ICIPE), the Desert Locust Control Organizationfor Eastern Africa (DLCO-EA) and others towhich pesticide is an important issue, areencouraged to play a significant role in thedevelopment and roll-out of the PSN programsin their respective region.

II. Workshop on Pesticide Risk Reductionthrough Stewardship – Experience of anInitiative in the Horn of Africa Sub-Region Work continued in 2008 to establish a similar

structure in the Horn of Africa sub-region. In theHorn, the PSN process was initiated throughcollaborative efforts among OFDA, USDA,DLCO-EA, the UN Food and Agricultureorganization’s Commission for Controlling theDesert Locust in the Central Region, variousnational ministries, non-governmentalorganizations, academia, research, private sector,and other stakeholders (DLCO-EA, 2009).During the course of the launching of the PSNprogram in the Horn of Africa sub-region, somefundamental procedures similar to thoseemployed during the Eastern Africa PSNinitiative were repeated. Among these were, thelaunching of needs assessments through the TTA,the development of an implementable PSNprogram and the establishment of a clear line ofcommunication traversing non-traditionaldomains.

As in the East Africa, the PSNP initiative in theHorn of Africa started with countless exploratoryconsultations, dialogue and discussions as wellas a number of face-to-face meetings and a pre-workshop seminar. These processes werefollowed by five days of intense workshop whichattracted partners and stakeholders from numberof neighboring countries in the Horn, includingDjibouti and Sudan (note: despite the fact thatinvitations were extended to Eritrea and Somalia,participants were not able to join their colleaguesat the workshop).

In the Horn of Africa sub-region, the initialprocess goes back to early 2008 when informalconsultations were carried out between OFDAstaff and overseas partners and the finalworkshop was launched in August, 2009 andgave birth to the nucleus of the PSNP. The PSNnucleus has since evolved to become a full-fledged association after receiving an officialregistration status in June, 2011 in Ethiopia. Theofficial registration of the PSA is the fruit ofunabated and unwavering commitments anddedications of members of the executivecommittee of the PSN and its partners, including

Yeneneh T. Belayneh


overseas sponsors. The association is nowrecognized as a registered not-for profit, non-governmental professional association under thename: Pesticide Stewardship Association–Ethiopia (PSA-E). Through these steps, thestatus of the PDS in each and every member-country in the sub-region can be examined andthe importance of institutionalizing the PSNprogram in improving the existing PDS can bedemonstrated.

Comparative analysis of the two sub-regionalPSNP initiativesThe observational lessons and experiences fromboth the Eastern Africa and the Horn of Africasub-regional PSNP initiatives clearlydemonstrated the stark similarities between thePDS in the two sub-regions. The two sub-regional workshops have defined clearly thestatus of the PSD in their respective regions.Furthermore, they have demonstrated the crucialrole that institutionalizing the PSNP can play inimproving the PDS at both the national and sub-regional levels. Doing so will not only contributeto but also guarantee building a culture ofstewardship through a network of stakeholdersin a manner that will guarantee sustainability andcontinuity.

The existing PDS in many of the two sub-regionsshared a great deal of similarities. Some of themost obvious similarities are as follows:

• Pesticide related problems in both sub-regions are as critical as they could ever be.

• Lack of adequate resources and weakenforcement capabilities are very muchsimilar in both regions.

• The level of disconnect between the pooland sink of knowledge, skills and expertisein one sub-region is a near-mirror-image ofthe other.

• There is a critical need for strong hands inmonitoring and enforcement of procedures,policies and regulatory standards aimed atimproving handling and minimizing misuseof pesticides among subsistence and large-scale farmers and vendors in both regions.

• Counterfeit pesticide products enjoy easymarket assess in both sub-regions.

• Stocks of obsolete, unusable and toxicpesticides exist in both regions.

• Diversions of products from intended use toinappropriate and risky businesses are alltoo common in both regions.

• Communications and interactions amongand between key stakeholders, includingthose that regulate, provide technical inputs,supply etc., are very weak in both sub-regions. To sum up, the problem of pesticidemisuse, abuse, and lack of knowledge andresources among the end-users and thosethat are responsible for monitoring andinspecting of these processes are abundantlyevident and the need to intervene andaddress these problems is very critical.

While the similarities among the existing PDS inthe two sub-regions have stark similarities, thedifferences were, at times, oblique. Among thesewere thatEastern Africa has a harmonizedregistration processes, but the Horn does notseem to possess such tool. In depth study of thebenefits and cons of the harmonization is beyondthe scope of this article, however, it is quiteevident that lack of harmonization couldencourage unabated movements of illegal andcounterfeit pesticides and chemicals. It is to benoted that one of the objectives of the PSNPinitiative is to ensure that the cross-bordermovements of such materials will be eliminatedthrough joint enforcement and policing as wellas information sharing.

Conclusion and recommendationsAn effective implementation of PSP requires a

coalition of diverse stakeholders and a PSN-driven synergy among public and the privatesectors, NGOs, research, academia and othersectors. Hence, coalition building should bestrengthened among diverse partners andstakeholdersto foster and strengthen PSNP.

Tremendous amount of undiscovered anduntappedtechnical skills and knowledge residewithin various local, regional, and internationalorganizations and institutions. These are essentialingredients for nurturing the budding PSNinitiatives and must be discovered and tappedinto.



Strengthening and linking internal and externalcapacities can improve PDS and significantlyimprove health and environmental as well aseconomic benefits. Potential partners andstakeholders should be sensitized to collaboratefor a better PSN and such efforts should bepursued to the extent possible.

In sub-regions/regions where pesticideregistration procedures are in the process ofharmonization or the process is laggingbehinddue to a weak coordination among partners, PSNis perceived as an important tool that can play acrucial role by promoting collaborations amongpartnersby creating a system that straddlespolitical boundaries. Hence this process shouldbe pursued to expedite the harmonizationprocess.

Many developing countries are plagued by freeand illegal movements of counterfeitchemicalsacross their porous bordersthatcontinue eroding their meager resources andadversely affecting the health and safety of theircitizens and contaminating their environment.Networking neighboring countries through thePSN can significantly improve policing and haltunwarranted proliferations of such chemicals andthereby avoid the threats they pose to theircitizens and the environment. Thus PSNP should

be widely and aggressively disseminated amongneighboring countries and build a culture ofstewardship, i.e., taking care of something thatone does not own. PSNP partners acrosspolitical borders are encouraged to actively shareinformation, collaborate with their counterpartsand create viable networks and deny marketaccess to illegal chemicals.

Evidence-based programs (EBP) and activitiesare the key to the success of, not only the PSN-PDS, but also other similar programs andinitiatives. This coupled with systematicallymeasuring and evaluating (SME) activities andprogress can yield desirable results and havepositive and lasting impacts on the waypesticides and other chemicals are handled, usedand managed. PSNP should strengthen its EBPand SME processes for better and lasting results.

“Proselytizing” beneficiaries to believe in andown PSN process by laying the foundation forsharing knowledge and entertaining innovativeideas is a huge step forward and an achievementthat one should rightfully cherish. Nonetheless,one ought to be mindful of the challenges that lieahead. One must appreciate the enormous effortsand dedications deemed necessary to establish afully operational system and maintain themomentum for better and lasting results.

Environmental contaminations like this one are the results of weak policies and enforcement (photo courtesyof Y. Belayneh).

While initiating the PSNP is a good beginningand the right path to pursue, strong commitmentsand sustainable engagements will remainessential to mainstream the program as part andparcel of the national and regional PDS. Withoutgenuine commitments and dedications, a process

or a system will undoubtedly vegetate at therealm of a mental exercise. Bilateral and multi-lateral partners can play an important role inhelping lay the foundation, jumpstarting theprocesses, offering tips and/or showing enhancedgenerosity, but much of the heavy lifting falls on

the shoulders of the national and regionalentities. Without them, good beginnings canforever dissipate into oblivion.

The collective vision and aspirationsto make adifference in the lives of the most vulnerablepeople and communities, including poor farmers,petty vendors, agricultural and health agents,NGOs, educators, the lonesome border controlofficer and many more can become a thing of thepast if coordinated and organized attempts arelaunched with utmost dedication.

The way forwardGiven that PSNP is a high-maintenanceinitiative, it is important to aggressively promoteand sale the idea across different regions byexploring opportunities beyond the horizon.Engaging diverse partners in the PRR processesthrough regular communications are essential

and play a crucial role as part of an overarchingstakeholder sensitization. Creating and nurturingthe culture of collaborations and information/knowledge sharing at all levels. Experimentingwith the newly created PSA as a guinea pig or a“blue” print for future PSAs and fine-tuning itthrough the process. Understanding the impact aPSP can have the way communities perceivepesticides and other agro-chemicals, encourageand support community initiatives andempowerment in PDS. UsePSNP to helppromote adoption and enforcement of relevantinternational conventions and protocolsandenvironmentally friendly policies at the nationaland regional levels. Maintaining strongcommitments and “sustainable” engagements asessential tools for mainstreaming PSNP to helpimprove PDS at all levels.


Yeneneh T. Belayneh

Desert Locust Control Organization for EasternAfrica (2009). Proceedings of the Horn of AfricaSub-Regional Pesticide Stewardship NetworkingWorkshop: A Strategy for Pesticide RiskReduction, Addis Ababa, Ethiopia, 160 pp.

Belayneh, Y.T. (2008, unpublished Trip Report).Pesticide Stewardship Network in EasternAfrica: A Strategy for Pesticide risk Reduction;Arusha, Tanzania; 32pp.

FAO-ILO-IUF (2005). Agricultural Workers andtheir Contribution to Sustainable AgricultureandRural Development: \IHPA\A paper on the role ofstewardship in pesticide risk reduction.docx, 82pp.

References


IntroductionFor many years, agriculture has been a traditionalproduction area in Azerbaijan. This productionarea primarily embraces plant-growing andanimal husbandry. One of the primary goals ofthe economic policy of Azerbaijan is to increaseagricultural production and improve local foodsupply chain.Currently grain production is beingseen as a high priority for agriculture. Plant-growing accounted for more than 63 percent andanimal husbandry 37 percent of the grossagricultural production last year. It is obvious that soils are still damaged from theuse of excessive amount of agrochemicals(fertilizers and pesticides), as well asfrom theheavy agricultural equipments that have beenused in order to get high productivity in theagriculture. These synthetic chemicals used inthe soil pose harmful effects on the developmentand activities of soil fauna which ensures naturalcontrol of microorganisms, earthworms and peststhat are transforming organic residues of plantand animal origin into humus. In general, the useof chemical substances leads to the disturbanceof biological circulation of the nutrient elements.

The goal of the research is to achieve effectiveland use management, prevent soil compression,maintain soil fertility by the use of crop rotation,increase agricultural production by theapplication of mixed sowing and byimprovementof local food supply chain.

Maximum lack of various food substances ornutrients can be observed in the soil without plantcover according to the research findings [3, 4, 5].Annual losses of nitrogen under differentgrowing conditions were as the followings:without plant – 69.6 kg/ha, crop rotation – 7.0kg/ha, perennial herbs – 2.2 kg/ha. For thatreason, we suggest striped planting method to beincorporated in our research instead of setting theland aside,and thus to prevent wind erosion in thearea. Wheat mixed sowing with legume crops inthe soil results always in plant cover (even afterreaping wheat) and with no negative processessuch as losses of nutrients and soil fertilitydegradation.

Materials and Methods

Description of the research fieldGaratorpag farm in Sheki region is located at aheight of 350-400 meters above sea level. Itextends between longitude 47° 30’ 15.43” eastand latitude 40° 47’ 15.06” north. The Neogenicand Anthropogenic remnants are widespread inthe area. The annual volume of sunny hours is2350 hours.The summer months account for 40%of the sunny hours. Through a year the volume ofsolar radiation is 122 kcal per square cm. Theaverage annual temperature equals 12˚C. It variesbetween 20-25˚C in July and August. The annualvolume of precipitation is 730 mm [1, 2, 7].

IMPACT OF WINTER WHEAT MIXED SOWING WITH LEGUMECROPS ON THE FERTILITY OF AGROGENIC CHERNOZEMS Amin BabayevAzerbaijan State Agrarian University

Figure 1. Field experiment

Babayev A.H.

Table 1. Impact of winter wheat mixed sowing with legume crops on the amount of humus in soil(2nd rotation), %

This can be explained by having a favourablecondition for humus forming microorganisms inthe treatment 4 rather than the others. Thus,wheat mixed sowing with melilot results inadequate accumulation of plant mass in the soil,as well as intensive humus forming process forthe next wheat planting at the expense of aerationand loosening during soil preparation. Plant growth and development depends on plantnutrition. Plants produce complex organic

substances with the help of solar energy by usingsimple mineral substances (CO2 and some salts)and water. High productive and sustainableagriculture consists of agrotechnical measuresintended for soil supply with optimum nutrientand water. A significant amount of nitrogen,phosphorus and potassium can be found in themajority of soil. However, the main part of theseelements constitutes a form misappropriation orless appropriation for the plants. For instance,


Research MethodologyThe research was conducted by applying steadyfield experiment (B.A. Dospexov, 1985). Thefield experiment was carried out in a grogenicchernozems of “Garator paq” rural farmenterprise by striped planting method with 7.2 mspacing between stripes.The scheme andexperimental treatments are given below:

1. Background–pure wheat planting+N60P60K60

2. Wheat→wheat→wheat→wheat3. Wheat+field pea→wheat→wheat→wheat4. Wheat+melilot→melilot →wheat→wheat5. Wheat+alfalfa→alfalfa→alfalfa→alfalfa

Close sowing with 7.5 cm space between rowswas carried out for all experimental treatments.Sowing norm for additional crops (legume

crops)embraced 50% of the sowing normintended for pure planting in mixed sowingtreatment. The experiment was conducted with 4repeatitionfor 3 years. The experimental bed area was 216m2 (7.2*30).

Results and Discussion

In the research area after two-year rotation thehumus percentage based on treatments wasrelatively different rather than control treatmentin agrogenic chernozem soils.According to table1, the highest humus content (corresp. 5.39% and3.44%) of 0-20 cm and 0-40 cm layers ofagrogenic chernozem soils was observed at thetreatment 4 (wheat+melilot→melilot→wheat→wheat).

IMPACT OF WINTER WHEAT MIXED SOWING WITH LEGUME CROPS ON THE FERTILITY OFAGROGENIC CHERNOZEMS

Table 2. Impact of field pea on the amount of food substances in soil

There is very little information in the currentliterature about the increase in the amount ofpotassium in the soil. This can be associated withthe soil texture of the research area. Additionallytaking into consideration the field pea propertiesto use not only mobile forms of potassium, butalso difficult appropriation forms for the plants(>0.001 mm clay minerals) leads to clearexplanation of the achieved results. According tothe results of 101 years experience on clay soilsin England, plants produce 3-4 times morepotassium from the soil together with crop ratherthan soil reserve of its mobile forms.

Conclusion

The highest humus content was observed in 0-20cm and 0-40 cm layers (5.39% and 3.44%,

respectively) of agrogenic chernozem soils in thetreatment of wheat+ melilot→ melilot→→wheat→wheat after two-year crop rotation inthe research area. The impact of leguminousplant cultivation on the amount of foodsubstances in agrogenic chernozem soils wasstudied. Field pea increases the amount ofnitrogen in the soil rather than winter wheataccording to the research results. The highestnitrogen content (16 times) was observed at 0-10cm top layer soil and generally decreased withsoil depth. Additionally, the amount of mobilephosphorus and potassium in the soil increasedduring field pea sowing.


nitrogen primarily belongs to complex organicsubstances (humus substances, proteins etc.), abig part of phosphorus belongs to mineral andorganic substances which can not be easilydissolved in water, and a substantial part ofpotassium belongs to aluminosilicate mineralsthat can not be dissolved in water.

Soil nutrient reserve is expressed with itspotential fertility. Soil ability to ensure highproductivity of agricultural plants (for exp. theamount of appropriation forms of nutrients forplants) is the major emphasis on the effective soilfertility assessment.

The impact of leguminous plant cultivation onthe amount of food substances in agrogenic

chernozem soils was studied. Field pea increasesthe amount of nitrogen in the soil rather thanwinter wheat according to the Table 2. Thehighest nitrogen content (16 times) can beobserved at 0-10 cm top layer soil and generallydecreased with soil depth. Because roundbacteria were more active on this layer.Additionally the amount of mobile phosphorusand potassium in the soil was increased duringfield pea planting. The notes ofthe increase in theamount of phosphorus in the soil as a result oflegume crops planting are described in theliterature. Such a fast increase in the amount ofnitrogen and phosphorus can be explained by theround bacteria’s activity in less productive soils.

1. Babayev A.H., Bashirov V.V., Kerimli A.V.,Guliyeva R.X. The expansion of energy andsoil conservation technologies under thecondition of small scale and retail land use //Theses of the international scientific-practicalconference dedicated to 80 years anniversaryof ASAU, 21-22 May, 2010. p. 26.

2. Babayev A.H., Abbasov Z.M., Bashirov V.V.,Mehdiyev I.T. Energy and economicefficiency of wheat production in ShekiGaratorpag rural farm enterprise on theapplication condition of energy and soilconservation technology// “Human andBiosphere” (MaB, YUNESCO) Scientificworks of Azerbaijan National Committee.ISSN 2079-3898. Edition 6, 2010, p. 65-76.

3. Grеко J. Soil protection from erosion. М.,Forest industry. 1983. 88 p

4. Zаslаvsкiy М.L., Lаriаnоv G. А., Litvin L.F.Mechanism and the process conformity. In thebook: Erosional processes. М., 1984. p.31.

5. Тоmpsоn L.М.,Тrоug F.R. Soil and itsfertility. М., Cо lоs. 1982. 462 p.6.

6. Mackenzie F.T., Mackenzie J. A. OurChanging Earth: An Introduction to EarthSystem Science and Global Environ mentalChange, Prentice Hall, 1995

7. World Resources 1992-1999: A Guide to theGlobal Environ ment, Oxford, 1992.


Babayev A.H.

References


AbstractEnvironmental pollution associated withdissipation of obsolete pesticides, including thepersistent organic pollutants, since Soviet eramay affect crop yield and its quality. Its increasedcontent in soils may come from more that 424pesticides warehouses and more than 1000places, which was used in the past for preparingof treatment solution for agricultural plants; onthe other hand, unfortunately, the increase mayhave an anthropogenic background. Given thefact that agriculture still is, and will remain amajor sector of the traditional economy, theMoldovan food products could imposethemselves on the international markets due theirgood biological qualities and safety. Therefore,quality control of agricultural products remainsthe primary task of the food safety, public healthand environmental security in the country intoGovernmental Program “European Integration:Freedom, Democracy, Welfare” for 2009-2014,Healthcare System Development Strategy forperiod 2008-2017, National Health Policy ofMoldova for 2007-2021, National Strategy onimplementation of Stockholm Convention onPersistent Organic Pollutants in the Republic ofMoldova, the National Strategy for SustainableDevelopment of the Agricultural Infrastructurefor 2008-2015, etc.

Key words: wine & apple export, a total ban,sample preparation, GC-MS analysis

Task 1. Pesticides residues control in wine.After the collapse of USSR, Republic ofMoldova (RoM) lost a large part of itsmanufacturing sector, including the fact that thecountry’s industrial hub was located in thebreakaway region of the Transnistrian Region.Either way, the results was that Moldova was

forced to rely even more heavily on agriculturaland wine exports.

Actually, the wine industry plays a significantrole in the Moldovan economy. Moldovais highly dependent on wine production;it is considered the backbone of the agriculturalsector. The RoM has 130,000 acres (530 km2) ofvineyards of which more than 90% are in privateownership. With its total harvest of 350-500thousand ton of grapes, Moldova produces 1,2-1,5 million hectoliter of the most prestigiousdomestic and European wines. Only 15% of theentire production is consumed within therepublic, 85% is exported to other countries,which amounts to a sales figure of 313 millionUSD.Being a small country with a continental climateand highly fertile soil, Moldova is one of the fewEuropean wine producers able to produce a widerange of wine styles.

In global terms, Moldova ranked 7th inoldovanwine collection “Mileştii Mici”, with 1.5 million

PESTICIDES RESIDUES CONTROL ON WINE AND APPLESEXPORTMariana Grama1, Freddy Adams2, Ludmila Siretanu3, Vladimir Musoi3, Iurie Pinzaru4

1 Ministry of Defence of the Republic of Moldova2 University from Antwerp, Belgium3 hytosanitation Product Test State Center, Ministry of Agriculture and Food Industry of the

Republic of Moldova,4 National Center for Public Health of the Ministry of Health of the Republic of Moldova

bottles, was included in the Guinness Book, asthe largest wine collection in Europe.

The wine industry was estimated to account forsomewhere near 25 percent of Moldova’s grossdomestic product (GDP), with 85 percent of thatwine exported to Russia.

In March 2006 Russia imposed a total ban onMoldovan wine based on claims ofcontamination by pesticides and heavy metalswhich pose health risk. This financiallydevastating ban led to losses officially reaching180 million USD in a country that was alreadyEurope’s poorest. Since November 2007 theNATO sponsored laboratory in Moldova plays asignificant role in easing re-export of Moldovanwine to Russia. It assists in winery inspectionsand assists in the imposition of stringent new

quality control standards. According to the Agro-industrial Agency“Moldova-Vin” Moldova exported wine to anumber of countries. In the period November toDecember 2007 export amounted to 99 millionUSD and in 2008 to 162.2 million USD.

Mariana Grama, Freddy Adams, Ludmila Siretanu, Vladimir Musoi, Iurie Pinzaru

Use of pesticides for protection of vineyards andother cultures against diseases is carried outaccording to the legislation and of the Republicof Moldova statutory acts and Instructions,namely EU Instruction 91/414 from June 1991.The pesticides to be studied were selectedaccording to testing on the basis of a survey ofplant protection products applied by wine andgrape producers in the Republic of Moldova.Currently, about 70 active ingredients areregistered in the Republic of Moldova for use inthe protection of grapes.

In order to enhance food security in the country,the State Center for Certification andRegistration of Phyto-Sanitary Means and

Fertilizers, equipped with sophisticatedequipment to test agricultural products forcontamination in the NATO Science for Peaceand Security Project 981186 “Clean-upchemicals – Moldova”, is authorized by theGovernment of the Republic to determineresidual pesticides in wine, especially the onesfor export. The monitoring programmer wascarried out in collaboration with about 40 wineproducers in three agricultural seasons (2007-2009).

The NATO-laboratory was accredited by theNational System for Certification of the Republicof Moldova on the basis of technical competenceand independence according to the European


PESTICIDES RESIDUES CONTROL ON WINE AND APPLES EXPORT

Table 1. The Moldavian wine exporting companies

Criteria SM EN ISO/CEI 17025:2006(Certificate No.SAMDCAECPLI01179 from 23February 2007). One field of activity of the

laboratory is to determine the active ingredientsin new pesticides imported into Moldova.


The approved methods involve the extraction ofpesticides, including the Persistent OrganicPollutants (POPs): DDT (and its isomers/metabolites DDE, DDD), alpha-, beta-, gamma-HCH, Aldrine, and Heptachlor, and also,deltamethrin for the export of wine to Belarus.

Besides chlororganic pesticides, which in theRoM are forbidden more than 30 years back, forexport wine in Russia and Ukraine we are testingthe fungicides and insecticides that were applied tograpes as metalaxyl, mefenoxam, penconazole,flutriafol, folpet, kresoxim-methyl, triadimefon,triadimenol, cymoxanil, famoxadone,dimethomorph, alpha-cypermethrin, and otherpesticides.

Reagents and sample’s preparation. Foridentification of some pesticides, are used theanalytical standards (> 95% pure) of DDT, DDEand DDD, alpha-, beta-, gamma-HCH, (fromRussian origin), kresoxim-methyl, dimethomorph,alpha-cypermethrin (“BASF”), cymoxanil,famoxadone, (“Du Pont”), triadimefon,triadimenol, folpet (“BayerCropScience”),metalaxyl, mefenoxam, penconazole, flutriafol(“Syngenta“).

The sample preparation follow the procedure:200 ml of wine is extracted with Hexane(Dichlormetane, Acetone) in triplicate, dried withanhydrous Na2SO4 purified with Aluminium and

then evaporated at temperature 40 °C, dissolvedin 1 µl Acetone.

GC-MS analysis. Quantities analysis of samplesof wine are analyzed using a Gas Chromatograph(GC Agilent Technologies 6890 N) connectedwith a mass selective detector (MSD AgilentTechnologies 5973) equipped with split/splitlessprogramming. The capillary column used is HP-5MS (30 m x 0.25 mm x 0.25 µm).

To avoid some reaction or converting of samplesinto another substance, helium is used as thecarrier gas. Helium with high purity 99.9999%is used at 10.48 psi and a constant flow of 37cm3/sec constant flow of 1.5ml/min and totalflow rate of 7.5 ml/min.

The temperature of the oven was programmedfrom 100 °C (hold for 0.5 min) to 180 °C (at 10°/min), to 250 °C (at 3 °/min) and to 290 °C at10 °/min (hold for 10 min). The front inlet anddetector (MS Quad and MS Source) temperatureis 275 °C. The prepared samples were injected1µl by applying the SPLITLESS.LOprogramming.

Results

The example of calibration curve for pesticidesresidues was prepared for concentrations: 1, 2.5,5, 10, 25 µg/ µl. The retention time of thepesticides is presented in table 2. Example ofcalibration curve is shown in figure 1.

Mariana Grama, Freddy Adams, Ludmila Siretanu, Vladimir Musoi, Iurie Pinzaru

Figure 1. Calibration curve for Metalaxyl


During 2007-2009 ca 1000 wine and grapessamples were analyzed. The results obtainedshow that the POPs (DDT, and itsisomers/metabolites DDE, DDD), alpha-, beta-,gamma-HCH, Aldrine and Heptachlor) were notdetected. In wine samples of several companieswere identified quantities of Metalaxyl andMefenoxam, which are active ingredients ofsome modern systemic fungicides, such asRidomil Gold („Syngenta”), Protexyl („StrandGroup Holdings”), Acedan (“Jingma ChemicalsLtd”), Metaxyl („Avgust”). They are applied onvineyards for the purpose of control diseasescaused by air- and soil-borne Peronosporales.The detected residues of Metalaxyl andMefenoxam in wine were generally below theRussian Maximum Residue Levels (MRL) forgrape (0.03 mg/kg) and the European Union MRL

(1.0 mg/kg). (see Table 2).

Introduction. Apple is the only fruit cropregistering dynamic development in Moldovaduring the past few years. Since 2007 67.9 haproduced a harvest of 4.88 ton/ha and a totalproduction of 331,352 ton)A. Moldova’s appleproduction industry accounts for about 70% ofthe country’s total orchard area. First, the appleindustry has a rich research and developmenttradition. Second, the apple industry isconcentrated in the northern parts of the countrywith higher precipitation rates and a climateunsuitable for other fruit crops. Third, apples areless labor intensive than most stone fruits.Finally, the biological characteristics of applesallow storing and selling the fruit long afterharvest.

Apple orchards offer a large variety of rawmaterial for the drying industry. A total of fifty-seven different varieties are grown in Moldova,of which 7-8 varieties are used for dryingincluding some fresh market- oriented varieties.In dried fruit production and export volumes,apples are positioned third.

European Union rules and regulations are strictfor trade in food products. The most importantones for dried fruits are the MRLs for Pesticides.The approved pesticide levels in imported fruitsare in Council Directive 90/642/EEC(http://europa.eu.int/comm/food/plant/protection/pesticides/index _en.htm). Besides there is the

Task 2. Pesticides residues control in apple

A Moldovan National Bureau of Statistics. 2008.


