Low POP Content Limit OF PCDD/F in Waste Evaluation of human health risks rEport 6418 • MARCH 2011 Low POP Content Limit OF PCDD/F in Waste Evaluation of human health risks SWEDISH ENVIRONMENTAL PROTECTION AGENCY Orders Phone: + 46 (0)8-505 933 40 Fax: + 46 (0)8-505 933 99 E-mail: [email protected] Address: CM Gruppen AB, Box 110 93, SE-161 11 Bromma, Sweden Internet: www.naturvardsverket.se/publikationer The Swedish Environmental Protection Agency Phone: +46 (0)8-698 10 00 Fax: +46 (0)8-20 29 25 E-mail: [email protected] Address: Naturvårdsverket, SE-106 48 Stockholm, Sweden Internet: www.naturvardsverket.se ISBN 978-91-620-6418-1 ISSN 0282-7298 © Naturvårdsverket 2011 Print: CM Gruppen AB, Bromma 2011 Cover photo: Viktor Sjöblom, Umeå SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Preface This study was initiated by the Swedish Environmental Protection Agency with the aim to investigate whether the suggested 15 ppb (15 000 ng TEQ kg-1) Low POP Content Limit (LPCL) for dioxin in waste is low enough to protect humans from toxicological health risks. The main focus of the study was to identify and quantify risk scenarios where contaminants originating from wastes are transferred from the environment to human food chains. The work consisted of three parts: i) a literature study to collect and analyse existing data and relevant information from the open literature, ii) two field measurement studies at sites where dioxin contaminated waste is produced and managed, and iii) a human health risk assessment including prediction of risks on the basis of the field data obtained Participants in the project were Annika Åberg (Umeå University), Karin Wiberg (Umeå University), and Annika Hanberg (Karolinska Institutet). This report is a first approach to investigate human health risks associated to PCDD/Fs and dl-PCBs in waste and waste management practices in the society. The issue is very complex and is not easily handled since it involves environmental and toxicological sciences as well as political, technical and economical perspectives. Therefore, the report does not aim to suggest new Low POP Content Limits for PCDD/Fs (or dl-PCBs) in waste, but rather highlight some issues that are important from the human health perspective. Hopefully, the results in the report may lead to stimulation of the scientific community to pick up this topic and develop science based new Low POPs Limits. The results do not reflect risks associated to diffuse pollution of PCDD/Fs or dl-PCBs in the environment and the fact that humans are exposed to environmental background concentrations. The basis for the study was to investigate how point sources may increase environmental levels and human body burdens in addition to exposure that originates from the atmosphere. Although the information in this report has been funded wholly or in part by the Swedish Environmental Protection Agency, it may not necessarily reflect the views of the Agency and no official endorsement should be inferred. Swedish Environmental Protection Agency, March 2011 Anders Johnson Head of a Environmental Assessment Department 3 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 4 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Abbreviations BAF BSAF BCF BIPRO b.w. BTF CNP COR CP DDT dl-PCB HCH HpCDD HpCDF HxCDD HxCDF IPEN I-TEF I-TEQ LPCL MSWI NGO OCDD OCDF PCB PCDD/F Bioaccumulation factor – the ratio of the concentration of a chemical in an exposed organism (all possible exposure routes) and the concentration of the chemical in an environmental compartment or in food. Biota-to-sediment or biota-to-soil accumulation factor - the ratio of the concentration of a chemical in an exposed organism (lipid normalised) and the concentration of the chemical in the sediment/soil (organic carbon-normalised). Bioconcentration factor - the ratio of the concentration of a chemical in an organism and the concentration of the chemical in the water at steady state. Beratungsgesellschaft für integrierte Problemlösungen, technical consultants in Germany. Bodyweight Biotransfer factor – the ratio of a chemical in an exposed organism and the daily contaminant input flux. Chlornitrofen, organochlorine herbicide Carry over rate, transfer efficiency between environmental media and biota. Chlorophenol Dichlorodiphenyltrichloroethane, organochlorine insecticide Dioxin-like PCBs, a group of twelve PCB congeners that exhibit the same mode of toxic action as PCDD/Fs. Hexachlorocyclohexane, organochlorine insecticide Heptachloro-dibenzo-p-dioxin Heptachloro-dibenzofuran Hexachloro-dibenzo-p-dioxin Hexachloro-dibenzofuran The International POPs Elimination Network Toxic equivalence factors for calculation of TEQ. Adopted by an international expert group (NATO/CCMS, 1988). Toxic equivalents, the product of the analytical concentration of a PCDD/F congener and its I-TEF. Low POP Content Limit, maximum residue limit for dioxins in waste products where recycling and/or management practices are not restricted. Municipal solid waste incineration Non-governmental organisation Octachloro-dibenzo-p-dioxin Octachloro-dibenzofuran Polychlorinated biphenyl Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans 5 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs PCP PeCDD PeCDF POP ppb TDI Pentachlorophenol Pentachloro-dibenzo-p-dioxin Pentachloro-dibenzofuran Persistent Organic Pollutant parts per billion, 1 µg kg-1 or 1000 ng kg-1 Tolerable Daily Intake – the tolerable average intake of a compound over a long term that does not result in human health risks. TCDD Tetrachloro-dibenzo-p-dioxin TCDF Tetrachloro-dibenzofuran TEQ Toxic equivalents, the sum of the products of the analytical concentrations of each dioxins or dioxin-like compounds multiplied with their individual TEF. TWI Tolerable Weekly Intake – the tolerable average intake of a compound over a long term that does not result in human health risks. WHO-TEF Toxic equivalents factors for calculation of TEQ for dioxins and dioxinlike com-pounds, adopted by WHO. WHO-TEQ Toxic equivalents, the sum of the products of the analytical concentration of dioxins and dioxin-like compounds and their individual WHO-TEF. 6 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Contents PREFACE 3 ABBREVIATIONS 5 1 1.1 SAMMANFATTNING Dioxinförorenat avfall i befintliga fallstudier 11 11 1.2 Halter i föda och exponering relaterat till lokala källor 12 1.3 Granskning av BIPROs riskbedömning 13 1.4 Exponeringsbedömning 13 1.5 Syntes 14 2 2.1 SUMMARY Dioxin contaminated waste in current case studies 17 17 2.2 Food and exposure levels related to local sources 18 2.3 Review of the BIPRO assessment 19 2.4 The exposure assessment 20 2.5 Synthesis 20 3 BACKGROUND 22 4 DIOXINS 23 5 5.1 DIOXIN CONTAMINATED WASTE Waste categories 25 25 5.2 Residues from thermal processes 26 5.2.1 Concentrations of pollutants 26 5.2.2 Case studies 27 5.3 Impregnated wood and waste wood litter 30 5.3.1 Concentrations of pollutants 30 5.3.2 Case studies 31 5.4 Chemical waste 32 5.4.1 Concentrations of pollutants 32 5.4.2 Case studies 32 5.5 E-waste recycling 33 5.5.1 Concentrations of pollutants 33 5.5.2 Case studies 33 6 6.1 HUMAN EXPOSURE Exposure via dietary intake 35 35 7 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 6.2 Exposure routes near local pollution sources 37 6.3 Human body burdens in local contamination scenarios 38 7 7.1 FOOD CHAIN CONTAMINATION RELATED TO LOCAL SOURCES 42 Agricultural food chains 43 7.1.1 Eggs and chickens 43 7.1.2 Milk and meat 45 7.1.3 Factors affecting transfer of soil pollutants to agricultural food chains 46 7.2 The aquatic food chain 49 8 8.1 REVIEW OF THE BIPRO RISK ASSESSMENT Application of safety factors and tolerable daily intake (TDI) 51 51 8.2 Correlating environmental levels to uptake into eggs 52 8.3 Contribution of dl-PCBs 52 8.4 Exposure from other sources 53 9 9.1 CASE STUDIES IN PERU AND THAILAND Case study 1: Zapallal waste site, Peru 54 54 9.1.1 Pollution of soil and sediment related to management of ashes 56 9.1.2 Bioaccumulation in biota 58 9.1.3 Conclusions 60 9.2 Case study 2: Phuket MSW Incinerator, Thailand 60 9.2.1 Pollution of soil and sediment related to management of ashes 61 9.2.2 Bioaccumulation in biota 64 9.2.3 Conclusions 64 10 10.1 HUMAN EXPOSURE ASSESSMENT RELATED TO ENVIRONMENTAL CONTAMINATION Method 65 65 10.2 Human exposure scenarios 66 10.3 Modelling bioaccumulation and exposure levels 67 10.4 Results 68 10.4.1 Ingestion of eggs 68 10.4.2 Ingestion of milk 69 10.4.3 Ingestion of meat 71 10.4.4 Ingestion of leafy vegetables 72 10.4.5 Ingestion of soil 73 10.5 Critical soil concentration levels 73 10.5 Critical soil concentration levels 74 8 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 11 11.1 SYNTHESIS OF THE RESULTS Risk scenarios 78 78 11.2 Exposure assessment 80 11.3 Uncertainties in the results 83 11.3.1 Identifying risk scenarios related to improper management of PCDD/F contaminated waste 83 11.3.2 Correlating environmental levels to human food chain contamination 11.3.3 Correlating environmental levels to improper management of waste in the field studies 84 11.3.4 Human exposure assessment 85 11.3.5 Estimated critical soil concentrations 87 11.3.6 Degree of protection with current Low POP Content Limits 87 12 CONCLUSIONS 89 13 RECOMMENDATIONS FOR FUTURE WORK 91 84 APPENDIX A Emission and Pollution Problem by dioxin in Peru 92 92 Introduction 92 Objectives 93 Methodology 93 Location of Zapallal Landfill 94 Description of the storage places of waste and residues 95 Types of identified residues 96 Storage of residues 98 Access to the landfill and the surrounding 99 Acknowledgment 100 References 100 APPENDIX B 102 APPENDIX C 103 APPENDIX C 104 APPENDIX C 105 APPENDIX D 121 REFERENCES 127 9 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 10 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 1 Sammanfattning Syftet med denna undersökning var att identifiera riskscenarier där förekomst av polyklorerade dibenso-p-dioxiner och dibensofuraner (PCDD/F:er) och dioxinlika polyklorerade bifenyler (dl-PCB:er) i avfall orsakar spridning av dessa toxiska föroreningar i miljön och överförs till människor genom föda och andra exponeringsvägar. Två fältstudier genomfördes på platser där avfall och aska förvaras och hanteras öppet, en i Peru och en i Thailand. Syftet med dessa var att studera graden av inverkan på omgivande miljö. För att kunna relatera människors exponeringsnivåer till det föreslagna Low POP Content Limit (LPCL)-värdet för PCDD/F genomfördes en riskbedömning med hjälp av en spridnings- och exponeringsmodell (CalTOX) samt med stöd av fältdata från Peru. Genom exponeringsberäkningar uppskattades punktkällors bidrag till humanexponering utöver den som man oundvikligen utsätts via diffusa utsläpp. 1.1 Dioxinförorenat avfall i befintliga fallstudier Vi identifierade fyra avfallskategorier som potentiellt viktiga inom ramen för projektets syfte: i) förbränningsrester, ii) kemiskt avfall, iii) träavfall samt iv) avfall från el-avfallsåtervinning. För kategorierna i, iii och iv finns ett fåtal antal rapporterade nutida fallstudier, medan det för kemiskt avfall framförallt är historiska incidenter som publicerats. Handel med och återvinning av träavfall kan vara av särskilt intresse då ett par nyligen genomförda fallstudier visar att denna avfallsfraktion har kontaminerat födokedjor i produktionssteget. För aska existerar i huvudsak en fallstudie och den rapporteras från Storbritannien, där bottenaska och flygaska från kommunal avfallsförbränning användes som gångmaterial inom ett odlingsområde, vilket ledde till kraftigt förhöjda halter i ägg från frigående höns. Samtliga incidenter som involverar träavfall eller förbränningsrester rapporteras från europeiska länder. Detta utesluter inte att allvarliga riskscenarier kan finnas även för utvecklingsländer. Tvärtom indikerar detta att om dessa problem kan uppstå i Europa, trots en i många fall väl förankrad och tillämpad lagstiftning, är sannolikheten att de ska inträffa i utvecklingsländer med svagare miljöövervakning förmodligen högre. Från dessa områden saknas dock ofta relevanta data. Eftersom flera typer av farliga ämnen kan förekomma i avfall och öppna deponeringsområden finns det en risk för att vissa människogrupper i utvecklingsländer (t.ex. skräpletare) utsätts för förhöjd 11 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs exponering. Hantering av avfall som innehåller PCDD/F kan därför vara ett allvarligt, om än inte väldokumenterat, problem för människor i fattiga länder. Det är ofta svårt att relatera en miljöpåverkan till hantering av avfall eftersom flera olika föroreningskällor kan existera inom avfallsområdet. Det är t.ex. svårt att skilja på förorening som sker genom spridning av aska från förorening som sker genom deposition av luftemissioner som orsakats av förbränning av avfall. I fältstudierna från Peru och Phuket kunde därför konsekvenser av öppen och oskyddad förvaring av aska inte utredas separat från luftemissionernas påverkan. 1.2 Halter i föda och exponering relaterat till lokala källor Flertalet studier har rapporterat om lokal förorening av mark och vatten som en följd av industriella punktkällor, spill, olyckor eller andra förorenande aktiviteter. Vid sådana platser kan förhöjd exponering av människor förekomma. Ofta är den relaterad till intag av lokalt producerad föda. I vissa fall, där t.ex. luft och jord är kraftigt förorenade, kan även kontakt med den abiotiska miljön, t.ex. intag av jord, ge upphov till hög exponering hos lokalbefolkning. Alla animaliska livsmedelsprodukter innehåller PCDD/F:er som ackumulerats från omgivningen och som härrör från historiska och dagsaktuella källor. Föroreningsnivån i livsmedel som producerats nära punktkällor är ofta relaterad till förhöjda halter i miljön. Detta kan i sin tur leda till en högre exponering hos människor som bor i närheten av källan jämfört med genomsnittsbefolkningen. Många studier har visat att intag av lokalt producerade frigående kycklingar/höns och deras ägg utgör ett högriskscenario. Det finns även studier som visar att bakgrundskoncentrationer i lantliga miljöer utan lokala s.k. hot-spots är tillräckligt höga för att ge upphov till höga halter av PCDD/F i ägg från frigående höns. Det är svårt att prediktera föroreningshalter i ägg med god noggrannhet. Överföringsvägarna mellan miljön och frigående hönor är många och komplexa, vilket innebär att exponeringsvägarna inte är lätta att beskriva med hjälp av modeller. Olika faktorer, som förorenings-sammansättning, uppfödningsförhållanden, jordtyp och växttäckningsgrad, m.fl. påverkar bioackumulationen. Resultat från enskilda studier kan därför inte användas för att ta fram generella bioöverföringsfaktorer mellan jord och ägg. Produktion av andra animaliska livsmedelsprodukter, såsom mjölk och kött, utgör också högriskscenarier i närheten av lokala källor. Enligt födointagsstudier från olika länder har den allmänna befolkningen ofta ett intag av PCDD/F som ligger nära eller överskrider WHO:s tolerabla intagsgränser, TDI, som anger det uppskattade dagliga intag som kan tolereras under lång tid utan att det förväntas ge upphov till hälsorisker för människor. Skillnaderna i intag är dock stora mellan olika länder. Ett fåtal studier har rapporterat om intag och kroppsbelastning i utvecklingsländer. Eftersom födointag och andra levnadsvillkor skiljer sig åt mellan 12 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs olika länder är det inte möjligt att använda data från den industrialiserade världen för att uttala sig om PCDD/F-exponering för människor i utvecklingsländerna. 1.3 Granskning av BIPROs riskbedömning I den riskbedömningen av PCDD/F som gjordes av en tysk konsultbyrå (BIPRO) på uppdrag av Europeiska Kommissionen utgick man från att det lagstiftade gränsvärdet för kommersiellt producerade ägg är korrelerat till risker för människors hälsa baserat på TDI. Eftersom det lagstiftade gränsvärdet i livsmedel inte grundar sig på en hälsoriskbedömning, kan en jämförelse mellan halter i livsmedel och gränsvärdet inte indikera risknivån avseende hälsoeffekter. Riskbedömningar bör därför inte enbart baseras på denna typ av jämförelser. I BIPROs riskbedömning utgår man ifrån att en PCDD/F koncentration på 30 pg WHO-TEQ g-1 fett kan accepteras för ägg. Genom att använda överföringsfaktorer mellan jord och ägg (s.k. BTFs, biotransfer factors) från två olika studier uppskattade man att den kritiska PCDD/F koncentration på 30 pg WHO-TEQ g-1 fett i ägg motsvarar en markkoncentration på 1 000 ng TEQ kg (1 ppb). En konsumtion av ett ägg per dag är tillräckligt för att ge ett signifikant bidrag till TDI om äggkoncentrationen är 3 pg TEQ g-1 fett eller högre. I motsats till slutsatserna i BIPRO-rapporten, tyder dessa intagsberäkningar på att koncentrationer i ägg inte bör vara högre än EU:s gränsvärde (3 pg TEQ g-1 fett). En sammanställning av litteraturdata och beräknade överföringsfaktorer från jord till ägg baserade på dessa data visade att överföringsfaktorerna varierar i hög grad och att dl-PCB är betydligt mer tillgängliga än PCDD/F. Med hänsyn till den stora variationen kan BTF från ett fåtal studier inte anses representativa för mer generella scenarier. Den överföringsfaktor som användes av BIPRO låg i det övre intervallet och deras riskbedömning underskattar därför förmodligen risken för upptag i ägg vid markkoncentrationer på 1 000 ng TEQ kg-1 torrvikt (1 ppb). Enligt överföringsfaktorerna som beräknades i denna rapport kan gränsvärdet för PCDD/F i ägg nås redan vid 1-70 ng TEQ i jorden (0,001-0,07 ppb). TDI omfattar toxiskt bidrag (TEQ-bidrag) från både PCDD/F och dl-PCB. Bidraget från dl-PCB beaktas inte i BIPROs riskbedömning, vilket ger en skev bild av riskerna. 1.4 Exponeringsbedömning Inom ramen för denna studie gjordes en exponeringsbedömning där kritiska markkoncentrationer beräknades. I denna bedömning användes uppmätta markkoncentrationer från fältstudien i Peru i två föroreningsscenarier: en med bakgrundshalter i marken (1,1 ng WHO-TEQ kg-1 torrvikt eller 0,001 ppb) och en med en lokal föroreningsnivå motsvarande 69 ng WHO-TEQ kg-1 torrvikt (0,069 ppb). Exponeringsnivåer för två olika populationer undersöktes. Skillnaderna mellan populationerna var relaterade till olika levnadsvillkor för landsbygd respektive stad, 13 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs vilket simulerade förväntade skillnader mellan industrialiserade länder och utvecklingsländer. Beräkningar gjordes i både för vuxna och barn. De exponeringsvägar som beaktades var intag av jord samt intag av lokalt producerad mat. Eftersom bioackumulationsdata för dl-PCB inte fanns tillgängliga inkluderades inte dl-PCB i detta steg av riskbedömningen. Det modellerade upptaget av PCDD/F i föda stämde i stort sett väl överens med fältdata från Peru och andra fallstudier. Den största avvikelsen erhölls för ägg, där modellen underskattade upptaget relativt kraftigt. Vid 1,1 ng WHO-TEQ våtvikt i marken (0,001 ppb) överskred aldrig exponeringen från respektive exponeringsväg 10 % av TDI för den mest känsliga populationen (barn i utvecklingsscenariot). Vid 69 ng WHO-TEQ våtvikt i marken (0,069 ppb) erhöll både barn och vuxna i utvecklingsscenariot en signifikant exponering via alla exponeringsvägar. För flera av exponeringsvägarna var de beräknade doserna för barn nära eller högre än TDI. För intag av jord kan dock risken vara överskattad då det antogs att tillgängligheten för absorption i matsmältningssystemet är 100 %, medan experiment har visat att biotillgängligheten för PCDD/F i jord är begränsad. Kritiska markkoncentrationer, som tillåter en lantlig livsstil för barn med högt intag av lokalt producerad mat men med acceptabla exponeringsnivåer, låg inom 7-25 ng WHO-TEQ kg-1 våtvikt (0,0070,025 ppb) för PCDD/F. Detta intervall minskar dock till 3-13 ng WHO-TEQ våtvikt (0,003-0,013 ppb) om man antar att 50 % av den totala TEQ exponeringen även kommer från dl-PCB. Det beräknade intervallet samt intervallets storlek påverkas av flera osäkerheter i modellerings-antagandena, t.ex. i) i vilken omfattning som enskilda exponeringsvägar förekommer tillsammans eller separat, ii) hur stor del av den intagna födan som är lokalt producerad, iii) mängden föda som intas, iv) mängden jord som intas. Eftersom riskbedömningen var baserad på hypotetiska populationer ansågs det mer lämpligt att identifiera ett intervall för kritiska markkoncentrationer snarare än ett enskilt värde. 1.5 Syntes Med stöd av resultat från flera befintliga studier samt en uppskattning av möjliga exponeringsnivåer för människor kan gränsvärdet på 15 ppb för PCDD/F i avfall anses förknippad med risk för människor. Allvarliga risker uppstår bl.a. om impregnerat trä eller aska tillåts komma in i produktionscykeln för animaliska livsmedel och naturliga betesmarker eller om människor utsätts för direktkontakt med jord/aska. Det begränsade antalet fallstudier som identifierats kan eventuellt indikera att olämplig hantering av PCDD/F kontaminerat avfall inte är särskilt vanligt. Å andra sidan finns tydliga indikationer på att PCDD/F kontaminerat avfall inte alltid hanteras på ett sätt som gagnar miljön eller människors hälsa. Öppna deponeringsområden och vattendrag i t.ex. Asien och Sydamerika är bevisligen recipienter för dumpning av högkontaminerat avfall. Om sådana aktiviteter har en lokal påverkan på halter av PCDD/F och dl-PCB i miljön eller för människor, tycks hittills inte vara fastställt 14 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs genom fältstudier av tillräcklig omfattning. Resultaten från fältstudierna i detta projekt visade att platser med öppen hantering och förbränning av avfall och aska har förhöjda halter av PCDD/F och dl-PCB, och dessa aktiviteter kan leda till förhöjda halter i omgivande miljön. Eftersom provtagningsplatserna var påverkad av flera källor (t.ex. luftburna emissioner från förbränning inom området) var det inte möjligt att särskilja bidraget från askhanteringen och bidraget från förbränningen. I riskbedömningen identifierades en kritisk markkoncentration för PCDD/F till 7-25 ng WHO-TEQ kg-1 våtvikt (0,007-0,025 ppb), eller 3-13 ng WHO-TEQ våtvikt (0,003-0,013 ppb) om man antar att dl-PCB kan stå för 50 % av TDI. För barn som lever i en lantlig miljö och vars mat är lokalt producerad motsvarar den kritiska markkoncentrationen en föroreningsnivå som sannolikt inte medför en exponering högre än TDI. Denna bedömning innehåller dock en rad osäkerheter, t.ex. teoretiska antaganden som inte verifierats samt naturliga variationer för de parametrar som ingår. En riskbedömning för hypotetiska populationer kommer alltid att innehålla stora osäkerheter då den är just hypotetisk. För vuxna individer kan intag av jord/aska vara en betydelsefull exponeringsväg i samband med yrkesmässig exponering. Preliminärt har den kritiska halten i fasta matriser för denna exponeringsväg bedömts ligga kring 200-1 000 ng WHO-TEQ kg-1 våtvikt (0.2-1 ppb), men denna bedömning beror bland annat på vilken biotillgänglighet man antar. Här saknas data för askmatriser. Fältdata visar att dl-PCB ackumuleras i biota i högre utsträckning än PCDD/F. De bidrar också signifikant till TEQ-värdet i livsmedel och ingår i TDI. Det faktum att dlPCB inte omfattas av föreslaget LPCL för PCDD/F kan bidra till felaktig bedömning av den totala risken som är kopplad till bioackumulation. 15 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 16 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 2 Summary The main focus of the current study was to identify risk scenarios where polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in wastes are distributed in the environment and transferred to humans via food and other exposure pathways. Two field studies were conducted at sites where wastes and ashes are managed and stored open, one in Thailand and one in Peru. The aim of these studies was to investigate the degree of local environmental impact. To be able to relate human exposure levels to the suggested LPCL for PCDD/F, a risk assessment was performed using a fate and exposure model (CalTOX), supported by field data from Peru. Additional human exposure from local sources was estimated in relation to inevitable human exposure related to diffuse emissions by exposure calculations. The aim of the exposure assessment was to establish whether point sources may contribute to human body burdens above the exposure levels that we are inevitably subject to from existing background levels as a result of diffuse pollution. 