Figure 2. Calibration curve forChlorpiryfos


Approved Additives Regulation which is basedon Directive 95/2/EC and deals with the non-nutritive substances, which can legally be addedto some or all food products.

Reagents and samples preparation. A multi-residue method of extraction andgas-chromatographic analysis was done for thequantification and confirmation of 21 pesticidesin apple fruits. Acetone, hexane, and dichloromethane wereused for the preparation of stock and workingstandard solutions, and also in the extractionprocedure. The active ingredients of pesticideswere obtained from various sources and were of>95% purity (Flutriafol, Lambda-cyhalothrin,Cypermethrin, Azoxystrobin, Difenoconazole(Syngenta, Switzerland), Triadimenol,Tebuconazole, Deltamethrin, Triadimefon,Folpet, Procymidone (Bayer, Germany),Kresoxim-methyl, Dimethoate (BASF,Germany), Diazinon, Captan (MakhteshimAgan, Israel), Chlorpyrifos (Dow AgroSciences,Austria), Metalaxyl, Phosalone (Ecolan, Russia).The concentrations of the working standardmixture solutions were 1, 2.5, 5, 10, 25 µg/µl.The original methods were applied [МУОМПППКВС, 1992; МУ ОМПППКВС, 2001]as follow: 25 g of the homogenized applesamples was extracted twice with 50 µl mixtureof acetone and water (1:1), for 1 h, at roomtemperature. Following shaking, the sample wereclarified and re-extracted (in triplicate) with 40µl hexane, or by 40 µl dichloromethane, in

dependence of target pesticide. The collectedextract was then evaporated at < 40°C to dryness,dissolved in a final volume of 1 µl by acetoneand analyzed for analytes content by GC/MSmethod.

GC-MS analysisQuantitative analysis of pesticide residues wereperformed using a gas chromatograph (GCAgilent Technologies 6890 N) connected with amass selective detector (MSD, AgilentTechnologies 5973) equipped with a SPLITLESSprogramming in the same way as pesticidesresidues control in wine (see in paragraph 1.).

ResultsIn the period of October 2008- April 2009, 68samples of apples were analyzed. Samples werecollected and represent farms from around theRoM.The example of calibration curve for pesticidesresidues in apple was prepared forconcentrations: 1, 2.5, 5, 10, 25 µg/ µl. Theretention time of the pesticides is presented intable 2. Example of calibration curve is shown infigure 2.As results of our work, ca 10% of total analyzedvolume of apple fruits intended for export toRussia was rejected because their highconcentration of residual quantities ofChlorpyrifos, exceeding the existent MRL. Itshould be noted that Russia’s standards ofcontent of many pesticides in agriculturalproducts are stricter (lower) than current EUrules and regulations. For example, the

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maximum residue levels of chlorpyrifos inRussia is 0.005 mg/kg, whereas in Europe it is0.5 mg/kg (see table 2). In conclusion, only 1.5%of the analyzed apple samples did not meetEuropean standards.n/a - not allowed; n/n – not normalized in thisenvironment.* MRLs utilized database:- Insertion of MRLs values of Reg. (EC) No

1050/2009 of 06 November 2009.substances: Acetamiprid, Azoxystrobin,Clomazone, Cyflufenamid, Emamectinbenzoate, Famoxadone, Fenbutatin oxide,Flufenoxuron, Fluopicolide, Indoxacarb,Ioxynil, Mepanipyrim, Prothioconazole,Pyridalyl Thiacloprid, Trifloxystrobin;

- Commission Regulation (EC) No 822/2009of 27 August 2009 amending Annexes II, IIIand IV to Regulation (EC) No 396/2005 ofthe European Parliament and of the Councilas regards maximum residue levels forazoxystrobin, atrazine, chlormequat,

cyprodinil, dithiocarbamates, fludioxonil,fluroxypyr, indoxacarb, mandipropamid,potassium tri-iodide, spirotetramat,tetraconazole, and thiram in or on certainproducts;

- Insertion of MRLs values of Reg. (EC) No256/2009 of 23 March 2009.substances: Azoxystrobin and Fludioxonil;

- Insertion proposed MRLs from SANCOdocument number 4232/2008 Rev 2 voted inMarch 2009.substances: Azoxystrobin, Chlormequat,Cyprodinil, Dithiocarbamates, Fludioxonil,Fluroxypyr, Indoxacarb, Mandipropamid,Spirotetramat, Tetraconazole, Thiram;

** Государственный Каталог пестицидов иагрохимикатов, разрешенных кприменению на территории РоссийскойФедерации, 2004, Москва: ОООО«Изд-во Агрорус», 589 стр.

*** Monitorul Oficial RM, 19 Dec.2003, Nr.248-253 (1341-1346).

AbstractThere are two types of container managementprogrammes: obsolete stock empty containerdispositions and programmes for managingcontemporary pesticide packaging as each isemptied. The former is usually a one-timecampaign that follows the consolidation andbulking of obsolete stocks. The latter, pesticidemanagement or stewardship programme iscontemporaneous to the annual use of pesticides.This latter effort is primarily differentiated fromobsolete stocks containers in that residueremoval is practiced as each pesticide is used.This proper rinsing of containers is neither thesum total of the qualifications for a successfulstewardship effort, nor is it even in the earlystages of programme development. That successis predicated on a number of decisions andassessments made in an approximate order. Notall of these tools have been provided inpreviously published guidance. Anunderstanding of the stakeholders andacknowledgement of their motivations arecritical in assigning financial and otherresponsibilities. Producers, users, and the publicpotentially receive economic or other benefitsfrom proper container stewardship. From thisacknowledgement, a return logistics paradigmcan reduce environmental health risks by movingrecovered packaging to a recycler or other finaldisposition. Assessing these endpoints includecommon evaluations for any nation or continent.Once the pathways for returned packaging areset, then the training programme to assureresidue removal as each package is emptied isinstituted. The author will list additionalconsiderations and provide resources for assuringthis residue reduction, return, low risk containerstewardship effort is established and sustainablymaintained.

Key words: pesticide container stewardship,establishing container recovery programmes,pesticides packaging

ArticleThere are over 30 nations with pesticidecontainer stewardship programmes. Reliablesources believe that there may be 20 more in justthe next five years. Yet, not one of today’s thirtyplus efforts are identical in structure or outcome.Some are efficient; some are cumbersome. Someare expensive. Several programmes repay asignificant portion of the expenses back to theorganizers; nevertheless, not one effort is closeto self-sufficiency.1 Some are strictly volunteerindustry efforts and others are governmentmandated or incentivized. In some countries,farmers and other commercial pesticide userscannot imagine business without their containerdisposal options, while users in other nationsgrumble about any mandate or quietly ignore thebest efforts and continue to discard spentpackaging inappropriately.What are thedifferences? And what more do governments orother stakeholders need to know other than theessential FAO-WHO Guidance on PesticideContainers and CropLife Roadmap? 2, 3

The effectiveness or inefficiencies of anypesticide container stewardship effort are directlythe result of the evaluation and implementationprocess that occurred or did not fully occur at theinitiation of this stewardship effort. There are aseries of steps that must occur in an approximateorder to assure a vital return and final dispositionoutcome conducive to protecting humankind andthe environments. Ignoring any of these stepsdoes not guarantee failure, but not fullyaddressing each issue does increase that negativeprobability. What are these steps?

DESIGNING AND IMPLEMENTING EFFECTIVE PESTICIDECONTAINER STEWARDSHIP PROGRAMMESRobert L. DennyArrowchase Environmental Project Management, Vilnius, Lithuania


DESIGNING AND IMPLEMENTING EFFECTIVE PESTICIDE CONTAINER STEWARDSHIPPROGRAMMES


Assessment of the PackagingThe scope and breadth of pesticide packaging is,today, greater than it has ever been. Dependingon cropping practices, range of farm sizes, typesof public health uses, and so many othervariables; pesticide containers can vary fromsmall rigid plastic bottles and even vials up toone-way packages that hold hundreds of litres ofliquid or dry product. Although plastics are thepredominant packaging medium, theirchemistries are not uniform. The resins used inmoulding the containers vary all over the map,not only as homogenous constructions, but oftenas co-extruded and co-blown materials that formvirtual sandwiches of materials that at timeschallenge the recycler’s best efforts at reuse. Inaddition to the ubiquitous rigid plastic containers,there are also thin film or woven bags, sachets,paper bags (usually with another material as aliner), aluminium canisters, gas cylinders, andcold rolled steel drums and cans. Increasinglytoo, there is also a spectrum of manufacturer ordealer supplied refillable containers and thesepose additional stewardship challenges.Although multi-trip containers theoreticallyaddress some aspects of material and containerstewardship, refillable containers also havestewardship challenges and have a lifespan.Refillable packaging must eventually meet somesort of final disposition.

An early step in assessing a containerstewardship programme, therefore, is a nationalcontainer inventory identifying: registrant, typeor use of the pesticide, active ingredient, numbersof units, volume, material of construction, andweight of the material of construction. Nationshave often limited the use-types subject tocontainer collection programmes. For instance,many collect rigid plastic containers only or rigidcontainers used strictly for crop protection.Others add structural pest and public healthvector control, veterinary or seed treatment. Aneven rarer group have added flexible bags assubject to return efforts. In truth, there areenvironmental-health benefits to the carefulstewardship of all of these packages. If thiscomplete inventory information is not readilyavailable, this fact points to the next step:

Regulatory Support or Impediments toStewardshipThere are several regulatory infrastructuredeficiencies if container inventory information isnot available at the national level. Everycompliance agency (or as in most countriesagencies) need (s) an accurate annual tabulationof all pesticides produced, formulated, orimported into and exported out of that country.A trained cadre of customs officials and producerestablishment pesticide officers assure that thedata are correct and the labels and contents andpackaging are in agreement, and thatlabels/labeling are in appropriate languages forthe users or pictogram supplements are available.This trained staff foils the presence of pirated-adulterated products (and their packaging) aswell. Pirated pesticides are a stewardship issue,too. These points are referenced in Articles 5 and6 of the FAO Code of Conduct.4 Anotheringredient in a stewardship oriented registrationsystem is the additional requirement of thepackage listing, including materials, used foreach size and formulation of a given product.This point is not directly referenced in the Codeof Conduct although the code referencesassessing fees that could, for example, be usedfor assuring safe packaging ( ), nor is it directlymentioned in the earlier Guidance Document forState control of pesticides. 5. However, the latterdocument does recommend that the Registrarspecify technical requirements for “safe andeffective packaging of pesticide”. In the sameparagraph (4.2.7) the document states: “If thenational Government has required approval ofthe types of containers into which pesticides areto be packaged and offered for sale, there willneed to be provisions to the legislation to enable”(this). Changes in packaging must beaccompanied by a simple notice to the regulatoryagency.

There is one other potential regulatory roadblockto collection and a successful final disposition ofpesticide containers. That impediment is thepresence of any classification of triple rinsed orthe equivalent containers as hazardous waste.Some governments in their haste to implementthe Basel Convention on the Control of

Robert L. Denny


Transboundary Movements of Hazardous Wastesimposed “hazardous waste” classification on allempty pesticides containers. The 2008 FAO-WHO Guidance (Sec 1.5.10) states: “FAO/WHOrecommend that countries should classifyproperly rinsed containers that have beeninspected as non-hazardous.” 2

Inventory of Assets Much is made of the stakeholders in previouspublications, so this will not be elaborated otherthan to say that every nation has the same classesof stakeholders: farmers, other commercial usersof pesticides, dealer-distributors, the pesticideindustry, businesses or even NGOs that couldbenefit from a return program, and the publicgood and environment. What is different thoughis that the relative numbers of each vary and thatfinancial and other intangible benefits of a return-logistics effort can benefit or burden each groupdifferently from one country to another. It isimportant to analyze these cost-benefits indesigning a returnable container effort.

The listing of assets is critical. Exactly whatqualifies as a positive ingredient in establishingreturnable pesticide programs is as varied as thecountries studied. For instance, in some Africannations there are state run entities that distributethe pesticides to a specific commodity group:cotton, cashews, coffee as examples. These sameorganizations are often quite adept at employingreverse logistics to recover the spent containers.The public good is sometimes a more immediatepayback than a for-profit distributor. Pesticideretailers also often deliver goods to the customersand return empty. Concerns regarding protectionthe cleanliness of the vehicle used for deliveriescan be overcome using impervious barriers. Thepresence of highly competitive recyclers cansometimes be employed as collector-processorsof spent packaging. A modern cement companyin Kenya routinely uses their bagged cementvans for recovering alternative fuels to fire theirsolid fuel kiln. Final disposition assets (e.g.recyclers or waste to energy facilities) alongtransportation corridors facilitate economicallyviable returnable container programs. It is evenbetter if a core group of these facilities can befound as close as possible to the places where

containers are used.

Other critical inventory items are to assess theprice(s) paid for scrap plastics of the types mostcommonly employed in regional pesticidepackaging. In some instances, waste-to-energypay for substitute solid fuels and this can alsodefer some reverse logistics costs. Capacitybuilding expertise in various governmental, non-governmental and even private institutionscannot be overlooked. Understanding howpesticide users get their information on use andapplication is another important resource. Insummary, potential assets and valued informationcan include: mechanisms for distributing both thepesticides and the knowledge on how to usepesticides, potential final dispositions for variouspackaging materials (e.g. recyclers, cement kilns)and the financial structure and potential forreverse distributions for each.

Motivator EvaluationOnce the assets and liabilities are tallied (andthere are more potential topics listed in both theWHO-FAO Guidance and the CropLifeRoadmap) then one often forgotten step is todetermine how each of these assets or strengthsversus liabilities or weaknesses impact the 4 bigmotivators to successful collections for eachclass of stakeholder (public-government,pesticide industry, distributor-retailer, user groupincluding farmers. The 4 motivators are:

• Environmental Stewardship-the desire toprotect the environment for the commongood

• Public Health- insistence on zero degradationof worker or health of the population as awhole

• Economics- fiscal impact on individualbusinesses, classes of industry, or a regionor nation.

• Regulatory (or purchasing agreement)Requirement- enforceable command andcontrol insistence on following a certainproscribed course of action.

As an example, if a given area already has aprohibition on discarding individual or largequantities of pesticide containers in landfills andopen burning and dumping is enforced, then a

DESIGNING AND IMPLEMENTING EFFECTIVE PESTICIDE CONTAINER STEWARDSHIPPROGRAMMES


voluntary collection effort will certainly collectlarge quantities of properly rinsed containers.From the economic side, if there are high feesassociated with disposal of containers incontrolled solid waste facilities, then a collectionprogram will survive and even thrive with noadditional incentive. However, if the onlymotivator is to protect environmental health; it isunfortunately true that only a minority of theusers and other members of the private sectorwill positively respond.

If the economic and command-controlmotivators are not strong enough to achievemajority participation for each class ofstakeholders, then some additional incentivemust provide the reason for participation. Thisadditional effort is usually referred to asExtended Producer Responsibility (EPR): theconcept that the producer’s responsibility neverends when the product is distributed, the resellersstewardship does not end when the product isbought at the retailer or dropped off at the farmor business. It even means that the farmer’sresponsibility is deeper than growing acommodity. To sell farm products into the richestmarkets now includes some sort of certificationthat the grower cares for their immediateenvironment and this care extends to bestenvironmental and agricultural practices.

This EPR takes many forms, is not uniform, yetall result from the concept: “if you sell it, you takeback” or, that is, take back any byproducts (e.g.packaging). How EPR is achieved though inevery instance involves either mandate(command and control) or economic incentive orboth. To date, approximately one third of thepesticide container stewardship programs dependon some form or EPR plus one state in the USA:California. 3

Implementation and Maintenance

There are examples of differing approaches toestablishing container collections on the web.Many references cite establishing pilot programsto flesh out business plans, fairly distribute costsand responsibilities. Other referencesrecommend the selection of schemes for either

collecting properly rinsed containers in reversedistribution or some post-use method for balingor other pre-processing prior to shipment to afinal disposition. There is no need to reviewthese points again. One area that does warrantsome further discussion is how to identifyadequate partners for final dispositions. The twomost common forms of end use are recycling intoproducts not suitable for consumer use and someform of waste-to-energy. In some rare instances,the only option for non-homogenous packages oflittle value is proper disposal. Prior to selectingany one of these end points (including disposal),an audit of the potential facility must assure thatenvironmental and worker and other humanexposures are minimized. Extremely importantis the ability of the chosen facility to keeprecovered pesticide packaging under cover in asecure area and assurances that it will not be usedor available for unauthorized reuse orremanufactured into future consumer products.Audits usually prescribe engineering alterations,especially for recycling facilities where resinwashing is a potential hazard for environmentalwater contamination. Breathing space air is anissue for workers in and around any heated resinextrusion operation and few recycling facilitieshave adequate evacuation to force proper freshair replacement. An example of an audit formcan be downloaded at the RobertLDenny.com/stewardship/pesticidecontainer website. Once afacility has been selected and all modificationsare in place, a quality assurance program isnecessary to maintain these environmental healthprotections. It is not enough to approve acollaborator one time. Follow-up audits arenecessary.

The FAO-WHO Guidance does address the needfor educational programs and lists all of thepossible public and private sources for deliveringthat training. Key points that are not adequatelyaddressed are that the training must begin withboth the trainers and the officials charged withcompliance. The training must be specific for thelocale and local conditions including the sizesand types of containers found in that country.Delivery of instructions are best when in thelanguage of small groups of users who can then

each practice the rinsing techniques on non-hazardous mixtures of faux pesticides usinghousehold foodstuffs (e.g. milk powder,molasses, powdered maize). An example ofadaptable training materials can be found at thisRobertLDenny.com/training&education link.

Conclusion

Pesticide container stewardship programmes area necessary part of pesticide use. Theemployment of this systematic approach beganin the wealthiest nations, yet the benefits are justas valuable in every nation, rich or developing.In fact, the environmental health benefits may begreater in nations with little pesticide use. Theintellectual and other resources necessary forimplementation of a successful program arefound through these steps and resourcesreferenced here.

References

1. Rando, J., Update on Brazilian Programmeaddressing 5 points..; Denny, R. L., Ed.Sao Paulo, 2011.

2. Guidelines on Management Options forEmpty Pesticide Containers. FAO-WHO:Rome, 2008.

3. Roadmap for establishing a containermanagment programme for collection anddisposal of empty pesticide containers.International, C., Ed. Brussels, 2010.

4. International Code of Conduct on theDistribution and Use of Pesticides(revised). November 2002 ed.; Council, F.,Ed. United Nations: Rome, 2005; p 41.

5. Guidelines for Legislation on the Controlof Pesticides. FAO, Ed. Rome, 1989; p 16.


Robert L. Denny


Abstract

Mosquito nets have apparently been around foras long as textiles, but the development of theLong Lasting Insecticidal Net, or LLIN, hasbrought new hope in the historic effort to curbthe scourge of malaria. As new infrastructure andmassive resources have mobilized nations toprovide “universal coverage” for at riskpopulations, some concerns have grown thatwithout better end-of-life management,unintended harm to environmental-health mayresult. In 2010, the WHO Global MalariaProgramme launched a Pilot Study in three nationsto study the technical, logistical and social orcommunity concerns revolving around the issueof LLIN stewardship. This presentation focuseson just one small aspect of that effort: are LLINsand associated packaging an emergingstewardship issue?

Key words: Malaria, mosquito nets, pesticidestewardship, packaging, pyrethroids, LLINenvironmental fate

Introduction

When the fourteen year old Global MalariaEradication Program was phased out in 1969, thissupposedly failed effort did prove thateradication was feasible when all of the availableresources were brought to bear on diseasecontrol. Malaria effectively disappeared in therelatively temperate climates of Europe andNorth America. Progress was also made in thetropics using the tools of the dayA in theCaribbean and Central America, though pocketsof resistance persisted in Nicaragua and Haiti. InAsia and the Pacific, malaria was eliminated insome regions or the incidence was significantlyreduced, as in India and Sri Lanka, only to riseagain when the eradication effort ceased.

Unfortunately, in Afghanistan and Indonesiathere was little progress at all. Throughout thisinternational campaign, the one most afflictedregion of the world, Sub-Saharan Africa,received little attention due to post-colonial warsand infrastructure instability in the region.1 Thisextreme level of malarial infection was due in thetechnology of the time or lack of capacitybuilding in the region. Both in the 1960’s, astoday, Sub-Saharan Africa is home to the mostvirulent of the 4 malarial plasmodia: Plasmodiumfalciparum and the year-round breeding groundof the most efficient alternative carrier of thatplasmodium, the anopheles gambiaemosquito.3In the late 1990’s, almost 40 yearsafter the sentiment was expressed that eradicationwas impossible, there was renewed hope.Insecticide Treated Nets (ITNs) coupled with anIntegrated Vector Control efforts were beginningto show the possibility of significant reductionsin malaria transmission in discreet areas. Ingreater Sub-Saharan Africa though, the impactsof the disease itself were worsening. This humantragedy only heightened the world’s attention toa continent that was now comparatively morestable as compared to the 3 previous decades. In1998, these developments culminated in the RollBack Malaria (RBM) initiative. This WHO effortled to the Abuja Declaration in April, 2000 where44 of the 50 African malaria infested nationspledged their support and determination tomobilize national resources necessary to combatmalaria3

A few years earlier, the Long Lasting InsecticidalNet or LLIN was developed, successfullydemonstrating that mosquito protection could beachieved over a course of 3 to perhaps 5 yearswith no retreatment. In these early privateapplications, the cost was prohibitivelyexpensive for widespread use. It would take

AN EMERGING STEWARDSHIP ISSUE: LONG LASTINGINSECTICIDAL NETS FOR VECTOR CONTROLRobert L. DennyArrowchase Environmental Project Management, Vilnius, Lithuania

AResidual insecticide spaying of homes with mostly DDT, anti-malarial drug treatment, surveillance and mo-squito habitat modifications.

large orders to drive the price down to somethingfeasible for RBM initiatives. The only missingingredient at this point was major sources offunding .The financial resources began to appear,just as there were strong more than just anyfailings of international interests, commitmentsfrom affected nations, and affordable tools forprotection if mobilized. Once these keypreconditions for effective malarial preventionand perhaps even eradication were in place, thenext step was to mobilize net distribution andother integrated vector control measuresimplementing the WHO stated goal of universalcoverage for impacted population. “Universalcoverage” is defined as one net for every twopersons in an at risk population. Since humanpopulations are neither invariably even innumber nor distributed in dual sleeping locationsnor are there always static members of everyhousehold, effective coverage strategies requiredividing the “at risk” population by a factor lessthan 2. One recent study estimated that numberas 1.604 and the Roll Back Malaria Program 1.8.

Although researchers have used communitystudies to estimate the number of needed LLINsin a discreet geographical area, the global “atrisk” population itself is less of an exact science.One difficulty is the accuracy of census andmedical records in some of the areas wheremalaria is endemic. In 2009, WHO estimatedthat of the then more than 6 billion people on theplanet, approximately half, or 3.3 billion, wereeither already infected or at risk of contracting

the disease.5 At the close of 2011, with the globalpopulation now pegged at 7 billion individuals, itis probable that these numbers of “at risk”persons may have grown due to regionalpopulation growth that is at times greater inmalaria prone areas than in more temperateclimates. Even with population growth, however,the Roll Back Malaria initiative can point tolessening mortality-morbidity data.2What then is “universal coverage” for globalpopulations at risk of contracting malaria? In allprobability, net utilization will never reach thelevel of:

This is a staggering number of nets. Atapproximately 500 gm/net this mobilizationwould require the continuous deployment of overa million tonnes of nets. Since nets needreplenishment, now thought more likely closer to3 years than the originally hoped for five years,the world’s public health infrastructuretheoretically could require replacing up to 700million nets per year. The potential impact ofnumbers this large is difficult to visualize. Usingan average of specified nets per full size shippingcontainers,6and imagining the containers werestacked in their normal orientation, the one yearcontribution of nets in 2.59 m high intermodalcontainers would rise 48,894 meters— over 5.5times the 8,848 m. height of Mt Everest.A Currentdistributions are not at these levels, but since2004 until mid 2011 almost a half billion nets7

have been distributed in Sub-Saharan Africaalone.B Any one of a number of promisingbreakthroughs, some announced just in recentmonths, could lower that “at risk” population inthe future. Examples include: potential vaccineseffective against either Plasmodium vivax or P.falciparum,8genetically modifying Anophelesmosquitoes to produce sterile offspring9, orspraying malaria spreading mosquitoes withgenetically modified fungi.10 As heartening asthese positive developments are, no one projectsthat these trends and discoveries will completely

Robert L. Denny

Figure 1. Malaria Distribution 1900-20022

A Based on fact that 80% of nets are polyester and 20% 40’ containers (12.19m length x 2.438 m width x 2.59min height) to ship a total 560m PES and 140m PE nets equals approximately 18,890 intermodal units.

B Number of LLINs distributed by donor programmes, excluding private purchases.


eradicate malaria in the near decade. In effect,there remains and there will remain the need formillions of LLINs as a part of any successfulmalaria control initiative.

A WHO Led Stewardship Pilot StudyAs thoughtful persons absorbed the reality of thesheer magnitude of this historic public healthintervention, some scientists and policy makersbegan to ask probing questions: Are thereunintended consequences from net uses otherthan as malaria prevention while sleeping? Whatis the environmental fate of spent nets? Are thereconsequences to unregulated disposal? It wasalways presumed that there would be someincrement of pyrethroids remaining in spent nets.Is the remaining residue significant and dothousands of nets and perhaps more in a givenwatershed trigger environmental-health impacts?Are there final dispositions for spent nets thatalso protect environmental-health? If there areacceptable end-of-life (EOL) disposition forLLINs, how should programmes collect andtransport nets to those disposal or recycling orenergy recovery facilities? And lastly, and mostimportantly, are their ethical, social, culturalissues that govern the degree of cooperation inreleasing nets for collection and EOLmanagement? These are some of the questionsthat confronted WHO’s Global MalariaProgramme in 2010 and prompted Recycling orDisposal of Insecticide Treated Nets used forDisease Vector Control. A Pilot Study in Kenya,Tanzania, and Madagascar. The study approachdivided the overlapping questions for assessmentusing three research teams: Technical, Logistics,and Community. The three target nationsprovided input on the same topical areas. Manyof the study research and findings are beyondthe scope of this brief presentation; however thefull report is scheduled for publication in 2012.This analysis will focus only on the preliminaryfindings related to LLINs as a potentialenvironmental stewardship issue.

Nets are fabricated from threads spun fromstrong polymer filaments. These woven textilesare designed to allow the maximum aircirculation while producing an opening that

restricts the passage of various species of

Anopheles mosquitoes. LLINs receive theirinsecticide dosage at different places in thecourse of fabrication, either before the weavingprocess or after, depending on the manufacturers’approach. As of today, there are three pyrethroidsused for coating or impregnation: permethrin,alpha cypermethrin and deltamethrin. At the start of this project there were only two

types of plastic fibres used worldwide: polyester(80% of all nets) and polyethylene (20% or theremainder of the nets). At least one designemploys two different resins in the same net.11

By the close of this project there was a thirdresin, polypropylene, used by a new entrant inthe LLIN market.12Mosquito nets come in anynumber of different shapes and sizes: conical,rectangular, and A frame. Not surprisingly, theweights of any given design are variable as well.The conventional wisdom is that LLINs weighapproximately half of a kilogram, but somedesigns may weigh considerably more.