2.1 Dioxin contaminated waste in current case studies We identified four major waste categories as being potentially important in the context of this study: i) incineration residues, ii) chemical waste, iii) waste wood fractions and iv) waste from e-waste recycling sites A limited number of recent case studies are reported for categories i, ii and iv, while case studies for chemical waste mostly are related to historical incidents. Trading and shipping of waste wood fractions may be of special importance since there are recently reported incidents where this waste fraction has contaminated human food chains at animal food production facilities. For ashes, we only identified one study, and it is reported from Britain, where bottom ash and some fly ash from a municipal waste incinerator were recycled as path material in an allotment area. This resulted in elevated concentrations in free-range chicken eggs. All incidents for waste wood and ash are reported from European countries, but this certainly does not exclude the possibility that that serious risk scenarios exist for developing countries as well. Since these problems can arise in Europe, in spite of well established and robust regulatory frameworks and practices, the probability of similar events occurring in countries with more limited environmental control is even 17 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs higher. However, environmental and food/feed control data from developing countries are often lacking. Since several hazardous pollutants may be present at high levels in waste and open waste dumping sites, some exposed subpopulations (e.g. waste pickers) are at risk for increased exposure. Management of PCDD/F contaminated waste may thus be a serious, but a so far, not well-documented problem. It can be difficult to relate an environmental impact to management of waste in areas where other sources co-exist. In the field studies in Peru and Phuket, consequences of open and unprotected storage of ash could therefore not be investigated separately from the influence of local air emissions. 2.2 Food and exposure levels related to local sources Several studies have reported local PCDD/F contamination of soils and waters related to industrial point sources, spills, accidents and other polluting activities. At these sites, elevated exposure levels of humans may occur, often related to consumption of locally produced food. In cases where abiotic media, such as soil or air, are severely polluted, direct exposure of the media, e.g. via ingestion of soil, could also result in high exposure of local inhabitants. All animal food and feed products contain PCDD/Fs as a result of accumulation from historic and current emissions from various sources. Levels of contamination in food and feed produced near local sources are therefore often related to elevated levels in the environment. This can then result in higher exposure of people residing in vicinity of the source, compared with the exposure levels for the overall population. A number of studies show that consumption of locally produced free range chickens and eggs is a high risk scenario. Some studies also show that environmental background concentrations in rural scenarios with no local pollution ‘hotspots’ can cause relatively high PCDD/F levels in free-range eggs. It is difficult to predict concentrations in eggs with high accuracy. The transfer routes between the environment and chickens are numerous and complex, and are not easily described by models. Factors such as congener composition (relative abundance of congeners) breeding and feeding conditions, soil type and vegetation cover, etc., will affect the bioaccumulation. Results from single case studies can therefore not be used to establish generic soil-to-egg transfer ratios. Production of other animal food products, such as milk and meat, is also a high risk scenario in the presence of local sources. According to dietary intake studies in different countries, generic population exposures are often close to, or exceed, the WHO Tolerable Daily Intake (TDI) value. The TDI is an estimate of the average daily intake of a contaminant that can be ingested over a lifetime without appreciable health risk. However, the intake levels differ considerably between different countries. A limited number of studies have dealt with human body burdens and dietary intakes for populations in developing countries. Since food consumption habits and living conditions differ between 18 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs different countries, it may be problematic to use data from industrialised country conditions to express an opinion of the PCDD/F exposure of humans in developing countries. 2.3 Review of the BIPRO assessment In the risk assessment of PCDD/Fs conducted by a German consultant (BIPRO) for the European Commission it was assumed that the legislated maximum level in commercial eggs is correlated to human health risks based on the tolerable daily intake (TDI). Since the maximum level in food is not based on a human health risk assessment, compliance of PCDD/Fs levels in eggs (or other food items) with the legislated limits is not an indicator of the risk level and should not be used as a criteria in a risk assessment. The risk assessment by BIPRO assumes that a PCDD/F concentration of 30 pg WHOTEQ g-1 fat is acceptable in eggs. By using soil-to-egg transfer factors (so called BTF, biotransfer factors) from two studies, they estimated that the critical PCDD/F concentration of 30 pg WHO-TEQ g-1 fat in eggs corresponds to soil concentrations of 1 000 ng TEQ kg-1 d.w. (1 ppb). A consumption of one egg per day is enough to yield a significant contribution to TDI if the eggs contain 3 pg WHO-TEQ g-1 fat or more. In contrast to the conclusions in the BIPRO report, these intake calculations indicate that egg concentrations should not exceed the EU limit value (3 pg WHO-TEQ g-1 fat). A compilation of literature data showed that estimations of soil-to-egg transfer of PCDD/Fs and dl-PCBs are highly variable, and that dl-PCBs are much more available than PCDD/Fs. Considering the large variability of the soil-to-egg transfer factors, selected bio-transfer factors from only a few studies are not representative of generic scenarios. The adopted transfer factor by BIPRO was in the upper range of those calculated from the literature. Thus, there is a risk that BIPRO significantly underestimates the risk for transfer of PCDD/F into eggs at soil concentrations of 1 000 ng TEQ kg-1 d.w. (1 ppb). According to the BTFs calculated from the literature, 3 pg WHO-TEQ g-1 fat in eggs can be reached already at soil concentrations of 1-70 ng TEQ kg-1 d.w. (0.001-0.07 ppb). The TDI includes exposure both for PCDD/Fs and dl-PCBs, and both compound groups may be transferred from solid waste matrices into human food chains, even though dl-PCBs are more available than PCDD/Fs. Since BIPRO did not consider the contribution from dl-PCBs in waste to the food chain transfer, their assessment does not reflect the total risk. 19 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 2.4 The exposure assessment The exposure assessment conducted within the current study was based on two contamination scenarios: one background scenario (1 ng WHO-TEQ kg-1 w.w. or 0.001 ppb in the soil) and one local contamination scenario (70 ng WHO-TEQ kg-1 w.w. or 0.07 ppb in the soil). Exposure levels of two different populations were investigated, reflecting different living conditions for rural/urban life styles and simulated expected differences between industrialised and developing countries. Each population consisted of adults and young children. Exposure pathways considered were ingestion of soil and locally produced food. Because of limited access to important bioaccumulation data needed for the model calculation, dl-PCBs were not included in the exposure assessment at this stage. The modelled accumulation in food was generally in good agreement with field data from Peru or other case studies. The most distinctive disagreement was for concentrations in eggs, where the model underestimated the risk. At 1.1 ng WHOTEQ kg-1 w.w. (0.001 ppb) in soil, the exposure levels of single exposure routes never exceeded 10% of TDI for the most sensitive target population (children in the Development setting). At 69 ng WHO-TEQ kg-1 w.w. (0.069 ppb) in soil, children and adults in the Development setting received significant exposure levels via all the exposure routes. For most of the routes, single doses of the children were close to or above the TDI. For ingestion of soil, however, the risk may be over-estimated since the availability for absorption in the digestive tract was assumed to be 100%, while experimental data have shown that the bioavailability is significantly reduced for pollutants present in soil matrices. Critical soil concentrations, which allow a rural life style with high ingestion rates of locally produced food but acceptable exposure levels in relation to TDI, were identified in the range 7-25 ng WHO-TEQ kg-1 w.w. (0.0070.025 ppb) soil for PCDD/F. The range is reduced to 3-13 ng WHO-TEQ kg-1 d.w. (0.003-0.013) if it is assumed that dl-PCBs will add to 50% of the total TEQ exposure. The precision of the range is affected by several uncertainties in the modelling assumptions, e.g. i) to what extent the exposure routes will exist simultaneously or alone, ii) the amount of ingested food that is locally produced, iii) food ingestion rates, and iv) the amount of ingested soil. Since the assessment were based on hypothetical populations, it was considered as more reasonable to identify an interval of critical soil concentrations, rather than one single value. 2.5 Synthesis Supported by results from existing case studies and the human exposure assessment, the suggested limit of 15 ppb for PCDD/Fs in waste is considered to be associated with risks for humans. There are e.g. risks if impregnated wood or ash is introduced in the production of animal food items or natural pastures, or if humans are subject to direct contact with soil/ash. 20 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs The limited number of existing case studies may indicate that improper management of PCDD/F waste is uncommon. On the other hand, there are indications that PCDD/F contaminated waste is not always managed having protection of the environment and human health in mind. Open waste dump sites and rivers in e.g. Asia and South America are potential targets for dumping of highly contaminated waste. If such activities do have an impact on local environmental PCDD/F or dl-PCB concentrations or human exposure levels, it is, so far, not well investigated. The minor field studies in Peru and Thailand confirmed that highly contaminated ashes are stored on open ground at sites where the waste is produced. The results indicated that such sites constitute PCDD/F and PCB pollution hot spots that may affect the surroundings by wind-blown distribution of ashes. Our field study did, however, not allow apportionment between contamination from ash residues and local air emissions from the recycling activities. In the risk assessment, a critical soil concentration of 7-25 ng WHO-TEQ kg-1 w.w. (0.007-0.025 ppb), or 3-13 ng WHO-TEQ kg-1 w.w. (0.003-0.013 ppb) if one assumes that dl-PCB contribute to 50% of the TDI, was identified. For children in rural setting and where the food is locally produced, the critical soil concentration corresponds to a level where the exposure is not likely to exceed TDI. The assessment includes a number of uncertainties, e.g. some of the assumptions have not been verified and the natural variability of the parameters was not taken into account. A risk assessment which is made for hypothetical populations will always suffer from a large degree of uncertainty. For adults, ingestion of soil and ash can constitute an important exposure route in occupational exposure scenarios. A critical solid matrices concentration has preliminary been assessed to 200-1 000 ng WHO-TEQ kg-1 w.w. (0.2-1 ppb) for this exposure route, depending on assumed internal bioaccessibility. Such data is lacking for ash matrices. Field data from several scientific studies show that dl-PCBs accumulate to a higher extent than PCDD/F in biota. Dl-PCBs contribute significantly to the total TEQ in food and risks can be assessed by comparing daily intake to the TDI for PCDD/Fs and dl-PCBs. Since dl-PCBs are not included in the suggested LPCL for PCDD/F, the total risk associated to exposure of PCDD/F and dl-PCB contaminated waste can be underestimated. 21 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 3 Background The production, use and release of persistent organic pollutants (POPs) are dealt with by the Stockholm Convention, which aims to reduce and eliminate the flows of these substances in the environment. PCDD/Fs and PCBs are two substance groups that are categorised as POPs in terms of persistence, environmental behaviour and toxicology. In order to classify and manage waste products in an environmentally sound manner, a suggested maximum level of 15 µg TEQ kg-1 (15 ppb) for PCDD/F in waste was first proposed by the Basel convention, and was later adopted by EU (BIPRO, 2005). The corresponding level for ∑PCB6 is 50 mg kg-1 (50 ppm). These levels are commonly referred to as the Low POP Content Limits (LPCL). Some PCDD/F contaminated waste products may be recycled in the society, and contaminants in the waste can therefore be distributed into the environment. There is an increased concern of environmental problems caused by uncontrolled dispose and recycling of waste and waste products. Urbanisation and industrial growth in developing countries stimulates the production of hazardous waste, and proper disposal strategies are needed to reduce environmental harm and human health risks in these countries (Omran & Gavrilescu, 2008). While many industrialised countries have an environmentally sound management of hazardous waste, developing countries lack much of the financial and political resources needed to treat the waste in a proper manner or to control possible health impacts from hazardous waste (Sonak et al., 2008; Yousif & Scott, 2007; Mbuligwe & Kaseva, 2006). These countries face also problems related to the absence of sanitary landfills, limited public knowledge about proper waste management practices and increasing illegal dumping. In some cases, hazardous waste is neither treated nor separated from the non-hazardous waste fraction, and the dump sites are neither lined nor covered. Local authorities do not necessarily consider environmental impacts of new or existing dump sites. Thus, waste deposits can be allocated to areas without considering the potential transport of hazardous pollutants, and monitoring and safeties practices such as covering and fences are neglected. Inspection of waste before dumping is not always occurring, and illegal dumping of toxic chemicals is not uncommon. Regulation of maximum levels of PCDD/Fs and dioxin-like compounds in waste is therefore important, both at national and international scales, in order to prevent further distribution of POPs in the environment and to protect human health. 22 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 4 Dioxins The chemical substances covered in this report are polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCB). PCDDs and PCDFs are usually treated as one compound group with the acronym PCDD/Fs and commonly referred to as dioxins. In this report, only 2,3,7,8-substituted congeners were considered. A number of PCBs share the same toxic mode of action as 2,3,7,8-substituted PCDD/Fs. These substances are called dioxin-like PCBs (dl-PCBs) or co-planar PCBs. Dl-PCBs consist of 12 non-ortho and mono-ortho substituted PCBs (PCBs 77, 81, 105, 114, 118, 123 126, 156, 157, 167, 169, 189; numbering according to IUPAC). 2,3,7,8-substituted PCDD/Fs and dl-PCBs have been assigned toxicological equivalence factors (TEFs) according to a scheme that originally was developed for PCDD/Fs (Van den Berg et al., 2006). TEFs are used to calculate toxic equivalence concentrations (TEQs) from analytical concentrations of single congeners. The total toxicity of a mixture of congeners is the sum of products of the analytical congener concentrations and their TEFs. There is no consistency of reported TEQ units in the literature since different TEF schemes have been developed (I-TEF, WHO-TEF, etc). When citing data, originally reported TEQ units have usually been cited. However, in some data compilations, it was not convenient to keep the original TEQ units and the generic expression “TEQ” was used instead. Empirical data from the field studies are reported as WHO-TEQ, following the TEF scheme from 2005 as presented in Table 1. 23 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Table 1. TEF scheme according to WHO (Van den Berg et al., 2006). Congener WHO-TEF 2005 2,3,7,8-TCDD 1 1,2,3,7,8-PeCDD 1 1,2,3,4,7,8-HxCDD 0.1 1,2,3,6,7,8-HxCDD 0.1 1,2,3,7,8,9-HxCDD 0.1 1,2,3,4,6,7,8-HpCDD 0.01 OCDD 0.0003 2,3,7,8 -TeCDF 0.1 1,2,3,7,8 -PeCDF 0.03 2,3,4,7,8 -PeCDF 0.3 1,2,3,4,7,8 -HxCDF 0.1 1,2,3,6,7,8 -HxCDF 0.1 2,3,4,6,7,8-HxCDF 0.1 1,2,3,7,8,9-HxCDF 0.1 1,2,3,4,6,7,8 -HpCDF 0.01 1,2,3,4,7,8,9-HpCDF 0.01 OCDF 0.0003 PCB #77 0.0001 PCB #81 0.0003 PCB #105 0.00003 PCB #114 0.00003 PCB #118 0.00003 PCB #123 0.00003 PCB #126 0.1 PCB #156 0.00003 PCB #157 0.00003 PCB #167 0.00003 PCB #169 0.03 PCB #189 0.00003 So far, Low POP Content Limits are only suggested for PCDD/Fs and the sum of seven PCBs (∑PCB7), while dl-PCBs are not yet suggested to be regulated. Because of their dioxin-like properties, however, they should ultimately be included in the LPCL for PCDD/Fs, since human health risks depend on both compound groups. This is also the reason to why both PCDD/Fs and dl-PCBs were addressed in this report. Two different concentration units for solid matrices are used in the cited literature. The units “ppb” and “ppm” are applied for the Low POP Content Limits, while universal units such as “ng kg-1” or “pg g-1” are used for empirical data in the open literature. The units are translated into each other according to ppb = parts per billion = µg kg-1 (or 1000 ng kg-1) = ng g-1 ppm = parts per million = mg kg-1= µg g-1 24 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 5 Dioxin contaminated waste 5.1 Waste categories Dioxin contaminated wastes are generated by different activities in the society and consist mainly of solid matrices. The industrial sector is the major producer of waste, and major amounts origin from municipal waste incineration (MSWI), power production, and metallurgical and steel alloy industries. A more comprehensive compilation of sources and dioxin waste flows is presented in BIPRO (2005). It was beyond the scope of this study to present a full review of dioxin levels in different waste fractions, but a selection of existing data is presented below to illustrate the contamination levels of different waste categories that were confirmed to be of importance in the context of this study: i) residues from thermal processes, ii) impregnated wood and waste wood litter, iii) chemical waste, and iv) residues from e-waste recycling These waste fractions are considered as important in relation to the produced amounts and known contamination levels (categories i-iii), or from case studies of sites were management/recycling of PCDD/F contaminated waste has harmed the environment or human food chains (categories i-iv). A thorough literature search for case studies and incidents that exemplifies environmental harm or human health risks caused by improper management of PCDD/F contaminated waste was conducted, but only a few relevant studies were found. These are presented in the following paragraphs. On the contrary, there are a number of studies that report upon national food contamination incidents, where human food chains were severely contaminated by PCBs or PCDD/Fs (Hoogenboom et al., 2004). Many of these cases were probably caused by illegal actions, accidents or unawareness of PCDD/F or PCB residue levels in products and ingredients that later were introduced into feed and food chains. However, the incidents were often tracked to small producers, which in the end had a large and negative financial impact on affected feed and food markets (Fürst, P., Plenary lecture Dioxin Conference 2009). The cases illustrate the ease in which food chains becomes negatively affected if materials are contaminated by processes in the modern society. 25 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 5.2 Residues from thermal processes 5.2.1 Concentrations of pollutants Incineration generates different types of solid residues, such as fly ashes, filter dusts, bottom ash and boiler ash. Major producers include municipal waste incineration plants (MSWI), power plants, metallurgical and chemical industries. Residues from thermal processes are also generated from metal recycling. These residues contain various levels of PCDD/Fs and dl-PCBs. Fly ash measurements have been numerous, while MSWI bottom ash and boiler ash are less frequently investigated. In Table 2, data from a number of references are compiled to illustrate expected PCDD/F levels. However, the compilation covers only a selection of studies and matrices. Table 2. Concentrations (ng TEQ kg-1) of PCDD/Fs in different incineration residues. Waste type PCDD/F (ng TEQ kg-1) Country Reference Fly ash, industrial & medical refuse 8 500-67 500 Colombia Aristizabal et al., 2008 Fly ash, power production 2.2-190 Mauritius Yive & Tiroumalechetty, 2008 Filter dust, galvanising plant 127-8 075 Spain Martinez et al., 2008 Ash, Waelz process 103 000 Taiwan Chi et al., 2008 Fly ash, secondary steel plant 1 899 Thailand UNEP, 2001 Bottom ash, MSWI 5-10 Thailand " Fly ash, MSWI 228-686 Thailand " Bottom ash, MSWI 0.2-245a various Vehlow et al., 2006 Boiler ash, MSWI 0.3-400b various " Fly ash, MSWI 120-41 4000a various " Bottom ash, MSWI 0.1-200 Sweden Svenska Renhållningsverksföreningen, 2001 Fly ash, MSWI 140-18 000 Sweden " Fly ash, bio fuels 120-270 Sweden Oehme & Muller, 1995 Bottom ash, bio fuels 0.2-1.1 Sweden " a b samples from 1990-2004; samples from 1990-1999 The expected range of PCDD/F concentrations in bottom ash from modern MSWI facilities is 1-30 ng TEQ kg-1. For recently produced fly ashes, the range is 100-10 000 ng TEQ kg-1 (Vehlow et al., 2006). During the past decade, PCDD/F concentrations in fly ash have decreased (Vehlow et al., 2006). The fuel type is of major importance for the final levels in the residues. Fly ash and bottom ash from bio fuel combustion usually contain lower levels (<300 ng TEQ kg-1; Table 2), than ashes from MSWI. However, mixing with PCDD/F contaminated wood fractions may elevate the levels by orders of magnitude (Oehme & Muller, 1995). Limited data exist for PCB levels in MSWI solid residues (Vehlow et al., 2006). When measured, dl-PCBs are generally not reported separately from other PCBs. Thus, it is 26 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs difficult to get good estimates of general levels in incineration residues. In the study by Vehlow and co-authors (2006), dl-PCBs contributed by 2-7% of the total TEQ in MSWI bottom ash, and by <1-10 % in MSWI fly ash. Other studies have reported a TEQ fraction of 1% for dl-PCBs in fly ash (Sakurai et al., 2003). Accidental fires will also result in residues contaminated with PCDD/Fs. Swedish experiments with e-waste and car tyre fires resulted in waste that contained 11-2 100 ng I-TEQ kg-1 (SP Swedish National Testing and Research Institute, 2005). The highest PCDD/F level was found in e-waste fire residues, while dl-PCBs were not analysed. There are different types of incineration waste that may contain PCDD/Fs or dl-PCBs. It seems that expected ranges in most waste products will fall below the suggested LPCL for PCDD/F. For dl-PCBs, knowledge about concentrations is limited. 5.2.2 Case studies A recent publication by Mari et al. (2009) reported on the impact on environmental levels and human health from a hazardous waste landfill in Catalonia (Spain) that receives PCDD/F contaminated residues. The landfill site operates according to national regulations, and waste management practices follows principles set by EU. The authors found a slight increase of PCDD/F concentrations in air and soil at the landfill, but in general terms, the concentrations were low and the human health assessment indicated no risk for local residents exposed to air or soil. The soil concentrations were 1.5 and 2.1 ng WHO-TEQ kg-1 d.w. However, this landfill is sealed and protected and is not representative of open landfills or other non-regulated waste sites. In the UK, there is one relevant case study (Pless-Mulloli et al., 2001) that illustrates how dioxin contaminated incineration residues will contaminate the environment and human food chains if the management and recycling practices are not fully controlled. During a period of 5 years (1994-1999), 2 000 tons of ash was recycled at 51 sites across Newcastle. 27 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs The egg concentrations in the Newcastle case correspond to 0.04-5.6 pg I-TEQ g-1 fresh weight (assuming a fat content of 10% in whole eggs). A daily consumption of one Newcastle egg (60 g) per day equals a human dose of 0.04 to 5.6 pg I-TEQ kg-1 b.w. and day (assuming a bodyweight of 60 kg). The recommended tolerable daily intake (TDI) for PCDD/Fs and dl-PCBs is 2 pg TEQ kg-1 b.w. and day. One of the sites consisted of allotment areas where animals (hen, ducks, pigeons and horses) also were raised. Ash samples from foot paths contained up to 9 500 ng I-TEQ kg-1, which is below the suggested LPCL of 15 000 ng TEQ kg-1, while the highest recorded soil concentration was 272 ng I-TEQ kg-1. Eggs from the allotments contained 0.4-56 pg I-TEQ g-1 fat, and the congener distribution patterns were similar to that of ash. It was concluded that PCDD/Fs had been transferred into chicken eggs, even when the animals did not have direct access to the contaminated footpaths. In the risk assessment, it was recommended that poultry and egg production should be restricted until the ash was removed. Other studies indicate that management of ashes might be a source of PCDD/Fs in local environments in poor countries, and that some populations might be at risk for elevated exposure, even though no cases studies are reported. In some countries, PCDD/F levels in incineration ashes is not regulated at all, and the residues are often mixed with household waste and disposed of in municipal solid waste landfills without previous treatment or protection of human health (Aristizabal et al., 2008). Elevated exposure to hazardous pollutant is therefore possible for people scavenging the landfills for recyclable material. The field sampling at the waste site Zapallal (Peru) that was performed within the current project showed that levels of PCDD/Fs in ash stored on open ground were close to the suggested LPCL of 15 ppb (Chapter 9). The final fate of the contaminated residues is not known, but according to a preinvestigation of the area by local NGOs, a nearby river is used for dumping of waste. In Europe, local NGOs have reported upon dumping of ash-like residues of unknown, European origin in Belaruchi (Belarus, Figure 1). The material was dumped on open, unprotected ground, and the residues contained approximately 1 000 ng TEQ kg-1 (1 ppb; personal communication J. Petrlik, Arnika, Czech Republic). 28 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Figure 1. Dumping of PCDD/F contaminated residues in Belaruchi, Belarus (J. Petrlik, Arnika). Open dumping of POP-contaminated waste can also affect wildlife (Watanabe et al., 2005). Uncontrolled management strategies will therefore result in that toxic substances are transferred into the environment with reduced possibilities to detect or measure impacts on the environment or human health. Regardless if dumping of PCDD/F contaminated ashes is a legal or illegal action, it will increase the environmental hazard at open dump sites. These areas are already known to contain elevated levels of hazardous compounds, such as DDT, PCBs and HCH (Minh et al., 2006). Dump sites may also contain elevated concentrations of PCDD/F due to e.g. open burning and recycling activities (Minh et al., 2003; Table 3). Dumping of PCDD/F contaminated waste from other activities will therefore become an additional source. Table 3. Reported PCDD/F soil concentrations (ng WHO-TEQ kg-1 d.w.) from open dump sites and control sites in Asian countries (Minh et al., 2003). Philippines Cambodia India VietnamHanoi VietnamHo Chi Minh Dump site 400-630 1.4-1 700 9.9-200 0.4-850 0.02-4.4 Control site - 0.031-4.5 0.05-0.34 1.0 0.36-1.2 Other risk scenarios for solid residues from thermal processes are related to recycling in e.g. geotechnical applications, construction materials and agriculture (Ferreira et al., 2003). However, few investigations have focused on the environmental impact with respect to organic contaminants for these recycling options. At the same time, there are known examples where town refuse waste ash has been used as fertiliser to increase the fertility of soil (Pasquini, 2006). 29 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Residues from electric arc furnaces and ashes containing high levels of zinc can be recycled in industrial processes, such as the Waelz process, to extract the metals. Since PCDD/Fs are regenerated in the process, the recycling may result in high emissions to air if the air pollution control devices are inefficient (Chi et al., 2006). Chi and coauthors demonstrated that 560 ng TEQ kg-1 recycled ash was emitted from one facility. This recycling option will therefore result in large emissions to air and highly contaminated solid waste residues are generated (Chi et al., 2008; Table 2) The management of PCDD/F contaminated waste is poorly regulated in some countries. Open, unprotected storage and dumping practices in poor countries may be risk scenarios with limited possibilities to detect and measure impacts of the environment and human health. 5.3 Impregnated wood and waste wood litter 5.3.1 Concentrations of pollutants PCDD/Fs are unintentionally formed during the production of e.g. wood impregnation chemicals (such as Ky-5, Dowicide G and other chlorophenol based agents). The production of these pesticides has ceased, but CP treated wood may still contain high levels of PCDD/Fs. In Table 4, wood and wood litter TEQ concentrations reported in the open literature are compiled. Table 4. Reported PCDD/F and dl-PCB concentrations (ng TEQ kg-1) in different wood fractions. Waste type PCDD/F dl-PCB Country Reference Wood at animal prod. facilities n.d.-91 620 - USA Huwe et al., 2004 Sleepers 21 000 0.93 Japan Asari et al., 2004 Waste wood chips 0.94 0.51 " " Untreated wood 0.006 0.30 " " Litter 0-0.86 0.19-240 " " PCP treated wood 11-315 000 - - Fries et al., 2002 Impregnated wood 67- 38 000 - various SEPA, 2009 - Italy Brambilla et al., 2009 Wood litter a 50 n.d.; not detected, a the concentration was published as 50 000 ng WHO-TEQ kg-1 but was corrected to 50 ng WHO-TEQ kg-1 after correspondence with the author; PCP: penta-chlorophenol Even though the TEQs are mostly related to PCDD/Fs, dl-PCBs can in some cases contribute significantly as well. However, not all studies have included dl-PCBs in the 30 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs analysis. The range of reported concentrations is large, but it is obvious that waste wood fractions will fall above and below the currently suggested LPCL. 5.3.2 Case studies As long as CP treated wood is in use, demolition of old wood constructions may result in highly contaminated waste wood fractions. Recent studies have shown that waste wood fractions may enter the human food chain via animal food production facilities (Brambilla et al., 2009; Diletti et al., 2005; Asari et al., 2004), and that shipping of contaminated wood between countries is a risk scenario. Maximum levels are legislated limit values for contaminants in food (see also Table 4). PCDD/F in eggs and egg products: 3 pg WHO-TEQ g-1 fat PCDD/F and dl-PCB in eggs and egg products: 6 pg WHO-TEQ g-1 fat PCDD/F in milk and dairy Two case studies report serious contamination of products: chicken eggs by penta-chlorophenol (PCP) 3 pg WHO-TEQ g-1 fat contaminated wood litter (Brambilla et al., 2009; PCDD/F and dl-PCB in milk Diletti et al., 2005). Both incidents took place in and dairy products: Italy. In one study, the wood litter contained 50 ng 6 pg WHO-TEQ g-1 fat WHO-TEQ kg-1, resulting in mean chicken egg concentrations of 46 pg WHO-TEQ g-1 fat (Brambilla et al., 2009; the published wood litter concentration of 50 000 ng WHO-TEQ kg-1 has here been corrected to 50 ng WHO-TEQ kg-1 after correspondence with the author). Brambilla and co-authors point also out that there is no legislation to prevent exposure of food-producing animals to bioaccumulative substances via materials, such as barns, stables or litter. In the other study, contaminated wood litter (50.8 ng WHO-TEQ kg-1) and wood shavings (40.1 ng WHO-TEQ kg-1) was used at the farm (Diletti et al., 2005). Chicken egg and chicken meat contained PCDD/Fs at levels significantly exceeding legislated maximum levels for food stuffs (eggs: 33 and 88 pg WHO-TEQ g-1 fat; meat: 45.2 pg WHO-TEQ g-1 fat). Recent incidents in Europe show that recycling of PCDD/F contaminated wood is a risk scenario for animal food production facilities. Waste wood concentrations were far below the suggested limit of 15 ppb for PCDD/F. 31 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 5.4 Chemical waste 5.4.1 Concentrations of pollutants The use and production of chlorinated pesticides and chemicals have polluted the environment with PCDD/Fs in several countries (Holt et al., 2010, Weber et al., 2008). Table 5 summarises concentrations of PCDD/Fs and dl-PCBs in some chemical products. Table 5. Reported PCDD/F concentrations (ng TEQ kg-1) of technical formulations. Product PCDD/F Country Reference PCP 140 000-5 400 000 Japan Masunaga et al., 2001 CNP 2 600-10 000 000 " " Chloranil 20-16 300 China Zhu et al., 2008; Zhang et al., 2002 Pentachlorophenol (PCP) and chlornitrofen (CNP) products may contain extremely high concentrations of PCDD/Fs. High levels may also be found in dye ingredients, e.g. chloranil, that are currently used in textiles, plastics and paints (Zhang et al. 2002; Zhu et al. 2008). The contamination levels seem to depend on the production date, since lower levels are often found in more recently produced chemicals (Masunaga et al., 2001; Zhu et al., 2008; Zhang et al., 2002). Since PCDD/Fs are detected in chemical formulations that are currently in use (Holt et al., 2010; Zhang et al., 2002; Zhu et al., 2008), waste from the production may also contain levels that are of concern. There is, however, limited data on PCDD/Fs concentrations of production waste categories in the open literature. Historically, the chemical industry has a large record of PCDD/F contamination incidents related to production of chemicals and handling of waste (Weber et al., 2008). Due to the high production volumes of the chemical industry in e.g. China, Zhu et al. (2008) addressed their importance as a relevant PCDD/F source. The problems related to pollutants in chemical waste are complex, since chemical recycling and remediation processes may generate emissions of other toxic compounds than the original ones (Braga et al., 2002). The toxicity of chemical waste is also dependent on mixtures of pollutants, and not only to PCDD/Fs. Chemical waste often consists of technical chemical formulations such as pesticides. The presence of a mixture of hazardous pollutants may result in that this waste category can be classified as a POP-waste based on other criteria than the abundance of PCDD/Fs. Chemical waste has been recognised as a growing environmental and human health risk problem in poor countries, as well as in industrialised ones (Holt et al., 2010). 5.4.2 Case studies Identified case studies related to management of PCDD/F contaminated chemicalwaste are mostly related to historical incidents (Asmus et al., 2008; Lee et al., 2006a 32 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs and b; Wu et al., 2001; Isosaari et al., 2000). The cases are characterised by large emissions of chemicals or production wastes to soil or waters. The magnitude of the contamination have resulted in severely contaminated food chains and elevated exposure of humans (Asmus et al., 2008; Lee et al., 2006a; Braga et al., 2002). No reports on recent incidents were found. 5.5 E-waste recycling 5.5.1 Concentrations of pollutants An ongoing formation source of PCDD/Fs is the recycling of e-waste in developing countries (Sepúlveda et al., 2009; Wong et al 2007; Leung et al 2007, Gullett et al., 2007). Besides of air emissions, incineration and recycling residues may contain high levels of organic pollutants. In Table 6, PCDD/F levels in different types of residues from the e-waste megasite Guiyu (China) are compiled. Since dl-PCBs were not included in the measurements, total TEQ levels in the waste fractions are most likely even higher. Table 1. Reported PCDD/F levels (ng TEQ kg-1) in waste products from e-waste recycling in China. Waste type PCDD/F Reference Ash 5 700 Zhu et al., 2008 Electronic shredder waste 66.9 Ma et al., 2008 Acid leachate 203-1 100 Leung et al., 2008 Cable wiring and plastic combustion residues 84-174 " Ash 155-14 400 Luksemburg et al., 2002 5.5.2 Case studies Even though e-waste sites are known for on-going contamination of the environment, few measurements of PCDD/F contamination related to management of residues from the recycling activities have been reported (Sepúlveda et al., 2009). Most concern has been raised about air emissions, and less focus has so far been paid to the management of the solid/liquid residues. However, in one study from the mega-site Guiyu, it was reported that PCDD/F polluted ash from the e-waste site at had been dumped in the adjacent Lianjing River (Luksemburg et al., 2002). Sediment samples from the dumping site showed extremely high contamination levels (up to 35 200 ng WHOTEQ kg-1 d.w.). At this site, the residents used water from the river for washing clothes and cleaning cookery utensils. Sediment samples 20 and 50 km downstream the e-waste site did, however, not contain elevated levels, which was tentatively explained by the low flow of the river. 33 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs E-waste recycling activities are known as on-going sources for formation of PCDD/Fs. Residues from the recycling are known to be contaminated with PCDD/Fs. However, limited data exist, and dl-PCBs have not been investigated. Dumping of PCDD/F contaminated e-waste residues in the local environment has been reported. 34 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 6 Human exposure There is a general consensus that humans are mainly exposed to PCDD/Fs and dlPCBs via the diet (Mato et al., 2007; European Commission, 1999). Most important are ingestion of food of animal origin, such as meat, dairy products, eggs and fat fish. In pristine environments, the background concentrations of both PCDD/Fs and dlPCBs are low and exposure via ingestion of soil and water or inhalation of air is insignificant. Tolerable weekly intakes (TWI) of PCDD/Fs and dl-PCBs for humans stand for a long-term weekly intake with no risk of negative effects of human health. The TWI recommended by the Scientific Committee on Food of the European Commission is currently set to 14 pg TEQ kg-1 b.w. week-1 (SCF, 2000). This recommendation is often expressed as a tolerable daily intake (TDI) of 2 pg TEQ kg-1 b.w. day-1. In 2000, WHO came up with a TDI of 1-4 pg TEQ kg-1 b.w. day-1, where the lowest level is a long term goal (WHO, 2000). The TDI is often used to evaluate results from dietary intake studies of different populations. 6.1 Exposure via dietary intake Dietary intake studies are used to estimate human exposure of pollutants from ingestion of food based on food concentration and food ingestion data. A compilation of data from dietary exposure studies for PCDD/Fs and dl-PCBs from different countries are presented in Table 7. The compilation should not be considered as complete, but illustrates the variation of human exposure levels for different age classes and countries. 35 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Table 2. Reported estimations of dietary intake of PCDD/Fs and dl-PCBs (pg TEQ kg-1 b.w. day-1) for human populations. Country Age Mean/median 90th or 95th percentile Netherlands 40 1.1 1.7 Baars et al., 2004 " 10 1.5 2.3 " " 2 2.8 4.4 " Italy 13-94 2.28 - Fattore et al., 2006 Reference " 7-12 3.37 - " " 0-6 5.34 - " Finland adult 1.5 - Kiviranta et al, 2004 Sweden <10 2.7-4.5b 4.6-9.3 Bergkvist et al., 2008 b " 11-24 1.5-2.1 3.3-5.1 " China - 1.4 - Zhang et al., 2008 Li et al., 2007 China 18-45 0.15-0.96 - Japan - 1.52 or 1.78a 2.91 Japan 17-72 1.06/0.79 - Arisawa et al., 2008 USA 0-1 42.0 - Schecter et al., 2001 " 1-11 6.3/6.1c - " " 12-19 3.5/2.7 c - " " 20-79 2.4/2.2 c - " " 80+ 1.8/2.0 c - " Egypt - 6.04-6.68 - Loutfy et al., 2006 estimated by deterministic or probabilistic approach; bdifferent genders and age classes; cmales and females, respectively; a As illustrated by Table 7, the estimated dietary intake levels differ between different countries. Some of the variation is likely related to differences in the applied methodology of the investigations, but more important factors are probably dietary habits, national and local contamination levels of food and geographical location of the populations (Arisawa et al., 2008; Chen et al., 2003; Undemann et al., 2009) 36 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Available data needed for estimation of Little is known about dietary exposure dietary intake exposure and human body levels of populations in developing burdens of environmental pollutants in countries. There are a large number developing countries and remote areas are of factors that contribute to the dietary exposure levels. Thus, it is not limited (Linderholm et al., 2009; Sun et al., possible to extract data for a 2005; Sun et al., 2006). Significant population in a specific region and uncertainties will therefore remain about then apply these data for populations the exposure levels of general populations in other parts of the world. and subpopulations in these areas, but A compilation of international data might be reduced by the global POPs shows that many populations are exposed for dioxins and dioxin-like monitoring program related to the PCBs at doses near or above the Stockholm Convention and the ongoing tolerable daily intake (TDI) of 2 pg global human milk study. The study by WHO-TEQ kg-1 b.w. and day. Loutfy et al. (2006) indicates that the exposure levels of general populations in developing countries may exceed the current exposure of the populations in industrialised countries. In contrast, low exposure levels have been estimated for populations in remote areas of e.g. China (Sun et al., 2005). In an international screening study of POPs in butter, it was concluded that butter from Asia, America and South African regions were less contaminated than butter from Europe, which indicate that the overall exposure level is lower in these countries (Santillo et al., 2003). However, the authors of this study stated that limited food concentration data from these regions exist, and the representativeness of existing samples for each region could not be guaranteed. Environmental and human living conditions are not the same in developing countries as in industrialised ones, and local sources such as waste dump sites and back-yard burning, may add to the total exposure, directly or indirectly (Kunisue et al., 2004). Since many poor people depend on food from the local environment, they are more vulnerable for contamination of food chains via local sources. In contrast, industrialised populations buy most of their food via groceries, where the food is commercially produced and controlled by national and international legislations. Dietary habits might also differ between urban and rural populations. 6.2 Exposure routes near local pollution sources Local PCDD/F sources may affect biotic and abiotic exposure media via emissions to air, water or soil. Direct exposure via these media contributes in general to no more than a few percent of the total dietary exposure. In local contamination scenarios, contaminated local food chains are often identified as the main risk scenario (Kao et al., 2007; Pirard et al., 2005; Pless-Mulloli et al., 2005). However, there are cases when local emissions have caused incremental human exposure by contact with soil and air. 37 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs The contamination of most concern in local contamination scenarios is the contamination of agricultural food chains, such as free-range chickens and eggs, and milk and meat from grazing animals (Chen et al., 2008; Turrio-Baldassarri et al., 2008; Cerna et al., 2007; Turrio-Baldassarri et al., 2007; Goldman et al., 2000; Harnly et al., 2000). Also aquatic food chains, such as fish and seashells for food consumption, may become contaminated. As presented in the following chapter, these dietary routes are widely associated to elevated human body burdens in the presence of local sources. Ingestion of vegetables, which normally contribute insignificantly to the daily exposure, may become significant if soil concentrations close to local sources are elevated (Nakagawa et al., 2002; Donato et al., 2006). Root crops grown in contaminated soil will contain higher levels of PCDD/Fs (Åberg et al., 2010), mostly due to accumulation in the peels (Engwall & Hjelm, 2000; Hülster & Marschner, 1993), and leafy vegetables may become contaminated by soil and dust particles that adsorb to leaf surfaces. 6.3 Human body burdens in local contamination scenarios Open waste dump sites have been recognised to contain high concentrations of organic pollutants, including PCDD/F. Millions of people in developing countries must rely on scavenging waste to earn their own living. Two studies report on body burdens of POPs in populations characterised by an intense contact with waste dump sites. Cuadra et al. (2006) found that children (age 11-15) working at a waste dump sites were more exposed to POPs than children in industrialised countries. They also found a gradient with decreasing exposure at increasing distance from the waste site. Santos et al. (2003) found that people living at a waste site displayed 2-155 times higher serum concentrations of POPs compared to a control group. None of the studies included measurements of PCDD/Fs or dl-PCBs. Several studies show that locally contaminated food chains may cause high exposure and/or elevated body burdens of local residents (Turrio-Baldassari et al., 2008; Ma et al., 2008; Chan et al., 2007; Lee et al., 2006a; Goldman et al., 2000; Harnly et al., 2000). Table 8 summarises results from a selection of studies where residential human body burdens of PCDD/F were studied in connection to various local exposure scenarios. Even though the studies are not fully comparable, the results are consistent in that they illustrate the significance of local exposure from human food chain contamination. The study by Kunisue et al. (2004) was performed at open waste dump sites for which environmental levels are reported in Table 3. In this study, elevated body burdens in people living near the dump sites were only found in India, presumably since a local animal food chain was contaminated via the waste site. High concentrations in soil at waste sites in Vietnam and Cambodia did not affect the body burdens of the residents (Table 8). 38 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Table 3. Reported human body burdens of PCDD/Fs (pg TEQ g-1 fat or pg TEQ g-1 hair) of residentials in local contamination scenarios together with reference values. Specimen Exposure scenario Exposed population Reference Population Country Reference Human milk e-waste site 21 9.35 China Chan et al., 2007 Placenta " 35.1 " " 11.9 a a Hair " 33.8 5.59 " " Human milk PCP contaminated site 17.5-187 9.65 China Wu et al., 2001 Serum PCP contaminated site, egg 26.7 17.0 USA Goldman et al., 2000 Serum egg and beef 63.7 17.0 USA " Serum MSWI, locally prod. food 49 31 Belgium Fierens et al., 2003 Serum MSWI, industrial area 31 31 " " Serum Hazardous waste incineration, locally prod. food 22.7±11.1 20±8.3 Taiwan Chen et al., 2006 Breast milk Dumping site, locally prod. food 21 8.3 India Kunisue et al., 2004 " Dumping site 5.6 5.3 Cambodia " Dumping site 6.0 6.3 Vietnam " " a pg g-1 dry weight The significance of dietary exposure routes is also illustrated in Figure 2, using data from Turrio-Baldassari and co-authors (2008) who investigated PCDD/F and dl-PCB TEQ serum levels in former workers and residents from a PCB contaminated area in Italy. People that consumed locally produced food were more exposed than people who were just living in the contaminated area. The study stresses also the fact that local sources may have a significant impact on human body burdens several decades after cessation of the contamination. However, Goldman et al. (2000) found that even short term (2 years) exposure from ingestion of locally produced food had a negative impact of human serum concentrations. 