How could nets pose a stewardship issue?It is not the intended “use” of LLINs thatsuggests a concern. The mass deployment ofLLINs promises one of the most historicvictories over this negative degradation tohuman, social and economic ills ever. Yet, thesheer size of the distributions without an end-of-life strategy raises questions. Manufacturers arerequired to assess the exposures and risk tohumans in an indoor environment as a part ofpreparation of dossiers needed for WHO

AN EMERGING STEWARDSHIP ISSUE: LONG LASTING INSECTICIDAL NETS FOR VECTORCONTROL

Figure 2. Intelligent Insect Control- design A

A Few Words About LLINs


Robert L. Denny

Figure 3. Gallery ofUnintended Uses

Rope woven from LLIN /Net usedfor Transport

Single almost new LLIN used as Chicken CoopImages Kenyan Div of Malaria Control unlessotherwise specified and single, fairly new net,

as packaging -S Hoibak

Common Use of Nets asFence or Screen KE and TZ

–M Munga Clltn

Single almost new LLIN used as Chicken Coop Uses as screens-Dadaab KE RefugeeCamp- S. Hoibak


approval. It is clear that the risk of low-levelpyrethroid exposures to humans of all ages,particularly as compared to the risk of malaria,is more than acceptable. Nets, however, are not

required to meet any standards foroutdooradaptive uses. And are nets usedoutdoors?


Figure 5. Net Distributions- Region ofMadagascar Gaël Du Châtellier

Figure 4. Net Distributions in Kwale Kenya-Sarah Hoibak

From interviews and other information gainedby Pilot Study consultants, and 3 countryregulators, adaptive reuses lead eventually touncontrolled disposal. This is the fate of almostevery LLIN. Methods of disposal include openburning (most common) followed by burial andopen dumping. Although not a part of theoriginal project proposal, WHO did becameaware of another issue shortly after the PilotStudy inception meeting. At that time therewere only two resins used for constructing nets,three active ingredients, and seven primaryproducers. Yet for packaging these millions ofnets, the manufacturers employed 12 different

resins, plus paper bags and metal strapping.13

This multitude of materials certainlycomplicates any effort to recover packaging asa material resource. But recycling of the LLINpackaging is not an option that is practiced oreven considered today. Mosquito net distributions fall into two separateapproaches- 1) delivery of nets inside of intactpackaging and 2) removal of the net prior todistribution and sometimes even assisting theusers in installing the nets in each dwelling. Inthis latter instance, the packaging is usuallycollected by the distribution entity and burned.When the nets are left in the hands of recipients,


there are reports of adaptive reuses that include,but are not limited to: book bags for schoolchildren, food-household storage and otherdomestic uses. Eventually, like the spent nets,these packages are discarded in anenvironmentally unsupervised manner. It is not surprising that packaging of nets havebeen overlooked as any concern: taken on anindividual basis it was presumed that any impactmust seem inconsequential. But like the netsthemselves or the pyrethroid loading on just oneindividual net, the impacts can be deceiving.When aggregated, considering that millions ofnets are often distributed in a densely populateddistrict or region, an individually small residue,assumes greater proportions when multiplied bynumbers with six zeroes. Several ofthemanufacturer’s utilize packaging that weighs

just +/-20 grams, excluding the baling andstrapping materials. This small mass though.multiplied for every million nets, means that 20tonnes of packages are almost certainlyimproperly disposed-again, often in a relativelysmall area.13 What are the consequences of thismagnified environmental loading?This WHO Pilot Study sought preliminaryanswers to these questions using three studies:1) Identify representative spent LLINs. Usingwidely accepted methods, characterize the rateof insecticide release through leaching. 2) Assessthe potential for transfer of insecticides fromLLINs to the envelope packaging. 3) Useestablished environmental modeling scenarios toassess potential riskspyrethroid transfers tovarious media in a geographical region.

Robert L. Denny


Leachate StudiesJust finding appropriate LLINs that wereidentifiably 3 to 5 years of age did prove to be achallenge. Promising leads, evaporated onseveral occasions due to the stocks being burned. Eventually, stocks slated for a USAID recyclingproject, were received from Madagascar inBaltimore Maryland USA, then sampled, andshipped half away around the world, pastMadagascar, to Intelligent Insect Control’sLabsin Hanoi. This Pilot Study project was scheduledfor completion prior to the date when these IICsamples were analyzed.The data were included.The information was too informative to omit. The experimental design utilized 12 polyethyleneOlyset® and 10 Permanet® 2.0 LLINs.Coincidentally, there were 5 samples each of two2 textile denier sizes of the Permanet LLINs.The first task was to determine how muchinsecticide remained in each net.Gaschromatography with Flame Ionisation Detection(GC-FID) as specified in the CIPAC Method:4503/m Permethrin (June 2010) was the selectedas the analytical technique. Each net wasidentified and segmented into samples by JSILogistics of Baltimore, MD USA and wrappedin foil paper for shipment to Viet Nam. Eachnumbered sample contained five 35 x 40 cmrectangles of netting: one from the roof and 4from the walls. Upon receipt, the IIC laboratorycut 100mm2 circles from each panel to determinethe current weight per m2. A second set ofsamples were carefully cut as squares from thesame netting, cleaning the cutting instrumentbetween net samples. The combined roof andside panel samples were extracted with xyleneand used to inject the gas chromatograph. 14, 15

For the Olyset® LLINs, original weight 500g, atmanufacture contained 20 g (+/- 3g/kg) and a cis-trans isomer ration of 50/50 with an outside limitof 30/70. The IIC analysis shows that on average10.7 g/kg remains although the variability islarge: 1.4 g-16.8 g/kg. The highest amount, over83% of the mean manufacturer’s weight, wasfound on the newest net, but the 2nd largestamount is from a net that was 3 years in age at thetime of collection. The lowest concentration of

active ingredient, 6.84%, was found on the netwithout a discernable manufacturer’s date. Thecis/trans isomer ratio is well within themanufacturer’s specification across the entirerange, indicating relatively uniform isomer decayor leaching rates. 1514

Ten Permanet® samples were similarly preparedfor analysis. All samples had legible Lotnumbers. Five nets were manufactured from 75denier fabric weighing 30g/m2 and the remaining5 nets were 100 denier textiles at 40g/m2. Bothhave a tolerance of +/-10%16

From the IIC Lab data, certain results areconsistent with expectations. The 75 denier andthe 100 denier nets have all gained weight, butthe 75 denier still weighs consistently less (34.91g/m2) than the 100 denier textile (45.03 g/m2). Allappear to have accumulated dirt and soilingaccording to the chief analyst at IIC, Hanoi. Inpractice, both denier fabric weights are treatedwith the same dosage per square meter at thetime of manufacture. This means that the dosageper kilogram is not the same and the 75 deniertextile should have a higher concentration ofdeltamethrin than the 100 denier fabric. In fact,even after years of use, this is still the case. The75 denier net has 0.4318 grams of a.i. perkilogram of textile. The 100 denier LLIN retainsless or only 0.3122 g/kg.13, 15

Since the 2 different textile sizes are dosed at thesame rate per area 17, one would expect thequantity per m2 over time for both textile sizes tobe approximately the same. It appears that thisis the case: 26.2% retention for the 75 denier netand 25.9% for the 100 denier. But the arithmeticmean hides significant variability. The range forthe 75 denier cloth is 0.9 -58% retention, and forthe 100 denier net: 0 to 80% retention ofdeltamethrin.13

For both Olyset® and Permanet® LLINs,these results indicate that something far moreimportant than age is impacting the quantityof active ingredient retained.To test for leaching, a standardized washprocedure was carried out on carefully cut, 2 ormore, 15 x 15 cm squares of textile from eachnet.A Analyses were conducted using the CIPAC

A Details of procedures provided in WHO Global Report.


B The smallest permethrin sample, by far, actually indicated a small gain in quantity after washing. C CIPAC method 331/LN/m/4 and other details available in WHO Global Report published 2012.D Data not taken as “new” net usually not considered for disposal/recycling final disposition


Method appropriate for the leachate and soil/grime/dirt fractions. Results indicate for allsamples from both manufacturers, the amount ofdirt or soil adhering to the nets after several yearsof service is significant. Yet, there seems to belittle correlation between the dirt retained and theactive ingredient remaining…and hence loss ofa.i. /leachate.13

If one outlier sample is discarded,B elevenOlyset® samples from nets originally weighing500 g. lost 0.569 g./kg or 5.59% permethrin(range -1.29 > -15.45%).18

If one sample is not considered since it is thesample with no discernable peak, then 9Permanet® 2.0 samples from nets originallyweighing 400 g. lost 0.075 g/kg or 23.62% (range-5.08 > 43.84%).18 Conclusion: even after threeto five years of use, in most cases, there are stillmeasurable residues leaching out of nets. Morestudy is needed to understand the huge variabilityin these data, although pyrethroid leachate, atsome level, is almost certainly a reality when netsare re-purposed for outdoor uses.

Packaging StudiesIt is a fact that there are an excessive number ofdifferent materials used for packaging LLINs.Some manufacturers see little reason to informWHO or donors when changes are made in theindividual net package, baling materials orstrapping. Aside from the obvious solid wastequestions that this suggests, when you multiplyeach package by millions there may be otherenvironmental concerns. At the start of this PilotStudy, anyone close to the issue assumed thatsome insecticide was transferred from the net tothe packaging. This was not considered a majorissue due to the low human toxicity of thepyrethroid class of insecticides. Nevertheless, adecision was made by the designers of this Pilot

Study to test the net-packaging interface, not inany comprehensive, industry-wide way, but moreas a small sample to see if further study wouldbe suggested. Intelligent Insect Control-SARL, asubcontractor to the Natural Resources Institute(parent institution of the Technical Team), used oneof their licensees: Bestnet Europe LTD simplybecause of their prior relationship. Bestnetmanufactures Netprotect®, a LLIN treated withdeltamethrin and packaged in PE-PET laminate. Again, the nets and packages were sampled andanalyzed according to international standardsC onrelatively recently manufactured nets and theirpackaging, stored for 2 months in a warehouse.Analyses determined the total deltamethrin, butimportantly the amount of insecticide on thesurface of the net and surface and total amountson and in the packaging. As expected, thepackaging absorbed and adsorbed a fraction ofthe amount of deltamethrin that was both on andin the LLIN 19.Nets however, are packed 10’s of thousands to ashipping container and often take weeks ormonths of shipping and storage until delivered.The team devised a shorter term ‘conditioning’regimen to simulate storage in tropical regions.Some of the designers suggested that this mighteven be too conservative for the conditions thatare actually encountered. Samples were storedin a constant temperature oven @ 54°C for 14days. Surface and total deltamethrinconcentrations were determined for the netsurface and the packaging. The heat conditioningdid drive the deltamethrin to the surface of thenet by factor of 1.7X. But the surprise was thedramatic increase of pyrethroid in the packagingmatrix, almost 20X (19.6).13Just how significantis this? The total weight of the package isapproximately 19 grams. This means that thetotal deltamethrin content of each bag could

range somewhere between 0.038 mg whenrecently manufactured to 0.78 mg after twoweeks of conditioning in an intermodal containerin a hot sun.13 There have been reports of someworkers who distribute nets exhibiting symptomsof pyrethroid exposures.20Another unknown isthe environmental impact of uncontrolleddisposal of packages, remembering that theBestnet product is just one of many packaging-LLIN interfaces. No one is suggesting that thisis a Bestnet problem, and the Technical Teamappreciated the willingness of Bestnet to supplysamples for these test. Instead, this is likely anindustry-wide, donor and institutional issue thatdemands attention. In one very short time-frame, millions of these packages could bedisposed either by distribution teams or users,depending on the authority’s choice. Andpackages, unlike impregnated or coated nets, donot release their insecticidal loading over time,but almost all at once. Questions inevitably ariseas to unnecessary impacts to both humans andthe environment from this one potential source.To their credit, WHO Global Malaria Programmeresponded swiftly to these revelations and hasalready published (draft)

Interim Recommendations on the SoundManagement of Packaging for LLINs.A Longterm solutions to this stewardship challengeremain. This task demands attention fromeveryone involved in malaria programmes. Andunlike the more complex questions of LLINstewardship, no one can credibly claim that themyriad of different resins employed forpackaging or even the fact of packaging itselfputs anyone at risk if more thoughtful packagingstewardship is implemented.

Environmental ModelingThese three approaches for assessing “if”unintended uses or uncontrolled disposal ofLLINs may pose any stewardship issues forhumans, and especially the environment, are notin chronological order. Due to the difficulty infinding test samples, the previous two approaches

came last. One study, conducted by the Institutefor Chemical and Bioengineering, ETH Zurich,is important for illustrating both the potential forharm to aquatic species from uncontrolleddisposal/mismanagement of LLINB as well as theuncertainty that confronts malaria programmepolicy makers. The ETH Zurich Institute conducted an“assessment of environmental exposure andassociated risk from uncontrolled disposal andrepurposing for unintended uses of long-lastinginsecticide-treated nets (LNs). (This modelingstudy) was conducted by constructing a numberof scenarios intended to represent a variety ofenvironmental and use conditions that could beencountered.21 These brief excerpts areunquestionably depriving reviewers of thisdocument a complete and comprehensive imageof the Institute’s findings, yet that in depthanalysis is outside of the scope of this overviewof potential emerging stewardship issues relativeto LLINs. The Institute’s work is suitable for aseparate, stand-alone presentation. There are twopoints though, that are cogent to this presentation.

1. The author’s wrote: “Because of the veryhigh toxicity of pyrethroid insecticides toaquatic organisms, it was found that disposalto water bodies was particularly problematic,and most scenarios led to levels in waterexceeding published maximum allowableconcentrations (MAC).21” And what does“disposal” to water bodies mean in thiscontext?

The Institute used a modeling scenariocalculating the pyrethroids released fromLLINs using the Small World mode,originally coded by Matt MacLeod. It is afugacity-based multimedia mass balance boxmodel that describes the environment as aseries of interconnected boxes, compartments,as they are usuallylabeled. For this discussionit is important to understand that anycompartment can consist of multiple phasesor physical states. For instance, the AirCompartment can contain the obvious

Robert L. Denny

A http://www.who.int/malaria/publications/atoz/final_draft_interim_recommendations01nov2011.pdfB Testing had not indicated packaging as a concern at this point.



Figure 6. “Small World” model representation. The inventory is the total mass of chemical present in a compartment at steady state.21

2. The authors of the Zurich Institute report alsowrote, more eloquently than summarizedhere, of the dearth of data available todefinitively predict with certainty the risk tomedia outside of the Water Compartment.Topics investigated included emissions tosoil, particularly to soil organisms andemissions to crops since use of nets for foodstorage and protection of crops andfoodstuffs is a common practice. There are anumber of statements such as, “there is highuncertainty surrounding the exact uptake of(pyrethroids) into plants...”or “uncertaintysurrounds the estimation of chemical half-lives in the vegetation compartment” or “oncrops (internally) the picture is less clear.”Also, there are less data useful for modelingnewer chemistries like cypermethrin, “one of

the most toxic of this pesticide class.” In fact,the authors said, “substitution of currentlyused chemicals (pyrethrin and deltamethrin)for more toxic ones, such as cypermethrin—could warrant more elevated (environmentalrisk) concern.” Yet, due to the lack ofestablished models using cypermethrin, mostof their scenarios were based on permethrinand deltamethrin.

In their conclusions, the Institute scientistsstated: The uncertainty related to pyrethroid fatein the crop cover scenario is perhaps highest. Itis unknown whether a substantial fraction of theAI in nets can be transferred to crop surfaces viaabrasion. Further, models of chemical fatewithin plants are not as well developed as forother environmental compartments, so high


gaseous components as well as solid or liquidaerosols. Most importantly, for this discussionit is critical to understand that the Fresh Watercompartment contains both the obvious liquid(water) phase and all things dissolved in it, butalso suspended solids. Pyrethroids have a remarkable affinity fororganic matter and are not particularlysoluble in water, hence making them ideal forbinding to textiles, for instance. These traitshelp explain how it is possible for largeaquatic ecosystems to have higherconcentrations of pyrethroids than chemical-

water solubility would predict. Thepyrethroids are bound to suspended sediments,plant materials, organic-rich substrates that inrainy wet regions, such as the tropics, cangenerate run-off from areas where pyrethroidsare disposed or used for unintended purposes.Alternatively in drier regions, pyrethroids areat times airborne as dust particles or aresuspended only to find their way intoprecipitation; thus ultimately entering into theWater Compartment. In this case of pyrethroidrisk, it is this Water Compartment that is of themost concern.

Robert L. Denny


uncertainties remain regarding distribution anddegradation rates. Although it is expected thatthe amount of AI transferred in this manner willbe much lower compared to, for example, directapplication in an agricultural setting, it maypresent a special exposure case, as nets may beused on ‘local’ (i.e. subsistence rather thancommercial) crops where pyrethroids would nototherwise be used. Thus, a closer examinationof this possible scenario and fieldmeasurements/analysis of transfer to vegetativesurfaces may be warranted. Because of the deliberately engineered long-lasting properties of these nets, which involve themigration of the AI to the surface, discarded netsmay pose particular problems as local ‘pointsources.’ However, this type of analysis isdifficult to pursue from a general perspective. Inorder to better quantify the risks of specific usescenarios for specific environments, a local casestudy might be warranted,…21”In summary, real data are needed for a definitiveassessment of environmental risk, particularly tofoodstuffs and crops. However, the suggestionof environmental risk from outdoor uses orunregulated disposal is strong, and when thepractice is near or in aquatic systems thepossibility of harm is more than a suggestion.

ConclusionIn one short presentation, it is impossible totreat this multi-dimensional topic of LLINstewardship fairly and clearly. There are somany overlaying concerns. And yet, one mustnever forget — malaria is a killer. Even now,well into the 21st Century, these tinyPlasmodia hop from anopheles mosquito tohuman host and back again and claim thelives of more than 781,000 peopleworldwide.22 Uncounted millions more areinfected and lessened as contributors tosociety. Each and every 30 seconds, eitherwhile I write this speech or as I deliver it, achild dies from this dreaded disease.23 No one

would suggest any action that might prevent achild or any adult from receiving theprotection they need to possibly prevent thismortality or morbidity. Still, we must ask thisquestion: Is it possible to keep thispredominant public health goal uppermost inpriority and minimize any or all unintendedconsequences to environmental health? If thisauthor did not believe it possible, thispresentation would never have been written.

Follow this issue:http://www.RobertLDenny.com

Figure 7. Image -Vestergaard-Frandsen Brochure


Bibliography


1. The History of Malaria, an AncientDiesease.http://www.cdc.gov/malaria/about/history.

2. Hay, S. C. G., A. Tatem, A. Noor, and R.Snow., The global distribution and populationat risk of malaria: past, present, and future.Lancet Infectious Dis. 2004,4 (6), 9.

3. Breman, J.; Alilio, M.; Mills, A., Conqueringthe intolerable burden of malaria: what’snew, what’s needed: a summary. Am J TropMed Hyg. 2004, 71 (2 Suppl), 1 - 15.

4. Kilian, A. M. B., H. Koenker, M. Lynch,How many mosquito nets are needed toachieve universal coverage?Recommendations for the quantification andallocation of long-lasting insecticidal netsfor mass campaigns. Malaria Journal 2010,9 (330), 9.

5. 10 facts on malaria. http://www.who.int/features/factfiles/malaria/en/index.html(accessed 2011-10-31).

6. MOSQUITO NETS-LLIN. Refugees, U. N.H. C. f., Ed. United Nations: Geneva, 2011.

7. Sub-Saharan Africa LLIN deliveries 2004-2nd quarter 2011. USAID: Washington,2011; p 1.

8. Singh, P. Press Release:The PATH MalariaVaccine Initiative announces collaborationto develop a new malaria vaccine aproachtargeted at Plasmodium vivax; PATH MVI:Washington, 2010-8-18, 2010.

9. Vontas, J. H. R., and L. Aphey,Transcriptomics and disease vector control.BMC Biology 2010, 8 (52), 4.

10. Padmanabhan, N., Genetically modifiedfungi kill malaria-causing parasites inmosquitoes. NIH News 2011-02-25, 2011.

11. PermaNet® 3.0 (Brochure) Vestergaard-Frandsen Group S.A.: Lausanne CH, 2011; p31.

12. Lifenet® mosquito nets: receive interimrecommendation from World HealthOrganization Bayer News Release 2011-05-05, 2011.

13. Dobson, H. e.-p. m., Technical workinggroup report. Natural Resources Institute:Greenwich, UK, 2011; p 256.

14. Nguyen, H. Test Report 2011-54/11CVN;Intelligent Insect Control: Hanoi, 2011-05-19, 2011; p 3.

15. Nguyen, H. Test Report 2011-53/IICVN;Intelligent Insect Control: Hanoi, 2011; p 3.

16. Duong, T. T., Information on decipheringVestergaard-Frandsen Batch Codes.Explanation to inquiry ed.; Denny, R., Ed.Vilnius, LT, 2011; p 3.

17. Vestergaard-Fandsen, Permanet 2.0-Specifications. Vestergaard-Fandsen, Ed.Lausanne, Switzerland, 2011.

18. Nguyen, H., PE-PET Nets from JSIChemical Retest after Washing. IntelligentInsect Control Laboratory: Hanoi, 2011.

19. Nguyen, H. Test of deltamthrin total contentand surface content of stored Netprotectnetting material... Intelligent Insect Controls.a.r.l. Laboratory Service: Hanoi, 2011; p 2.

20. Greer, G., USAID, RE: Adverse Reactionsto Pyrethroids. Rune Bosselmann, I., Ed.Milano, 2011; p 1.

21. Ng, C. A., A. B. Acuna, M. ScheringerEnvironmental Risk Assessment forRepurposing and Uncontrolled Disposal ofLong-lasting Insecticide-Treated (LLIN)Bednets; ETH: Zurich, CH, 2011.

22. WHO Malaria Fact Sheet No. 94.http://www.who.int/mediacentre/factsheets/fs094/en/.

23. UNICEF Immunization-why are childrendying? http://www.unicef.org/immunization/index_ why.html.

The Centre is an independent department at theFaculty of Science, Masaryk University, with itsown research and development, educationalprograms and expert activities within the field ofenvironmental contamination. The Centrefocuses on persistent organic pollutants (POPs),polar organic compounds, toxic metals and theirspecies and natural toxins - cyanotoxins.

The research centre was established as theNational POPs centre of the Czech Republic in2003 and got a lot of experience with transferringof the scientific knowledge into the field ofapplication, executing field and laboratoryexperiments and measurements to collectnecessary information for the implementation ofthe Stockholm Convention as well as withorganizing various conferences, workshops andtraining programs focused on the capacitybuilding and transfer of knowledge. RECETOXparticipated in the development of the Nationalinventory and National implementation plan inthe Czech Republic and continues to serve as ascientific base for the implementation of theConvention. Since 2005, the RECETOX monitoring andeducational activities spread over the area ofCentral and Eastern Europe, and endorsement ofRECETOX as the Stockholm ConventionRegional centre for capacity building and transferof technology in the region of Central andEastern Europe was the logical step completingthe previous efforts. In this role, the centreadvocates the idea of the specialized centerscapable of providing technical assistance in, aswell as outside their own region.The Centre offers the strongest expertise in thearea of POP analysis ranging from thedevelopment of sampling techniques (for air as

the key matrix in the Global Monitoring Plan, butalso for water, for which the need increases withnew and more soluble substances added to thelist of SC) and their application in the field,through the development and application ofanalytical methods (not only) for new chemicalsplaced on a list of the SC, up to theimplementation of pilot studies and long-termmonitoring programs, management and dataprocessing and development of environmentaldatabases. Complementarily, the Centre alsoprovides a base for eco-toxicological studiesfocused on the effect of chemicals on livingorganisms, the analysis of the environmental andhuman risks and impacts of chemical pollutionon biodiversity.

In these areas, the Regional centre providestechnical support not only in Central and EasternEurope, but also in other regions where suchexpertise is missing, such as Africa, Asia orPacific. In these regions, the RC helps with theimplementation of the Global Monitoring Planand execution of the short-term, as well as long-term measurements. Last, but not least, theRegional Centre contributes to regional capacity-building needs. The International SummerSchool organized in cooperation with theSecretariat of the Stockholm Convention and theMinistry of Environment plays a major role. Theschool is offered (and used) worldwide andrepresents one of the most important tools forcapacity building and the effectivenessevaluation under the SC.

POPS MONITORING

RESEARCH CENTRE FOR TOXIC COMPOUNDS IN THEENVIRONMENT (RECETOX)Ivan HoloubekRecetox (Research Centre For Toxic Compounds In The Environment)Regional Pops Centre Of The Stockholm Convention On Persistent Organic PollutantsNational Pops Centre Of The Czech Republic, Masaryk University

SESSION 5.


RESEARCH CENTRE FOR TOXIC COMPOUNDS IN THE ENVIRONMENT (RECETOX)


Next important activities in the CEE region are:

MONET EU project that is focused on long-term monitoring of air quality at backgroundlocations has been proposed. Given the fact, thatthere are no consistent data on air quality in mostof Europe (with the exception of few EMEPstations), such a large scale monitoring campaignis unique and helps to compare the sites acrossthe continent.

GENASIS (The Global EnvironmentalAssessment and Information System), the expertsystem representing a new generation of multi-dimensional software for expert analysis ofenvironmental data, was developed by theResearch Centre for toxic compounds in theenvironment into a form that is used to visualizeand interpret data from the Czech nationalinventory updating. The initial phase of theproject focuses on data from regular monitoringprograms that provide a general overview ofspatial and temporal trends in concentration ofpollutants in different environmental matrices.All data available on POPs in ambient air of theCzech Republic as well as results of the MONETinternational studies are currently part of thesystem. The GENASIS project is driven by theneed of having all valuable data on the presenceand environmental distribution of hazardouscompounds in one database accessible to a widespectrum of users. Thus, GENASIS was offeredto the Secretariat of the SC as a tool forvisualizing data reported under the GMP. The

Centre is keen to cooperate in its developmentwith other monitoring projects, in order to deliverthe most comprehensive information.

Support and measurements in CEE region: Inaddition to long-term large-scale studies, thecentre also support the short-term campaigns inorder to obtain the pilot data on contamination ofthe CEE region.In Azerbaijan, a single large-scale campaign wasperformed in cooperation with the University ofLancaster in order to screen the situation withcontamination ambient air (by passive sampler),soil and butter in 2010. In Kazakhstan andKyrgyzstan two UNDP/GEF projects are toensure minimization of PCB releases andsubsequent health and environmental impactsthrough systematic capacity development forsound PCB management in the countries. TheCzech Republic (represented by RECETOX) isseen as a good partner for the projects, because ofthe country’s experience in strengthening andimproving national environmental policy andmanagement. The Czech experience inaddressing hot-spots and identifying priorityareas and sectors for risk assessments,monitoring and clean-up will also be veryvaluable for Kazakhstan and Kyrgyzstan.