39 pg WHO-TEQ g-1 fat, upperbound estimates SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Non-ortho PCB 400 Mono-ortho-PCB 350 PCDD/F 300 Total TEQ 250 200 150 100 50 0 GPB R-SE R-S R-SSW PWF FWP CCF Figure 1. Serum concentrations (pg WHO-TEQ g-1 fat, upper-bound estimates) of sub-populations in Brescia, Italy (Turrio-Baldassari et al., 2008). GPB=general population in Brescia; R-SE, R-S and RSSW=local residents in contaminated subareas southeast, south and southwest of the industrial area; PW =present workers at the industrial area; FWP=former workers of the PCB factor; CCF=consumers of locally produced food. High consumption of fish and seafood is usually correlated to high PCDD/F body burden even at background level conditions (Mato et al., 2007; Lee et al., 2007; Chen et al., 2003; Kiviranta et al., 2002). Contamination of aquatic food chains is therefore a risk scenario that significantly can increase human body burdens in the presence of local sources (Lee et al., 2006b; Chen et al., 2006b; Wu et al., 2001). Since fishing populations generally are at higher risk than non-fishing populations (Harris & Jones, 2008; Weintraub. & Birnbaum, 2008; Bilau et al., 2007), these risk scenarios are relevant for e.g. Asian countries, where the consumption of fish and sea food usually is high. Contaminated aquatic food chains may also affect human exposure via consumption of wild-bird eggs (Ryan et al., 1997). No studies were found for cases that related contaminated aquatic food chains to current management practices of PCDD/F contaminated waste. There are indications on that contaminated waste is dumped into e.g. rivers close to waste dumping and recycling sites, but no detailed investigations were performed (Luksemburg et al., 2002). Known examples of serious contamination incidents are mostly related to former chemical production activities (Chen et al., 2006b; Lee et al., 2006a and b; Wu et al., 2001; Isosaari et al., 2000). 40 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Studies of human exposure related to open waste dump sites show that people with intense contact with the sites have elevated concentrations of POPs in their bodies. In local contamination scenarios where human food chains are contaminated, elevated human body burdens have been detected regularly. In some cases, ingestion of soil may be important as well. 41 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 7 Food chain contamination related to local sources In order to control and reduce human dietary exposure of dioxins and dioxin-like compounds for the general population, the European Union has legislated maximum levels for PCDD/F and dl-PCB of 1.5-6.0 pg WHO-TEQ g-1 fat in commercially produced food products (European Commission, 2006; Table 9). Maximum levels have also been laid for PCDD/F in animal feed stuff (European Commission, 2000), where 0.75 pg TEQ g-1 is applicable for vegetable feed. Table 4. Maximum levels of PCDD/Fs and dl-PCB in food stuffs (European Commission, 2006). Food stuff Origin PCDD/F PCDD/F + dl-PCB maximum levels maximum levels Meat and meat products pg WHO-TEQ g-1 fat 4.5 1.0 “ 1.5 2.0 “ 4.0 pg WHO-TEQ g-1 ww 8.0a pg WHO-TEQ g-1 fat 6.0 “ 6.0 Beef, sheep 3.0 Pork Poultry Fish and fish products - 4.0 Milk and dairy products - 3.0 Eggs and egg products - 3.0 The maximum levels are usually referred to when contamination of food products is investigated. However, they are not based on human health risks; instead they are founded on a statistical assessment of levels in European food stuff. Thus, if the maximum levels are used as reference levels in a risk assessment, it is important to remember that they do not represent “safe” food contamination levels with respect to human health risk. A good understanding of the bioaccumulation process of PCDD/Fs and dl-PCBs into human food chains is required for adequate human health risk assessment in connection to management of contaminated waste. In the following, the current knowledge on the transfer of PCDD/Fs and PCBs in to agricultural and aquatic food chains in the presence of local pollution sources is briefly reviewed. 42 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 7.1 Agricultural food chains 7.1.1 Eggs and chickens It has been shown that poultry are extremely vulnerable for exposure of environmental contaminants. High levels of PCDD/Fs in eggs, chickens and ducks have been reported for areas close to waste incinerators (Pirard et al., 2005), chlorophenol contaminated land (Åberg et al., 2010; Goldman et al., 2000, Harnly et al., 2000), metal processing plants (Hsu et al., 2007), ash contaminated areas (Pless-Mulloli et al., 2001) and other industrial facilities (e.g. cement kilns, chemical manufacturing, incinerators, waste dump sites, IPEN, 2005). In the study conducted by IPEN, 20 chicken egg samples collected in 17 different countries were analysed for PCDD/Fs and dl-PCBs. The sampling sites were selected to represent different local contamination scenarios, and the levels found generally exceeded the legislated maximum level (3.2-140 pg WHO-TEQ g-1 fat; Figure 3), once again demonstrating the risk for enhanced human exposure in connection to food production and contaminated sites. 160 140 dl-PCB PCDD/F pg WHO-TEQ/ g fat 120 100 80 60 40 20 C C ze ch ze Rep ch u R bli c ep u Pa bli ki c s C Ta tan ze n , ch z a R nia ep , ub Tu li c r U key ru gu , ay , M oz US am A , Ph bi q i li ue, pp in Be es la , ru s, In d Sl i ov a, ak R ia , us s M i a, ex ic o, In di Ke a, n Se ya, ne g R al, us Bu si a lg , ar ia Eg , yp t, 0 Figure 3. Egg concentrations (pg WHO-TEQ g-1 fat) reported by IPEN (2005). 43 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Despite low internal bioaccessibility of One experimental study show that PCDD/Fs that are adsorbed to solid matrices free range chickens that are (Budinsky et al., 2008; Wittsiepe et al., 2007; exposed to PCDD/F contaminated ash may produce eggs containing Morinello et al., 2006; Ruby et al., 2002), a PCDD/F levels that exceeded the recent study by Shih and co-authors (2009) legislated maximum limit of 3 pg showed that fly ash contaminated feed can WHO-TEQ g-1 fat by far. increase the PCDD/F levels in eggs. In a The PCDD/F concentration ash controlled experiment, chickens were fed by was below the suggested Low fly ash (containing 201 ng TEQ kg-1) at 0.3 and 0.6 weight % of the commercial feed. The eggs reached maximum levels of 2.2 and 3.7 pg WHO-TEQ g-1 fat during the feeding trials, while the maximum levels of the control group were 1.4 pg WHO-TEQ g-1 fat. Lee et al. (2009) also reported elevated PCDD/F levels in duck eggs in a field case, where farmers used fly ash as a feed additive to improve the colour of the yolk. The high susceptibility for environmental pollutants of poultry often results in high levels of PCDD/Fs and dl-PCBs in free range eggs already at low environmental levels (Van Overmeire et al., 2009a and b; Schoeters & Hoogenboom, 2006; Pussemier et al., 2004). Contamination levels of free-range eggs reported from international studies are compiled in Table 10. Based on existing case studies from Europe, the suggested provisional Low POP Content Limit is not low enough to prevent severe food chain contamination if recycled waste wood is introduced to chicken production facilities. Empirical data show that chickens that are exposed to wood containing 50 ng WHO-TEQ kg-1 (0.05 ppb) may produce eggs with concentrations significantly exceeding the maximum limits (88 pg WHO-TEQ g-1 fat or 8.8 pg WHO-TEQ g-1 whole egg). For a person (60 kg) that consumes one egg per day (60 g), the intake equals a dose of 8.8 pg WHO-TEQ kg-1 b.w. and day. The exposure of children eating the same amount will be even higher. The tolerable daily intake (TDI) that 44 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Table 5. Concentrations of PCDD/Fs and dl-PCBs (pg TEQ g-1 fat) in free range egg (compilation of data from Schoeters & Hoogenboom, 2006). Country Breeding cond. PCDD/Fs Mean Min-Max Mean Min-Max Switzerland Free range - 2.3-19 - - Germany Free range - 0.4-22.8 - - Germany Free range 4.4 <d.l.-22.8 - - 0.7-7-7 - 0.7-5.8 12.9 2.1-26 - - Netherlands Organic U.K. Free range dl-PCBs Site description After fly ash removal France Free range - 6.3-121.6 - 0.35-46.4 MSWI surroundings Belgium Free range 9.9 - - - Private gardens Belgium Free range 0.4-18 - 0.4-270 Private farms Ireland Free range 0.5 <d.l.-0.8 0.3 0.4 Ireland Organic 1.3 2.7 1.4 3.9 d.l.: detection limit A major exposure route of free range chickens is ingestion of soil (Van Overmeire et al., 2009b; Schuler et al., 1997), but other exposure routes may contribute. There is a consensus that free-range chickens are more exposed for environmental pollutants than caged chickens, which are completely fed with commercial and controlled chicken feed (Schoeters & Hoogenboom, 2006; Pirard et al., 2005). There are also examples of how PCDD/F or PCB contaminated waste products and recycled substrates have been introduced in to the poultry food chain via production of animal feed (Bernard et al., 2002; Hoogenboom et al., 2009; Hoogenboom et al., 2004; Llerena et al., 2003; Malisch, 2000). The cases differ in how the contamination aroused, but together they illustrate the ease in which human food chains can become severely polluted by accidental, illegal or unconscious use of recycled substrates and materials. Another risk scenario is recycling of PCDD/F contaminated wood that is used as animal bedding in chicken production facilities (Diletti et al., 2005; Brambilla et al., 2009). The wood shaving litter reported by Diletti and co-authors contained only 4050 ng WHO-TEQ kg-1, which resulted in egg and meat concentrations as high as 88.1 and 45.2 pg WHO-TEQ g-1 fat. Considerable risks related to recycling of PCDD/F contaminated waste will therefore exist at residue levels corresponding to the suggested LPCL of 15 000 ng TEQ kg-1 (15 ppb). 7.1.2 Milk and meat PCDD/Fs and PCBs accumulate in milk and meat products from grazing cattle. At low environmental concentrations (background levels), feed and grass appears to be the major exposure pathways (McLachlan et al., 1990). Bioaccumulation may account for a 6-fold increase of PCDD/F levels in cow’s milk as compared to levels in the diet (Huwe & Smith, 2005). 45 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Elevated soil concentrations constitute risk scenarios for grazing cattle due to direct ingestion of contaminated soil or feed. A number of studies report contamination of cow’s milk and other animal food products due to local sources (Esposito et al., 2009; Turrio-Baldassari et al., 2007; Costera et al., 2006; Lindström et al., 2005; Schulz et al., 2005: Table 11). Table 6. Concentrations of PCDD//Fs and dl-PCBs (pg TEQ g-1 fat) in contaminated meat and milk products produced near local sources. Product PCDD/F dl-PCB Country Reference Milk from goat 2.84-6.93 2.01-2.58 France Costera et al., 2006 Fat from beef 27.2 - USA Goldman et al., 2000 Mutton 3.2 3.9a Sweden Lindström et al., 2005 Beef 0.46 - Germany Schulz et al., 2005 Milk from cows 3.47-6.13 - " " Mutton 0.6 - " " Milk from sheep 1.63 - " " Milk from cow 5.07-8.14 - Brazil Braga et al., 2002 a PCB 77, 126 and 169 only PCDD/F in contaminated sediments may also affect agricultural food chains due to flooding (Stachel et al., 2006; Lake et al., 2005; Alcock et al., 2002). An important case study illustrating this risk scenario is the flooding of river Elbe, where grazing animals were affected by contaminated feed and soil (http://elib.tihohannover.de/dissertations/gudek_ws08.html). As for poultry and egg, there are several known incidents where the agricultural food chain has been contaminated via feed additives from recycled substrates (Malisch, 2000), the use of CP treated wood in animal production facilities (Brambilla et al., 2009; Fries et al., 2002; Huwe et al., 2004) or when contaminated wood was used for drying animal feed substrates (Hoogenboom et al., 2004). Recent studies by Diletti et al. (2008) and Esposito et al. (2009) show that improper waste management strategies related to burning and dumping of waste, can affect animal food and feed contamination levels on regional scales. 7.1.3 Factors affecting transfer of soil pollutants to agricultural food chains There is a wide range of factors that governs the rate of migration of pollutants from soils to animals, e.g. the characteristics of the pollutant source, soil type, vegetation cover, climatic and hydrological conditions, behaviour of the animals, breeding and feeding conditions, physical-chemical properties of the pollutants, etc. A detailed assessment of each factor is not possible in most investigations; an overall uncertainty can be obtained when studying the food chain transfer. 46 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs In order to illustrate the range of uncertainty in the migration from soil to egg, egg/soil concentration ratios (egg concentrations in pg TEQ g-1 fat and soil concentrations in pg TEQ g-1 d.w.) were calculated for PCDD/Fs, dl-PCBs, and the sum of PCDD/F and dl-PCB using data from a number of studies (Åberg et al., 2010; van Overmeire et al., 2009b; Pirard et al., 2005, Harnly et al., 2001; Schuler et al., 1997; Figure 4). The approach assumes that soil is a major source for PCDD/Fs and dl-PCBs in eggs, and contribution from additional sources, such as animal or organic feed, are disregarded. The total number of soil and egg data pairs was 45 for PCDD/Fs and 35 for dl-PCBs and PCDD/Fs+dl-PCBs, respectively. The two studies used in the BIPRO risk assessment, yielding a soil-to-egg transfer factor of 33, are not included in the calculation which was based solely on data in the peer-reviewed journals. ) 120,0 Q E T ( 100,0 s o it 80,0 a r. c 60,0 n o c li 40,0 o s o -t 20,0 g g E 0,0 PCDD/F dl-PCB PCDD/F+dl-PCB 1 4 7 10 13 16 19 22 25 28 31 34 37 40 43 total number of data pairs Figure 4. Calculated egg/soil concentration ratios (pg TEQ g-1 fat/pg g-1 d.w. soil) obtained by using published data. 47 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs The results illustrate two important aspects: i) the egg/soil concentration ratio for transfer of PCDD/F from soil to egg in the BIPRO assessment was 33, which exceeds the highest ratio found in our study, and ii) the biotransfer of dl-PCBs is much higher than for PCDD/F. This implies that they may constitute a significant food chain risk even if the environmental TEQ levels are lower than for PCDD/Fs. In the data set, dl-PCBs contributed on average to 47% of the total TEQ in eggs, while the average TEQ contribution in soil was 17%. The risk assessment presented in the BIPRO report used a soil-toegg transfer ratio of 33. This value is in the upper range of those that were calculated from a large number of data in the open literature (see Figure 4). The transfer of dl-PCBs from soil to egg is more efficient than the transfer of PCDD/Fs. Dl-PCBs can therefore constitute a significant risk for food chain transfer, even at Statistics for the ratios in Figure 3 are summarised in Table 12. The mean ratio for dlPCBs is 6 times higher than the ratio for PCDD/Fs, and the mean ratio for PCDD/F + dl-PCBs are almost twice as high as for PCDD/Fs solely. The coefficient of variance (COV) exceeds 100%, which indicate a high variability of the data. Table 12. Statistics for egg/soil concentration ratios (pg TEQ g-1 fat/pg g-1 d.w. soil) calculated from published data. (COV = coefficient of variance, standard deviation as a percentage of the mean value). Min PCDD/F dl-PCB Sum of PCDD/F and dl-PCB 0.4 1.1 0.5 Max 26 101 22 Mean 3 17 5 Std. dev. 4 20 5 COV (%) 134 119 104 Although some of the variation probably can be attributed to application of different TEF-concepts, differences in data processing, congener composition of the soil etc., the results clearly demonstrate that a generic transfer ratio for soil to egg for PCDD/Fs and dl-PCBs is hard to establish. Since the uncertainty of predicting the transfer is high, precaution is required when trying to generalize the expected transfer. It has been stated, that PCBs are of minor toxicological importance for incineration residues compared to the PCDD/Fs because of low dl-PCB TEQ fractions in the residues (Vehlow et al., 2006), Since dl-PCBs apparently are transferred to a higher extent than PCDD/Fs, such assumption may lead to biased risk assessment. Even though it would be of great importance, a similar uncertainty analysis was not made for transfer from soil into milk and meat food chains for a very simple reason; data to investigate the relation between soil contamination levels and milk and meat concentrations from grazing animals is quite limited. However, the range of 48 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs uncertainty for milk and meat transfer is expected to be just as large as for free-range eggs. The soil-to-biota transfer ratios measured on the basis of total TEQ-levels depends partly on the congener composition of the source, since the transfer efficiency and persistence of pollutants in tissue depend on factors such as the chlorination degree and substitution pattern of the congeners (Costera et al., 2006; Schuler et al., 1997: McLachlan et al., 1990: Thomas et al., 1999a and b). For 2,3,7,8-substituted CDD/Fs, lower chlorinated congeners has usually a higher transfer rate than highly chlorinated congeners, depending on congener specific availability in the matrices (Schoeters & Hoogenboom, 2006; Hoogenboom et al., 2006; Schuler et al., 2007; McLachlan et al., 1990). Biotransfer assessments that only consider total TEQs in different media may therefore be of limited use for extrapolating risks to other scenarios with another composition of the PCDD/F source. 7.2 The aquatic food chain The biotransfer and bioaccumulation processes in the aquatic environment follows the same principles as described for the terrestrial environment, but aquatic contamination scenarios are often more complex since sediment dynamics, hydrology and bioconcentration (passive uptake of truly dissolve contaminants in water) becomes additional factors. Temporary pollution events, such as serious accidents or spills as well as long-term dumping of PCDD/F contaminated waste, can negatively harm aquatic systems for long times (Birch et al., 2007; Marvin et al., 2007; Suarez et al., 2005; Malve et al., 2003). PCDD/F and PCB contaminated waters and sediments may also cause transfer of the pollutants to agricultural food chains if the water is used for irrigation or if pastures are flooded (Zhao et al., 2006; Lake et al., 2005). As mentioned before, few cases studies of aquatic systems that are directly related to the aim of this study were found. Instead, there are several examples of large scale, historical contamination of water and sediment caused by former direct emissions of chemicals or residues from chemical production (Shen et al., 2008; Birch et al., 2007; Micheletti et al., 2007; Knutzen et al., 2003; Isosaari et al., 2002; Bopp et al., 1991; Wu et al., 2001), or situations were multiple anthropogenic sources and atmospheric deposition have affected waters and sediment, (e.g. Shen et al., 2009; Zhang et al., 2009; Castro-Jimenez et al., 2008; Micheletti et al., 2007, Bruckmeier et al., 1997). The limited number of relevant reports may indicate that such events do not occur frequently, or that the extension of the pollution results in detectable impacts of lakes and rivers. However, a few case studies indicate that such activities actually are occurring. In the pre-investigation report for the Zapallal waste site in Peru, it was stated that solid residues were regularly dumped in a nearby river, and Luksemburg et al. (2002) found high PCDD/F concentrations in sediment in Lianjing River due to dumping of ash from a nearby e-waste recycling site. It is also possible that 49 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs environmental PCDD/F concentrations have not been monitored at on-going aquatic dumping sites. Historically, aquatic systems have been severely polluted by emissions from chemical production facilities. No recent incidents related to the scope of this report were found. However, there are indications on that PCDD/F contaminated waste is dumped in rivers close to areas where the waste was generated. 50 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 8 Review of the BIPRO risk assessment In the BIPRO report, safe levels of PCDD/Fs in waste (< 1 000 ng TEQ kg-1) were estimated by considering a worst case scenario where human health risks are related to consumption of home-produced chicken eggs (page 349-351; BIPRO, 2005). This risk assessment is reviewed here from a human health perspective. 8.1 Application of safety factors and tolerable daily intake (TDI) The BIPRO report refers to the European maximum levels of PCDD/F in eggs of 3 pg TEQ g-1 fat, and states that this level is based on TDI estimations for a safe level of exposure proposed by WHO (page 350). This statement is not correct as the maximum levels for dioxin-like pollutants in food were introduced because it was concluded by the European Commission that there is no safety margin between the current exposure of the European population and the TDI. The TDI means the life-long daily intake of contaminants without risk of negative health effects. For PCDD/Fs, EU's Scientific Committee on Food (SCF, 2001) has decided on a TDI of 2 pg TEQ kg-1 b.w. day-1. The European maximum levels for food were set in order to enforce reduction of the highest concentrations of PCDD/F and dl-PCBs in the most contaminated food and thereby reduce the exposure of the European population. The maximum levels are therefore not directly based on the TDI and human consumption rates of different food items. This means that if humans are exposed to food with levels of PCDD/F and dlPCBs below the limit, the total exposure will decrease, but the exposure level may or may not be lower than TDI. The frequency of consuming dioxin contaminated food items will decide if TDI is exceeded or not. In calculating a TDI from a no-effect level in an animal toxicity study, uncertainty factors are usually applied to compensate for lack of knowledge regarding possible interspecies (rat-to-human) and inter-individual variation in sensitivity. In the risk assessment from SCF, an assessment factor of 10 was used. This factor was based on known variability in the biological half-life of PCDD/F between individuals (factor 3.2) and a factor for extrapolation from an effect-level to a non-effect level (factor 3). The factor of 10 used in this case is exceptionally small; usually a factor of 100 is applied. In the BIPRO report, it was stated that only intra-species variation (variation in response of individuals, usually a factor 10) had to be taken into account and this statement justified an increase of the maximum level in eggs from 3 pg TEQ g-1 fat to 30 pg TEQ g-1 fat. Considering the unusually small uncertainty factor underlying the TDI, this adjustment is not appropriate. 51 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs The BIPRO report states further “Consequently 30 pg/g fat must be assumed as critical contamination level.” and “It has to be taken into account that these limits include safety factors following the precautionary principle which have been excluded for the above worst case estimation.” The uncertainty factor of 10 used for the TDI calculation is based on extrapolation to a no-effect level as well as to account for known inter-individual variation in elimination of dioxins from the body, i.e. to protect also more sensitive individuals. The factor of 10 is not used based on the precautionary principle, which on the contrary is used in the risk management step, often based on lack of data. The precautionary principle is not used in risk assessment and is not handled with assessment factors. The intake level of TDI * 10 (assessment factors) thus corresponds to the dioxin level in rats causing toxic effects. Thus the factor of 10 was used to come to a safe level for (also sensitive groups of) humans. 