RECETOX also puts a lot of effort into theawareness rising among the professionals, legalstate and regional authorities, private companies,students and general public

CENTRAL EUROPEAN AMBIENT AIR ORGANOCHLORINEPESTICIDES LONG TERM TRENDSIvan Holoubek, Jana Klánová, Jiří KohoutekRECETOX, Masaryk University, Kamenice 126/3, 625 00 Brno, Czech Republic


AbstractKosetice observatory is a facility of the CzechHydrometeorological Institute which is a part ofEuropean Monitoring and Evaluation Programme(EMEP) network. Now this observatory representsalso very important site of the Global POPsmonitoring of the Stockholm Convention.Persistent organic pollutants (POPs: PCBs,DDTs, HCHs, PAHs) have been monitored in allenvironmental matrices using the integratedmonitoring approach, which world-wide uniqueset of data. Data from the period 1996-2010 ofintegrated monitoring at Kosetice observatorywere used in this project to assess long-termtrends of POPs in the ambient air in the Europeancontinental background.

Generally, the atmospheric levels of POPs in thisCentral European background station aresignificantly higher than those in other EMEPstations localized mostly in Northern andWestern Europe. Long-term trends of POPconcentrations in the ambient air and otherenvironmental compartments show a slowdecline in the last years for most of investigatedcompounds. This is consistent with data reportedfrom other European sites. The long-termbackground monitoring is an excellent way tostudy the regional levels and trends and also apowerful tool for evaluation of the impact ofvarious local and regional events – fromindustrial accidents to natural disasters. Thisconceptual approach has the potential to play acrucial role in the implementation of regional andglobal measures and conventions on persistenttoxic substances.

Key words: Persistent organic pollutants, longterm global and regional monitoring of ambientair

IntroductionPersistent organic pollutants (POPs) represent

several classes of organic chemicals includingpolychlorinated dibenzo-p-dioxins and furans(PCDDs/Fs), polychlorinated biphenyls (PCBs),organochlorine pesticides (OCPs) and otherindustrial and agricultural chemicals, newly alsobrominated flame retardants for examplepolybrominated diphenyl ethers orhexabrombifenyl and fluorinated substances.Also polycyclic aromatic hydrocarbons (PAHs)are often included in this group of compoundsbecause of their potential for long-range transporteven though their physicochemical properties donot suggest the persistency and bioaccumulationpotential.POPs including organochlorine pesticides arepersistent, with high potential to the accumulationin abiotic environmental compartments, strongtendency to bioaccumulation in human andwildlife and bio magnifications in food chains,with a very broad range of potential harmful anda strong potential to the long range transportround the Globe.They have been the subject of scientific interestand also the subject of international regulationtools such as international conventions ordirectives for the last few decades. The mostimportant now are the Stockholm Convention(SC) on POPs and Convention on Long Rangetransport of Air Pollution (CRLTAP) and itsPOPs Protocol, the first from the global point ofview, the second for the European, regional pointof view. Both Conventions developed, adoptedand implemented the long-term monitoringprogrammes.The effectiveness of the Stockholm Convention(SC) according to Article 16 of the SC shall beevaluated after four years since its entry intoforce, and periodically thereafter at intervals tobe decided by the Conference of the Parties(COP). Global Monitoring Plan (GMP) has beendeveloped with the aim to evaluate whether thePOPs actually were reduced or eliminated on the

Figure 1. Only six (out of fifteen) EMEP sites reported POPs in both, air and wet deposition,in 2004

All measurements assigned to EMEP stations(including VOCs, POPs and heavy metals) arecurrently implemented in Košetice [5-8], andmonitoring design is based on the EMEP POPmonitoring strategy EMEP from 1998. Samplesof the ambient air, wet deposition, surface water,sediment, soil and biota, as the key componentsof the environmental system, are collected. Theecosystem indicators are further applied todetermine the current state, anthropogenicimpacts and influences, and to predict the future

changes of terrestrial and freshwater ecosystemsin a long-term perspective. A dataset generatedin ten years of integrated monitoring in Košeticewas used in this study to assess the CentralEuropean trends in background levels ofpersistent organic pollutants. This dataset is from1988 produced by the RECETOX, MasarykUniversity, Brno, Czech Republic.

CENTRAL EUROPEAN AMBIENT AIR ORGANOCHLORINE PESTICIDES LONG TERM TRENDS


global scale [1,2]. CRLTAP has a monitoring strategy andprogramme so EMEP (European Monitoring andAssessment Programme). The main objective ofEMEP Programme is to provide Governmentsand subsidiary bodies under the CLRTAP (TheConvention on Long Range Transboundary AirPollution, signed 1979) with qualified scientificinformation to support the development andfurther evaluation of the international protocolson emission reductions negotiated within theConvention. Map of the EMEP stations withPOPs monitoring activities (including analyzedmatrices) is presented in Figure 1 [3,4]. The distribution and number of sites measuringPOPs are insufficient, but possibly will the EUsdaughter directive on PAHs and the StockholmConvention on POPs have a positive effect alsoon the number of EMEP sites. At present, onlyone observatory from this network is located in

the Central and Eastern European region –Košetice observatory in the Czech Republic.

Methods

Sampling siteKošetice observatory (last to the right) was theonly site where POPs were/are also determinedin other environmental matrices. Košeticeobservatory of the Czech HydrometeorologicalInstitute is located in the southern CzechRepublic (N49°35´; E15°05´) [5,6]. The climaticclassification of the region is moderately warmand moderately humid upland zone with a meanannual temperature of 7.1 °C, mean annual totalprecipitation of 621 mm, between 60 and 100days with snow-cover per year, 1800 hours ofsunshine per year, and prevailing westerly winds.Observatory was established as a regional stationof an integrated background monitoring networkin the late 1970s [7,8].

Figure 2. Hexachlorobenzene (HCB) and pentachlorobenzene (PeCB) (determined from 2001) inambient air (ng m-3), Košetice observatory, 1996-2008 (weekly sampling).

Ivan Holoubek, Jana Klánová, Jiří Kohoutek


Sampling, analysis, QA/QCSelection of compounds, methods of sampling,sample preparation, analysis including QA/QCprocedure, were published recently [7].

ResultsThe results from this observatory represent avery unique set of data [5-7]. The ambient airmeasurements exist since 1988. But, from 1996until now, the used sampling and analyticalmethods are the same and results comparable. Itmeans that we have a set of approximately 800samples (53 per year) of POPs in ambient air,which in EMEP represents the central Europeanbackground site. This set is very robust, has along-term level of information, world-wideunique and represents a very solid base forevaluation of temporal and seasonal trends ofPOPs in ambient air on the European continental

background level.

Concerning to the ambient air levels of OCPs,their profiles and long-term trend are representedin the figures 2-5). Most of these compoundswere banned in Europe in 80s and their maximaare not connected to their production or seasonalapplication. They are present in atmosphere dueto volatilization from the old deposits (soils,sediments, wastes) or due to long-rangeatmospheric transport from the regions wherethey are still being applied or were frequently andintensively used. In agreement with thishypothesis, elevated levels of organochlorines areobserved in warmer seasons when increasingtemperatures enhance evaporation of thesecompounds. This seasonality is not as wellpronounced as it is in the case of PAHs, but it canstill be detected for pesticides in Figures 2-4[5-7].

Figure 3. Hexachlorocyclohexanes (HCHs) in ambient air (ng m-3), Košetice observatory,1996-2008 (weekly sampling).

Figure 4. DDTs in ambient air (ng m-3), Košetice observatory, 1996-2009 (weekly sampling).



Annual median air concentrations werecalculated for all subgroups (PAHs, PCBs, HCB,HCHs and DDTs) and resulting values werecompared to evaluate the long-term trends foreach group of compounds in the period of 1996-2008 (Fig. 5). Trends which were presented in

[7] continue [2].While PAH levels have beenquite stable in the last decade, PCBs showedgenerally decreasing trends. Pesticides fluctuatedshowing highest atmospheric concentration intwo periods immediately following the majorfloods (1997 and 2002) [2].

The integrated monitoring programme allows forcomparison of the long-term trends of the POPlevels in various matrices. Data from Košeticeintegrated monitoring can be used for anassessment of sources and distribution processes,and for validation of long-range transport andenvironmental fate models [9,10].

Conclusion

Integrated monitoring at Košetice observatoryrepresents very unique sets of long-termenvironmental data on the Central Europeanbackground level. These long-term results ofPOPs determination in air and otherenvironmental compartments serve as a veryuseful base for the evaluation of temporal andspatial trends of POPs on a regional scale, a basewhich can used for model validation,

comparative studies, prognosis, scientificprojects, for a study of environmental processes.

The observed trends of environmental scaleconfirm the decreasing trends in the last years inthe Central and Eastern Europe, which is in verygood agreement with other European sites andsites from other part of the Globe.

Acknowledgements

This paper was/is supported by the CETOCOENproject (CZ.1.05/2.1.00/01.0001) of theEuropean Structural Funds, the INCHEMBIOLproject (MSM 0021622412) of the Ministry ofEducation of the Czech Republic and theMinistry of Environment of the Czech Republic(SP/1b1/30/07).

Figure 5. Time-bound trends of the atmospheric levels of POPs in Košetice.

Ivan Holoubek, Jana Klánová, Jiří Kohoutek


References



1. UNEP Stockholm Convention on PersistentOrganic Pollutants. Stockholm Conventionon Persistent Organic Pollutants 2001,decisions, information documents,http://www.pops.int

2. Draft revised Guidance on the Globalmonitoring plan for persistent organicpollutants, UNEP, May 2011,UNEP/POPS/COP.5/INF/27

3. Aas, W. & Breivik, K., Heavy metals andPOP measurements, 2004, EMEP 2006

4. UN-ECE, The Convention on Long-rangeTransboundary Air Pollution., 1998.EMEP’s homepage. http://www.nilu.no/projects/ccc/emepdata.html.

5. Váňa M., Holoubek I., Pacl A., Pekárek J.,Smrčková V., Machálek P., Helešic J., ŠedaZ., Adamec V., Janouch M., Honzák J.,Ansorgová A., Kohoutek J., Holoubková I.,Šatalov V., Dutčak S., Fottová D., Hruška J.,Hofman J. & Anděl P.: Quality of the NaturalEnvironment in the Czech Republic at theRegional Level. Results of the KošeticeObservatory. ČHMÚ Praha, 2001, 189 pp.,ISBN 80-85813-88-2.

6. Váňa M., Holoubek I., Pekárek J.,Červenková J., Čech J., Machálek P., JanouchM., Macoun J., Horálek J., Rychlík Š.,Hnilicová H., Klánová J., Jarkovský J.,Kohoutek J., Helešic J., Šeda Z., Kubík V.,Dvorská A., Světlík J., Rulík P., Molnár M.

& Tomášková L., Košetice observatory – 20years. ČHMÚ Praha, 2007, 151 s., ISBN978-80-86690-46-9.

7. Holoubek I., Klánová J., Jarkovský J. &Kohoutek J., Trends in background levels ofpersistent organic pollutants at Koseticeobservatory, Czech Republic. Part I.Ambient air and wet deposition 1988-2005.J. Environ. Monitor. 9 (6), pp. 557 – 563,2007.

8. Holoubek I., Klánová J., Jarkovský J., KubíkV. & Helešic J., Trends in background levelsof persistent organic pollutants at Koseticeobservatory, Czech Republic. Part II.Aquatic and terrestric environments 1988-2005. J. Environ. Monitor. 9 (6), pp. 564 –571, 2007.

9. Dvorska A., Lammel G., Klanova J. &Holoubek I., Košetice, Czech Republic – tenyears of air pollution monitoring and fouryears of evaluating the origin of persistentorganic pollutants. Environ. Pollut. 156 (2),pp. 403-408, 2008

10. Komprda J., Kubošová K., Dvorská A.,Scheringer M., Klánová J., & Holoubek I.Application of an unsteady stateenvironmental distribution model to adecadal time series of PAH concentrations inthe Central Europe. J. Environ. Monitor., 11,269 – 276, 2009.

BULK ATMOSPHERIC DEPOSITION OF PERSISTENT TOXICSUBSTANCES (PTS) ALONG ENVIRONMENTAL GRADIENTS INBRAZILRodrigo Ornellas Meire; Torres; João Paulo Machado TorresBiophysics Institute, Rio de Janeiro Federal University, CCS, 21941-902 Rio de Janeiro, Brazi


AbstractBulk atmospheric deposition for selected Per-sistent Toxic Substances (PTS) was performedalong environment gradients (urban-rural-remote sites) in Brazil. This work is motivatedby the lack of knowledge on the fate of PTS andits imitations in South America, particularlyalong environment transects. Bulk samplers(polyurethane foams 1x1m2) were fixed oversummer and winter periods at urban, rural andmountain sites (2005-2007) comprised differentregions of Brazil. Organochlorine pesticides(OCs) and polychlorinated biphenyls (PCBs)were analyzed by gas chromatography with elec-tron capture detection (Shimadzu 2010, 20i CG-ECD). As a result, urban sites reported thehighest overall deposition rates for PTS, whichranged from tens to thousands of pictogram perm2 per day. The results of this study are importantin showing that even regulated, selected PTS arestill impacted by local and regional emissions inBrazil, probably associated with the historicaland continued emissions from old PTS stocks.

Key words: Persistente Toxic Substances(STPs); atmospheric deposition; organochlorinepesticides; PCBs; endosulfan; DDT; environmentgradients; Brazil

IntroductionPersistent Toxic Substances (PTS) areenvironmentally persistent substances that can befound in remote areas far removed from theirsources that still display some level of toxicity.Their transport from emission sources arecontrolled by climate and geographicalparameters like precipitation rates, winds andlow temperatures1. Due to their physicalchemical properties, these semi-volatilecompounds can be present in the atmosphere gasphase and/or bound particles that are susceptible

to atmospheric removal largely driven bydeposition mechanisms2.

According to the South America UNEP PTSregional report, the massive use of PTS in SouthAmerica is derived mainly from industrial,agricultural and sanitary uses3. Historically,Brazil is one of the most South Americancountries that experienced an extensive use ofPTS in the past which may include legacycompounds as PCBs, DDT, lindane andtoxaphene4. Although there is a still hugeknowledge gap on the PTS fate in Brazil,previous studies have pointed out high levels ofPTS in many abiotic and biotic environmentalmatrices5,6. Nevertheless, just a few of them arefocused on PTS atmospheric studies where it isbelieved that is the main transport of these semi-volatile compounds in the environment7,8.

The present work makes a screening of selectedPTS atmospheric deposition followingenvironment gradients which were fixed indifferent parts of Brazil (Northern-Southeast-Southern). Bulk atmospheric deposition systemswere performed for selected PTS during 2005-2007 at urban, suburban, rural and remote sites.This work is motivated by the lack of knowledgeon the fate of PTS and its imitations in SouthAmerica, particularly along environmentaltransects.Materials and MethodsDeployment: This work included nine monitoredsites in Brazil following environmental gradients(urban-suburban-rural-remote sites) in Rio deJaneiro, Santa Catarina and Acre states withsampling conducted during 2005-2007. Remotesites included two high mountain sites that wassituated at the National Park of Serra dos Orgãos– LAT 22o26’56’’S LOG 42o59’05’’W – Rio de

BULK ATMOSPHERIC DEPOSITION OF PERSISTENT TOXIC SUBSTANCES (PTS) ALONGENVIRONMENTAL GRADIENTS IN BRAZIL


Janeiro State and the National Park of SãoJoaquim – LAT 28o00’49’’S LOG 49o35’17’’W –Santa Catarina State.For each monitored site, twoPU foams samplers were deployed followingover winter and summer periods forapproximately 30 days each. The samples weredeployed along environmental gradients andmounted in open areas (1.5-2.0 m above ground)to ensure no obstruction airflow. Field blankswere deployed once during each season for thetwo National Parks involved (n=4 in total).Extraction and Analysis: Sample preparation,extraction and clean-up were modified fromPereira et al., 2007. Briefly, the PU foamssamples (effective area = 0.36 m2) were Soxhletextracted over 20 hours with 250 mL ofpetroleum ether. The extracts were cleaned usingan open column filled with 3 g of deactivatedacid silica (10%) topped with 2 g of alumina and0.5 g sodium sulfate, and then eluted with 25 mLof dichloromethane/methanol mixture (9:1). Thecleaned extracts were concentrated by rotaryevaporation and nitrogen blow-down to a volumeof 500 µL and solvent exchanged to isooctane.Tetrachloro-m-xylene (TCMX) was added as aninternal standard (100 ng) for volume correctionto all sample extracts prior to analysis. Theinstrumental analysis of the extracts was carriedout by gas chromatography with electron capturedetection (Shimadzu 2010, 20i CG-ECD).

Extracts were analyzed for the presence of targetcompounds that included polychlorinatedbiphenyls (PCBs) and organochlorine pesticides(OCs). Samples were screened for 28 PCBs:PCBs -8, -18, -28, -31, -44, -52, -66, -77, -81, -101, -105, -114, -118, -123, -126, -128,-138,-153, -156, -167, -169, -170, -180, -187, -189, -195, -206, -209; and 24 OCs: α, β, γ and δ

–hexachlorocyclohexane (HCHs),hexachlorbenzene (HCB), aldrin, dieldrin,endrin, isodrin, heptachlor, heptachlor epoxide,cis-chlordane, trans-chlordane, endosulfan I(Endo I), endosulfan II (Endo II), o,p’-DDE,p,p’-DDE, o,p’-DDD, p,p’-DDD, o,p’-DDT,p,p’-DDT, metoxichlor, mirex. Limits ofdetection (LOD) in air samples were defined asaverage of field blanks (n= 4) plus three timesthe standard deviations.

Results and Discussion

Method recoveries for target PTS were generally> 85%. No recovery correction was applied tothe results. In this study, the LOD values rangedfrom 0.1 ng to 6.5 ng for OCs and 0.03 ng to 6.9ng for PCBs. The results were reported only ifthe signals exceeded the baseline noise valuesthre times. In this study, both laboratory and fieldblanks were below the LOD values for all targetcompounds.As a result, urban sites reported the highestoverall deposition rates for PTS, which rangedfrom tens to thousands of pictogram per m2 perday (table 1). On the other hand, no clear trendswere observed for seasonal variations of PTSdeposition rates. Among OCs, DDT and itsmetabolites were constantly detected in relativelyhigh deposition rate levels (>1000 pg.m-2.day-1).Following this, other legacy and current-usepesticides as HCH, dieldrin, aldrin, metoxichlor,chlodanes, HCB and endosulfans were alsodetected in this study (10-100 pg m-2 day-1). Hightotal endosulfans (alpha + beta isomers)deposition rates were main observed at rural andmountain background sites, which probablyindicate the high potential of this current-useinsecticide to a long range atmospheric transport(Figure 1).

*Urban sites – Rio de Janeiro, Santa Catarina and Acre states; Suburban sites – Rio de Janeiro and Santa CatarinaStates; Rural sites – Santa Catarina States; Remote sites – Rio de Janeiro and Santa Catarina States.

Figure 1. Deposition rate (pg m2 day-1) concentrations in different environment sites.

regulated, selected PTS are still impacted bylocal and regional emissions in Brazil, probably

associated with the historical and continuedemissions from old PTS stocks.

Rodrigo Ornellas Meire; Torres; João Paulo Machado Torres


For the sum of PCBs, extremely high depositionrates were also mainly observed at urban sites(>5000 pg m-2 day-1) reached basically 2 to 4times higher compared with overall remote andrural monitored sites (Table 1). In a previewstudy, Pereira et al.(2007) have also reported asimilar deposition trends with extremely highPCB levels close to industrialized and urbanareas (Rio de Janeiro State) that reached 6 to 10-folds higher compared to background sites.

Historically, Brazil is one of the most PCBconsumers where around 6.7% of the totalamount of Aroclor was consumed4. Althoughthere is a still huge knowledge gap on the PCBfate, for the majority of the South Americancountries, previous studies have pointed out thepresence of different PCB congeners in manyabiotic and biotic environmental matrices5,6

These results are important in showing that even

1. Daly & Wania, 2005. Environ. Sci. Technol.,39: 385-398.

2. Pereira, 2007. Chemosphere, 67: 1728-1735 3. UNEP, 2002. RBA of PTS. UNEP-

Chemicals, 91 pages.4. Almeida et al., 2007. Quim. Nova, 30: 1976-

1985. 5. Lailson-Brito et al., 2010. Environ. Pollut.,

158: 1800-1808.

6. Dorneles et al., 2010. Environ. Sci. Technol.,36: 60-67.

7. Santos, et al., 2004. Atmospheric Environ.,38:1247-1257.

8. Meire et al., 2010. Organohalogenatedcompounds, 72, 164-167.

9. Pereira et al., 2007. Chemosphere, 67: 1736-1745.

References

BULK ATMOSPHERIC DEPOSITION OF PERSISTENT TOXIC SUBSTANCES (PTS) ALONGENVIRONMENTAL GRADIENTS IN BRAZIL


Acknowledgements

This work was partially funded with resourcesfrom CNPq – Prosul (014/2006, Brazil). Specialthanks to the “Instituto Chico Mendes deBiodiversidade” (ICMBio) that permitted our

access at the two National Parks investigated. Dr.Torres is Researcher of CNPq - Level 2, “JovemCientista do Nosso Estado” (FAPERJ) andAdvance Fellow at the Mount Sinai School ofMedicine and is funded by Grant1D43TW00640.

CASE STUDY OF OBSOLETE PESTICIDES POLLUTION AROUNDTHE PESTICIDES LANDFIL FROM THE REPUBLIC OF MOLDOVAMariana Grama1, Freddy Adams2, Ludmila Siretanu3

1 The Ministry of Defence of the Republic of Moldova, Chisinau, Republic of Moldova2 The University from Antwerp, Belgium3 The Ministry of Agriculture and Food Industry, Chisinau, Republic of Moldova


AbstractThe pesticides landfill located in the southernpart of the Republic of Moldova in the UnitTerritorial Autonomy Gagauzia area is consideredas one of the national priority sites and requiresurgent attention in order to eliminate acute risksfor public health and environment. Over theperiod 1977-1987, 3,940 tons of pesticide waste,collected from various locations in the country,were buried there, including 654.1 tons of DDTs.The site is only a few km away from theUkrainian and Romanian borders and close towatersheds discharging in the Prut River and theDanube near to its estuary. Under the Action Planfor Implementation of Stockholm Convention onPersistent Organic Pollutants, were conductedresearch studies around the site in the NATOScience for Peace Project “Clean-up chemicals –Moldova” and showed migration at least 10dangerous pesticides (atrazin, simazine, alpha-HCH, beta-HCH, Gamma-HCH, delta-HCH,dazomet, prometryn, triflualin, DDTs) andsulphur containing compounds characterized inthe mass spectra through 6, 7 or 8 sulfur atoms.Thus, it will contribute in solving the mostpressing issues related to environmental qualityand human health, the integration of environmentalconcerns in national economy sectors andpromotion of sustainable development. Key-words: obsolete pesticides residues,Science for Peace and Security Programm,inhomogeneous distribution, environmentalmonitoring

BackgroundIn 1970 a special dump site was built in thesouthern part of the country, in the proximity ofthe village Cismichioi that is located in the UnitTerritorial Autonomy Gagauzia area of theRepublic of Moldova. Over the period 1977 -1987, 3,940 ton of pesticides waste, collected

from various locations in the country, wereburied there, including 654.1 ton of DDTs. The pesticide landfill at the Cismichioi site isconsidered as one of the national priority sitesand requires urgent attention in order to eliminateacute risks for public health and environment.The 2.3 ha site contains 16 distinct burialmounds, most of which are visible from thesurface. In only 4 of these sites the wastes wereburied in protected conditions, in the others thechemicals are only kept isolated from thesurrounding soil with a layer of plastic foil. Thesite is only a few km away from the Ukrainianand Romanian borders and close to watershedsdischarging in the Prut River and the Danubenear to its estuary. Local administrative and environmental officialsclaim that the occurrence of cancer is abnormallyhigh in the area. In addition, many people reportbreathing difficulties. Local residents also claimthat in warm weather conditions (summermonths) fog can be seen rising from the site thatmoves in the direction of the village ofCismichioi, which is located southeast of thelandfill.

Study Areas and SamplingThe particular area of research was selected froma number of other ones on the basis of the largeamount of buried pesticides (close to 4,000 tonof pesticides waste) and of the toxicity andpersistence of these compounds (POPs and otherpesticides). The geographic proximity toRomanian and Ukrainian borders (5-10 km) andto the Lower Danube and Black Sea also playeda role in the selection of the site. Four areas (located to the North, East, Southernand the West outside the landfill) were selectedfrom which samples were collected to obtaininformation on the environmental status ofresidues in the selected area. The most important

The general strategy for sampling wasdesigned to obtain answers to the followingquestions:

• to study more prominent pesticidesmigration at different distance far fromlandfill parallel with landfill wall;

• to study the variety of pesticide residuescontent dependent on the sampling period;

• to investigate how pesticides migrate independence of depth of sampling.

A total of 216 soil samples were collected inthe study areas between February 2009 andAugust 2009 in different weather conditions:spring (April with wet weather and heavy winds),summer (May to August hot, so usually a dryperiod with heavy winds but including samplingduring June, after rain showers) (Fig 1). On everyselected sampling point were collected topsoil(from 0 to 30 cm) and subsoil (from a depth of 90cm to 100 cm) using a soil auger. The top surfacelayer with vegetation was always removed. Aftereach sample was collected, the soil auger wasrinsed with tap water and dried before the nextuse.

The results as shown in the tables that followprovide the average of 3 separate analyses. Incase one of the analyses provided one resultbelow the detection limit, the average of the tworemaining analyses is reported. Most of thesamples analyzed were obtained to the South and

the West because these are the directions of waterflow away from the site.

ChemicalsHigh purity grade solvents such as hexane,Chromasolv® (Sigma-Aldrich, gradepurissimum, assay ≥97.0%) and dichloromethaneChromasolv® (grade purissimum, assay≥99.8%) were purchased from Sigma Aldrichand were used for GC-MS analysis.Exceptionally technical purity grade reagents ofhexane with grade purissimum with assay ≥95%and acetone grade purissimum, assay ≥99% fromFluka were used, which were distilled andevaluated by GC-MS analysis for purity checksprior to their use for analysis.

Pesticide StandardsA number of pure compounds were used aspesticide standards and were obtained from thecompanies as indicated:

- From Blok-I (НПК «Блок-1»), Russia:atrazine 98.9% (Russian State standardsample-74-90-98), simazine 99.5% (ГСО-75-05-98), DDT 99.0% (Russian Statestandard sample ГСО-7379-97), gamma-HCH 99.6% (Russian State standard sample11-34-2005);

- From Ecolon (НПК «Эколон»), Russia:DDE 99.0% (standard sample 01-03), DDD

CASE STUDY OF OBSOLETE PESTICIDES POLLUTION AROUND THE PESTICIDES LANDFILFROM THE REPUBLIC OF MOLDOVA


questions to be answered were whether pesticideresidues levels in soil could be linked to dispersal

from the landfill site and how high could be riskfor public health, fauna, flora, etc.

Figure 1. A map of the area which indicates the sampling locations (distance not to scale)

1 Klissenko, M.A., Alexandrova, L.G. The determination of residual quantities of pesticides (russian), Kiev:Zdorovia, p.174, 1983.

Mariana Grama, Freddy Adams, Ludmila Siretanu


99.0% (standard sample-02-03) , alpha-HCH 98.6% (standard sample-12-06),beta-HCH 98.7% (standard sample-11-06)

- From Mackteshim Agan, Israel: promertryn99.5% (7287-19-6).

Sample Extraction The soil samples were dried at room temperaturefor 120 h in a separate room from the analyticallaboratory. The analysis of each sample wasexecuted in triplicate: each dry soil samples (10g) was weighed and 20 mL of H2O was added.To the sample mixture were added 40 mL ofacetone and shaken using a shaker (type OS-10,„Biosan”, Lituania) for 1h. The extract wasfiltered through paper filter (type ODS C18 SPE,AccuBond, Agilent). The soil extract was thensubject to the clean-up.