8.2 Correlating environmental levels to uptake into eggs The BIPRO assessment used a soil-to-egg concentration ratio that was adopted from two studies only, and from these two studies they concluded that a soil concentration of 1 000 ng TEQ kg-1 (1 ppb) would result in a critical value of 30 pg TEQ g-1 fat in eggs. As previously shown, the applied correlation exceeded the highest egg/soil concentration ratio that was calculated from other studies (Figure 4). If one assumes that egg/soil concentration ratios for PCDD/Fs ranges between 0.4 and 7 (minimum level and mean + one standard deviation; Table 12), this implies that 30 pg TEQ g-1 fat in egg will be exceeded at concentrations of approx. 4-75 ng TEQ kg-1 d.w. in the soil. Consequently, the European maximum level of 3 pg TEQ g-1 fat in eggs can be exceeded at levels that are ten times lower, i.e. at soil concentrations of approx. 0.47.5 ng TEQ kg-1 d.w. The estimated “safe” waste concentration of 1 000 ng TEQ kg-1 of BIPRO therefore underestimates the risk related to ingestion of home produced chicken eggs. 8.3 Contribution of dl-PCBs The risk assessment of BIPRO never discussed if and how the presence of dl-PCBs in waste will affect the risk assessment. Even though the LPCL for PCDD/F refers to this compound group only, the exclusion of dl-PCBs may result in biased risk assessments. Since the TDI includes both PCDD/Fs and dl-PCBs, only a fraction of this value should be TEQs deriving from PCDD/Fs. Even though the literature survey showed that information of dl-PCBs in waste is limited, it was clearly shown that the food chain transfer efficiency of this compound group is high compared to PCDD/Fs. As long as dl-PCBs are not included in the LPCL for PCDD/Fs, the estimated risk associated to food chain transfer of pollutants in waste may be underestimated. 52 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 8.4 Exposure from other sources Most populations are exposed to PCDD/F and dl-PCBs primarily via their diet (Chapter 6). This overall exposure is caused by low environmental levels that exist even in pristine environments. The safety margin between the recommended TDI (2 pg TEQ kg-1 b.w.) and the overall, baseline exposure is generally low, which indicates that most populations do not tolerate additional exposure from local sources. From a human health perspective, it is therefore not recommended that 100% of TDI is allowed to origin from local sources without including other exposure. 53 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 9 Case studies in Peru and Thailand As a first attempt to achieve empirical data that correlate PCDD/F and dl-PCB levels in waste to those in the nearby environment, a field sampling study was performed at two sites where PCDD/F contaminated waste is produced and managed. The sampling sites were identified in discussion with the non-profit environmental organisations Arnika and IPEN, and criteria for the selection of the sites were: i) open and unprotected storage of ashes in areas close to residential surroundings, ii) potential exposure via residential human activities and iii) unproblematic access to the area to avoid political conflicts After pre-investigations of a limited number of possible sites, the waste site Zapallal (Peru, Appendix A) and the Phuket waste incineration facility (Thailand) were chosen. The objectives of the field sampling were to investigate if the local environments were affected by solid waste residues (ashes) and to produce data for a human exposure assessment from a generic perspective. 9.1 Case study 1: Zapallal waste site, Peru The Zapallal waste site is situated north of Lima, Peru. The area is used for recycling and dumping of different waste types (Figure 5). Activities in the area are e.g. cable burning, burning of lead batteries, metal smelting, disposal of urban waste, etc. Management of the ashes include disposal at a nearby garbage dump site for solid waste and dumping into the nearby Chillon River. The climate is very arid, and there are two main wind directions, towards east or west. Figure 5. Photos from Zapallal waste site, Peru. It is estimated that 30 000 people live in the vicinity of the waste site area, and that the zone around the landfill has 54 consolidated urban allotments (Appendix A). The distance between the landfill and nearest inhabitants is approximately 800 meter. The area with burning and melting activities is situated next to the 54 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs residential areas, and free range chickens and ducks are held close to the site. Open ash piles are stored on the ground, and the risk of windblown transport in the area is therefore very high. Because of the dry climate, no vegetables are grown in the area. However, drought resistant plants, such as Yucca, Agave and Ficus are found. The field sampling at Zapallal took place in the end of May, 2009. In total, 22 samples of soil, ash, eggs, plants and sediment from the waste site and the surroundings and 6 reference samples of soil, sediment and eggs from the rural area Trapiche, more than 50 km from Zapallal, were collected (Table 13). Table 13. Samples from the Zapallal waste site, May and July 2009. Sample Sampling area (Appendix B) Site description Picture (Appendix C) Soil 1:1,2,4,5 Soil 1 Near industrial allotments at Zapallal waste site 6 Soil 2 Soil 2 200 m from industrial allotments 6 Soil 3 Soil 3 300 m from industrial allotments 6 Soil 5 Soil 5 1500 m from industrial allotments 7 Soil 7 (ref) - Reference area,4 km from Zapallal 23 Soil 8 (ref) - Reference area, 11 km from Trapiche 24 Soil 9 (ref) - Reference area, 22 km from Trapiche 25 Soil 10 (ref) - Reference area, 30 km from Trapiche - Ash 1 Ash 1 Cable burning 11 Ash 2 Ash 2 Burning of plastic film 12 Ash 3 Ash 3 Burning of lead batteries 13 Sediment 1 - Chillon River, 2-3 km south of Zapallal 14 Sediment 2 (ref) - Reference area, Chillon River, Trapiche, 50 km upstream sediment 1 16 Plant 1:1,2,4 Soil 1 Near industrial allotments at Zapallal waste site at soil sampling sites 19 Plant 2 Soil 2 200 m from industrial allotments 20 Plant 3 Soil 3 300 m from industrial allotments 21 Plant 4 Soil 4 500 m from industrial allotments 22 Plant 5 Soil 5 1500 m from industrial allotments 7 Plant 6 Soil 6 4000 m from industrial allotments 8 Egg 1 Eggs 1 Free range chicken, 500 m west of industrial allotments 17 Egg 2 Eggs 1 Free range ducks, 500 m west of industrial allotments 18 Egg 3 Eggs 2 Free range ducks, western parts of waste site 12 Egg 4 (ref) Trapiche Reference samples, free range chickens 55 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 9.1.1 Pollution of soil and sediment related to management of ashes Results for soil, ash and sediment samples from Zapallal and the surroundings are presented in Table 14. Soil from the waste site (soil 1:1-5) contained 6.5-15 ng TEQ kg-1 d.w., and was significantly elevated compared to soil sampled 1500 m distance from the site (0.4 ng TEQ kg-1 d.w.). Reference soil from Trapiche contained 0.068 to 1.7 ng WHO-TEQ g-1 d.w. The soil concentrations decreased with distance from the waste site, which show that Zapallal is a local source. DlPCBs contributed to approximately 20 %, of the total TEQ in soil. The organic carbon (OC) content was estimated from loss-on-ignition values (LOI), assuming that the OC-content constituted half of LOI. The OC-content in the soil samples varied from 0.4 to 2.5% and no correlation was found between OC and TEQconcentrations. Sediment from close to the waste site (Sediment 1) contained higher levels (1.7 ng TEQ kg-1 d.w.) than the reference (upstream) sample (Sediment 2, 0.3 ng TEQ kg1 d.w.). TEQ concentrations in ash samples varied. Ash pile 1 contained almost 14 000 ng TEQ kg-1 d.w., which is close to the suggested LPCL of 15 000 ng TEQ kg-1 for PCDD/Fs. Ash samples 2 and 3 contained much lower levels, 56 and 150 ng TEQ kg-1 d.w.. Dl-PCBs contributed to 8-13 % of the total TEQ in ashes. Table 14. Concentrations (ng TEQ kg-1 d.w.) of PCDD/Fs and dl-PCBs in soil, ash and sediment samples from Zapallal waste site and Trapiche (ref). PCDD/F dl-PCB Sum TEQ ng TEQ kg-1 d.w. ng TEQ kg-1 d.w. ng TEQ kg-1 d.w. Soil 1:1 8.8 2.6 12 Soil 1:2 10 2.9 13 Soil 1:4 11 3.5 15 Soil 1:5 5.3 1.3 6.5 Soil 2, 200 m 3.3 0.86 4.2 Soil 3, 300 m 3.6 0.94 4.5 Soil 5, 1500 m 0.32 0.10 0.4 Soils 7-10 (ref) 0.05-1.2 0.018-0.48 0.068-1.7 Ash 1 12 000 1 700 14 000 Ash 2 50 6.1 56 Ash 3 140 12 150 Sediment 1 1.3 0.41 1.7 Sediment 2 (ref) 0.23 0.09 0.3 56 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs PCDD/F homologue group distribution profiles for soil and ash samples are presented in Figure 6. The ash profile is characterised by a large fraction of PCDF in relation to PCDD. The most dominating congeners belong to the HxCDF and HpCDF homologue groups. PCDF made up 80% of total PCDD/F levels in ash. Soil samples from the waste site area contained lower levels of PCDFs; here they made up only 55% (average for soil 1-3). The presence of HxCDF and HpCDF was not as dominating as in ash. In soil 5, sampled at 1500 m distance from the waste site, the PCDF fraction was even lower (approx. 40 %), and the abundance of HxCDF and HpCDF was also lower. In the reference soil samples from Trapiche, PCDDs were more abundant than PCDFs, which constituted only 30% of the total levels (average for soils 7-10). OCDD was the most abundant congener in the reference soil. This pattern is usually attributed to long range transport and is typical for pristine, unpolluted environments. The dissimilarities between ash and waste site soil samples (average soil 1-3) indicate that also other sources, such as atmospheric deposition, are contributing to the soil contamination. TCDD Average soil 7‐10 (ref) PeCDD HxCDD Soil 5 (1 500 m) HpCDD OCDD TCDF Average soil 1‐3 PeCDF HxCDF Average Ash 1‐3 HpCDF OCDF 0% 20% 40% 60% 80% 100% Figure 6. Homologue profiles for PCDD/F in soil and ash samples from Zapallal and Trapiche (reference soil). The concentrations are expressed as fractions (%) of total PCDD/F concentrations (pg g-1or ng kg-1). The homologue profile of the sediment sample from the waste site area (Sediment 1, Figure 7) was not similar to the ash samples, indicating that dumping of incineration residues did not cause the elevation. The pattern seen in both sediment samples remind of the reference soil pattern, with a high abundance of OCDD. 57 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Figure 7. Homologue profiles for PCDD/F concentrations in sediment samples from Zapallal and Trapiche. The concentrations are expressed as fractions (%) of total PCDD/F concentrations (pg g-1or ng kg-1). 9.1.2 Bioaccumulation in biota Egg yolk from the waste site and the surroundings contained 5.8 to 7.7 pg TEQ g-1 fat, where dl-PCBs contributed to 40-60 % of the total TEQs (Table 15). In contrast, egg concentrations from the reference site Trapiche were up to 55 times lower. PCDD/F concentration in eggs from Zapallal exceeded the European legislated maximum levels of 3 pg WHO-TEQ g-1 fat. Table 15. Concentrations (pg TEQ g-1fat) of PCDD/Fs and dl-PCBs in egg yolk from Zapallal waste site and Trapiche (ref). Egg 1 (chicken) PCDD/F dl-PCB Sum TEQ pg TEQ g-1fat pg TEQ g-1fat pg TEQ g-1fat 3.4 2.4 5.8 Egg 2 (duck) 3.8 2.4 6.2 Egg 3 (chicken) 4.4 3.3 7.7 Egg 4 (chicken, ref) 0.12 0.2 0.14 PCDD/F homologue distribution patterns in eggs did not differ much between the sampling sites (Figure 8). Despite a high presence of PCDF in soil at the waste site compared to the reference site, this pattern was not reflected in the egg samples. The PCDD/F pattern in eggs did not indicate a high impact from contaminated ash. 58 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs TCDD PeCDD Egg 4 (ref) HxCDD HpCDD OCDD TCDF PeCDF Average Egg 1‐3 HxCDF HpCDF OCDF 0% 20% 40% 60% 80% 100% Figure 8. Homologue profiles for PCDD/F in egg samples from Zapallal and Trapiche. The concentrations are expressed as fractions (%) of total PCDD/F concentrations (pg g-1or ng kg-1). Plants from the waste site contained various levels of PCDD/Fs and dl-PCBs (Table 16). In general, it seems that plant species in close proximity to the waste site were more contaminated (0.013 to 9.1 pg TEQ g-1 w.w.) than the reference samples (0.8 and 1.7 pg TEQ g-1 w.w.). However, some of these differences are likely due to species-specific variation. Yucca and Agave concentrations differed by more than two orders of magnitude for samples originating from the waste site. The concentrations in Agave from the waste site were also 60-130 times lower compared to the reference site samples of an unknown species. Dl-PCBs accounted for 11-65% of the total TEQ in Yucca samples from the waste site. Table 16. Concentrations (pg TEQ g-1 w.w.) of PCDD/Fs and dl-PCBs in plants from Zapallal waste site and its surroundings. dl-PCB Sum TEQ pg TEQ g w.w. pg TEQ g-1 w.w. pg TEQ g-1 w.w. Plant 1:1 (Yucca) 5.2 3.9 9.1 Plant 1:2 (Yucca) 3.2 1.8 5.0 Plant 1:4 (Agave) 0.012 0.001 0.013 Plant 2, 200 m (Ficus) 2.2 2.0 4.2 Plant 3, 300 m (Ficus) 4.4 3.1 7.5 Plant 4, 500 m (Ficus) 2.0 2.3 4.3 PCDD/F -1 Plant 5, 1 500 m (ref, unknown species) 0.6 1.1 1.7 Plant 6, 4 000 m (ref, unknown species) 0.3 0.5 0.8 PCDD/F homologue distribution patterns of plants from the waste site (average plant 1:1-2 and average plant 2-4) were not remarkably different from each other (Figure 9). In general, all plant samples had high accumulation of PCDFs in relation to PCDDs. 59 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs TCDD Average Plant 5‐6 (ref) PeCDD HxCDD HpCDD Plant 2‐4 (Ficus) OCDD TCDF PeCDF HxCDF Average Plant 1:1‐2 (Yucca) HpCDF 0% 20% 40% 60% 80% 100% OCDF Figure 9. Homologue profiles for PCDD/F in plant samples from Zapallal and Trapiche. The concentrations are expressed as fractions (%) of total PCDD/F concentrations (pg g-1or ng kg-1). 9.1.3 Conclusions Soil from the waste site was clearly enriched with PCDF compared to the reference soils, indicating dioxin contamination from the waste management activities at the site. Eggs sampled closed to the waste site contained levels that exceed European maximum levels for PCDD/Fs in eggs, and the levels in eggs and plants were clearly elevated as compared to levels in samples from reference sites. Based on homologue distribution patterns in ash and soil samples, it can be concluded that the waste site is a source for PCDD/Fs and PCBs affecting the surroundings. It is, however, not possible to conclude from our investigation whether it is air emissions and deposition from the recycling activities or distribution of contaminated ash that is the main cause of the impact. It is also worth to note that our results reflect only a momentary picture of existing sources and their environmental impact. 9.2 Case study 2: Phuket MSW Incinerator, Thailand A minor field sampling study was made in the area of the Phuket MSW incinerator in Thailand in June 2009 (Appendix D). The plant receives municipal waste from Phuket city, and had earlier problems with high PCDD/F emissions. Today, the incineration process and the flue gas cleaning have been improved, and the PCDD/F emissions have decreased. However, ash from the incineration process is stored in open piles at the facility (Figure 10). Industrial waste water ponds discharge into surface waters outside the plant, where local inhabitants catch fish for consumption. 60 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Figure 10. Ash deposit area and ash sampling at Phuket Incineration facility. A total of 10 samples of soil, sediment, ash, and fish from the incinerator area, and 2 reference soil samples 10 km from Phuket city were collected (Table 17). Table 17. Field samples from Phuket MSW incinerator, June 2009. Sample Description Soil 1 (ref) Patong Beach town, 10 km from Phuket town Soil 2 (ref) Patong Beach town, 10 km from Phuket town Soil 3 Soil sample in front of main office Soil 4 Soil from landfill area Sediment 1 Sediment from ash deposit lake Sediment 2 Sediment from lake near comb Ash 1 Ash, one week old, taken from laboratory Ash 2 Ash from ash deposit Ash 3 Ash from landfill Ash 4 Grey ash from lower part of site Ash 5 Ash samples (grey) from close to house where family is living Fish 1-3 Fish from lake down side ash store 9.2.1 Pollution of soil and sediment related to management of ashes Soil from the incineration area contained 5 and 12 ng TEQ kg-1 d.w., while the reference soil samples from Patong Beach had significantly lower levels (0.7 and 1.0 ng TEQ kg-1 d.w.; Table 18). Dl-PCBs contributed to <4% of the total TEQ in the soil samples. Sediment from the ash deposit lake was severely contaminated, containing 2 800 ng TEQ kg-1 d.w.. In comparison, sediment from the outlet outside the industrial area contained only low levels of PCDD/Fs and dl-PCBs (1.8 ng TEQ kg-1 d.w.). The OC content (estimated from LOI, see section 9.1.1) in the soil samples varied (1.5-8%), but no apparent correlation was found between OC and TEQ-concentrations. 61 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Concentrations in ash samples ranged from 6.6 to 8 300 ng TEQ kg-1d.w.. The ash sample that was taken close to the residential houses contained 3 200 ng TEQ kg-1 d.w.. Dl-PCBs contributed to less than 5% of the total TEQ in ash. Table 18. Concentrations (ng TEQ kg1- d.w.) of PCDD/Fs and dl-PCBs in soil, ash and sediment samples taken at or near the Phuket incineration facility. PCDD/F dl-PCB Sum TEQ ng TEQ kg-1 d.w. ng TEQ kg1 d.w. ng TEQ kg1 d.w. Soil 1 (ref) 0.68 0.022 0.7 Soil 2 (ref) 1.0 0.028 1.0 Soil 3, office 4.7 0.20 5.0 Soil 4, landfill 11 0.42 12 Sediment 1, ash deposit lake 2 700 97 2 800 Sediment 2, outlet 1.8 0.066 1.8 Ash 1, bottom ash from burner 6.2 0.35 6.6 Ash 2, ash deposit 7 200 210 7 400 Ash 3, landfill 8 000 255 8 300 Ash 4, industrial area 3 600 68 3 700 Ash 5, industrial area, close to families 3 200 72 3 300 Average PCDD/F homologue distribution profiles of soil samples from the facility were not similar to the pattern found in ashes (Figure 11). In general, the ash samples had a higher fraction of PCDF relative to PCDD. The soil at the facility was dominated by OCDD, which had a much lower abundance in ash. The divergence in congener composition in soil and ash matrices indicates that ash is not a major source for soil contamination at this site. The homologue profiles in the soil reference samples was completely dominated by OCDD, which accounted for 94% of total PCDD/F. Similar patterns have been found elsewhere in the world (Muller et al., 2002; Prange et al., 2002). 62 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs TCDD Average soil 1‐2 (ref) PeCDD HxCDD HpCDD Average Soil 3‐4 OCDD TCDF PeCDF HxCDF Average ash 1‐5 HpCDF OCDF 0% 20% 40% 60% 80% 100% Figure 11. Relative homologue distribution patterns for PCDD/F in soil and ash samples from Phuket and the reference area. The concentrations are expressed as fractions (%) of total PCDD/Fs (pg g-1or ng kg-1) for the homologue groups. The homologue distribution pattern of the contaminated sediment sample (sediment 1) from the pond was similar to that of ash (Figure 12). The pattern of sediment sample 2 from the discharge area outside the industrial facility was more similar to the pattern in soil from the facility. The results do not indicate at transport of contaminants from the contaminated pond to the recipient. TCDD PeCDD Sediment 2 HxCDD HpCDD OCDD TCDF PeCDF Sediment 1 HxCDF HpCDF OCDF 0% 20% 40% 60% 80% 100% Figure 12. Relative homologue distribution patterns for PCDD/F in sediment from Phuket. The concentrations are expressed as fractions (%) of total PCDD/Fs (pg g-1or ng kg-1) for the homologue groups. 63 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 9.2.2 Bioaccumulation in biota The fish samples contained 1.2 to 5.6 pg TEQ g-1 fat, where dl-PCBs added to 530 % of the total TEQ. Since no reference samples exist from the area, it is difficult to estimate the impact of the contamination in a regional/national perspective. Compared to international data, the concentrations are in the lower range of those measured in other studies (Moon & Choi, 2009). The homologue distribution pattern did not indicate any impact related to ash management practices (not illustrated). 9.2.3 Conclusions Soil concentrations at the Phuket incineration plant were somewhat elevated compared to the reference site, but PCDD/F homologue distribution patterns indicate that the soil is mainly affected by another source than incineration residues. Ash samples that were stored in open piles in the area contained up to 8490 ng TEQ kg-1, and high concentrations (2 170 ng TEQ kg-1) were also found in ash piles close to residential houses. The same homologue distribution pattern as in ash was found in a contaminated sediment sample from the waste water pond. However, there were no indications of further contamination of recreational surface water in the discharge area outside the facility or in fish. 64 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 10 Human exposure assessment related to environmental contamination 10.1 Method This chapter presents a human exposure assessment where elevated environmental PCDD/F concentrations are coupled to exposure levels and human health risks. The assessment is based upon PCDD/F congener distribution patterns from Peru, and fate and exposure modelling was used as a complementary method to examine the relation between environmental concentrations and human exposure. Even though dl-PCBs contribute to the total exposure of humans, the modelling and evaluation of model outputs was made only for PCDD/F because experimental BTFs that are necessary to describe the uptake from soil and feed into animals was not easily available for dl-PCBs. As a foundation in the assessment, two human exposure scenarios were created to illustrate differences in human behaviour and food consumption characteristics related to industrial and developing countries, respectively. Each exposure scenario contained also two different receptors: adults and children, to cover age related differences, such as body weights and behaviour. Since exposure of humans to PCDD/Fs and dl-PCBs is primarily related to ingestion of food, and in some cases soil, other exposure routes (such as dermal contact, inhalation and ingestion of drinking water, fish or root-crops) were not considered in the assessment. For aquatic exposure pathways, it is difficult to relate the bioaccumulation to local soil concentrations and a different modelling approach is needed. The aquatic system is also affected by several sources that are distributed over a regional scale. Inhalation exposure of PCDD/F is more relevant for e.g. occupational scenarios (Shih et al., 2006) since indoor air concentrations might be affected by contaminated dust particles from occupational activities (Åberg et al., 2010) and limited air exchange rates may increase contamination of air. It is less important for residential outdoor exposure. Root crops were excluded since they are affected by contaminants in the root zone and in our scenarios we assumed that contamination from improper waste management strategies (e.g. dumping) will affect only surface soils. For food ingestion pathways, the external dose was estimated by modelling the uptake of contaminants in biota as a function of two different soil concentrations in the scenarios. The input soil concentration was selected to represent a background scenario (1 ng TEQ kg-1) and a local contamination scenario with a high (but not extremely high) soil concentration of 70 ng TEQ kg-1, yielding model out puts expressed on fresh weight basis. Estimated exposure doses of PCDD/Fs in the scenarios were evaluated against the TDI of 2 pg TEQ kg-1 b.w. day-1. 