Clean-up of soil extractsAfter the first extraction 10 mL hexane wasadded to the soil samples and then extractedagain with a mixture of 10 mL water and 30 mL ofacetone. After filtration, to the extract collected inan Erlenmayer flask were added 180 mL H2O and40 mL hexane, extracted with hexane in duplicate,dried with anhydrous Na2SO4 and then evaporatedat temperature 400C on a rotary evaporator(Heidolph Laborota-4000 G3 Efficient, Germany). The extracts were dissolved in 1 mL acetone. Noadditional clean-up was needed and the extract

was ready for GC-MS analysis1.

Gas Chromatographic - Mass SpectrometricanalysisQuantitative analysis of the residues of POPs andpesticides in soil was done using a gaschromatograph (GC Agilent Technologies 6890N) connected with a mass selective detector(MSD, Agilent Technologies 5973) equippedwith a SPLITLESS.LO programming. Thecapillary column used is HP-5MS (30m x0.25mm x 0.25 µm). Helium with high purity of99.9999% was used as the carrier gas at 10.48psi, at a constant flow of 37 cm3/sec. Samples (10µL) were injected in the splitless mode with atotal flow rate at 7.5 mL/min. The front inlet anddetector (MS Quad and MS Source) temperatureswere: 275, 150 and 230°C, respectively. Thetemperature program of the oven was: 100°C(held for 30 seconds), 10°C/min to 180°C,3°C/min to 250°C, 10°C/min to 290°C and thenheld at that temperature for 10 min. An exampleof a typical mass spectrum (DDT) is shown inFigure 2.

The procedure used for GC-MS analysis ofpesticides residues in soil was provided byProfessor Adrian Covaci (University of Antwerp,Belgium) and Dr. Lourdes Ramos (ConsejoSuperior de Investigaciones Cientificas, Madrid,Spain).

Figure 2. Mass spectrum of DDT showing the target ion (235)

2 Soil Quality. TCVN 5941 – 1995.

Pesticide Residues in soilBetween February 1, 2009 and December 31,2009, 216 soil samples were analyzed by GC-MSand HPLC for the selected more toxic andpersistent pesticides in the environment. Theanalysis of these 216 samples of soils wasrepeated three times for its quality assurance.Thus 711 soil samples in total were analyzed. Pesticides were identified in 77 % (167 samples)of the soil samples tested. The pesticides such assimazine, atrazine, prometryne and DDT and itsbreakdown products (p,p-DDD and, p,p-DDE)summarizes the occurrence of the pesticidesdetected in study area soils.

Pesticide Residues in soil samples fromNorthern part of landfillThe study concentrated on the 30-cm surface/topsoil layer. Nine samples were taken from thenorthern part of landfill, at 5 m away from wallof the dump site and with a distance of 10 mbetween samples. DDTs was the only pesticidedetected in soil samples from this area. The

DDTs breakdown products (DDE and DDD)were detected in 8 out of 9 samples. DDT wasdetected in 6 samples. Other pesticides such asα-HCH, β-HCH, γ-HCH, atrazine andprometryne were systematically looked for butnever appeared with a concentration above thedetection limit.The results for the sum of DDT and relatedcompounds are summarized in the Figure 3.

Pesticide Residues in soil samples from Easternpart of the landfill.

The study was again concentrated on 30-cmsurface/top soil layer. Twenty one samples weretaken at a 5-metre distance from the wall of thedump compound and with a distance 10 mbetween each sample (Fig 1). Six pesticides weredetected in soil samples from this area. Compounds such as α-HCH, β-HCH, γ-HCHwere systematically looked for but not detected.All pesticides detected in these samples were<MRL except for simazine in one sample (at 0.23mg/kg). We point to the following observations:



Results

CalibrationLinear calibration curves were found betweenpeak areas and analyte concentration over thewhole range studied. Calibration curves wereobtained for the quantification using a mixture ofstandard solutions of chlorinated pesticidesdissolved in hexane and mixture standardsolutions of simm-triazine pesticides dissolvedin acetone at a concentration 1, 5, 10, 25 and 50

µg/mL. Retention time, masses and relativeabundance of the confirmation ions to thequantification ion were used as identificationcriteria.

The content of all pesticides detected in soilsamples during this study were presented inmg/kg dry weight and compared with maximumresidues level (MRL) for each pesticide. Theretention time and MRL for select pesticides arepresented in Table 1.

Table 1. Analytical details

Pesticide Residues in soil samples fromSouthern part of landfillForty samples were taken 50-cm surface/top soillayer at distances ranging from 30 m, 2000 m,5000 m and 7000 m away from the landfill sitewall. This direction slopes into a hill.

Prometryne was not detected in any of thesamples. The DDT compounds and atrazine werealways <MRL. Results are as follows (see Figure5 a, b, c, d). DDT was detected below thequantification limit (0.1 mg/kg) in 3 samples outof 10 at 30 m with a maximum concentration of0.006 mg/kg. At 2000 m it was detected in 7samples out of 10 samples with a maximum

concentration of 0.015 mg/kg while at 5000 mone sample showed DDT with a maximumconcentration of 0.011 mg/kg. At 7000 m 10samples DDT and DDE were detected with amaximum concentration in one sample of 0.034mg/kg. Atrazine was detected below thequantification limit (0.5 mg/kg) at 5000 m in 3soil samples with a maximum concentration(0.022 mg/kg) and at 7000 m, in 8 samples witha maximum concentration 0.41 mg/kg. HCHspesticides were detected in 3 soil samples at 5000m and 7000 m each with a maximumconcentration 0.35 mg/kg above the MRL (0.1mg/kg).



1. DDT and its breakdown products (DDE andDDD) were detected <MRL (0.1 mg/kg) in allthe samples. The maximum concentrationencountered was 0.057 mg/kg).

2. Atrazine was detected in 5 soil samples withmaximum concentration (0.033 mg/kg) i.e.well below the MRL of 0.5 mg/kg.

Prometryne was detected in 4 samples withmaximum concentration of 0.083 mg/kgagain < MRL. Simazine was detected in 6samples; one concentration exceeded theMRL value at 0.23 mg/kg. HCHs productswere not detected (Fig 4).

Figure 3. Pesticide Residues in soil samples from Northern part of landfill

Figure 4. Pesticide Residues in soil samples from Eastern part of the landfill

Figure 5a. Content of pesticides residues detectedin soil samples at 30 m away from the landfill.

Figure 5b. Content of pesticides residues detectedin soil samples at 2000 m away from the landfill.

Figure 5c. Content of pesticides residues detectedin soil samples at 5000 m away from the landfill.

Figure 5d. Content of pesticides residues detectedin soil samples at 7000 m away from the landfill.

3 Covaci A., Hura C. Schepens P., The Science of the Total Environment 280 (2001) 143-152

Pesticide Residues in soil samples from Westernpart of landfillTable XIII summarizes the results for a total of145 samples were taken at different distancesfrom the dump site (20, 100, 110 and 200 m) indifferent sampling periods (29 April 2009, 27May 2009, 26 June 2009 and 13 August 2009).Samples were taken from the 50 cm surface/topsoil layer and at 1 m depth.

The results show that DDTs products weredetected below the MRL in a number of samplesat all distances with a maximum concentration of0.016 mg/kg at 20 m and a maximumconcentration of 0.268 mg/kg at 100 m above theMRL at 0.1 mg/kg. HCHs products weredetected only in one samples at 100 m (0.09mg/kg) and two positive measurements at 280 m(0.02 mg/kg). Simazine, atrazine and prometrynewere occasionally, but not systematically,detected at concentrations exceedingoccasionally the MRL values.

DiscussionThe results obtained show that the concentrationlevels of the pesticides overall do not exceed thesafety limits. Up to the present time, the site doesnot seem to discharge pesticides in theenvironment. MRL or MAC values are onlyexceeded in a few of the samples analyzed.

With the information available in the literature itis possible to compare the results obtained withother data obtained elsewhere. One basis ofcomparison is soil from a rural area near Iassy,Romania where DDT levels are 0.228 + 157mg/kg3. In other Romanian locationsconcentration levels of 0.0625 + 0.044, 0.303 +0.087 and 1.05 + 0.69 (near Timisoara, Arad,Ploiesti, Cernavoda) are reported. Another studyreports concentration of organochlorinecompounds in the following range: 0.2–1.4, 5–56, and 5–95 ng/g of soil for HCB, sum HCHs,and sum DDTs, respectively4. Overall, the resultsobtained do not show abnormal levels ofpollution with the compounds that could point toleakage of the pollutants from the storage site.



3 Dragan D., Cucu-Man S., Dirtu A.C., Mocanu R., Van Vaeck L., Covaci A., Intern. J. Environ. Anal. Chem.Vol. 86, No. 11 (2006) 833–842

ConclusionIt appears from this limited study that until nowthere is no dramatic increase in pesticide levelsaround the Cismichioi landfill. However, illegaluse, package deterioration, or accidents maycause localized or widespread pollution at this

and other sites, thus representing a potential riskto human health and the environment. Hence,further studies in this area are needed in order toassess the levels of pesticides until the site isremediated.



The results show a quite inhomogeneousdistribution of the concentration levels. Hence, itis not possible to see any systematic trends as afunction of distance or depth. Figures 5 a-d andFigure 6 SUM DDTs (a) and Simazine (b)illustrates this for measurements to the South ofthe landfill.

Figure compares the concentration of the sum ofthe DDT products at the surface and that at adepth of 1 m on the west of the landfill with thesurface concentration being systematicallyhigher than that in depth. A similar observationcan be made for simazine.

Figure 6a. Comparison of surface and depth concentration of DDT at depth 1 meter forlocations at 200 m to the west of the landfill

Figure 6a. Comparison of surface and depth concentration of simazine at depth 1 meter forlocations at 200 m to the west of the landfill

PERSISTENT ORGANIC POLLUTANTS IN THE FRAMEWORK OFMONITORING OF AGRICULTURAL SOILS IN THE CZECH REPUBLICMiroslav Florián, Jaroslav Staňa, Šárka PolákováCentral Institute for Supervising and Testing in Agriculture (ÚKZÚZ), Division of Feed andSoil Safety, Hroznová 2, 656 06 Brno, Czech Republic, [email protected]


AbstractPersistent organic pollutants (POPs) arerepresented by a group of substances, which arevery stable in the environment and can betransported for a long distance. They areaccumulated in all animals, including humansand can cause many health problems. In order toprevent further spread of these compounds theStockholm Convention on Persistent OrganicPollutants was created. The Czech Republicsigned and ratified the Convention in 2002.Seven substances from the Convention (7 PCBcongeners, HCB, 4 HCH isomers and DDT andits metabolites) are monitored by the CentralInstitute for Supervising and Testing inAgriculture (ÚKZÚZ). POPs have been observedby ÚKZÚZ since 1994 at 40 monitoring plots.These plots are a part of so called Basal SoilMonitoring System (BSM), which has been inoperation since 1992 and consist of 214monitoring plots. Soil samples are collectedevery year from topsoil and subsoil layers. Inorder to get the information about possibletransmission of POPs from soil to plant, thesystem was enlarged to monitoring of POPscontent in plants. For this purpose 12 monitoringplots with elevated POPs contents in soil wereselected for plant sampling.Long-term soil monitoring gave us informationabout POPs content and its changes inagricultural soils. POPs contents are stableduring the years with the exception of PCBs.Contents in topsoil are higher than in subsoil.POPs contents in plant samples are below thelimit of quantification except for two samples –rape and clove-grass mixture. It seems to beobvious that POPs contents in plant is not solelydependent on POPs content in soil but that theuptake is influenced by the type of plant andother environmental conditions.

Key words: persistent organic pollutants (POPs),soil, plant, monitoringIntroduction Persistent organic pollutants (POPs) aresubstances which persist for a long time in theenvironment. They have some typicalcharacteristics – high tendency tobioaccumulation in fatty tissues of humans andwildlife, high level of chemical and biologicalstability and by an ability of long-distancetransport. Due to these characteristics, they areable to disperse thousands of kilometres from thesource and to contaminate the whole biosphere.It is generally known that the cyclic evaporationfrom soil and water surface which causes airdrifting of POPs in the form of vapour and dustand subsequent rain, snow or solid particlesdeposition is the mechanism explaining the POPsmobility in the environment. Persistent organic pollutants are created byprocesses in nature (e.g. volcanic activities,fires), however, the overwhelming part of theirsources is of anthropogenic origin. Observing ofthe beginning of the food chain – soil quality – isone of the ÚKZÚZ tasks. For this purpose theCentral Institute for Supervising and Testing inAgriculture monitors the contents of selectedPOPs (7 PCB congeners, HCB, 4 HCH isomers(a-, b-, g-, d-) and DDT and its metabolites) inagricultural soils and plants.

Material and methodsSoils Soil samples were taken within Basal SoilMonitoring System (BSM). The system wasestablished in 1992, when also the first sampleswere taken in basal net (basal soil monitoringsubsystem) of 190 monitoring plots. Five yearslater, in 1997, there was established thesubsystem of contaminated plots. In total 27monitoring plots were created on the sitescharacterised by inorganic contamination of both

Fig. 1 Parameters determined in the samples within individual sampling schemes

As mentioned in Fig. 1, POPs are analysed insamples taken annually. The samples of arablesoils are taken from topsoil (according to thethickness of the horizon, maximally to 30 cm)and from subsoil (30–60 cm), within hop gardensfrom topsoil (10–40 cm) and subsoil (40–70 cm);within permanent grassland from three horizons(0–10 cm, 11–25 cm, 26–40 cm; always after theremoval of top turfy layer). Samples for POPsanalysis are taken by zig–zag pattern. Samplingfor this purpose was started in 1994. At firstsamples from plots, on which wheat was planted,were taken (alterative set of plots). In 1997 astable/fix set of 40 plots in BSM system and 5plots in protected areas were set in. ÚKZÚZsamplers are responsible for good-qualitysampling. Polychlorinated biphenyls (PCB) havebeen determined since 1994: in 1994–1997 3congeners were determined (138, 153 and 180),other 3 congeners were added in 1998 (28, 52and 101) and 7 indicator congeners have beendetermined since 2002. Analysis of organochlorinepesticides (OCP) – hexachlorocyclohexane (HCH),hexachlorobenzene (HCB) and DDT and itsmetabolites have been run since 1994, too, withshort break/interruption in 1998 and 1999.From 2000 PCB analyses and later on also OCPwere performed exclusively in ÚKZÚZ

laboratory in Brno. In 2004 this test/method wasaccredited and the compatibility of results wasensured as well. From this point of view onlydata collected after 2004 (including) werestatistically processed in MS Excel 2003, NCSS2001, Statistica v 6.0.

PlantsWith regard to the big environmental importanceof POPs our BSM programme was enlarged tomonitoring POPs contents in plants. Based on thehighest contents of POPs in BSM soils 12monitoring plots were chosen as suitable forplants sampling. This sampling was started in2010. Sampling scheme for plants is the same asfor soils. One composite plant sample consisted of at least10 increment samples and was taken from eachmonitoring plot (only edible part of plant or plantfor feeding). Above–ground part of plant was notwashed off. Samples, ranging from 500g to2000g, were weighed, packed in plastic bags,labelled and immediately transported in a coolingmobile box to the laboratory. In case of seeds sampling (cereals, rape, poppy)samples were exsiccates, seeds were beaten out,and then weighed. These samples were notcooled down.

Miroslav Florián, Jaroslav Staňa, Šárka Poláková


anthropogenic and geogenic origin. Monitoring plots are defined as rectanglesmeasuring 25m x 40m (1000m2). Each plot ischaracterised by geographical coordinates,

landscape morphology and climatic and soilconditions. There are three sampling schemes inthe frame of monitoring.

PERSISTENT ORGANIC POLLUTANTS IN THE FRAMEWORK OF MONITORING OFAGRICULTURAL SOILS IN THE CZECH REPUBLIC


Results and discussionSoilsEvery year 90 soil samples are collected andanalysed. The contents of HCH in BSM soils aremostly negligible. Majority of the samples do notexceed limit of quantification (LOQ = 0.5 ppb).The LOQ is usually exceeded only in samplesfrom 10 monitoring plots. The maximal value(12.5 ppb) was determined on hop-garden in2010. Statistical differences between years orhorizons were not found. Based on BSM data itwould be easy to think of HCH contents in Czechagricultural soils as irrelevant. But lindan (g-isomer of HCH) was a widely used pesticide andgeneralization of the statement mentioned aboveis possible only towards larger areas. For example,HCH contents determined in organomineralhorizon A were many times higher on the areas ofSouth and Western Bohemia (Čermák et al., 2008)- in arable soils up to 15.4 ppb, in grassland up to21.1 ppb and in forest soils up to 59.0 ppb anddifferences between cultures were statisticallysignificant there.

The contents of HCB ranged from < 0.5 ppb to52.1 ppb. The maximal values were detected onsouth-eastern and western parts of the CzechRepublic. These locations correspond tolocations contaminated by DDT substances.There is evidence that HCB was found as animpurity in chlorine pesticides (Škrbić et Durišić-Mladenović, 2007). The HCB contents in topsoiland subsoil differ significantly.

The contents of sum of DDT (DDTtotal = o´,p´-+ p´,p´- isomers of DDT + DDE + DDD) inBSM soils are relatively low. As in the case ofHCH when evaluating the locality-burden localconditions must be taken into account (e.g. oldcontamination, historical application ofpesticides). For example the above-mentionedarea of South and Western Bohemia (Čermák etal., 2008) is characterised by higher median ofDDTtotal in organomineral horizon A of arableland (42.7 ppb) than BSM soils (and maximalvalues totalled 879 ppb). The ratio betweenindividual substances of DDT (DDD, DDE,DDT) rises in sequence DDD < DDE < DDT.The contents of DDTtotal in topsoil are higherthan in subsoil (with the exception of grassland).

These differences are significant. The contents ofDDTtotal are stable and do not vary significantlythrough the years.

The contents of PCB (sum of 7 indicatorcongeners) ranged from 1.75 to 98.8 ppb andvaried through the years, but not through thecultures. The PCB contents in topsoil are higherthan in subsoil. Quite remarkable locality isStudniční hora (KRNAP – The KrkonošeMountains National Park). Thanks to its altitudeit has a relevant proportion/ratio of the highmedians (and averages) in soils originated fromprotected areas and confirms the big importanceof long-range transport of PCB.

The key for selection of monitoring plotsdesigned for plant sampling was that minimallyone parameter must exceed limit of particularPOP content in soil.

PlantsAs mentioned above, 12 plant samples designedfor POPs determination were first collected in2010. The contents of POPs are under limit ofquantification (LOQ = 0.05 ppb) almost in allsamples with the exception of two samples - rapeseed and clover-grass mixture (tab. 3).In case of rape seed the contents of 3 PCBcongeners, g-HCH and 3 DDT substancesexceeded LOQ. In case of clover-grass mixtureonly p´,p´-DDE is above LOQ. All these valuesare very low.Also from the point of view of existinglegislation, the determined POPs contents inplant samples are low and safe and do not poseany risk for feed/food chain or human health. From our data it is clear that POPs content inplant does not only strictly depend on POPscontent in soil, but also on the type/genus ofplants.

ConclusionsBSM data give important information aboutPOPs content in agricultural soils in the CzechRepublic. Within more than 10 years ofobserving stable contents of organochlorinepesticides in BSM soils were statisticallyapproved. In contrast to these substances PCBcontents in soils are fluctuating during the years.

1. Čermák, P. (2008): Obsahy rizikových prvkůa látek a základní agrochemické charakteristikypůd v oblasti jižních a západních Čech. ÚKZÚZBrno, 68 s. ISBN 978-80-7401-010-1.http://www.ukzuz.cz/Folders/3318-1-Publikace.aspx

2. Poláková, Š. (2011): Závislost obsahů POPsv rostlinách na obsahu POPs v půdě – zprávaza rok 2010. ÚKZÚZ, Brno, 7 s.http://www.ukzuz.cz/Folders/Articles/46610-2-Monitoring+pud.aspx

3. Poláková, Š., Kubík, L., Němec, P. et Malý,S. (2010): Bazální monitoring půd, 1992 -2007. ÚKZÚZ, Brno, 45 s.http://www.ukzuz.cz/Folders/Articles/46610-2-Monitoring+pud.aspx

4. Škrbić, B., Durišić-Mladenović, N. (2007):Principal component analysis for soilcontamination with organochlorine compounds.Chemosphere, vol. 68, is. 11, s. 2144-2155.

References

Miroslav Florián, Jaroslav Staňa, Šárka Poláková


Higher contents in topsoil than in subsoil wereapproved for OCP as well as for PCB. Localitieswith increased HCB contamination correspondwith localities with increased DDT level ofcontamination.

Plant samples collected on BSM plots containedvery low amounts of POPs (POPs contents in themajority of samples were below the limit of

quantification). Based on BSM data it is clearthat POPs contents in plants do not depend onPOPs content in soils. This conclusion will haveto be confirmed statistically. Data from BSM areused as a background for specific studies such aspossible soil contamination due to floods or firesof industrial buildings etc.

APPLICATION OF SEMIPERMEABLE MEMBRANE DEVICE FORASSESSMENT OF NON-POLAR ORGANICS IN SURFACE ANDUNDERGROUND WATEROcelka, T.1, Kurková, R.1, Mach, S.1, Pavliska, L.21 Institute of Public Health, Ostrava, Czech Republic, [email protected] 2 E&H services, Inc., Prague, Czech Republic


The City Jaworzno belongs to the largest townsin Poland. Its area is 152.7 km2 with more than96 000 inhabitants. Its biggest environmentalproblem is related to the contaminated area in thevalley of Wawolnica Brook as a result of achemical plant’s recent activities from 1928.Since then plant protection products have beenproduced, preparation for hygiene and otherchemical products has been carried out. Toeighties of the twentieth century, the valley ofWawolnica brook was the site of hazardouswaste collection from this production.

Release of non-polar organics from industrialactivities was assessed by SemipermeableMembrane Device (SPMDs) tool, as a techniquescommonly used in various environmentalapplications for water monitoring. A standardSPMDs were used, delivered as a standardsampling system from a vendor, with its ownproduction of QA/QC. Within two deployments,assessment of non-polar organics was performed.Evaluation of ambient concentration was realizedusing PRCs approach, as published recently.Using of SPMDs was applied in accordance withISO 17025 standard. Further evaluation of data

sets by marginal and multivariate data analysissupported interpretation of main sourcesidentification.

This work was realised under FOKS (Focus onKey Sources of Environmental Risks) project,with co-funding by ERDF (Central Europe).

Key words: Passive sampling, POPs, OCPs,robust data analysis

POP PESTICIDES IN AMBIENT AIR FROM MONET NETWORK –LEVELS AND TRENDSIvan Holoubek, Jana Klánová, Pavel Čupr, Petr Kukučka, Jana Borůvková,Jiří Kohoutek, Roman Prokeš, Radovan KarešRECETOX, Masaryk University, Brno, Czech Republic


AbstractThe effectiveness of the Stockholm Convention(SC) on Persistent Organic Pollutants (POPs)shall according to Article 16 be evaluated fouryears after the date of its entry into force. GlobalMonitoring Plan (GMP) has been developed withan objective of evaluating whether the POPsactually were reduced or eliminated on the globalscale. As one of the key matrices for the globalmonitoring, an ambient air was selected. Twoapproaches of sampling exist – active using thehigh volume samplers and passive air samplers(PAS) as new tools for the air quality monitoring.

MONET programme (MONnitoring NETwork)is driven by RECETOX as the Regional Centreof the Stockholm Convention for the region ofCentral and Eastern Europe on the national scale(MONET-CZ, containing 37 sites including 15backgrounds), and regional scales – the Central,Southern and Eastern Europe and Central Asia(MONET-CEECs), the Pacific Islands (MONET-PIs), the African continent (MONET-AFRICA)and newly whole Europe (MONET-Europe). Thesamples are collected in 28-days and theyrepresent 13 samples from each site every year.

Key words|:Stockholm Convention, MONET, persistentorganic pollutants (POPs), ambient air monitoring

Introduction – The Stockholm Convention onPOPs and their effectiveness evaluationThe Stockholm Convention on PersistentOrganic Pollutants (POPs) [1] entered intoforce on May 17, 2004, and has currently 173signatory parties (May 16, 2011). The mainobjective of the Stockholm Convention (SC) isto protect human health and environment frompersistent organic pollutants by reducing oreliminating their releases into the environment.

According to Article 16 of the Convention, itseffectiveness shall be evaluated four years after the

date of its entry into force, and periodicallythereafter every 6 years [1]. The objectives of thePOPs Global Monitoring Plan are to evaluatewhether the POPs actually were reduced oreliminated as requested in Articles 3 and 5 of theConvention. The information on environmentalbackground levels of the chemicals listed in theannexes is a precondition for monitoring of trendsover time [1]. In order to meet the objectives of theGlobal Monitoring Plan (support the preparation ofregional reports of comparable information onenvironmental background levels), the guidancemust be provided on how the information is to becollected, analyzed, statistically treated, andreported [2].

Polyurethane foam based passive samplers forsampling of POPs in ambient air As the air pollution became an issue of greatpublic health concern and the internationalconventions and new regulations introduced theirdemands, a pressing need to obtain more airpollutants including POPs data in a cost-effectiveway appeared. Global Monitoring Plan has beenprepared for the purpose of the StockholmConvention with the objective of establishingbaseline trends at global background sites [2]. Itwas the main goal of the first step of this Globalmonitoring programme – the determination ofbasic global information in 2009. When developedparties are to conduct source inventories, identifyongoing sources, and provide environmentalmonitoring evidence that ambient levels of POPsare declining [2,3].Developing countries inparticular require cost-effective and simpleapproaches. The experiences from the first reportin 2009 and the list of newly adopted POPs, willbe used for the second assessment in 2015.

Based on the long-term work of manyinternational experts, the Guidance for the GlobalMonitoring Plan [2], was prepared. As one of thekey matrices, the ambient air was selected. We

POP PESTICIDES IN AMBIENT AIR FROM MONET NETWORK – LEVELS AND TRENDS


have two basic principles for the sampling ofambient air for POPs determination – a passivesampling and an active one, consisting of highvolume air samplers. Since the high volume airsamplers as expensive devices requiring reliablepower supply as well as trained operators are notwidely available, the air monitoring of POPs hasonly been conducted a limited number of sites.This was also one of the reasons, why a lot ofvarious new types of passive air samplers (PAS)as new tools for the air quality monitoring wereintroduced in the last years [3-6]. PAS representa cheap and versatile alternative to theconventional high volume air sampling and theyhave been currently recommended as one of themethods suitable for the purpose of new long-term monitoring projects. They are capable ofbeing deployed in many locations at the sametime, which offers a new option for the largescale monitoring. As it provides informationabout long-term contamination of selected site,passive air sampling can be used as a screeningmethod for semi-quantitative comparison ofdifferent sites with the advantage of lowsensitivity to accidental short-time changes inconcentration of pollutants. It was demonstrated that passive air samplersusing polyurethane foam (PUF) filters aresuitable to study vapour-phase air concentrationsof POPs, particularly of more volatilecompounds [7-10]. They were successfullyapplied as a tool for POPs monitoring on theglobal, regional, national levels and also at alocal scale, where they are able to provide site-and source-specific fingerprints. Further they canbe used to conduct screening surveys to help toidentify the sources [9,10]. This tool based onexperiences and results from the long termtesting and broad applications was recognized asvery useful and effective for the determination oftemporal, seasonal and spatial trends on theglobal, regional and local scales [11].