65 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 10.2 Human exposure scenarios The two exposure scenarios will here after be called the Industrial setting and the Development setting. Each scenario included two age groups: children (4 years) and adults (>17 years). Average food consumption data for Swedish children (NFA, 2003) and adults (NFA, 2002) was used as food consumption rates in the Industrial setting, which aims to represent European conditions. The scenario included the same soil ingestion rates that are used for sensitive land use in the Swedish model for setting remediation soil guideline values: 120 mg day-1 for children and 50 mg for adults. To compensate for that most of the food in industrialised countries is bought from groceries, only a fraction of the totally ingested food (10 % of vegetables and root crops, 10 % of milk and meat and 50% of eggs) was assumed to be locally produced. Bodyweights of the children and adults were 18 and 70 kg, respectively. The Development setting aimed to represent underprivileged living conditions in developing countries and assumes that all the food stuff is collected or produced in the nearby surroundings. Food ingestion data from Wang et al., (2009) were used for adults. Since food ingestion data for children was not included in this reference, the relative differences of food intake rates for adults in the developing and the industrial settings was assumed to be the same for the children. It was further assumed that: a) 100 % of ingested food was of local origin b) the amount of ingested soil was 10 times higher than in the industrialised setting due to a rural life style and limited access to hygienic facilities, such as tap water for rinsing and cleaning food, hands, etc. Bodyweights of children and adults were lower than in the Industrial setting (12 and 60 kg, respectively) to account for lower body weights of e.g. Asian people. It is important to stress that this scenario does not necessarily represent a specific region or country, but illustrates how different living conditions will affect human exposure levels. Table 19 summarise the human exposure parameterisation. 66 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Table 19. Exposure parameters for adults and children in the Industrial and Development settings. Industrial setting Development setting Exposure parameters Adult Child Adult Child Bodyweight (kg) 70 18 60 12 Ingestion of eggs (g kg-1b.w. day-1) 0.2 0.3 0.5 1 -1 -1 Ingestion of milk (g kg b.w. day ) 4.9 22 1 6 Ingestion of meat (g kg-1b.w. day-1) 1.6 3.8 1.9 7 -1 -1 Ingestion of vegetables (g kg b.w. day ) 3.6 7 3.9 11 Ingestion of soil (mg day-1) 50 120 500 1 200 Fraction of local prod. eggs (%) 50 50 100 100 Fraction of local prod. milk (%) 10 10 100 100 Fraction of local prod. meat (%) 10 10 100 100 Fraction of local prod. vegetables (%) 10 10 100 100 10.3 Modelling bioaccumulation and exposure levels The four exposure scenarios were coupled to bioaccumulation of PCDD/Fs by the multimedia fate and exposure model CalTOX, which previously was applied and evaluated for PCDD/F contaminated land (Wiberg et al., 2007, Åberg et al., in preparation). A simple evaluation procedure was applied to reduce some of the uncertainties that are coupled to a model based risk assessment, where biotic samples from Peru and other relevant studies were used to evaluate the bioaccumulation predicted by CalTOX. By adding this step in the risk assessment, higher confidence in the interpretation of the final results is achieved. A reference soil concentration of 1 ng WHO-TEQ kg-1 was used as input for a background concentration scenario (BS), which serves as a baseline with no influence of a local source. This level corresponds to reference soil concentrations from Peru. A soil concentration of 70 ng WHO-TEQ kg-1) was used as input for a local contamination scenario (LCS). This level was chosen in order to illustrate the impact from a site with high, but not extremely high, soil contamination. The modelling scheme is summarised in Table 20. Since the model scenarios included PCDD/Fs only, the estimated TEQs do not reflect the total dioxin exposure since the contribution from dl-PCBs are not considered. Table 20. Modelling scheme for the Industrial and Development setting at two input soil concentration levels. BS=background concentration scenario, LCS= local contamination scenario BS (1 ng WHO-TEQ kg-1) LCS (70 ng WHO-TEQ kg-1) Industrial setting Adult/children Adult/children Development setting Adult/children Adult/children 67 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 10.4 Results 10.4.1 Ingestion of eggs As discussed in Chapter 7, reliable estimates of bioaccumulation of PCDD/Fs into eggs are usually difficult to achieve. At the same time, there is a consensus that ingestion of free-range eggs could be a risk even at non-polluted sites and there is a need to correlate environmental PCDD/F concentrations to those in free-range eggs for different scenarios. In Table 21, egg concentration outputs from the BS and LCS scenarios are compared to estimated levels in eggs using mean soil-to-egg BTFs from literature data (Chapter 7; Table 12) and measured egg concentrations from the field study in Peru. The comparison shows that the model outputs for the BS soil contamination levels were in agreement with egg concentrations from Zapallal and Trapiche. Since the exact soil concentrations at the egg sampling sites were not analysed, the site specific egg-soil concentrations ratios are not known and the agreement between modelled and measured concentrations cannot be fully evaluated. However, we expect that the site at Zapallal is less contaminated than our local contamination scenario. According to literature derived soil-to-egg BTFs, 10 times higher egg concentrations than estimated by the model is to be expected at the BS and LCS soil contamination levels. The modelled exposure doses for the Industrial and Development settings might therefore be biased so that exposure levels are underestimated at least one order of magnitude. Table 21. Modelled, estimated and measured egg concentrations (pg TEQ g-1 w.w.). BS=Background scenario, LCS=local contamination scenario, BTF=average egg-soil concentration ratios calculated from literature data (see Chapter 7). Egg concentrations (pg TEQ g-1 w.w.) Model output, BS 0.018 Model output, LCS 0.33 Estimated with mean egg-soil BTF=3, for BS soil conc. (1 ng TEQ kg-1). 0.3a Estimated with mean egg-soil BTF=3, for LCS soil conc. (70 ng TEQ kg-1 d.w.) 21a Reference egg sample, Peru 0.01a Egg samples Zapallal, Peru 0.3-0.4a a ssuming 10 % fat in whole eggs Modelled exposure doses via ingestion of free range eggs for adults and children in the Industrial and Development settings are presented in Table 22. At background concentrations, the highest predicted exposure level did not exceed 1% of TDI. At the higher soil contamination level of 70 ng TEQ/kg, the maximum exposure dose approximated 17% of the TDI for children in the Development setting. Since we 68 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs expect that the model has underestimated the egg concentrations at least one order of magnitude, it is well justified to multiply the doses by a factor of 10. Consumption of locally produced eggs contributes then to 13 and 25 % of the TDI for the Industrial setting at 70 ng TEQ kg-1 and to 65-170 % of the TDI in the Development setting. Table 22. Modelled exposure doses (% of TDI) via ingestion of free-range eggs for adults and children in the Industrial and Development settings. A 10-fold adjustment upwards is justified since the model probably have underestimated the egg concentrations according to Table 21. Soil conc. (ng TEQ kg-1) Exposure dose Industrial setting (% of TDI) Exposure dose Development setting (% of TDI) Adults Children Adults Children BS 1 0.080 0.14 0.42 0.90 LCS 70 1.3 2.5 6.5 17 There was a significant difference between exposure levels for the model populations, which depend upon food consumption habits, body weights and the fraction of locally produced food that are ingested (Table 19). The exposure levels differ by one order of magnitude between the highest exposed group (children in the Development setting) and the lowest exposed group (adults in the Industrial setting). Considering that the bioaccumulation in CalTOX might be underestimated at least on order of magnitude, the dose of the highest exposed group might be significant (~10% of TDI) already at 1 ng TEQ kg-1 in soil. For populations relying on locally produced free-range eggs, this exposure route alone could then contribute to more than 100% of TDI at 10-100 ng TEQ kg-1 in soil. 10.4.2 Ingestion of milk Modelled concentrations for milk and meat in the BS and LCS are compiled in Table 23. Since reference data from Peru is missing, the model outputs are compared to selected data from the literature. The reference studies represent nonpolluted, background scenarios and local contamination scenarios with elevated PCDD/F levels in soil (23 ng TEQ kg-1 in the UK study, 0.19-13 900 ng TEQ kg-1 in the vicinity of a pasture in Brazil, pasture soil concentrations were not reported). There are few case studies where contamination of milk have been related to soil concentration levels in the pasture, thus the reference studies are not necessarily exact matches of the contamination levels in the modelling scenarios. However, they do indicate that the modelled milk concentrations are realistic and representative of generic non-polluted environments and local contamination cases. In other evaluations of performance of CalTOX in contaminate site scenarios, it was indicated that the model outputs for biotransfer into milks yield reliable estimates as long as experimental BTFs are used (Wiberg et al., 2007, Åberg et al., 69 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs in preparation). Thus, we believe that the exposure assessment is not significantly biased for this exposure route. Table 23. Modelled cow’s milk concentrations (pg TEQ g-1 w.w.) in the risk assessment together with reference data from the literature. BS=Background scenario, LCS=local contamination scenario. Milk concentrations (pg TEQ g-1 w.w.) Model output, BS 0.027 Model output, LCS 0.41 Milk samples from food basket study, Spain 0.045a.e Milk samples from rural sites, Switzerland 0.018a,d Milk samples from polluted site, Brazil 0.25a,b Milk samples from polluted soil site, UK 0.21a,c a assuming 5 % in whole milk, bBraga et al., 2002, cLake et al., 2005, dSchmid et al., 2003, Fernandez et al., 2004 e Modelled exposure doses via ingestion of locally produced milk in BS and LCS are presented in Table 24. In a non-polluted environment, the high ingestion rates of locally produced milk in the Development setting contributed to 8 % of TDI for children, while the exposure of adults in the Industrial setting did not exceed 1% of TDI. At 70 ng TEQ kg-1 soil, the exposure levels for children in the Development setting exceeded TDI. Also the adults achieved high exposure doses, corresponding to ~15% of TDI. Even for people in the Industrial setting, the exposure of children was high (45% of TDI), while the exposure of adults were 7.5% of TDI. Table 24. Modelled exposure doses (% of TDI) via ingestion of milk for adults and children in the Industrial and Development settings. Soil conc. (ng TEQ kg-1) Exposure dose Industrial setting (% of TDI) Exposure dose Development setting (% of TDI) Adults Children Adults Children BS 1 0.6 2.9 1.2 8 LCS 70 7.5 45 15 125 Similarly as for eggs, there are inherent uncertainties in modelling the bioaccumulation. Site specific factors such as the magnitude and spatial distribution of local PCDD/F contamination in soil, seasonal changes and feeding conditions will also affect the contamination levels in the milk. However, according to the initial evaluation, the estimates in Table 24 are considered as reliable, but significant uncertainties exist in this estimation. 70 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 10.4.3 Ingestion of meat Modelled outputs for meat are presented in Table 25. No reference studies were available that allowed a full scenario comparison between modelled and measured data since published beef concentrations are not always matched to soil concentrations from pastures usually. The selected references used in Table 25 represent background concentrations in beef (Bergkvist et al., 2008), and situations were a local contamination source was present (Stachel et al., 2006; Lindström et al., 2005). Data from Lindström et al. originated from a site with similar TEQ soil concentration (86 ng WHO-TEQ kg-1 d.w.) as for our local contamination scenario. The comparison shows that the model outputs are representative of generic background conditions as well as where local sources exist. Table 25. Modelled beef concentrations (pg TEQ g-1 w.w.) in the risk assessment together with reference data from the literature. BS=Background scenario, LCS=local contamination scenario. Meat concentrations (pg TEQ g-1 w.w.) a Modell output, BS 0.016 Model output, LCS 0.17 Beef, background concentrations, food basket, Sweden 0.029a,d Beef, flooding event with local contamination, Germany 0.16a.b Sheep muscle, contaminated saw mill site, Sweden 0.22a,c b c assuming 7 % fat in meat, Stachel et al., 2006 Lindström et al., 2005, dBergkvist et al., 2008 Modelled exposure doses for ingestion of meat at environmental background concentrations, resulted in a maximum exposure dose of 5.4% of TDI for children in the Development scenario (Table 26). At the higher contamination level, the exposure dose of children increased to 80% of TDI, while exposure levels for adults and children in the Industrial setting did not exceed 4.3% of TDI. Also adults in the Development setting received a significant exposure dose at the higher contamination level. Table 26. Modelled exposure doses (% of TDI) via ingestion of meat for adults and children in the Industrial and Development settings. (ng TEQ kg-1) Exposure dose Industrial setting (% of TDI) Exposure dose Development setting (% of TDI) Adults Children Adults Children BS 1 0.1 0.3 1.4 5.4 LCS 70 1.3 4.3 16 80 Soil conc. 71 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 10.4.4 Ingestion of leafy vegetables Modelled outputs for exposed produce concentrations (leafy vegetables) are presented in Table 27. Since this output is affected by soil particle adsorption on the leaf surfaces, and the adsorption efficiency in reality depend on e.g. climate, soil properties, leaf size, height above ground and leaf surfaces, it is difficult to find matching reference data. Plant samples from Peru were therefore used as reference values, even though they are not eatable vegetables. The plant samples were also rinsed before analysis, thus they did not contain adsorbed particles as the leafy vegetables do in the model simulation. Despite this, the modelled contamination levels of exposed produce were low in comparison to the measured levels of rinsed plants, up to a factor of 10 in both scenarios. This indicates that the human exposure assessment might have yielded an under estimated exposure dose in the simulation. However, it is important to stress that concentration data for plant species that are consumed by humans are missing. The field data also indicated species-specific variation of plant concentrations, which in turn were not normalised to account for varying water content. Table 27. Modelled plant concentrations (pg TEQ g-1 w.w.) in the risk assessment together with reference data from Zapallal and Trapiche. BS=Background scenario, LCS=local contamination scenario. Vegetable concentrations (pg TEQ g-1 w.w.) Model output, BS 0.038 Model output, LCS 0.53 Plant samples 5-6, reference samples, Trapiche 0.33/0.58 Plant samples 1-4, waste site samples, Zapallal 0.01-5.2 At background concentrations, the exposure of the most exposed group was 6.5% of TDI (Table 28), while the least exposure corresponded to only 0.25% of TDI. At the high soil level, children in the Development setting received an exposure dose constituting 90% of TDI. The exposure dose of the adults was 30% of TDI. The maximum exposure in the Industrial setting was 5.5% of TDI. Table 28. Modelled exposure doses (% of TDI) via ingestion of exposed produce for adults and children in the Industrial and Development settings. Exposure dose Development setting (% of TDI) (ng TEQ kg-1) Exposure dose Industrial setting (% of TDI) Adults Children Adults Children BS 1 0.25 0.41 2.7 6.5 LCS 70 2.6 5.5 30 90 Soil conc. For exposed produce, the model assumes that contaminated soil particles are adsorbed to the leaf surfaces. Rinsing of the products will therefore decrease the 72 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs external dose. Since no reference data was available to evaluate the modelled accumulation in the exposed produce, the precision of the model output is insecure. 10.4.5 Ingestion of soil Since the model assumes that initial soil concentrations (i.e. BC and LCS concentrations of 1 and 70 ng TEQ kg-1) decreases over time because of transport and degradation processes, the soil ingestion exposure levels in Table 29 were estimated for soil concentrations of 1 and 60 ng TEQ kg-1 d.w. At the BS contamination level, ingestion of soil resulted in a maximum exposure dose equal to 6.3% of TDI for children it the Developing setting. At 60 ng TEQ, the exposure of this target group increased to 380% of TDI. The assumed soil ingestion rates included in this scenario were not supported by e.g. experimental data, so the assumption may be unrealistic. On the other hand, it is reasonable to believe that people living at poor conditions will ingest more soil and other particles, compared to people in industrialised countries. The modelling results show that the external exposure via ingestion of soil is a potentially important exposure route in the presence of local sources. In the current example, no consideration was taken to the reduced availability of PCDD/Fs on soil particles for absorption in the digestive system (Budinsky et al., 2008; Ruby et al., 2002; Morinello et al., 2003). This approach may in turn lead to that the health risk related to soil ingestion is exaggerated. Table 29. Modelled exposure doses (% of TDI) via ingestion of surface soil for adults and children in the Industrial and Development settings. Soil Conc. (ng TEQ kg-1) Exposure dose Industrial setting (% of TDI) Exposure dose Developing setting (% of TDI) Adults Children Adults Children BC 1.0 0.03 0.4 0.4 6.3 LCS 62 2.0 25 23 380 At the highest input soil concentration (70 ng TEQ kg-1 soil), the estimated exposure levels for single exposure routes of the most sensitive population exceeded TDI by far. At the same environmental concentrations, the exposure level of the most and least sensitive populations differed by one to two orders of magnitude. 73 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 10.5 Critical soil concentration levels Some general conclusions can be drawn from the exposure assessment, the modelling exercises and the supporting field data; i) even at moderately elevated soil concentrations (e.g. 50-100 ng TEQ kg-1) local food and soil ingestion pathways may add significantly to recommended TDIs of local residents, ii) the exposure levels differ by orders of magnitude depending on the environmental concentrations and living conditions of the people. Estimated exposure levels for populations in the Developing settings as functions of increasing soil concentrations, are presented in Figure 13 a and b for illustrative purposes. In these figures, the egg exposure routes were adjusted upwards by a factor of 10 to compensate for that the model predicted lower levels than estimated by soil-egg BTFs from the literature. The exposure estimates assume 100% availability for internal absorption of contaminants in all matrices. Critical soil concentrations that result in total exposure levels equal to 100% of TDI, were 45 ng TEQ kg-1 (0.045 ppb) for the adults, and 7 ng TEQ kg-1 (0.007 ppb) for the children. The scenarios simulate that the target populations are selfsupporting when it comes to food, such as leafy vegetables, milk, meat and freerange-eggs. Additional exposure via inhalation, ingestion of fish and other food products may exist but these was not taken into account, and nether was additional exposure through ingestion of dl-PCBs. 74 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Figure 13. Summary of estimated exposure levels (ingestion of soil, total ingestion o food and total exposure) for a) adults and b) children in the Development setting. Critical soil concentrations that result in total exposure levels equal to 100% of TDI, were 45 ng TEQ kg-1(0.045 ppb) for the adults, and 7 ng TEQ kg-1(0.007 ppb) for the children. For children, almost 40% of the dose was related to ingestion of soil, an exposure route which contains a high degree of uncertainty since soil ingestion rates differ considerably between individuals and are difficult to determine (US EPA, 2003). By excluding a correction factor that accounts for reduced absorption efficiency in the digestive tract of soil-associated contaminants (corresponding to 20-60% of the total concentration; Ruby et al., 2002), this exposure route may have been overestimated by a factor of 2-5. Even in a “best case” scenario assuming 20% availability, soil ingestion would have contributed to 100% of TDI for children in the Development setting at soil concentrations close to 80 ng TEQ kg-1. Considering that residues from thermal processes in general contain levels of PCDD/Fs that exceed this concentration by far (Table 2), ingestion of soil/dust/ash is an alarming risk scenario if local communities are exposed to concentrated waste that are introduced into their surroundings. Ingestion of soil may result in high exposure levels for children and adults. This exposure route contains several uncertainties and a reduced internal bioaccessibility of solid matrices is not always taken into account in exposure assessments. At soil concentrations of 80 ng TEQ kg-1 (0.08 ppb), the For adults, the tolerance level are higher, mostly due to higher body weight and a behaviour that in general prevent high soil ingestion rates. Adults can, however, become exposed via occupational activities that increase their soil ingestion rates. They can also be subjected to exposure of concentrated waste during handling of concentrated waste. 75 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Table 30 illustrate soil ingestion exposure for adults in the Development setting at different solid matrices concentrations, assuming an internal availability that ranges 20-100% of the total concentration. In the worst case scenario (assuming 100% accessibility), 1 000 ng WHO-TEQ in the solid matrices resulted in 370% of TDI. In a best case scenario (assuming 20% accessibility), a solid matrices concentration of 1 000 ng WHO-TEQ still yielded a significant exposure corresponding to 74 % of the TDI. Table 30. Estimated adult soil ingestion exposure (% of TDI) for the Development setting at different solid matrices concentrations (ng WHO-TEQ kg-1) assuming different internal availabilities after exposure. Solid conc. (ng TEQ kg-1 d.w.) 100 % availability 50 % availability 20 % availability 1 0.4 0.2 0.1 62 23 11 4.6 1 000 370 190 74 If the soil ingestion rate for children was extremely exaggerated in the Development setting, this exposure pathway can be excluded from the model assessment for illustrative purposes. A certain amount of soil will still affect the exposure, since soil particles contaminates the terrester food chains via pasture soil and grass. By excluding soil ingestion exposure, the critical soil concentration that corresponds to 100% of TDI increases to 12 ng TEQ kg-1 for children in the Development setting. If the amount of ingested food is reduced by 50%, if e.g. the food ingestion rates were overestimated by a factor of 2, or if only 50% of the total consumption was locally produced, the critical soil concentration would be ~25 ng TEQ kg-1. However, if all the original assumptions in the scenario are realistic, 25 ng TEQ kg-1 in soil corresponds to 300% of the TDI of the children. The exposure assessment is affected by several uncertainties which are related to human exposure parameters and assumptions about population behavior. As illustrated above, there are a number of assumptions that will affect the levels of the critical soil concentrations. The exposure assessment is therefore limited by the fact that individual variations of food and soil ingestion rates are not covered by the methodology we used. Average intake rate values are not representative of consumption patterns that usually are highly variable in true populations. As mentioned before, some of the parameters were also defined using rough assumptions, even though they were justified from expected population differences related to e.g. the degree of industrialisation of different regions and living conditions (rural or urban). The fact that little is known about current human exposure levels of populations in developing countries makes it challenging to assess current baseline exposures in non-polluted environments. 