RECETOX pilot studiesPassive air samplers of this design were firstintroduced in the Czech Republic in 2002 duringthe European screening campaign performed byLancaster University and focused on theatmospheric levels of POPs [7,12]. Since 2003,

this research topic has been developed in theRECETOX in cooperation with LancasterUniversity and Environment Canada. RECETOX conceptual approach andcontribution to wide application of this methodwas oriented to the long-term study of effects ofenvironmental variables to applicability of thistechnique for the long-term monitoring anddetermination of temporal, seasonal and spatialtrends on the global, regional and local scales.Samplers were calibrated against the highvolume samplers in the field conditions, and theirsensitivity, capacity, robustness, as well as aninfluence of the various meteorologicalparameters on their performance were assessed[13]. PAS have been continuously deployed inthe regular atmospheric monitoring of POPs inKošetice station since 2003 side by side withactive samplers to compare information derivedfrom both techniques. A core network of the Czech Republic wassignificantly altered based on the evaluation ofthe results from the pilot study in 2005. The newdesign was introduced and initiated in January,2006. Thirteen 28-days samples are collectedfrom each of 37 sampling sites [14,15]. Thissampling period and frequency was/is used inmain part of MONET sampling sites andcampaigns. This monitoring network – MONET-CZ is still flexible and allows furtherimprovements. At the same time, the backboneof the network allows performance and advancedinterpretation of the short term spin-off casestudies. The feasibility of the long-term application ofpassive air samplers for the evaluation ofpersisting influence of the war damages on theatmospheric contamination of the WesternBalkan region was assessed in this study. Resultsof this project were compared to those of theprevious high volume sampling campaigns(APOPSBAL Project) [16,17]. As Central,Southern and Eastern Europe is the region with alack of data on the atmospheric POP, threescreening campaigns were organized between2006 and 2008 (MONET-CEECs). Samplingsites for the first phase of the MONET-CEECsProject, have been selected in cooperation with

Ivan Holoubek, Jana Klánová, Pavel Čupr, Petr Kukučka, Jana Borůvková, Jiří Kohoutek, RomanProkeš, Radovan Kareš


the local partners in all participating countries[18,19]. The philosophy was the same as for themodel network in the Czech Republic: 5-20sampling sites were selected per country(according to the size of each country) and theywere monitored for 5 months. In addition to the Central and Eastern Europeanregion (CEEC), 26 sites from the Africancontinent (MONET-AFRICA) and 21 sites fromthe Central Asia (former Soviet Union countriesas a part of MONET-CEECs) were monitored in2008 and 3 sites from the Pacific Islandsbetween 2006 and 2007 (MONET-PIs).MONET-AFRICA now continues by the secondphase (2010-2012) [20-22].Previous RECETOX studies [10,11] confirmedthat PAS are sensitive enough to mirror evensmall-scale differences, which makes themcapable of monitoring of spatial, seasonal andtemporal variations. Passive samplers can beused for point sources evaluation in the scale ofseveral square kilometres or even less - from thelocal plants to diffusive emissions fromtransportations or household incinerators - aswell as for evaluation of diffusive emissions fromsecondary sources. While not being sensitive forshort time accidental releases, passive airsamplers are suitable for measurements of long-term average concentrations at various levels.

Methods - sampler, sampling and analysisPassive air sampling device used in the pilotstudies and MONET programme, methods andsample preparation, analysis including QA/QCprocedure are describe in the RECETOX papersand reports [9-11,14,15].

ResultsAs Central, Southern and Eastern Europe is theregion with a lack of data on the atmosphericPOP, three screening campaigns were organizedbetween 2006 and 2008 (MONET-CEECs). Inaddition to the Central and Eastern Europeanregion (CEEC), 26 sites from the Africancontinent (MONET-AFRICA) and 21 sites fromthe Central Asia (former Soviet Union countriesas a part of MONET-CEECs) were monitored in2008 and 3 sites from the Pacific Islands between2006 and 2007 (MONET-PIs).

Concerning to OCPs, the levels of HCHs weregenerally low (median value below 30 ng filter-1)except for the sites where it was produced orstored. The highest median levels were measuredat several sites in Romania (Turda 2.3 µg, Onesti1 µg filter-1), similar extreme (2.5 µg filter-1) wasalso found at Kitengela site in Kenya. Hundredsof nanograms of HCHs per filter were measuredin Ufa and Chapaevsk in Russia, near theSpolana chemical factory in the Czech Republicor in Skopje, Macedonia. There were countriesas Kyrgyzstan or Romania where all thesampling sites had elevated PCB levels.

Median levels of DDTs stayed below 100 ng perfilter at most of the sites. There were, however,the sites with medians higher than the order ofmagnitude. The highest median level was foundat Kitengela site in Kenya (2.5 µg filter-1), thevalues higher than 100 ng filter-1 were also foundin Dakar (Senegal) (360 ng filter-1), Asela(Ethiopia), Bamako (Mali), Kyiv (Ukraine),several sites in Bucuresti (Romania) orKyrgyzstan.

Median values of hexachlorobenzene (HCB)were below 10 ng filter-1 at most of the sites.Concentrations several times higher were foundin Ivansedlo (Bosnia), Ufa and Chapaevsk inRussia, Kyiv (Ukraine) and Cairo (Egypt). Thehighest median level was measured in thevicinity of the chemical factory Spolana in theCzech Republic (88 ng filter-1), and near thechemical complex in Chapaevsk. The sites withthe highest median levels of pentachlorobenzene(PeCB) as a degradation product of HCBcoincided with those with the highest levels ofHCB (Spolana, Chapaevsk) but elevatedconcentrations were also found at all sites ofKyrgyzstan, in Asela (Ethiopia), Kitengela andDandora (Kenya).

For the purpose of the Global monitoring,however, only the background sites are ofinterest. To give an overall comparison of thebackground POP levels in all investigatedcountries, only the background sites wereselected from the database based on availableinformation and measured levels. Each countrywas represented by one background site. Thebackground site in Kyrgyzstan had the highest

median levels of HCHs, followed by the sites inTogo, Tunisia, Romania, Moldova, Ukraine andSerbia. As the background levels of HCHs areusually quite uniform, such results indicate somelocal sources of HCHs. South Africa and Fijiwere found to be the cleanest sites in the project.As expected, the highest levels of DDTs weredetermined in Central Africa, especially inEthiopia and Sudan. High concentration,however, we also found in the South-EasternEurope (Moldova and Romania). Zambia, Maliand Ghana were elevated, too.In contrast, Central Europe had the concentrationof HCB several times higher than other regions.Even though HCB distributes very well over thelarge areas, we can still observe highconcentration in Central Europe (CzechRepublic) and Central Asia (Kyrgyzstan) whencompared to the other regions (as Africa).Situation is not so clear for PeCB as adegradation product of HCB. The only site withsignificantly higher levels of PeCB was inKyrgyzstan.

Future of MONETIn case of the CEEC, it has been recognized thatknowledge on Western European POP levelswould greatly improve the understanding toCEEC data. It was the first step and based on this,the harmonization of the monitoring activities in

both parts of Europe is a logic step to gainsystematic information on the levels and trendsof the atmospheric pollution in this continent.

Using mainly the EMEP stations participating inthe previous MONET activities and new onesfrom the rest of European countries and based onthe agreement between RECETOX and EMEP,the MONET-Europe, was established in 2009.The goal is to maintain sustainable PASmonitoring at the majority of sites. That wouldsignificantly improve the understanding of thesources, fate and transport of POPs in Europe andprovide rich information for the modellingdatabases. At the same time, it would createnecessary synergies between the StockholmConvention and Convention on Long-RangeTransboundary Air Pollution (See Fig. 1).

In 2009, the Conference of the Parties of the SCdecided that levels of POPs in core matrices willbe assessed every six years assuming that such aperiod will be sufficient for establishment of thetemporal trends. As the Košetice station is theonly site worldwide where active and passivesamplers have been co-employed for full sixyears so far, results from this station have animportant role in the intercalibration of bothtechniques, comparison of trends derived fromboth datasets, and development of future globalmonitoring programmes [16-18]. Long-term

Figure 1. European passive air monitoring network.



Figure 2. Global distribution of the sampling sites with on-going air monitoring. MONETsampling sites are coloured blue.

ConclusionFor many of the participating countries the datafrom MONET programme are the first data onthe atmospheric levels of POPs [16-23]. This wasthe reason why the background monitoring wasaccompanied with the screening of the extent ofcontamination in the individual countries. Tocarry these activities beyond the point of the firstscreening, best candidates for the backgroundmonitoring have to be selected in every region,and resources have to be sought to make theprogram sustainable. Now, the harmonization of the monitoringactivities in both parts of Europe to gainsystematic information on the levels and trends

of the atmospheric pollution over this continent,has been started in 2009. The EMEP stations inwhole Europe participate in this now MONETphase which is focused on the improvement ofthe understanding to the sources, fate andtransport of POPs in Europe and the providingrich information for the modeling databases.

AcknowledgementsThis paper was/is supported by the CETOCOENproject (CZ.1.05/2.1.00/01.0001) of theEuropean Structural Funds, the INCHEMBIOLproject (MSM 0021622412) of the Ministry ofEducation of the Czech Republic and theMinistry of Environment of the Czech Republic(SP/1b1/30/07).

References



sustainability of such monitoring programmes isof a great importance for a success of the Global

monitoring plan (Fig. 2).

1. UNEP Stockholm Convention on PersistentOrganic Pollutants. Stockholm Conventionon Persistent Organic Pollutants 2001,decisions, information documents,http://www.pops.int

2. Draft revised Guidance on the Globalmonitoring plan for persistent organicpollutants, UNEP, May 2011, UNEP/POPS/COP.5/INF/27

3. Harner, T., Bartkow, M., Holoubek, I.,Klanova, J., Wania, F., Gioia, R., Moeckel,C., Sweetman, A. J. & Jones, K. C., Passiveair sampling for persistent organic pollutants:Introductory remarks to the special issue.Environ. Pollut. 144, pp. 361-364, 2006.

4. Peters, A. J., Lane, D. A., Gundel, L. A.,Northcott, G. L. & Jones, K. C., Acomparison of high volume and diffusion



denuder samplers for measuring semivolatileorganic compounds in the atmosphere.Environ. Sci. & Technol. 34, pp. 5001-5006,2000.

5. Harner, T., Farrar, N. J., Shoeib, M., Jones,K. C. & Gobas, F., Characterization ofpolymer-coated glass as a passive air samplerfor persistent organic pollutants. Environ.Sci. & Technol. 37, pp. 2486-2493, 2003.

6. Shahir, U. M., Li, Y. H. & Holsen, T. M., Drydeposition of gas-phase polycyclic aromatichydrocarbons to greased surrogate surfaces.Aerosol Sci. Technol. 31, pp. 446-455, 1999.

7. Jaward, F. M., Farrar, N. J., Harner, T.,Sweetman, A. J. & Jones, K. C., Passive airsampling of polycyclic aromatic hydrocarbonsand polychlorinated naphthalenes acrossEurope. Environ. Toxicol. Chem. 23, pp. 1355-1364, 2004.

8. Harner, T., Shoeib, M., Diamond, M., Stern,G. & Rosenberg, B., Using passive airsamplers to assess urban - Rural trends forpersistent organic pollutants. 1.Polychlorinated biphenyls and organochlorinepesticides. Environ. Sci. & Technol. 38, pp.4474-4483, 2004.

9. Klanova, J., Kohoutek, J., Hamplova, L.,Urbanova, P. & Holoubek, I., Passive airsampler as a tool for long-term air pollutionmonitoring: Part 1. Performance assessmentfor seasonal and spatial variations. Environ.Pollut. 144, pp. 393-405, 2006.

10. Cupr, P., Klanova, J., Bartos, T., Flegrova, Z.,Kohoutek, J. & Holoubek, I., Passive airsampler as a tool for long-term air pollutionmonitoring: Part 2. Air genotoxic potencyscreening assessment. Environ. Pollut. 144,pp. 406-413, 2006.

11. Klánová, J., Čupr P., Holoubek, I.,Borůvková, J., Přibylová, P., Kareš, R.,Kohoutek, J., Dvorská, A. & Komprda, J.,Towards the Global Monitoring of POPs.Contribution of the MONET Networks.RECETOX MU Brno. RECETOX-TOCOEN REPORTS No. 357. 2009;ISBN 978-80-210-4853-9; MASARYKUNIVERSITY 2009.

12. Jaward, F. M., Farrar, N. J., Harner, T.,Sweetman, A. J. & Jones, K. C., Passive air

sampling of PCBs, PBDEs, andorganochlorine pesticides across Europe.Environ. Sci. & Technol. 38, pp. 34-41, 2004.

13. Klánová, J., Čupr, P., Kohoutek, J. & Harner,T., Assessing meteorological parameters onthe performance of PUF disks passive airsamplers for POPs. Environ. Sci. Technol. 42(2), pp. 550-555, 2008.

14. Klánová, J., Čupr P., Kohoutek, J.,Holoubek, I.: Application of Passive Samplerfor Monitoring of POPs in Ambient Air. PartI: Model monitoring network in the CzechRepublic (MONET-CZ), 2006. RECETOXMU Brno. RECETOX-TOCOEN REPORTSNo. 318. August 2007.

15. Klanova, J., Cupr, P., Borůvková, J.,Kohoutek, J., Kareš, R., Přibylová, P.,Prokeš, R., Holoubek, I.: Application ofpassive sampler for monitoring of POPs inambient air. IV. Model monitoring networkin the Czech Republic (MONET-CZ 2007),2008. Masaryk Univerzity, Brno, CzechRepublic. ISBN 978-80-210-4696-2

16. Klánová, J., Kohoutek, J., Kostrhounová, R.& Holoubek, I., Are the residents of formerYugoslavia still exposed to elevated PCBlevels due to the Balkan wars? Part 1: Airsampling in Croatia, Serbia, Bosnia &Hercegovina. Environ. Int. 33 (6), pp. 719-726, 2007.

17. Klánová, J., Kohoutek, J., Čupr, P. &Holoubek, I. Are the residents of formerYugoslavia still exposed to elevated PCBlevels due to the Balkan wars? Part 2:Passive air sampling network. Environ. Int.33 (6), pp. 727-735, 2007.

18. Klánová, J., Čupr P., Holoubek, I.:Application of Passive Sampler forMonitoring of POPs in Ambient Air. Part II:Pilot study for development of themonitoring network in the Central andEastern Europe (MONET_CEEC), 2006.RECETOX MU Brno. RECETOX-TOCOEN REPORTS No. 319. August 2007.

19. Klanova, J., Cupr, P., Holoubek, I.,Borůvková, J., Přibylová, P., Kareš, R.,Kohoutek, J.: Application of passive samplerfor monitoring of POPs in ambient air. V.Pilot study for development of the



monitoring network in the Central andEastern Europe (MONET-CEEC 2007),2008. Masarykova Univerzita, Brno, CzechRepublic. ISBN 978-80-210-4697-9

20. Klanova, J., Cupr, P., Holoubek, I.,Borůvková, J., Přibylová, P., Kareš, R.,Kohoutek, J., Dvorská, A., Tomšej, T.,Ocelka, T.: Application of passive samplerfor monitoring of POPs in ambient air. VI.Pilot study for development of themonitoring network in the African continent(MONET-AFRICA 2008), 2008.Masarykova Univerzita, Brno, CzechRepublic, ISBN 978-80-210-4739-6

21. Klánová J., Čupr, P., Holoubek, I.,Borůvková, J., Kareš, R., Tomšej, T. &Ocelka, T., Monitoring of persistent organicpollutants in Africa. Part 1: Passive airsampling across the continent in 2008. J.Environ. Monit., 11, pp. 1952–1963, 2009.

22. Lammel, G., Dobrovolný, P., Dvorská, A.,

Chromá, K., Brázdil, R., Holoubek, I. &Hošek, J., Monitoring of persistent organicpollutants in Africa. Part 2: Design of anetwork to monitor the continental andintercontinental background. J. Environ.Monit., 11, pp. 1964–1972, 2009.

23. Klanova, J., Čupr P., Holoubek, I.:Application of passive sampler fordetermination of the POPs concentrations inambient air. Part III: Pilot study in theSouthern Pacific, Fiji, 2006. RECETOX MUBrno, RECETOX-TOCOEN REPORTS No.320. August 2007.

MONITORING OF RESIDUES OF PERSISTENT ORGANOCHLORINEPESTICIDES IN SOILS OF UZBEKISTANBakhriddin NishonovHydrometeorological Research Institute, Tashkent, Uzbekistan


AbstractLarge amount of pesticides were used inagriculture of Uzbekistan in the past. At present,toxic and persistent pesticides are prohibited touse in Uzbekistan. Persistent pesticides such asDDT and HCHs can be preserved in soil for along time and can be a source of surface- andground water contamination. Therefore,monitoring of these pesticides in soils ofagricultural areas is one of the tasks of statemonitoring program of Uzbekistan. In this paperthe results of pesticides monitoring in soils ofagricultural areas in Uzbekistan during 2005-2010 are presented. Results show the decreasimgtrend of pesticides concentrations in soil ofUzbekistan. For the period of observations, HCHisomers, DDT and its metabolites weredetermined in soil mostly in amounts less thantheir maximal admissible concentrations.

Key words: Organochlorine pesticides, residue,soil, contamination, monitoring

Introduction Modern agricultural production depends on theuse of pesticides. Pesticides used to controlplants, fungi and animals can be harmful tohumans and useful to plants. The widespread useof pesticides in agriculture increased the publicconcern due to the presence of their residues inthe environment and food. Organochlorinepesticides (OCPs) such as DDT and Lindane (γ-HCH) are known as persistent and it is requiredto control and monitor their residues in theenvironment (air, water, soil and biota) and foodaccording to the international and national rules.In 1960-1990, pesticides were used in Uzbekistanin large amounts for increasing cotton yield [1].This was the cause of environmentalcontamination by pesticides in the country.Though the application of these pesticides inUzbekistan was banned (DDT since 1983 andLindane since 1991), their residues are observedin soil until present time due to their high

persistency [2]. Control of OCPs in soil nearformer agricultural aerodromes, warehouses andburial sites is being carried out by StateCommittee of Nature Protection. Systematicmonitoring of these pesticides in soil ofagricultural areas in all provinces of Uzbekistanis carried out by Center of HydrometeorologicalService of Uzbekistan (Uzhydromet). Assessmentof soil contamination by persistent pesticidesresidues is the actual task and in this paper theresults of pesticides monitoring in soils inUzbekistan for 2005-2010 have been analyzed.

Sampling Monitoring sites of Uzhydromet are located inthe 107 districts of all provinces of Uzbekistanrepresenting arable soil (under cotton, wheat, andrice), vineyards, horticulture. Soil samples fromthese sites are collected every year (in spring andin autumn) to analyze residues of persistentpesticides [3].

MethodsThe methodology used for analysis of pesticideresidues in soils was in accordance with thestandard procedures used by Uzhydromet [4,5].Organochlorine pesticides were analyzed by gaschromatography with electron capture detector(ECD) [4,5]. The analytical procedure for soil samples is asfollows: drying until air-dried condition at 20oC;extraction of pesticides with n-hexane + acetone;sample cleanup, using concentrated sulfuric acidfor elimination of organic substances; drying ofextract with sodium sulphate; reconcentration ofthe extract; and injection of the extract into thechromatograph. Maximum admissible concentration (MAC) ofpesticides in soil for HCH isomers and for DDTand its metabolites is 0.1 mg/kg [6].

Results and DiscussionThe wide use of pesticides results in theirdistribution as most hazardous contaminants in

Table 1. Frequency of detection and exceeding of MAC of pesticides residues in soils

detected pesticides was 33.21% and 35.63% forα-HCH, and 18.66% and 19.05% for γ-HCH in2005 and 2010, respectively. Concentrations ofα-HCH were between BD-0.0065 and BD-0.0231 mg/kg, γ-HCH BD-0.0082 mg/kg andBD-0.0089 mg/kg, respectively. Observed

maximum concentration of HCHs in soil was 10time lower than their MACs. Meanconcentrations were 0.0005 mg/kg and 0.0012mg/kg for α-HCH and 0.0002 mg/kg and 0.0001mg/kg for γ-HCH, respectively.

Table 2. Pesticides residues in soils of Uzbekistan

Bakhriddin Nishonov


the environment. Under the influence of variousfactors pesticides are transformed and migratefrom soil to other components of theenvironment. In Uzbekistan contamination of the environment(air, soil, surface water) by pesticides was a veryactual problem in 1960-1990 because of its largeuse to increase cotton yield [1]. Although thepesticides use has decreased in Uzbekistan forthe last 15-20 years, the problem of theenvironmental contamination by pesticidescontinue to be actual because of at present newpesticides are used in agriculture [2,7].Uzbekistan State Register of Chemical andbiological plant protection reagents includesmore than 180 substances (i.e. pesticides and

others) allowed for using in agriculture [7]. The persistent organochlorine pesticides (POPs)can be accumulated in food chain until hazardouslevels even if their amounts in soil are very small. Pesticides residues have been monitored in soilsof all provinces of Uzbekistan. According to soilmonitoring data, the detection frequency forDDT and associated metabolites in 2005 and2010 were 92.54% and 90.80% of samples,respectively (Table 1). Concentrations of sum ofDDT in soil were between below of detectionlimit (BD) to 0.498 mg/kg and to 1.47 mg/kg,mean concentrations were 0.072 mg/kg and0.054 mg/kg (Table 2), the exceeding of MACwere for 22.39% and 13.79% samples,respectively. The frequency of samples with

Spatial and temporal trends in residues of DDTand HCH isomers in soils of agricultural areas in

different provinces of Uzbekistan are shown inFig.1-4.

Figure 1. OCPs residues in soils of Uzbekistan (2005, 2010)

Figure 2. Sum of DDT and its metabolites in soils of Uzbekistan (2005, 2008, 2010)

Figure 3. α-HCH residues in soils of Uzbekistan(2005, 2008, 2010)

Figure 4. γ-HCH (Lindane) residues in soils ofUzbekistan (2005, 2008, 2010)

MONITORING OF RESIDUES OF PERSISTENT ORGANOCHLORINE PESTICIDES IN SOILS OFUZBEKISTAN


1. Environmental protection and naturalresources use. Report of State Committee ofNature Protection of Uzbekistan. Tashkent,“Ukituvchi”. 1993. 90 p.

2. Monitoring and assessment of state of theenvironment. Report on environmental stateand natural resources use in the Republic ofUzbekistan in 2007-2009. State Committeeof Nature Protection of Uzbekistan. Tashkent.2010. 104 p.

3. Soil quality monitoring year-books in theactivity territory of Uzhydromet for 2005-2010. Tashkent. Uzhydromet. 2006. 2007.2008. 2009. 2010 2011.

4. Temporal methodical recommendations forcontrol of soil contamination. Eds.S.G.Malakhov. Part I. Moscow.Gidrometeoizdat. 1983.128p.

5. Unified methods of monitoring forbackground pollution of the naturalenvironment. Eds.F.Ya.Rovinskiy. Moscow.Gidrometeoizdat. 1986.182p.

6. Bespamyatnov G.P, Krotov Yu.A. MAC ofchemical substances in the environment.Moscow. Chemistry. 1985. 528 p.

7. Register of Chemical and Biological PlantProtection Reagents, allowed to use inUzbekistan. Tashkent. 2007. 215 p.

References

Bakhriddin Nishonov


The results of monitoring data for 2005-2010show that the concentration of HCH isomers insoils is much lower than the maximum allowableconcentration. Concentration higher than MACis observed for DDT and associated metabolites.Soil contamination by sum of DDT in local levelis observed in Andijan, Fergana and Khorezmprovinces of Uzbekistan.

Conclusion The findings of the monitoring data allow toconclude that the concentration oforganochlorine pesticides in soil did not decreasesignificantly during last years [2,3]. Highamounts of pesticides residue are observed insoils near former agricultural aerodromes,warehouses and burial sites, according to StateCommittee of Nature Protection data [2].

GENASIS: SYSTEM FOR THE ASSESSMENT OF ENVIRONMENTALCONTAMINATION BY PERSISTENT ORGANIC POLLUTANTSIvan Holoubek1, Ladislav Dušek1,2, Jana Klánová1, Miroslav Kubásek2, Jiří Jarkovský2,Roman Baroš1, Klára Kubošová1, Zdeňka Bednářová1, Richard Hůlek2, Jiří Hřebíček2

1 Masaryk University, RECETOX, Brno, Czech Republic2 Masaryk University, IBA MU, Brno, Czech Republic


AbstractThe current environmental monitoring andresearch activities produce large quantities ofdata on all environmental matrices and a numberof chemical and biological endpoints. Productionof a considerable amount of data has beencurrently typical for all fields of human activitiesand concerns environmental research andmonitoring. Thousands of projects have been inprogress on the national and international level,which generate data that must be administered,processed, analyzed, and interpreted. However,there is a paradox in this situation that we sufferfrom the lack of representative data, since theirproduction has not been accordingly supportedby development of systems that make themaccessible for analysis; we currently face the“Data rich but information poor” problem whenbased on these quantities of data only small partof information is utilized for interpretation ordecision support. The proposed GENASIS system aims in itscurrent version on the problem of persistentorganic pollutants and the analysis, visualizationand interpretation of data from their monitoringnetworks. The project exists within the frame ofthe Stockholm Convention tools and itsobjectives are availability of a user-friendlysystem for the visualization and analysis ofcontamination of all environmentalcompartments by persistent organic pollutantsand evaluation of actual POPs contamination, itslong-term trends and seasonal fluctuations. TheGENASIS project utilizes data from national andinternational monitoring networks to obtain as-complete-as-possible set of information and arepresentative picture of the environmentalcontamination by POPs. Project outcomes shouldbe useful as an information source both for laypublic and experts, as well as for the process ofthe Stockholm Convention implementation.

Key words: Persistent organic pollutants; expertsystém, evaluation of environmental data

Introduction - Stockholm Convention andgoals of GENASIS project The Stockholm Convention on PersistentOrganic Pollutants (POPs) was adopted in May2001 with the objective of protecting humanhealth and the environment from persistentorganic pollutants. Parties to the StockholmConvention are required to develop NationalImplementation Plans (NIPs) to demonstrate howthe obligations of the Convention will beimplemented. Taking into account thecircumstances and particular requirements ofdeveloping countries, in particular the leastdeveloped among them, and countries witheconomies in transition, especially the need tostrengthen their national capabilities for themanagement of chemicals and wastes, includingthrough the transfer of technology, the provisionof financial and technical assistance and thepromotion of cooperation among the Parties [2].Stockholm Convention and its articles representsa legal base for the development of global andnational monitoring programmes and tools foreffective evaluation of the Convention measures.However, we still face the problem with lack ofrepresentative data, accessible for analyses,because their production has not beenaccordingly supported by the development ofsystems that make them accessible for analysis[3,4]. Information and expert system GENASISrepresents an example of contribution to thistopic.