76 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Despite limited possibilities to take all variables and uncertainties in local contamination scenarios into account, the assessment indicate that critical soil concentrations of PCDD/Fs for sensitive target groups (such as children in selfsupporting and rural settings), are found in the range of 7 to 25 ng TEQ kg-1. Estimated adult exposure at these levels will not exceed 20-70% of TDI, given that the assumptions for this target group were realistic. However, it is important to stress the fact that high ingestion rates of a single, locally produced food item (such as free-range eggs), may result in a significant exposure level even at these soil concentrations. By using the sum of multiple exposure routes to identify critical soil concentrations, one assumes that the target group is exposed via several routes simultaneously. This assumption is not necessarily true, but represents a worst case. Again, there is a significant uncertainty of how important different exposure routes are for different individuals in a given population. One clear limitation of this assessment was that dl-PCBs were not included. A general assumption is that dl-PCB contributes to approximately 50% of the TEQ in food, and that only 50% of TDI can be accounted for by PCDD/Fs. Thus, it is reasonable to adjust the critical soil concentration downwards by a factor of two. It then results in 3 to 13 ng TEQ kg-1 in soil for children with high ingestion rates of locally produced food. It is also important to stress that modelled soil concentrations represent average levels in soil for a specified area that is simulated by the model. Thus, the highest, tolerable level in soil has not been specified by the calculations. 77 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 11 Synthesis of the results 11.1 Risk scenarios By reviewing the literature, only a few case studies showed or indicated that management of PCDD/F contaminated waste has been a major, local source. The contaminated waste materials in the most relevant case studies were impregnated wood and incineration residues. The review showed that a serious risk scenario is prevailing if waste wood fractions are reused as bedding or construction material in animal food production facilities. Considering that PCDD/F waste wood concentrations of 40-50 ng WHOTEQ kg-1 resulted in severe egg contamination (33-88 pg WHO-TEQ g-1 fat (Diletti et al., 2005), the suggested LPCL of 15 000 ng TEQ kg-1 (15 ppb) is not low enough for this waste fraction. Frequently occurring food contamination incidents show that animal food production facilities are sensitive targets for contaminants that are introduced via recycled/uncontrolled material, even though the majority of the incidents were unintended. Contaminated waste wood fractions can also enter biofuel incineration facilities, resulting in higher pollutant concentrations in the residues. For incinerations residues, several options for recycling and reuse seem to exist. A serious risk scenario is prevailing if the material is used in areas close to animal food production facilities or if the application allows direct contact with the waste by local residents or workers. In the New-castle case study (Pless-Mulloli et al., 2001), the highest measured PCDD/F concentration in recycled ash was 9 500 ng ITEQ kg-1 (9.5 ppb), while free range chicken eggs from the contaminated recycling area contained 0.4-56 pg I-TEQ g-1 fat. Even though it was not possible to establish a quantitative correlation between the PCDD/F egg and recycled ash concentrations, the results shows that the suggested limit of 15 ppb for PCDD/F in waste does not allow unrestricted reuse of ash that do not exceed this criteria. Since moderately elevated environmental levels (e.g. 10-50 ng TEQ kg-1 in the ground) are high enough to cause significant exposure levels of local residents living under rural conditions and relying on locally produced food, the impact from highly contaminated waste in certain areas can be detrimental if the waste is reused with limited awareness of possible consequences. Experiments with ducks that were fed with contaminated fly ash (containing 201 ng TEQ kg-1 or 0.2 ppb), showed that the eggs became contaminated despite a restricted bioavailability of PCDD/Fs in solid matrices and rather low ash concentrations (Shih, 2009). In spite of an extensive record showing that management of solid and liquid waste has historically been important as local pollution sources, the limited number of recent contamination cases may indicate that improper management of PCDD/F 78 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs waste is not a common source for PCDD/F and PCB contamination of human food chains or human exposure today, at least not in the developed part of the world. On an international level, there are, however, indications that PCDD/F contaminated waste is not always managed to avoid negative environmental or human health effects. Open waste dump sites and rivers in developing countries are potential targets for dumping of highly contaminated waste. In these countries, open dumping can affect subpopulations that scavenge the waste fill for recyclable materials. The resources to detect and measure such impacts are usually limited in these countries. There is also an occupational hazard for people managing the waste sites. Overall, open access to highly contaminated waste sites can affect wildlife, since birds and other animals feeding on the sites accumulates the pollutants (Watanabe et al., 2005). So far, it seems that human health effects related to open dumping of PCDD/F contaminated waste is not well investigated. The minor field studies in Peru and Thailand confirmed that highly contaminated ashes are stored on open ground at sites where the waste is produced. In theory, wind-blown distribution of ashes is a highly relevant contamination scenario that can affect the surroundings. Our field study did, however, not allow distinction between distribution of ash residues from other local sources, such as air emissions and subsequent deposition from the recycling activities. It is important to keep in mind that areas that are affected by multiple sources are even more sensitive for additional pollution. Possible consequences of improper ash management strategies can, in most cases, only be discussed from a theoretical point of view. One special case where recycling of contaminated incineration residues may result in high emissions of PCDD/Fs to the surroundings is when the Waelz process is applied. This is a recycling technique that uses a thermal process to reclaim metals. If POP contaminated ash is used in the process, efficient air pollution control devices are needed to reduce the PCDD/F emissions from the flue gases. Compared to incineration of waste, the emissions from recycled POP contaminated ash in the Waelz process may be considerably higher. In the literature study, only one study dealt with this issue. A more comprehensive investigation is probably needed to conclude whether this recycling application is of special interest in the context of this study. Special cases where PCDD/F contaminated waste have caused severe impact of local environments are management of chemical waste from e.g. organochlorine production, but most existing cases seem to be legacies of the past. Since chemical wastes contain a mixture of hazardous pollutants, they might be classified as POP contaminated waste by other criteria than PCDD/F. Detected levels of PCDD/Fs in recently produced chemicals from e.g. Asian countries indicate that waste streams in chemical industries can be contaminated as well. A more thorough research into this issue is needed before the importance of these waste streams can be established. 79 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Another area with ongoing production of POP contaminated waste is e-waste recycling. So far, most studies have focused on environmental impacts generated during the recycling activities, and less focus has been put on the waste fractions. A limited number of studies show that residues from incineration contain high levels of PCDD/Fs, and that generated waste products have be dumped in the local environment. Via ingestion of locally produced food, humans get exposed of accumulated contaminants and correlations between high body burdens and ingestion of locally contaminated food have been observed. However, little is known about current baseline exposure of people in developing regions, and it is not appropriate to extrapolate data between different regions or cultures, since living conditions and dietary habits differ. 11.2 Exposure assessment The exposure assessment that were based on environmental concentrations from the field study in Peru, identified adults and children, living under rural conditions and are more or less self-supporting with food, as sensitive receptors for local environmental pollution. A critical PCDD/F soil concentration of 7-25 ng TEQ kg1 was estimated for children. Within this range, it seems that a rural lifestyle with a high proportion of ingested locally produced food probably can be maintained by young children and adults without exceeding the TDI. However, this range assumes that dl-PCBs do not contribute to the total risk, an assumption which likely underestimates real case scenarios, as discussed earlier (and also later). For direct exposure via ingestion of soil, the levels in waste/solid matrices should probably not exceed 200-1 000 ng TEQ kg-1 for adults. This range is estimated from exposure dose calculations using assumptions for adults that must be verified, e.g. for occupational exposure scenarios. The estimated range is also dependent the internal bioaccessibility of PCDD/Fs in solid matrices. Results from a number of studies of soil show that if 100% internal accessibility is assumed, the exposure dose via ingestion of soil is overestimated, since the accessibility usually ranges 20-60%. The accessibility of pollutants from ashes is not necessarily the same as in soil, since ash has another physical and chemical composition. It is important to stress that there are several assumptions underlying the identification of the critical soil concentration, and many of these assumptions have not been verified by e.g. experimental data for real target populations. There are also inherent uncertainties in several steps of the assessment, and these uncertainties affect the accuracy of the critical soil concentration. Major uncertainties are i) to what extent the exposure routes will exist simultaneously or alone, ii) the amount of ingested food that are locally produced, iii) food ingestion rates, and iv) the amount of ingested soil. Since the assessments were based on 80 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs hypothetical populations, it was considered as more reasonable to identify an interval of “critical soil concentrations” rather than one single value. The estimated ranges for the critical soil concentrations were found by using “acceptable exposure levels”, which here was 100% of TDI, since the scenario was assumed to simulate self-supporting residents. One major limitation of the exposure assessment was that dl-PCBs were not taken into account, and this was because of theoretical limitations; experimental data necessary to yield reliable modelling results was not easily available. Since the currently suggested LPCL does not include dl-PCBs, the final risk related to exposure of dioxin and dioxin-like compounds from solid matrices (e.g. ash or soil) might be underestimated. Soil-to-egg BTFs from a selection of studies show that dl-PCBs are more available, which might counteract the fact that dl-PCBs are present in lower TEQ concentrations then PCDD/Fs in soil and ash. Field data from Peru support this finding, since the TEQ fraction related to dl-PCBs were much higher in biotic samples, compared to the abiotic matrices. If a risk scenario includes only exposure via ingestion of soil or solid matrices (e.g. in an occupational scenario), dl-PCBs might be of minor importance as long as their internal bioaccessibility do not exceed the accessibility of PCDD/F. Since the TDI includes both PCDD/Fs and dl-PCBs, a downward adjustment of the critical soil concentrations to 3-13 ng TEQ kg-1 for PCDD/Fs may be justified to allow additional exposure of dl-PCBs. In an exposure assessment where the accumulation of PCDD/Fs and dl-PCBs are processed together, it is recommended to review and adjust these limits. Since typical background PCDD/F soil concentrations (0.14-4.1 ng TEQ kg-1 d.w., Rogowski & Yake, 2005; 0.62-1.6 ng WHO-TEQ kg-1 d.w., Matscheko et al., 2002) that are only affected by atmospheric deposition or urban sources are close to the critical limits calculated in this study, the margins until the soil may become a significant source is small. Even soil concentrations at strictly regulated hazardous landfills are close to the lower end of this interval (1.5-2.14 ng TEQ kg1 d.w.; Mari et al., 2009), and soil at unregulated open waste dump sites may exceed the interval by far (0.02-1 700 ng TEQ kg-1 d.w.; Table 3, Minth et al., 2003). However, some of the impact at open waste sites can be attributed to open burning of waste. The fact that soil at regulated hazardous waste sites contain higher PCDD/F concentrations than reference areas (Mari et al., 2009), indicates that waste sites in general may contain elevated concentrations of PCDD/Fs that originates from solid waste. The landfill investigated by Mari et al. (2009) has been receiving PCDD/F contaminated waste for ~10 years only. The soil sampling at Zapallal in Peru showed a gradient, with decreasing PCDD/F concentrations at increasing distance from the waste site (Figure 6). Thus, possible exposure hazards associated to elevated soil concentrations will have limited spatial distribution. 81 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Studies of POP body burdens for waste picking children at open waste sites have shown that open dump site areas contribute to human exposure (Cuadra et al., 2006). This conclusion was also drawn by Santos et al. (2003), who investigated the exposure of organochlorine pesticides in residents at an open dump site area. Even though PCDD/F or dl-PCB was not investigated, it is most possible that the body burdens of these substances might have been elevated as well. Cuadra and coauthors found also a gradient with decreasing POP concentrations in non-working children as the distance to the waste site increased. Kunisue et al. (2004) showed a strong correlation between elevated TEQ concentrations in soil at Indian open dump sites and high body burdens in human milk (Table 8). The exposure was caused by buffaloes grazing at the polluted site and high ingestion of bovine milk. For PCDD/F, most case studies have focused on scenarios that include dietary exposure pathways (Chapter 6), but our exposure assessment show that ingestion of solid matrices (soil or ash) may be significant contributors at solid matrices concentration of 10-100 ng WHO-TEQ kg-1 d.w. (Figure 13). Results by TurrioBaldassari et al. (2008) indicate elevated TEQ serum concentrations in residents exposed to contaminated soil, but no local dietary exposure, at an former industrial area (15-1 034 ng WHO-TEQ kg-1 d.w., including both PCDD/F and dl-PCB; Turrio-Baldassari et al., 2007, see also Figure 2). However, the serum concentrations were not significantly higher than reference concentrations for less exposed populations. Despite elevated soil concentrations at open dump sites (Table 3; Minh et al., 2003), local residents were not subject to elevated exposure as long as local food chains were not contaminated (Kunisue et al., 2004, see also Table 8). In summary, open waste sites (or other areas that receives PCDD/F contaminated waste) may be a local source of PCDD/F and dl-PCBs, and soil concentrations may exceed levels that are considered as “safe” for self-supporting populations. Few investigations of PCDD/F and dl-PCB body burdens and exposure levels in local residents at such sites have been performed. If local food chains become contaminated, there is an obvious risk for elevated body burdens. If local dietary exposure pathways are absent, the risk depends on the intensity of contact with contaminated solid matrices, which in turn depend on human behaviour. Little is known about possible effects associated to this exposure route. 82 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 11.3 Uncertainties in the results In the following paragraph, uncertainties related to the results in this report are briefly discussed. 11.3.1 Identifying risk scenarios related to improper management of PCDD/F contaminated waste This task was formulated from a very broad perspective, but was limited by a vague opinion of the kind of waste categories that actually were of importance. Focus was therefore put on incineration residues, since they globally are produced in huge volumes and are of contemporary and future relevance. Furthermore, they were treated by the BIPRO report. Contaminated waste wood fractions were added, since the literature study identified several relevant case studies related to the purpose of the project. This fraction is generated during demolition of old buildings and wood constructions where chlorophenol impregnated wood have been used. Chemical waste and residues from e-waste recycling were included since results from other studies indicate that these on-going activities may generate “new” types of PCDD/F contaminated waste. Other recently produced PCDD/F contaminated waste types may of course exist, but they have neither been directly or indirectly identified in the literature search. Production waste from organochlorine industry can contain high levels PCDD/Fs and other unintentionally produced POPs (Weber et al. 2008). While such chemical waste in industrial countries are incinerated in dedicated hazardous waste incinerators, such facilities are lacking in developing and transition countries still today. Therefore, it will be important to control such wastes in these countries. The literature search was made using the scientific data base Web of Science. It covers a broad range of scientific journals with topics related to environmental science. However, chemical abstracts, technical reports and conference proceedings are not included in this data base. Relevant information that was not identified in our literature search may therefore exist. Technical reports and conference proceedings that have been cited in this report was either found as references of cited journal articles, or they were known by participants in this project. The identified risk scenarios are mostly based on empirical evidence to show that they are relevant, even if the likelihood that they will occur depend on factors that could not be assessed by this project. Other risk scenarios, which so far have not resulted in site investigations or other measurable impacts of the environment or human health, may exist as well. A compilation of internationally reported data for PCDD/F in different waste categories was made. It does not claim to give a complete picture of contamination 83 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs levels in waste, but was compared to the suggested Low POP Content Limit to investigate residue levels in relation to the LPCL. Limited information exists for dl-PCBs in waste. It is therefore difficult to quantify the total risk in scenarios that include transfer of dioxins and dioxin-like compounds into food chains. In the exposure assessment, it was assumed that dl-PCBs will constitute 50% of the total exposure. 11.3.2 Correlating environmental levels to human food chain contamination This is an extensive research area. The cited references were selected since they illustrate consequences of local contamination scenarios. Food chain contamination at background conditions were of limited interest. Since site-specific circumstances will influence the bio-transfer of pollutants, it is difficult to describe the impact of local contamination scenarios in general terms. However, a quite large number of studies were cited, and they are consistent in that they show that local sources are of great importance for local food chain contamination. The difficulties arise when this impact must be described quantitatively. Field data is usually presented in different ways and for different purposes, and there are a limited number of studies where data can be used to address the biotransfer variability related to different field conditions. In this report, the variability for transfer into free-range eggs was described quantitatively by calculating soil-to-egg concentrations ratios and analysing their statistical distributions. The same could not be made for beef or milk transfer due to lack of data. The biotransfer variability is a high source of uncertainty in risk assessments that rarely is taken into account. It could not be fully incorporated in the exposure assessment in this report either, even though it was used to evaluate assumptions in the risk assessment by BIPRO and the reported exposure assessment. Since uncertainties exist in all stages of a risk assessment, the most comprehensive way to handle them is to use probabilistic approaches, but this was beyond the scope of this project. By excluding the uncertainty related to biotransfer variability, a full understanding of how the risk is distributed within a population is never gained and the final risk estimate can be overestimated as well as underestimated. 11.3.3 Correlating environmental levels to improper management of waste in the field studies One of the largest uncertainties related to the scope of this report is probably how to quantify possible impacts from contaminated waste on environmental concentrations. This correlation does not only depend on pollutant concentrations in waste, but also on the amount of waste that is distributed into the environment, how the waste is managed/recycled and the spatial distribution of the waste in affected areas. 84 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Even though a number of studies show that the presence of local pollution sources may affect human food chains, it is difficult to empirically show that improper management of waste will affect local environmental concentrations. To be able to plan a field study that fulfils its purposes, good knowledge about the sampling sites and some knowledge about local environmental concentrations are usually necessary. The field studies that were performed within this project were the first at the selected study sites. In the initial planning stage, information about the sites was compiled by local NGOs, and their information was later used to set up a sampling scheme. Existing measurements of environmental concentrations did not seem to exist, so the sampling was planned from theoretical expectations about pollution sources and the fate of contaminants in the environment. Even though the results showed that highly contaminated ash was managed at the sites and that the surroundings were affected by the activities at the sites, it was not possible to distinguish between ash distribution and other local sources. The fact that air emissions from the recycling/incineration activities probably are additional sources complicated the evaluation of the results. Since air and flue gas measurements were not performed, the field study was not designed to be able to separate the impact of the two sources (air emissions and contaminated ash). Overall, sampling and measurements of flue gas and air are difficult to perform to get representative results. Considering the improved knowledge about fate and distribution of pollutants at the study sites, it might be possible to follow-up the first sampling to further investigate and separate the impact of the different sources, if necessary. 