System is targeted for managers andenvironmental scientists working in the field ofPOPs investigation at all possible levels of thisproblem (sources, fate, levels, distribution,human exposure, toxicology and ecotoxicology,human and ecological risk assessment). Primary

Table 1. GENASIS input data

Ivan Holoubek, Ladislav Dušek, Jana Klánová, Miroslav Kubásek, Jiří Jarkovský, Roman Baroš,Klára Kubošová, Zdeňka Bednářová, Richard Hůlek, Jiří Hřebíček


goal of the project is to develop multilayerinformation system for management ofenvironmental data with special attention toPOPs. As a calibration datasets, the system workswith accessible sources from the CzechRepublic; potentially later from other countriesof the Convention. The project aims to serve asscientific, contract-based repository of dataprovided by participating partners, based onexhaustive audit of data available from theNational POPs Inventories, NationalImplementation Plans and other national sourcesof relevant information.Principal aim of these activities is thedevelopment of a sophisticated interactive tool,which will offer a sufficiently effective systemallowing to search for connections andcausations among problems of the environment,public health status, and other fields of humanactivities [5].

GENASIS in development: primary data usedas calibration and training datasetsThe GENASIS system is built as a modularstructure providing complex services to a wide

range of potential users. The initial version of thedatabase launched in 2010 contains data from thelong-term integrated monitoring of persistentorganic pollutants at the Košetice observatorywhich is a part of the European Monitoring andEvaluation Programme (EMEP) [6-8], and long-term data from the ambient air MOnitoringNETworks (MONET) in the Czech Republic,Central and Eastern Europe, Africa, Central Asiaand Pacific Islands [9-14]. Furthermore, the data from the large-scalemonitoring of soil, sediment, and surface water[7,13] have been recently included in a newversion the GENASIS system, which is currentlylaunched (see Table 1). Enhanced analytical toolsallowing implementation of algorithms forspatial analyses, and modules enablingcomparative analyses of multiple substances ormatrices will be also introduced [15,16]. Basedon the contract signed between RECETOX andthe Czech Ministry of Environment, an import ofdata from external sources will also be initiatedin 2011. Compatibility of the GENASIS systemwith existing databases is crucial in order toassess the environmental patterns, calibrate the

The system architecture (Figure 1) encapsulatesall steps involved in data validation, processingand analyzing. It is ensured by robust set ofsoftware components which are interlinked onthe basis of conceptual data model. The mostimportant tools are listed as follows:1. Primary data repository (archive) – import of

data from different sources, safe archiving ofprimary data of participating partners, export ofdata to higher layers of the system

2. GENASIS data warehouse – comprehensiveassembly of databases, extending primarydata in dimensions generated by validationand analyses (transformation functions,aggregation codes, external information,space- and time- related coordinates, etc.)

3. GENASIS GIS module – geographicinformation system supplying functionsdirectly implemented in the data warehousetoolkit

4. GENASIS on-line data browser - on.-lineworking interactive software facilitating dataaccessibility to a wide community of users;both widely open and authorized access to thedatabase content is possible in the system

5. GENASIS on-line reporting – interactivereporting system enabling comprehensivereporting over pre-processed data; reportsdeveloped specifically for some databases (ondemand) are possible as well

6. GENASIS e-learning tools – set of softwaretools supporting interactive educational casestudies or other outcomes with e-basedlearning content (tutorials, methodical guides,e-courses, etc.)

7. GENASIS web portal – comprehensiveumbrella supporting all software tools andfacilitating their accessibility (data browser,reporting system, e-learning functions). Portalserves as a platform for communication ofproject goals, approaches and outcomes.

Combination of many types of data (emissionsand releases inventories, monitoring of abioticmatrices, biomonitoring, total diet studies,

human risk assessment, food chaincontamination) provides an ideal platform forcomplex multivariate description of analyzedsites from retrospective viewpoint, supplied withprospective identification of risks. Multivariatenature of GENASIS data structure supports awide spectrum of descriptive and comparativemultivariate analyses, suitable for mutualcomparison of sites and/or comparison ofexamined sites with reference data. Protocolprocessing of reference data (both from time andspace point of view) includes comparativemodeling and looking for reference-relatedanalogies. Main added value of GENASISarchitecture can be seen in the field of dataprocessing, namely in the following aspects:

▪ Hierarchical structure of systemcomponents advances the data analysis.The conceptual model intrinsicallydistinguishes hierarchy of data descriptorswhich facilitates implementation of toolsfocused on data analysis and knowledgemining. Using the hierarchy of descriptors,data and meta data repositories, we caneasily decide whether the data are useful fora particular analysis.

▪ GENASIS supports robust referencecomparison of values. Regarding dataanalysis, very important attribute of theproposed system is incorporation ofmeasurement level and its characteristics.Validity criteria reflect some precisionmeasures as well as reference values orprotocol standards. A measured valuecannot be interpreted and analyzed withoutreference to a defined measurementstandard.

▪ Stratified analyses and integration ofdifferent data sources. The multilayerinformation system supports processing ofenvironmental data from various sources,followed by subsequent validation,advanced analyses and spatial presentationsupported by the geographic information

Architecture and functionality of the GENASIS system

GENASIS: SYSTEM FOR THE ASSESSMENT OF ENVIRONMENTAL CONTAMINATION BYPERSISTENT ORGANIC POLLUTANTS


indicator systems, and implement the legislationrequirements. A fully developed system will

serve as an interactive, on-line working, nationalPOPs inventory of the Czech Republic.

systems (GIS). Hierarchical relationshipsbetween primary data repository and datawarehouse potentiates automated SW toolsand functions.

The functionality of the GENASIS system isoptimized for the fields of environmental riskassessment, scientific analyses of environmentaldata, and as expert information service formanagers and institutions on the national, regionaland global levels. It provides user friendlyanalyses for both expert and non-expert users. Inaddition to it, targeted presentations of data couldbe produced automatically on request.

Figure 1. GENASIS system architecture

Figure 2. Entry page ofthe GENASIS system

Users interfaceWeb interface follows current standards. The example is shown in Figure 2.

ConclusionsThe presented system GENASIS (The GlobalENvironmental ASsessment and InformationSystem) represents a case of the new generationof software for the visualization and analysis ofdifferent data levels. An advantage of the systemis a possibility of combination of data fromdifferent sources based on a universal data modelthat may be filled from any database. The systemwill also be applicable in the risk situationsmanagement due to automatic mode of dataprocessing. System expert tools enable use ofexternal information sources and knowledgeincluding panel of experts’ entry within thesolution of specific problems. Different levels of

information service will be ensured by modernweb technology. Modern GIS methods will beapplied to the project solution using technologyof shared map servers. The actual version of thesystem GENASIS is available on the website [1].Any comments are welcomed.

AcknowledgementsThis paper was/is supported by the CETOCOENproject (CZ.1.05/2.1.00/01.0001) of theEuropean Structural Funds, the INCHEMBIOLproject (MSM 0021622412) of the Ministry ofEducation of the Czech Republic and theMinistry of Environment of the Czech Republic(SP/1b1/30/07).

Ivan Holoubek, Ladislav Dušek, Jana Klánová, Miroslav Kubásek, Jiří Jarkovský, Roman Baroš,Klára Kubošová, Zdeňka Bednářová, Richard Hůlek, Jiří Hřebíček


1. GENASIS system, www.genasis.cz,RECETOX, Masaryk University, CzechRepublic.

2. UNEP Stockholm Convention on PersistentOrganic Pollutants. Stockholm Convention onPersistent Organic Pollutants 2001, decisions,information documents, http://www.pops.int

3. Luis, G.B. (2006): Principles for evaluatinghealth risks in children associated withexposure to chemicals. Environmental healthcriteria 237, WHO Library Cataloguing-in-Publication Data. World Health Organization2006.

4. JRC ISPRA (2007): 2nd edition of theTechnical Guidance Document (TGD) onRisk Assessment of Chemical Substancesfollowing European Regulations andDirectives.

5. Holoubek, I. (2004): Monitoring, modellingand information system for persistent organicpollutants. In: Prastacos, P., Cortés, U., de Leon,J. L. D., Murillo, M. (Eds.): e-Environment:Progress and Challenges. Research onComputing Science. Vol. 11, 117-134, IPNCIC Mexico.

6. Holoubek, I., Klánová, J., Jarkovský, J. &Kohoutek, J., Trends in background levels ofpersistent organic pollutants at Koseticeobservatory, Czech Republic. Part I. Ambientair and wet deposition 1988-2005. J. Environ.Monitor. 9 (6), pp. 557 – 563, 2007.

7. Holoubek, I., Klánová, J., Jarkovský, J.,Kubík, V. & Helešic, J., Trends inbackground levels of persistent organicpollutants at Kosetice observatory, CzechRepublic. Part II. Aquatic and terrestricenvironments 1988-2005. J. Environ.Monitor. 9 (6), pp. 564 – 571, 2007.

8. Dvorska, A., Lammel, G., Klanova, J. &Holoubek, I., Košetice, Czech Republic – tenyears of air pollution monitoring and fouryears of evaluating the origin of persistentorganic pollutants. Environ. Pollut. 156 (2),pp. 403-408, 2008

9. Klánová, J., Kohoutek, J., Hamplová, L.,Urbanová, P. & Holoubek I., Passive airsampler as a tool for long-term air pollutionmonitoring: Part 1. Performance assessment

for seasonal and spatial variations. Environ.Pollut. 144 (2), pp. 393-405, 2006.

10. Čupr, P., Klánová, J., Bartoš, T., Flégrová, Z.,Kohoutek, J. & Holoubek, I.: Passive airsampler as a tool for long-term air pollutionmonitoring: Part 2. Air genotoxic potencyscreening assessment. Environ. Pollut. 144(2), pp. 406-413, 2006.

11. Klánová, J., Čupr, P., Holoubek, I.,Borůvková, J., Kareš, R., Tomšej, T. &Ocelka, T., Monitoring of persistent organicpollutants in Africa. Part 1: Passive airsampling across the continent in 2008. J.Environ. Monit. 11, pp. 1952-1963, 2009.

12. Klánová, J., Čupr, P., Kohoutek, J. & Harner,T., Assessing meteorological parameters onthe performance of PUF disks passive airsamplers for POPs. Environ. Sci. Technol. 42(2), pp. 550-555, 2008.

13. Růžičková, P., Klánová, J., Čupr, P., Lammel,G. & Holoubek, I., An assessment of air-soilexchange of polychlorinated biphenyls andorganochlorine pesticides across Central andSouthern Europe. Environ. Sci. Technol. 42 (1),pp. 179-85, 2008.

14. Klánová, J., Čupr, P., Holoubek, I.,Borůvková, J., Přibylová, P., Kareš, R.,Kohoutek, J., Dvorská, A., Komprda, J.(2009): Towards the Global Monitoring ofPOPs - Contribution of the MONETNetworks. RECETOX, Masaryk University,Brno, Czech Republic.

15. Komprda, J., Kubošová, K., Dvorská, A.,Scheringer, M., Klánová, J. & Holoubek, I.,Application of an unsteady stateenvironmental distribution model to adecadal time series of PAH concentrations inthe Central Europe. J. Environ. Monit., 11,pp. 269–276, 2009.

16. Kubošová, K., Komprda, J., Jarkovský, J.,Sáňka, M., Hájek, O., Dušek, L., Holoubek, I.& Klánová, J., Spatially resolved distributionmodels of POP concentrations in soil: Astochastic approach using regression trees.Environ. Sci. Technol. 43, pp. 9230-9236,2009.

References

GENASIS: SYSTEM FOR THE ASSESSMENT OF ENVIRONMENTAL CONTAMINATION BYPERSISTENT ORGANIC POLLUTANTS


TOOLS FOR THE ASSESSMENT OF PESTICIDE SITES

POPS SITE ASSESSMENT WITH THE SWIFT SITE ASSESSOR, ANEW COMPUTER AIDED TOOL FOR SITE ASSESSMENT ANDMANAGEMENTFokke B.F.1 Lud D.2, PoIjegort, J.3

1 Tauw bv, Deventer, The Netherlands 2 Tauw GmbH, Regensburg, Germany3 Tauw bv, Amsterdam, The Netherlands

SESSION 6.


Due to the severe environmental impact of manyPOPs sites in the EECCA region, there is a needfor cost effective, sustainable solutions for POPssite assessment and management. This requiresa thorough understanding of the risks andsuitable remediation technologies. TAUWproposes use a new computer aided tool to set upa site specific conceptual site model (CSM) tofacilitate site assessment and management. ACSM visualizes available information about asite in a schematic structure and makes it easierto assess a site with a very limited amount of sitespecific information. This new computer aidedtool for site assessment, the swift site assessor,SSA, enables the users to actively set up theCSM of a specific POPs site. Cyclic refinementof the CSM can be done very easily after a shorttraining period. Thereby the computer aided toolsupports the involvement of local stakeholders.Gaps of information can be identified with aCSM; special elements of the swift site assessorsuch as automatic signals can support thisprocess. In an iterative process, informationgathered in subsequent refinement steps can beintegrated easily in the CSM. If used in theframework of an integrated approach for POPssites as proposed by TAUW, a CSM set up withthe swift site assessor can be a valuable tool for

better risk assessment, risk mitigation andsustainable management of POPs sites.

Key words:Computer aided assessment tool,Conceptual site model CSM, swift site assessorSSA, POPs site, risk assessment, site management,stakeholder participation, training

Introduction

In many of the EECCA countries POPs sites havesevere environmental impact. Therefore there isa need for cost effective, sustainable solutions forPOPs site assessment and management. Thisrequires a thorough understanding of the risksand suitable remediation technologies. TAUWproposes the use a new computer aided tool toset up a site -specific conceptual site model(CSM) to facilitate the site assessment andmanagement. A CSM visualizes availableinformation about a site in a schematic structure,it clarifies links between the source and thereceptor (e.g. contaminated soil and grazingcattle). This makes it easier to understand whatcauses unacceptable risks and where actions needto be taken to reduce risks to an acceptable level.An example of a simple conceptual site model isgiven in Figure 1.

Figure 1. Example of a conceptual site model of a POPs site with source (contaminated soil &pesticide), exposure pathways (e.g. direct contact), transport/contaminant migration (e.g. run offto surface water) and receptors (cattle, humans) and gaps of knowledge depicted with question

marks. Graph and photographs: Tauw.

POPS SITE ASSESSMENT WITH THE SWIFT SITE ASSESSOR, A NEW COMPUTER AIDED TOOLFOR SITE ASSESSMENT AND MANAGEMENT


New computer aided tool: Swift site assessorSSA

The new computer aided tool swift site assessor,SSA, can be used to set up a conceptual sitemodel in a simple, standardized way. The SSA isintended to support the assessment of a site evenwith a very limited amount of site specificinformation (e.g. if analytical data on soil orgroundwater quality are lacking), this is achievedin a stepwise approach, which allows a first riskpre-screening during site walkover. It enablesthe users to actively set up the conceptual sitemodel of a specific POPs site after a short periodof training. As the swift site assessor is acomputer aided tool, cyclic refinement of theCSM can be done very easily after a shorttraining period. The pre-screening can be refinedin subsequent steps in a stepwise approach, ifmore site information is gathered. Thereby thecomputer aided tool stimulates a process oflearning and understanding. The swift siteassessor has advantages for knowledge transferand improves current practice of siteinvestigation and site management. It also

supports the involvement of local stakeholders.Even though computer based new learningtechnologies are only technologies and as suchdo not guarantee better knowledge transfer andstakeholder participation, TAUW feels that usingnew technologies has an added value for POPsprojects. Visualisation can be facilitated by thecomputer aided tool. The CSM promotes detailedunderstanding of site characteristics and criticalcontaminant-receptor linkages, such ascontamination of topsoil and agricultural use oftopsoil (e.g. cattle grazing on POPs sites withcontaminated topsoil). The computer aided toolfurther promotes the understanding of requiredmeasures for risk reduction (e.g. topsoilremediation or change of land-use) and can becombined with other tools for site assessmentsuch as PSMS, the POPs toolkit or the UNIDOcontaminated site investigation and managementtoolkit.

The position of the new SSA tool in the overallprocess of site investigation, site assessment andsite management is given in Figure 2.

Figure 2. Position of the Swift Site Assessor, SSA, in the process of site assessment and sitemanagement

Fokke B.F. Lud D., Pottjegort, J.


Gaps of information can be identified with aCSM; special elements of the swift site assessorsuch as automatic signals can support thisprocess. In an iterative process, informationgathered in subsequent refinement steps can beintegrated easily in the CSM (stepwiserefinement from preliminary CSM to finalCSM). This feedback loop of CSM set up withthe SSA resembles general management cycles,because it comprises elements of conceptionalthinking/defining, checking and redefining.Thereby the SSA can support the overallmanagement process of POPs site management.

Conclusion

If used in the framework of an integratedapproach for POPs sites as proposed by TAUW,a CSM set up with the swift site assessor can bea valuable tool for better risk assessment, riskmitigation and sustainable management of POPssites.

The advantages of the computer aided tool are:(1) an easy visualization of the situation at thePOPs sites (source, path and receptors) also witha limited amount of site specific information, (2)

facilitation of the iterative process of making aconceptual site model, (3) better understandingof potential risks and necessary mitigationmeasures, during whole process of siteassessment and management, (4) simplegathering of specific site information with thecomputer aided tool for trained field workers, (5)possibility to integrate digital information inother tools (e.g. PSMS), (6) simple informationexchange with experts, as information collectedcan be exchanged among collaborating parties(7) facilitation of mitigation and managementmeasures, guidance of site management process(8) the computer aided tool can also be used fortraining purposes.

References

FAO Pesticide Stock Management System.http://psms.fao.org

POPs toolkit. www.popstoolkit.com

UNIDO contaminated site investigation andmanagement toolkit http://www.unido.org/index.php?id=5631

FAO’S PESTICIDE STOCK MANAGEMENT SYSTEM RISKASSESSMENT OF CONTAMINATED SITESRichard Thompson and Russell CobbanUN Food and Agriculture Organisation


FAO has developed the Pesticide StockManagement System as a tool for membercountries to assist them in their management ofpesticides throughout their life-cycle. The tool isbased on a web-based application allied to paperbased forms. The application supports two primefunctions. The first function supports themanagement of the use of pesticides including:registration, import and quality control, and stockmanagement through the distribution chain toend users. The second function supports themanagement of end of life of pesticides inparticular, obsolete pesticides and contaminatedmaterials.

The second function provides tools for thedevelopment and implementation ofsafeguarding and disposal strategies. Thisincludes: the inventory of pesticide materials andthe environmental condition of pesticide stores;comparative risk assessment of stores; and theirprioritization for remediation. The data gatheringforms/questionnaires and comparative riskassessment methodologies are designed to beused by national staff without recourse to

external environmental or pesticide expertise andto provide objective results.

The comparative risk assessment methodology iscurrently based on two risk factors, one for thepesticide materials (Fp) and the other for storeconditions and local environment (Fe). The riskfactors are calculated automatically usinginventory data and the risk questionnaire.

Fp is based on:• toxicity (WHO classification of the

pesticide)• integrity of the container• quantity

Fe is based on:• Condition of the store (integrity of the

building)• Conditions inside the store (storage

management etc)• Environment around the store

(settlements, agriculture, water sources etc)This methodology has proved very effective inallowing national teams to compare the risksbetween stores and to identify which stores

Richard Thompson and Russell Cobban


should be prioritized in any subsequentsafeguarding activities. It also assists in theselection of stores suitable for use as collectioncentres of safeguarded materials prior totransportation to disposal facilities. The detailedmethodology can be found in FAO’s guidancedocument “Environmental Management Tool KitVolume 1 (http://www.fao.org/agriculture/crops/obsolete_pesticides/en/).This algorithm for calculating risk scores workswell for the objective risk assessment andprioritization of above ground pesticide stores bynational teams. However the algorithm does notaddress the risks of contaminated sites or buriedpesticides. As the focus of obsolete pesticidesinitiatives move towards reducing the risks posedby contaminated sites and buried pesticides, FAOis in the process of developing the methodologyto better address these situations. Detailed assessment of a contaminated site isextremely expensive involving the design andimplementation of a sampling plan at variousdepths, chemical analysis, geological survey,mapping, and the development of a conceptualsite model to identify the sources, pathways andreceptors. Many projects have been completedwith only the risk assessments being done andwith no interventions to reduce the risks. It isimportant that projects with limited funds areable to undertake a low cost pre-screening toidentify the priority sites, where the funds can beused to carry out the detailed survey and toundertake risk reduction interventions.

The objective of the enhanced risk assessmentmethodology in PSMS is to allow a nationalteam, with the minimum reliance on expensiveexternal expertise, to undertake this pre-screening. FAO is reviewing existingcontaminated site prioritization methodologies toidentify the most appropriate or those that can beadapted for this purpose. Amongst those beingreviewed are:

• ECOS methodology used in Moldova• Hatfield/WB• TAUW• CCME (as used in UNIDO’s methodology)

The methodology will consider 3 factors –sources, pathways and receptors. Each factor willbe assessed with a standard questionnaire relatedto an algorithm that produces an objective riskscore. The aim of this enhancement is to allowsites with contaminated soil and buried pesticidesto be included in the comparative risk assessmentand their prioritization for detailed investigationand subsequent risk reduction strategies. Outputsfrom the site prioritization tool will be comprisedin a graphical and easy to understand format.

A NEW INTEGRAL APPROACH FOR POPS SITES – HOW TOPRIORITIZE POPS SITESLud D.1, Bouwknegt M.2, Fokke B.F.21 Tauw GmbH, Regensburg, Germany 2 Tauw bv, Deventer, The Netherlands

Figure 1. Infinitive assessment cycle(redrawn after Harmsen, 2011)


AbstractMany POPs sites are sites with severeenvironmental impact and unacceptable risks tothe environment and human health. However, atmany sites, investigation, mitigation measures andmanagement of the sites are delayed or stoppeddue to lack of funding and end up in an infinitiverisk assessment cycle. Based on experience in the EECCA region wepropose a new integral approach forinvestigation, risk assessment, remediation andmanagement of POPs sites. This new integralapproach is centred around the conceptual sitemodel (CSM). The CSM is a schematicrepresentation of available information andrelevant source-exposure pathway-receptorlinkages. Our approach also integrates availabletools for site inventory, investigation and riskassessment Costly analyses can be reduced to aminimum. The completed site assessment resultsin appropriate mitigation and managementmeasures (repackaging, cleaning pits, hot spotremoval, remediation). The new integral approach helps to (further)improve repackaging and site clean-up, supportssite management and makes investigation morecost-efficient.

Key words:Conceptual site model, POPs toolkit, PSMS, riskassessment, site management, swift site assessor,Tegsis soil data management system, UNIDOContaminated Site Investigation andManagement Toolkit

IntroductionFor POPs sites in the EECCA region there isusually little site specific information availablefor a detailed risk assessment of POPs sites, oftenanalytical data on soil and groundwater

quality are lacking. Awareness of theenvironmental and human health risks of POPsis either lacking and or financial resources forinvestigation or safeguarding measures arelimited. The collapse of national structures haslead to severe deterioration or reuse of manyformer pesticides storage sites. Currentlynumerous POPs sites represent unacceptablerisks to human health and the environment. Forsome of the sites in region, acute poisoning ofhumans and animals has been reported.However, at many sites, investigation, mitigationmeasures and management of the sites aredelayed or stopped due to lack of funding. Delayslead to an infinitive risk assessment cycle(Figure 1), which is difficult to break.

Lud D., Bouwknegt M., Fokke B.F.


Based on our experience with investigation andassessment of POPs sites in the EECCA regionwe propose a new integral approach forinvestigation, risk assessment, remediation andmanagement of POPs sites.

New integral approach

This new integral approach is based on theconceptual site model (CSM). The CSM is aschematic representation of available siteinformation and is a basic element of the siteinvestigation process; see for example ASTMstandard E1689-95 (2008) or Keijzer et al.(2010). The CSM contains information onrelevant sources and linkages between sourcesand receptors (exposure pathway-receptorlinkages). The CSM is a tool to clarify whichactions need to be taken to reduce risks to anacceptable level and to manage the site.

There are different tools available for theassessment of contaminated sites designed fordifferent purposes. The FAO tool PSMS(pesticide stock management system, seereferences PSMS) is intended to record andmonitor pesticide stocks (inventory) and theirusage. PSMS has been developed for stockpilesof pesticides in Africa and has been used in manycountries, also in the EECCA region. A moredetailed tool, the POPs toolkit (see referencesPOPs toolkit) was designed by HatfieldConsultants and the Worldbank for a thoroughassessment of POPs sites in an interactive anditerative process of contaminated siteprioritization and site management. The POPstoolkit has been developed for POPs projects inSE Asia, for which detailed site information isneeded. Another tool is the UNIDOContaminated Site Investigation andManagement Toolkit. The UNIDO Expert Groupon POPs has written this handbook oncontaminated site investigation and management

as part of a regional project in Nigeria andGhana. Our proposed integrated approachcombines these and other tools into a cyclicprocess of site investigation, risk assessment,mitigation and site management.

Based on our experience, there are differentcategories of POPs sites; each category of siteshas certain characteristics, which haveconsequences for the investigation and riskassessment strategy. Some different categories ofPOPs sites identified in the EECCA region are:storage site with pesticides in store, storage sitewith buried pesticides, empty stores(contaminated building material mainly), siteswith hotspots and topsoil contaminationdispersed over large area (e.g. agro-aviationsites).In our approach we suggest to use the knowledgeabout the specific characteristics of thesecategories of sites in order to make the approachmore cost efficient. An overview of the newintegrated approach for POPs sites is given inFigure 2. During the first site walkover apreliminary version of the CSM is set up. Duringthis step, the site is categorized, e.g. as a storewith stocks of pesticide or as a site withpesticides buried in pits. A gap analysis leads toa stepwise refinement of investigation efforts.Depending on the category of sites, further steps(site inventory, complete site assessment and riskmanagement and mitigation measures) arechosen. For a specific site, only thoseinvestigation and assessment steps are takenwhich are necessary for the specific category ofsites. For a site with reclaimable pesticides, aninventory of existing stocks can be made usingPSMS, for sites with pesticides buried in pits, apit survey is needed, etc. This means that, byusing expert knowledge about the categories ofsites, costly analyses and assessment steps can bereduced to a minimum.

Figure 2. New integral approach for POPs sites based on the stepwise refinement of the conceptualsite model integrating different tools for site assessment for different categories of sites

A NEW INTEGRAL APPROACH FOR POPS SITES – HOW TO PRIORITIZE POPS SITES


Pre screening of risks at an early stage can helpto avoid acute poisonings. The gap analysis canhelp to avoid, that the site walkover or siteinventory is finished too early (prior to gatheringthe required information). Information of theCSM can then be used for risk analysis withdifferent tools, e.g. the PSMS environmentalmanagement toolkit, the POPs toolkit or withother exposure models based on a site specificapproach.

The CSM promotes understanding of sitespecific exposure pathways linking source (e.g.pure pesticide or contaminated soil) and receptor(humans or animals), it visualizes site specificrisks and clarifies the need for mitigationmeasures for the specific site.

The completed site assessment results inappropriate mitigation and managementmeasures depending on the category of site.Existing stocks of POPs pesticides can berepacked for appropriate destruction, pits can be

cleaned using suitable techniques, hot spots andcontaminated building material can be removedand soil and groundwater contamination can beaddressed by suitable measures.

ConclusionWith the new integral approach a preliminaryrisk assessment is made at an early stage andrefined stepwise, integrating several tools. Thisstepwise integrated approach has severaladvantages (1) Standardisation of the inventoryand investigation process while still allowing asite specific approach. This helps to (further)improve repackaging and site clean-up. (2)Clarification of the (consequences of) specificlinks between source and receptor and therebysupporting site management. This makes theprocess more transparent for local stakeholders.(3) Cyclic/stepwise completion of CSM, whichallows a site specific refinement of investigationefforts and is more cost-efficient and supportssite management.

References

Lud D., Bouwknegt M., Fokke B.F.


1. ASTM standard E1689-95 (2008) Standardguide for developing conceptual site modelsfor contaminated sites. http://www.astm.org/Standards/E1689.htm

2. FAO Pesticide Stock Management System.http://psms.fao.org

3. Harmsen 2011. www.naturalcap.eu/downloads/pragmatic_approaches_to_tackling_probl_pesticides_african.pdf

4. Keijzer, Pijls & Hartog (2010) Handreikingvoor het opstellen van een conceptueelmodel. SKB project PT8444 (guideline onhow to set up a conceptual site model, inDutch) http://www.soilpedia.nl

5. POPs toolkit. www.popstoolkit.com6. UNIDO contaminated site investigation and

management toolkit http://www.unido.org/index.php?id=5631

PERSISTENT ORGANOCHLORINE PESTICIDES CONTAMINATIONOF THE SURROUNDINGS OF RUDNA GORA. RESULTS FROM2007-2010Urszula Rzeszutko, Stanisław Stobiecki, Tomasz Stobiecki, Kazimierz WaleczekInstitute of Plant Protection – National Research Institute, Sosnicowice Branch, Poland


AbstractThe Rudna Gora landfill contains at least 160POPs. That is the reason why we havesystematically monitored the area since 2007.Within the last 4 years we have been takingsamples of water and sediments from the bottomof the Wawalnica Stream and Przemsza River,located in the basin of the Vistula River flowinginto the Baltic Sea. The results of the analysesindicate presence of large amount of alphahexachlorocyclohexane (α-HCH), betahexachlorocyclohexane (β-HCH), lindane(γ-HCH) and isomers of DDT.

GC/ECD (gas chromatography with electroncapture detection) was used to determinepresence of organochlorine pesticides and for therecent two our years our qualitative results wereconfirmed by means of GC-MS (qaudrupolemass analyzer). The analytical method wasvalidated.

Key words: Rudna Gora landfill, POPs,pesticide determination, gas chromatography,organochlorine pesticides

IntroductionThe „Rudna Gora” landfill contains about 160thousand tons of waste, including 88 thousandtons of hazardous waste left over after productionof plant protection products (includingmanufacturing of HCH) at “Organika Azot”Chemical Plant in Jaworzno. The landfill islocated directly next to the plant, in southernPoland. It was closed just a few years ago. In2007-2010, Institute of Plant Protection -National Research Institute, Sosnicowice Branch(IPP-NRI) conducted observations of the level ofcontaminants present in surface watercoursesaround the area and random testing of wetlandsand trenches around the landfill. The testing was

performed at the Department of PesticideResidue Testing, which adjusted its analyticalmethods to test environmental samples with highconcentrations and versatility of contaminants,which differ from the standard tests of pesticideresidues routinely conducted by theDepartment’s lab.

This paper is a continuation of the presentationon the Rudna Gora landfill at a previous HCHForum [1, 2] and shows the results of trackingcontaminants present in surface watercoursesthat carry pollution from the plant and landfilltoward the Baltic Sea. It also describes themethods used for preparing the samples forchromatographic analysis and conditions forchromatographic determination.

Site descriptionThe location of the landfill is quite peculiar. It islocated on permeable formations, in an areaenvironmentally damaged by mining and aformer sandpit quarry. Such conditions make iteasy for the contaminants to migrate and polluteadjacent surface waters. Most at risk is theWawalnica Stream flowing through the plantpremises which drains into the Przemsza Rivervalley and joins the river about 1.5 km awayfrom the landfill. Przemsza is a tributary of theVistula River, which flows into the Baltic Sea. At the Plant, the Wawolnica stream collects thetreated sewage water released from the Plant’swater treatment facility. The level ofcontaminants in the stream is monitored by thePlant at 6 different locations. Additionally,independent monitoring is performed by theProvincial Inspection of EnvironmentalProtection, supported by IPP-NRI at twolocations: Wawolnica - bridge in Leg above itsestuary into Przemsza and at Przemsza - at the“Jelen” water marker below the Wawolnicaestuary (Fig. 1).

Figure 1. Water sampling locations.

Urszula Rzeszutko, Stanisław Stobiecki, Tomasz Stobiecki, Kazimierz Waleczek


Until 2009, the Wawolnica stream was alsocollecting water coming from the trenchesaround the landfill on the south side. In April2009, the Plant completed a project involvinginstallation of a gate cutting off water flowingfrom the trenches to the Wawolnica stream andredirecting landfill leachates to a retention pondand then to the Plant’s water treatment facility.[3]

Testing methodsPreparation of water samplesA 500 ml analytic sample of water is taken froma larger water sample. After being placed in aseparator, 10 ml of saturated sodium chloridesolution is added to the sample. The mixundergoes double extraction withdichloromethane in the amount of 100 ml andthen 50 ml to isolate the active ingredient presentin the mix. About 5 minutes after shaking, thebottom organic layers go through a filter withahydrous sodium sulfate. The extract is thendried in the presence of sodium sulfate, thenplaced on a rotary evaporator to dry outcompletely. The dry residue is dissolved in 5mlof acetone. Acetone extract is tested for thepresence of chlororganic insecticides.

Preparation of sediment samplesA 20 g sediment sample is dried for 3 days inroom conditions, and then initially shaken for 1hour in the presence of 100 ml acetone, afteradding 1 ml of deionized water. After about 10minutes the extract was decanted. Then, 100 mlof deionized water and 10 ml saturated sodiumchloride solution are added to the filtrate. Themix undergoes double extraction withdichloromethane in the amount of 100 ml andthen 50 ml. About 5 minutes after shaking, thebottom organic layers go through a filter withahydrous sodium sulfate. The extract is thendried in the presence of sodium sulfate andplaced on a rotary evaporator to dry outcompletely. The dry residue is dissolved in 5mlof acetone. Acetone extract is tested for thepresence of chlororganic insecticides. [4]The extracts were analyzed using GC. In orderto obtain a satisfactory separation of activeingredients, capillary column and programmedtemperature increase were used. The results ofGC and column parameters are illustrated below:

Chromatography conditions:Gas chromatograph: Agilent 6890Column: HP-5 (30m x 0,32 mm x 0,25 µm)Detector temperature µECD: 300ºCDispenser temperature: 250ºC

Table 1. List of active substances that were determined, limits of determinability, averagerecovery values obtained for the sediments and water.

ResultsTables 2-5 show the results of tests performed onwater and sediment samples taken from twolocations: the bridge in Leg and Przemsza Riverby the “Jelen” water marker. Water samples fromthese locations were collected until 2007. At thesame time, water and sediment samples were

being collected. Systematic monitoring indicateshigh levels of POPs. Such a high concentration ofactive ingredients made it necessary to dissolvethe samples multiple times as well as look fororganic pollutants (in particular in thesediments).

PERSISTENT ORGANOCHLORINE PESTICIDES CONTAMINATION OF THE SURROUNDINGSOF RUDNA GORA. RESULTS FROM 2007-2010


Temperature program: Tp-100˚C to 180˚C w/increase rate of 5˚C/min, retention time 1 min,from 180˚C to 260˚C, increase rate 10˚C/min,retention time 2 min, from 260˚C to 280˚C,increase rate 20˚C/min, retention time 7 min,Total analysis time: 38 minutes.Injection type: SplitlessAmount of injected sample: 2µlGC/MD was used to confirm the qualitativedeterminations of substances in the extracts ofacetone sediments and water. Following are theparameters of GC analysis.

Gas chromatograph Agilent 7890A with MDCapillary column HP - 5MS UI (30 m × 0,25 mm× 0,25 µm film), Detector temperature: MS: 230˚COven temperature: 70˚C

Total flow rate 34 ml/minDispenser temperature: 250˚CTotal analysis time: 52 minutes.Injection type: SplitlessAmount of injected sample: 1-5µl

Determined substances - detection limits,average recovery valuesThe analytic methods used for the testing wereverified by conducting a thorough methodvalidation. Limits of determination were set andrecovery values were checked. Calibrationcurves for the test substances ranged from 0.01 to1 µg/l for water and from 0.001 to 1 mg/kg forsediments. Table 1 presents a list of activesubstances that were detected, detection limitsand average recovery values obtained for thethree fortification levels (from 0.01 to 5 µg/l forwater and from 0.001 to 5 mg/kg).

bdl – below detection limit



Table 2. Results of water analyses for samples taken from Wawolnica river by the Leg

Table 3. Results of analyses of sediment samples taken from the bottom of Wawolnica by thebridge in Leg

bdl – below detection limitTable 4. Results of analyses of water samples collected from Przemsza river at “Jelen”

watermarker

Table 5. Results of analyses of bottom sediment samples collected from the Przemsza at“Jelen” water marker

Urszula Rzeszutko, Stanisław Stobiecki, Tomasz Stobiecki, Kazimierz Waleczek


SUMMARY

1. Stobiecki S., Silowiecki A., Stobiecki T.,Waleczek K., Sliwinski W., 2007: Disposalof pesticide waste In Poland – current state.Proceedings 9th International HCH andPesticides Forum. Chisnau, Republik ofMoldova: p. 125-128.

2. Stobiecki S., Waleczek K., Stobiecki T.,Stadniczuk M., 2009: The biggest P.O.P.cleanup problem In Poland – „Rudna Gora”industrial landfill for hazardous waste.Proceedings 10th International HCH andPesticides Forum, 2009. Masaryk University,Brno, Czech Republic: p. 72-77.

3. Waleczek K., 2010: Protection of humans,animals and the environment from the

negative effects of plant protection productsalong with the food safety control.Monitoring of storage sites around the placeof storage of plant protection. Institute ofPlant Protection - National ResearchInstitute. Program Wieloletni 2006-2010: p.79-95.

4. Giza I., Sztwiertnia U., Stobiecki T., 2001:Analiza odciekow z terenu modelowegoskładowiska nieprzydatnych srodkowochrony roślin. Wyniki badan 1998-2000.Politechnika Czestochowska.Mikrozanieczyszczenia w srodowiskuczłowieka, p. 127-132.

REFERENCES

PERSISTENT ORGANOCHLORINE PESTICIDES CONTAMINATION OF THE SURROUNDINGSOF RUDNA GORA. RESULTS FROM 2007-2010


Tests of water and bottom sediment samplescollected from the Wawolnica Stream (by thebridge in Leg, above its estuary onto thePrzemsza River and from Przemsza by the“Jelen” water marker, over 2 km below theWawolnica estuary) indicate that contaminantsare constantly being transported this way towardthe Vistula River. The tested samples were foundto contain significant amounts of HCH isomers,in particular α-HCH and γ-HCH isomers. Thesituation has improved somewhat since April2009, when contaminants from the trenches

around the landfill were cut off with a gateinstalled to prevent them from flowing into theWawolnica Stream. It did not resolve theproblem entirely, since the Wawolnica streamcontinues to collect contaminants from thePlant’s landfill as well as sewage released fromthe Plant’s water treatment facility.It is crucial to keep up the research by the samelab and apply consistent testing methods to seehow the situation proceeds over a longer periodof time.

CONCEPTUAL SITE MODEL AS A BASIS FOR THE ASSESSMENTAND REMEDIATION OF BURIAL SITESMarten van der WijkHead of Soil and Environment Department at Witteveen+Bos, Netherlands


AbstractThere have been valuable initiatives to solveproblems with POPs pesticides recently. Lessattention has been paid to the problems of burialsites containing large quantities of POPs pesticides.Problems with the POPs burial sites, however,are very serious. Burial sites cause a more diffuseand wider spreading of contaminants towards theenvironment than stocks.

Vakhsh burial site in Tajikistan is a good examplefrom post-Soviet countries of such a burial site.The site contains large volumes of POPspesticides that were mixed with soil and spreadaround the site, because of the activities of localpeople that dug up the pesticides to sell them atthe market.

The Volgermeerpolder in the Netherlands is acomparable example from Western Europe. TheVolgermeerpolder too contains large volumes ofPOPs pesticides. Both sites actually contain suchlarge volumes of hazardous material that totaldestruction of the chemicals has becomeunaffordable expensive.

Instead of expensive waste destruction Tauw andWitteveen+Bos proposed for both sites to workwith a risk based conceptual site model as thebasis for the assessment and remediation of theburial sites. The risk based remediation solutionis a valuable alternative for rehabilitation of thePOPs and other hazardous waste sites. Thisapproach provides chances for cost effectivesolutions. At both sites no significant pollutionwas detected in the surrounding environment.Direct contact risks can be taken away byremoving hot spots for destruction, or bycovering them with a clean top layer. The riskbased approach does require ongoing monitoringto detect possible pollution early and act ifunexpectedly the levels go up.

Tauw and Witteveen+Bos propose a structuredSite Assessment in 4 steps with a risk basedconceptual site model approach to prepare for

rehabilitation, mitigation, remediation measures.

Both the Volgermeerpolder and Vakhsh haveproven that the site assessment using the conceptof making a preliminary Conceptual Site Modelcan provide the basis for:

- A reliable understanding of the site- A realistic basis for the planning of risk

based and cost effective remediationsolutions.

- A useful tool for site management

Key words: Assessment of POPs pesticidesburial sites

ArticleThere have been valuable initiatives to solve theurgent threats to public health, nature, andenvironment of obsolete stocks of POPspesticides in the last decade. In interesting pilotprojects more and more obsolete stocks of POPspesticides from developing countries have beenrepackaged and removed for destruction inincineration facilities in Europe. Less attentionhas been paid to the pressing problems of burialsites that contain large quantities of obsoletestocks of POPs pesticides. Burial sites cause amore diffuse and wider spreading ofcontaminants towards the environment thanstocks.

The Vakhsh burial site in Tajikistan containsaround 8,000 tonnes of POPs. The POPs aremixed with soil because local people dug up thepesticides to sell them on local markets. As aconsequence the amounts of polluted materialseriously increased up to about 40,000 tonnes,making the total disposal of all this material tooexpensive.

Waste miningThe Vakhsh burial site for instance, situated some120 kilometre south east from the Tajik capitalDushanbe, contains around 8,000 tonnes of POPspesticides (see Fig. 1). Originally the site waswell designed. Under Soviet rule the site was

Figure 1. Vaskhsh burial site

To tackle the problems of burial sites containinglarge quantities of obsolete stocks of POPspesticides the consortium of Tauw,Witteveen+Bos, IHPA and Mileukontaktdeveloped a step-wise approach for the assessmentand management of POPs burial sites. Thisapproach includes the formulation of a ConceptualSite Model. The Conceptual Site Model is avisual or narrative report outlining the hypothesisof a complex pollution situation in a simplifiedway. The Conceptual Site Model is based on asource path receptor analysis to assess the risksof the sites and prioritize necessary remediationmeasures. On the basis of field surveys andinvestigations the contaminated area and its hotspots can be located.

The Volgermeerpolder dump siteThe Volgermeerpolder dump site and the Vakhshburial site will be used to demonstrate theeffective approach of drawing up a ConceptualSite Model. The Volgermeerpolder is an area ofapproximately 105 hectares, which in the twentiethcentury was used as a dump site for largequantities of chemical waste with a total volumeof 6 million cubic meters. For instance 30.000barrels of pesticide production waste weredumped, resulting in one of the most contaminatedareas in Western Europe. The Volgermeerpolder(52°44’ N, 5°15’ E) is located 5 kilometres northof the city of Amsterdam, in a marshy polderwith shallow groundwater, open water and a deeppeaty soil. After a period of planning and designing

CONCEPTUAL SITE MODEL AS A BASIS FOR THE ASSESSMENT AND REMEDIATION OFBURIAL SITES


well managed and strictly guarded. Caused bythe collapse of the Soviet Union, civil war andeconomic crisis, however, no funds remainedavailable to keep the management of Vakhsh inplace. Local people dug up the pesticides fromthe trenches to sell them at the market. As aconsequence the pesticides mixed with soil andthe Tajik government ended up with such largeamounts (about 40,000 tonnes) contaminatedmaterial that repackaging and removal of all thismaterial for destruction would be too expensive.Similar events with waste mining anddegradation of management and maintenancehappened at smaller burial sites in the region likefor instance at Suzak in Kyrgyzstan and atYangiariq in Uzbekistan. Comparable large scaleburial sites also exist in Europe. One example is

the Volgermeerpolder, were 30.000 barrels ofpesticides were dumped. The common characteristics are that a cocktail ofhazardous and non-hazardous waste is dumped,the volumes are large and at the time of dumpingnobody realized that this would have enormousenvironmental consequences. The difference isthat the management in the beginning was poorin Europe whereas in the former SovietRepublics the management was well organized.Nowadays it is vice versa. The difference is alsothat at most sites in Western Europe mitigationmeasures are implemented whereas in the formerSoviet Republics the government has so manyother pressing short term problems to solve thatremediation of the dump sites is low on thepolitical priority list.

On the basis of the Conceptual Site Model it wasconcluded that the environmental conditionswere more or less in a status quo and no majorchanges would occur in the coming decades. TheConceptual Site Model confirmed the decisionnot to make a detailed inventory and siteinvestigation of the landfill body itself, but toapply intensive monitoring of the periphery ofthe landfill body. To save cost on the chemicalanalyses the sum parameter for extractablehalogen compounds (EOX) was used to detectPOPs pesticide migration. Extensiveenvironmental monitoring during theconstruction works confirmed once again thatenvironmental conditions were stable.

Permanent monitoringOn the basis of the Conceptual Site Model it was

also concluded that a risk based remediationsolution was the best alternative for rehabilitationof the site. This approach provides chances forcost effective solutions. Direct contact risks weretaken away through the application of a clean toplayer. The groundwater was the only potentialpath for spreading of the pollution into thesurrounding environment. For that reason, themigration of contaminants in the groundwaterwill be permanently monitored. However, overthe past decades there was practically nocontaminant migration via groundwater due tothe peat layer also underneath the site, which wasblocking the migration of contaminants.

The Volgermeerpolder remediation projectdemonstrates that the Conceptual Site Modelapproach provides chances for low cost site

Table 1. Conceptual Site Model for the Volgermeerpolder (reference 1)

Marten van der Wijk


the remediation of the Volgermeerpolder took 5years and was finished in 2011.

In a limited number of piezometers and sedimentsamples from the landfill body itself a typical setof pollutants was detected (e.g.monochlorbenzene, dioxins, and chlorophenols).The pollutants were mainly related to the dump ofthe pesticide residues and its degradation products.The concentrations in the sediments andgroundwater were in most cases extremely high(up to a total sum of 40,000 µg/l). Given thecoherent pollution profile in the piezometers andspot samples, a preliminary decision was reachednot to make a detailed inventory and investigationin the landfill body itself. The pollution source (i.c.the landfill body) was to a certain extentapproached as a black box, although the results ofthe sampling campaign and some limitedhistorical information were available about the

chemical waste which was dumped.

Peaty soilDespite the large volumes of chemical wastewhich were dumped at the landfill and theobserved contamination of the landfill bodyitself, no significant pollution was detected in thesurrounding environment (the peaty soil, theground- and surface water) during monitoringperiod of more than 30 years. After an in depthanalysis of the source, paths and receptors aConceptual Site Model was drafted. On the basisof this model it was assessed that biodegradationof the pollutants inside the landfill body andnatural attenuation processes in the surroundingpeaty soil were the key determining processesresulting in the prevention of pollution spreadingto the surrounding environment. The finalConceptual Site Model of the Volgermeerpolderis given in table 1.



assessments and cost effective remediation/rehabilitation solutions. However, it has to bementioned that for the synthesis of an appropriateConceptual Site Model the availability of welltrained professionals on areas as (hydro) geology,risk assessment, soil sciences and site assessmentare a prerequisite.

Vakhsh burial siteThe Vakhsh burial provides another examplehow the Conceptual Site Model approach wasused to conduct a low cost site inventory andassessment. After the preliminary assessmentconducted by the project Consortium, a group oflocal professionals was trained in the siteassessment approach to draw up a ConceptualSite Model. The local professionals refined thepreliminary Conceptual Site Model.

Vakhsh is situated in a dendritic valley system.At the lower valleys of this system small streamsare present, which are fed with a system of waterpipes. These streams are directed towards anagricultural area approximately 7.5 kilometresfrom the site. Groundwater is not present in thefirst 100 meters. It is assumed that at the burialsite at least a 60 meter thick layer of loess ispresent. The infiltration rate is low because of thelow annual precipitation.

The burial site is located at the floor of a smallvalley and does receive external surface runoff.At the bottom of the valley the surface runoffleaves the site uncontrolled. At the floor of thevalley 41 sarcophagi were constructed. Startingfrom the seventies of the last century, obsoleteand POPs pesticides were safeguarded in thesesarcophagi. The current situation is presented inFig. 2. In the last decade extensive illegal wastemining has occurred. In some of the trenches, theobsolete and POPs pesticides have been almostcompletely removed for commercial purposes. Inother trenches only part of the obsolete and POPspesticides have been removed by waste miners,mostly young man lacking any personalprotective equipment. In a minority of thetrenches the obsolete and POPs pesticides arestill present.

Cattle drinking water from open pitsThe waste mining activities have resulted in thedeterioration of the concrete sarcophagusconstructions and the damage of originalpackaging material and finally the mixing ofobsolete and POPs pesticides and soil over anextended area of the valley bottom. This hascaused the spread of obsolete and POPspesticides by wind erosion and surface runoff,accelerated by the absence of vegetation cover atthe central part of the burial site.

Within a radius of the first few kilometres aroundthis site there are only a few scattered farmslocated at the lower parts of the valley floors. Thetotal population of this area is most likely limitedto a maximum of a few hundred persons. A smallgroup of farmers and their herds visit the burialsite on a regular basis. It is estimated that at least20,000 thousand heads of cattle are depending onthe area directly surrounding the burial site.Apart from the limited local population living atthe farms around Vakhsh and the illegal wasteminers it is assumed that no significant numbersof trespassers will enter the burial site due to itsisolated position. However, given the lack offences, the absence of vegetation and thepresence of open pits, people and cattle can havedirect contact with the pesticides. Foot prints ofcows and cattle dugs were observed in the openpits and there was evidence that cattle weredrinking from the pits. The remains of a deadcow were observed on the perimeter of the burialsite.

Given the depth of the groundwater and thepresence of water lines in the area it is not likelythat contaminated natural groundwater is used asdrinking water. Wind erosion, surface erosionand run off as well as windblown pesticides (dueto the illegal digging) can cause the penetrationof pollutants into the surrounding environmenton a regional scale. Pollutant can also enter thefood chain by direct contact of the cattle at theburial site and uptake of pollutants in thesurrounding environment. Field observationsprovided only limited evidence for wide spreadand/or intense spreading of pollutants into thesurrounding environment. An overview of the

Table 2. Conceptual Site Model for the Vakhsh burial site (reference 3)

Conceptual Site Model used in the riskassessment is given in table 2.With the Conceptual Site Model drawn up it wasconcluded that the current situation at the Vakhshburial site posed a direct and unacceptable threatto public health and the environment. It wasadvised to implement measures on the short term toreduce the immediate risk, starting with theremoval of hot spots.The preliminary Conceptual Site Model wasverified by laboratory analysis. First, analytical

results of EOX confirmed the presence of heavilycontaminated soil in and near the 41 trenches.The presence of certain pesticides such as DDTwas confirmed with a number of specificanalyses. Furthermore, analytical results on EOXconfirmed the field observations that no wideand/or intense spreading of pollutants into thesurrounding environment exists. Although the laboratory tests were limited to 20samples, the results were coherent with theassessment of the Conceptual Site Model.

Marten van der Wijk


Site Assessment in 4 steps The Conceptual Site Model assessment approachconsist the following steps:1. Site Walkover

• Review of historical and backgroundinformation (e.g. logbooks of burial siteand geological maps) and analysis of aerialphotographs (e.g. Google Earth);

• Preliminary Health and Safety assessmentfor first field visit;

• Visit to the surrounding environment andwalk around at the (safe) perimeters of thesite, to observe the general conditions in thefield;

• Determination of preliminary ConceptualSite Model. Perform a gap analysis toassess the focus of the field investigation;

2. Site inventory• Based on the gap analyses, plan field

visit(s) including limited sampling of thehot spot zones, taking into account allavailable information, data and observationresults;

• Detailed Health and Safety assessment andplanning for visit to the hot spot zones;

• Field visit to hot spot zones for detailedobservations and assessments during initial

visit. Take selected samples during thesecond stage of the visit;

3. Complete site assessment• Evaluation and elaboration of a draft

final Conceptual Site Model. Perform apreliminary risk assessment to completethe first Conceptual Site Model;

• Perform a gap analysis with the focus onremediation/ rehabilitation measures ofthe site;

• Report the final Conceptual Modelincluding the concepts of theremediation/ rehabilitation options.

Site management• Selection of rehabilitation, mitigation,

remediation measures based on riskreduction, environmental merits andcosts

• Implementation of site rehabilitation,mitigation, remediation measures

Steps 1 till 4 can normally be executed within alimited time span. The time needed for the laststep depends on the measures to be implementedthe time and budget available. Apart form the lowcosts for the site assessment the Conceptual SiteAssessment approach also provides fast results.

Figure 2. Map of Vakhsh burial site. All trenches have been numbered and colors are assignedreflecting the state; large scale digging (blue), small scale digging (orange), undisturbed (green)

(reference 3)



1. G.Buijs & H. van der Pal (2011) Remediationof the Volgermeer: history, facts and figureshttp://www.naturalcap.eu/downloads/remediation_of_the_Volgermeerpolder.pdf

2. H. Groot, A. Langenhoff, J. Olie & H. Veld(2011) Peat and Landfills Unravelling themysterious world of peat and contaminantshttp://www.naturalcap.eu/downloads/peat_and_landfills.pdf

3. Tauw Consortium (2009) Interim reportObsolete Pesticides Technical study in theRepublic of Tajikistan http://milieukontakt.net/en/wp-content/ uploads/2009/12/R009-4640777BFF-beb-V01-NL1.pdf

References

Marten van der Wijk


Conclusion and recommendations• The examples of the Volgermeerpolder and

the Vakhsh burial site show that theConceptual Site Model approach providesa basis for low cost and rather fast siteassessments.

• Given the extent and nature of both sites atraditional detailed site survey and fieldinvestigation can only be organized againstenormous costs, in a period of years andonly under the umbrella of a full sizeremediation project.

• At the Volgermeerpolder the ConceptualSite Model assessment results have beenconfirmed with the results of thesuccessive Environmental Monitoring.

• At both sites the EOX sum parameter hasshown to provide reliable results againstlow costs

• Both the Volgermeerpolder and Vakhshhave proven that the site assessment usingthe concept of making a preliminaryConceptual Site Model can provide thebasis for:

- A reliable understanding of the site- A realistic basis for the planning of risk

based and cost effective remediationsolutions.

- A useful tool for site management • Using the above described method for site

assessment of landfill sites, is a valuableaddition to the already existing siteassessment tools like PSMS, Unido Toolkit, and the Hatfield POPs toolkit.

• Although a Conceptual Site Model can bedrafted without any computer model it isrecommended to work with some kind offixed format (e.g. xls evaluation sheet). Inthis way different sites can be compared ina national assessment and the need forremedial actions prioritized on a nationalor regional level.

• Furthermore it is recommended to make aninventory of the obsolete and POPspesticides using PSMS once have beenextracted from a burial site during futureremediation projects, to facilitate thetemporarily safe storage and finally theproper destruction.

HCH CONTAMINATION IN THE SABIÑANIGOS´S ... - IHPA

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