11.3.4 Human exposure assessment Overall, the major uncertainties in the exposure assessment are probably related to human behaviour, and if exposure will result in elevated body burden or not. Exposure doses and elevated body burdens related to PCDD/F contaminated solid matrices in the environment are not addressed as often as dietary exposure pathways. Some additional data may exist for occupational exposure scenarios, where the exposure pathways are different compared to local residents. Considering that the Low POP Content Limits are applicable to solid matrices, this exposure route should be investigated more carefully to improve our understanding of how PCDD/F contaminated waste may affect human health. Sparse pollution data exist for waste site scenarios, which are believed to be relevant for the purpose of this project. Existing studies represent either regulated hazardous waste sites that operates according to European principles, or nonregulated open waste sites in developing countries where burning of waste also is performed. Between these two “extremes”, there are probably other representative waste site scenarios, which perhaps never have been investigated. It would therefore be desirable to identify waste sites (or other sites that receives PCDD/F contaminated waste) that are operated at different conditions, and to perform risk assessments at the sites to get more information about contamination levels in the 85 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs waste and the surroundings, as well as body burdens of people that reside or work in the area. The model populations in the exposure assessment were parameterised using empirical data that represents “average persons”. In some cases, rough assumptions were made from a theoretical point of view, and these assumptions were not supported by field data. The strong impact of different human behaviour was illustrated by the human exposure outputs, which ranged over one to two orders of magnitude for the model populations. By using averages, the exposure of parts of populations is underestimated, while 90th or 95th percentile point estimate values can overestimate the exposure. Again, a probabilistic approach is more suitable to illustrate ranges of human exposure levels taking intra-population variability into account. It is likely that deterministic risk assessments exaggerate the risk. To be able to correlate environmental levels to human exposure, a multimedia modelling approach was applied. The advantage of the method is that multiple fate and exposure routes can be investigated in different scenarios for a range of environmental levels. The disadvantage of modelling is that it relies on numerous assumptions and simplifications that cannot always be supported by empirical data or by site specific knowledge. For the purpose of this report, the model was applied for generic local contamination scenarios, where field data from one of the case studies was used as input to define the environmental concentrations. By using empirical field soil concentrations as input, a realistic contamination scenario was assessed. The soil input data was characteristic for incineration sources, and the congener patterns showed high levels of lower chlorinated PCDFs. Theoretically, pollution by sources exhibiting incineration congener composition constitutes high risk scenarios, since the lower chlorinated congeners are more mobile and bioavailable and will more easily be transferred into food chains. Some of the model uncertainty derives from the applied BTFs. Methods where BTFs can be estimated for super-hydrophobic compounds, are associated with a high degree of uncertainty. This uncertainty will exist for all model calculations that rely on BTFs. To improve the confidence in the model outputs, field data from the current project and other field studies were used to evaluate the performance. This approach contributed to reduce some of the uncertainty related to uncertainties described above. In most cases, the model outputs were found reliable, and adjustments were only justified for transfer into eggs, where a comprehensive set of empirical soil-toegg concentrations ratios were used to calculate reference data. The evaluation was limited by the fact that few case studies have been performed at the same environmental concentrations as in the modelling scenarios, and it was not always possible to relate reported concentrations in biotic matrices to soil concentrations in the reference studies. Since the selected model has been applied and evaluated for PCDD/F in other scenarios that were not part of this project, earlier gained 86 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs experience in evaluating and interpreting the model outputs were valuable. Since the model was applied using a deterministic approach, parameter uncertainties were not included. The deterministic approach conflicts the empirical evidence that biotransfer into human food chains is highly variable. Thus, deterministic results can unconsciously result in misleading feelings of “safe and easy decisions”. 11.3.5 Estimated critical soil concentrations The estimated critical soil concentrations are affected by previously discussed uncertainties. Additional uncertainty arise when multiple exposure routes are summed to a total exposure level, which then was used to identify critical soil concentrations where people can live without exceeding a certain portion of the TDI. If one supposes that target populations should be able to live without limitations on a contaminated site, this approach might be justified. By using the sum of multiple exposure routes, the total risk is, however, easily (although not always intended so) exaggerated since point estimates usually include some safety margins and these are added when the exposure routes are combined. It can also be questioned how likely it is that the behaviour of a population are characterised by “worst case behaviour” for all exposure routes. It does not have to be likely that people rely on getting or buying food produced at a local site to 100%. In identifying critical soil concentrations or any other limit values, one must define an acceptable exposure level, which can be TDI or a portion of TDI, depending on the human exposure scenario and the context it simulates. Finally, anyone should be aware of that modelled soil concentrations represent average levels in soil for a specified area that is represented by the model landscape. Average, tolerable soil concentration level allows variable soil concentrations where the highest, tolerable level actually has not been specified. Again, the spatial distribution of soil concentrations and activities related to human behaviour is of importance for the final risk and the modelling results should not be misinterpreted as a maximum allowable soil concentration. 11.3.6 Degree of protection with current Low POP Content Limits The ultimate aim of the project was to investigate whether the suggested Low POP Content Limits for PCDD/Fs is low enough to prevent human health risk. Even though empirical evidence is limited to a few case studies, and there still exist knowledge gaps that limits the understanding of how contaminants in waste will affect humans, the combined results using a range of methods points toward a “no” as an answer of the question. In relation to the concentrations that are found in waste, local environments cannot contain those high levels while keeping safety margins for human health. Still, the main uncertainty related to this task is related the one that was discussed in paragraph 3: what are the possibilities that improper management of contaminated waste will cause serious environmental contamination? Under what 87 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs circumstances will such scenarios come true? To what extent can environmental levels become affected by the waste? Since this project focused on human health risks, no efforts have been made to identify the risk related to fate and distribution of PCDD/Fs from an ecological point of view. Studies have identified open dump sites as sources for PCDD/F in wild birds. Another issue that has not been discussed in this report is long term consequences for the society if POP contaminated wastes are recycled and pollutants are reintroduced into the environment. 88 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 12 Conclusions • There exist several cases that illustrate large negative impacts related to direct emissions of waste and waste water into the environment, although only a few of them represent current incidents and most of them are related to chemical production. Recent incidents have occurred in Europe and illustrate how improper recycling of ash and impregnated wood may contaminate human food chains. Empirical results from actual cases indicate that the currently suggested LPCL for PCDD/F is not low enough to prevent serious contamination of human food chains. • Considering the high concentrations of PCDD/Fs in different waste fractions, direct exposure via ingestion of soil/solid matrices are of great concern. The importance of this exposure route is less thoroughly investigated compared to dietary pathways for scenarios with elevated levels of PCCD/Fs and dl-PCBs in soil. Exposure calculations for PCDD/Fs and studies of human POP body burdens at open waste sites indicate that PCDD/F contaminated waste may be a risk for populations with intense and regular contact with the waste is intense. • Dietary exposure assessments show that exposure levels of people in many countries are close to or exceed the recommended TDI. Limited data exist for populations in developing countries. For most populations, this means that an allowable incremental exposure related to waste can only account for a minor part of the TDI. • Limited data exist for dl-PCB concentrations in waste. Even though existing data indicate that dl-PCB account for a minor fraction of the total TEQ, the higher accessibility of this compound group may lead to a significant contribution to total TEQ if the waste is introduced into the environment and its pollution enter food chains. So far, the impact of dlPCBs in waste has not been fully investigated. • A critical soil concentration of 7-25 ng WHO-TEQ kg-1 (0.007-0.025 ppb) for PCDD/Fs was identified for children in rural and self-supporting settings. The criterion was that the total exposure summed for multiple exposure routes should not exceed TDI. If additional exposure from dlPCBs is assumed to account for 50% of TDI, this limit should be adjusted downwards to 3-13 ng WHO-TEQ kg-1 (0.003-0.013 ppb). A number of uncertainties were identified that affect the accuracy and the span of the range. The critical soil concentrations represent only average levels in soil and not the maximum tolerable levels. Still, the range is far below the suggested Low POP Content Limit of 15 ppb, and suggests a high risk for 89 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs scenarios where PCDD/F contaminated waste contaminate the environment. • For adults, ingestion of soil or ash can become an important exposure route during e.g. occupational exposure. Ingestion of soil/solid matrices is also important for children in residential scenarios. Critical solid matrices concentrations for adults can probably be found in the range of 200-1 000 ng WHO-TEQ kg-1 (0.2-1 ppb) depending on the assumed internal bioaccessibility of solid matrices, the soil ingestion rate and what fraction of TDI that is considered as an acceptable exposure dose. This range is far below the suggested Low POP Content Limit of 15 ppb. • Existing data show that the internal bioaccessibility of PCDD/F in soil is strongly reduced. No data was found for PCDD/F in waste matrices, neither for dl-PCBs in soil or waste matrices. By assuming 100% bioaccessibility in exposure calculations, the risk related to ingestion of soil/solid matrices is exaggerated. • Results from the field studies in Peru and Thailand showed that the open waste sites are local sources to the environment and that highly contaminated ash was stored open. However, it was not possible to determine the relative impact of management of PCDD/ contaminated solid waste from local air emissions. 90 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 13 Recommendations for future work The results in this report was a first approach to investigate human health risks associated to PCDD/Fs and dl-PCBs in waste and waste management practices in the society. The issue is complex and is not easily handled, since it involves environmental and toxicological sciences as well as political, technical and economical perspectives. Therefore, the aim of this report was not to suggest new Low POP Content Limits for PCDD/Fs (or dl-PCBs) in waste. The results highlight some issues that are important from a human health perspective and that parties involved in the process of setting Low POP Content Limits should consider. Our recommendations for future work in this issue are: • To discuss consequences of including or excluding dl-PCBs in the Low POP Content Limits. This task might require more information about expected levels in waste, consequences for the exposure assessment, discussion about economical, technical and political consequences, etc. • To consider how to deal with the wide range of uncertainties that are incorporated in all risk assessments. It is more advantageous to apply a probabilistic approach that incorporates data uncertainty and variability than to rely on point estimates. To avoid speculations and “best guesses”, it is preferable if relevant and realistic waste management scenarios can be identified. Empirical data can then be collected for known cases, and the data can thereafter underlie the development of scientifically based limit values. Exposure to solid matrices is a risk factor due to extremely high concentrations in some waste products. The contact intensity to solid waste varies among different exposure groups and the soil/dust ingestion parameter is usually associated with a high uncertainty. Considering the high TEQ levels in solid waste, it is possible that airborne exposure may be of concern for some occupational indoor environments. Handling of PCDD/F contaminated waste close to areas with animal food production is another important risk scenario. • To consider if the international perspective continues to be of importance. If so, more information should be found out about exposure routes and body burdens of people that belong to risk scenarios in developing countries (e.g. waste pickers at open waste dump sites or people that are working with POP contaminated waste). This is probably a major task that requires identification of suitable sites, knowledge of emissions and environmental levels and sampling of human serum for exposed people and control groups. 91 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Appendix A Preliminary study of the waste site Zapallal, Peru Emission and Pollution Problem by dioxin in Peru (Luis Gomero Osorio) Introduction The Action Network in Alternative Agriculture (RAAA) joined with Japan Offspring Fund (JOF) and worked in a coordinate way in 2001. It was in order to analyse samples of urban residue incinerators and this work involved many countries in the Asia – Pacific Region. The results of this study showed a high level of dioxin emission in Peru. The sample of Zapallal landfill gave a result higher than the permitted limits (3 ng – TEQ/g according to WHO). This landfill is located in the Carabayllo district in the north of Lima city. The analysis of ash residues showed the presence of dioxin 14 ng-TEQ/g; it represented a 466 % more than the permitted limits. Moreover, two samples were taken in other places, one of them was taken from the Cockroach landfill (nowadays has been closed) and the other was taken from the COR-PAC incinerator (located in the International Jorge Chavez Airport, nowadays the incinerator has not worked). The levels of dioxin for both samples were 0.19 and 0.36 TEQ/g respectively. The values are lower than the permitted limits by WHO. In 2006, the Project PNI – COP determined the emissions of PCDD/PCDF estimated by Peru. In order to get it, the reference that was used were the data for 2003 year as a base, belonging to the incineration category of waste; the total emission was 21 g TEQ/a by air way and was 17 TEQ/a by waste way of PCDD/PCDF. According to the regional distribution of the emissions of PCDD/PCF into the air, it has been determined that the Lima city has a great emission of it; it is higher than 10 TEQ/ year. It happens because of the difficulties for management and the final disposal of the solid waste. The reason of this situation is because of open field burning of solid and dangerous waste. Moreover, according to the inventory of dioxin and furan of solid waste of municipalities in Peru, the emission into the air is approximately 0.09 g TEQ/year. The reason of this is because of open field burning. 92 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs The inventory in its conclusions mentions that the process of open field burning represents 61% of the emissions of dioxin and furan into the air and it is followed by the production of ferrous metals and no ferrous metals with 20% and the incineration of residues with 11%. DIGESA did a monitoring of air quality in the study zone of the Zapallal landfill in 2008; it was specifically in the Lomas the Carabayllo Human Settlement. The monitoring stations were located within a radius of about one km in relation to the landfill. This public institution concluded that there were different sources of pollution in the zone, such as smelting enterprises, recycle of lead and aluminium, accumulated solid residues, removal of land surrounding the quarries, recycle of garbage and burning organic waste, animal husbandry (pork), landfill, unpaved roads and hills without vegetation. The monitoring determined that the mean of concentrations of particulate material by 24 hours was lower than 10 microns PM10. The other three stations showed values higher than the National Standard (of 150 µg/m3). This situation is an evidence of the air pollution in this zone and the population is exposed to a great health risk. The pollution produced by open field burning is permanent especially in the urban zone where there are final disposal of solid waste or landfill. In addition, there are some complementary activities that are developed near the landfill. They contribute with emissions of toxic gases and pollutants as dioxin and furan. Therefore, it is very important monitoring the air quality with frequency in order to take corrective actions. Objectives To evaluate possible levels of exposure and risks in places where the polluted residues with PCDD /F are stored or they are reused. To collect detailed information about selected places, all of them are in order to have a plan of sampling and identify the possible places of taking sample. Methodology To elaborate the present report, the first step was to get actualised information about the emissions of dioxin and furan in the country. The information was taken from institutions as DIGESA – Health Ministry, Carabayllo Municipality and Callao – DISA. The information was collected and it was used as a technical support of the present report. In addition, the influence zone was visited by the researchers and they went around all the area of the Zapallal landfill, moreover, the smelting enterprises and the storage of segregated material were visited. It had been taken photos of the actual situation of this place and it was done a meeting with the leaders of the base organisations and the technician of the Municipality. Moreover, there was a 93 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs directly communication with the technicians of the sanitary area of the International Jorge Chavez Airport. I. The Zapallal Landfill Location of Zapallal Landfill The Zapallal landfill is located in the right side of the Chillon River between the Campana and Cabrera hills. It belongs to the Carabayllo district, province and department of Lima. The landfill has a surface of 440 hectares of which 60% (260 ha) is used for landfill and the other 40% of this area is not appropriate for this activity. In the first part of the Project, an area of approximately 11 ha was included in which it has been distributed the platforms of final disposal of urban waste. Moreover, there were special areas for final disposal and/or confinement of hospital and industrial residues. The estimated minimum lifetime is 30 years. The ecosystem that is part of the Zapallal landfill is conformed by a sub tropical – desert zone, clay soils, and it is extremely dry. There are not enough flora and wildlife. There are arachnids and lizards. The flora is limited and is composed by cactus. It happens because of different factors such as lack of water and extreme aridity. The pluvial precipitation is low and is limited to drizzle in winter; the monthly rainfall goes to 0 a 6 mm. The monthly mean temperature goes to 17 to 25 ºC, the 94 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs mean annual relative humidity is 80 a 90% and the predominant direction of the wind is for the southeast. The superficial and subterranean waters are absent. Description of the storage places of waste and residues LANDFILL Approximately 600 Ton/day of solid waste that came from household activities is disposed in this place, and almost 3 Ton/day of waste that comes from the health centres is disposed there, too; therefore, there are special cells to confine this dangerous waste by security. A significant number of poor people have been established near the landfill. The population of this area faces up the typical problems of the peri–urban zones such as the lack of water and the sanitation; moreover, the incipient level of urban consolidation, the high incidence of transmissible illnesses, and others problems. GARBAGE DUMP The garbage dump is almost 30 years. Therefore, it means that it is a high infectious focus not only for the bacteria that are common in the solid waste, but also for the process of burning of organic residues accumulated by long time. All of these produce emissions of noxious gases that go into the air of the zone. The garbage dump is surrounded by approximately 350 families. In addition, the garbage dump has 300 thousand cubic meters of accumulated waste; actually there are not mechanisms to eradicate it. It is important to mention that this garbage dump is located to 1500 m from the Zapallal landfill. This garbage dump is not used for final disposal these days. ILLEGAL SMELTING ACTIVITIES There are illegal smelting activities in the zone, 10 of these places have been identified, but nowadays only three are working and they smelt metals such aluminium and copper. Moreover, asphalt is produced in an artisanal way, batteries are recycled to get lead, and some minerals are milled. Noils that are produced by residues of hydrocarbon and used oils that comes from other places. All of these materials are using for generating energy. In addition, smelting activities are doing in an artisanal way and they are using plastic materials for incineration. 95 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs STORAGE OF SEGREGATED PRODUCTS The recyclers take materials from the landfill and they stored them in these places. This activity is not legal and it is prohibit doing inside the landfill. However, the population located near the zone puts in dangerous situation its life and health because they enter to collect the materials so that they can have the opportunity to sell them in the market. The waste that has not been sold is burned in an open field near closed yard. Children and teenage participate of this activity to burn waste. It is important to mention that the municipal waste of the landfill that was burning in open field has diminished according to the estimated number in 2001 when the evaluation of dioxin was done. The management is better these days. Nowadays the burning is been doing in the properties that are totally closed. Types of identified residues RESIDUES OF THE ILLEGAL AND ARTISANAL SMELTING ACTIVITIES Ten smelting enterprises were identified in this place. However, nowadays only three are working and are producing emissions of toxic substances into the air because of the materials that are used to generate energy; these are based in hydrocarbon residues (noils) (see Table 1). This residue is the most used in all of the smelting activities that have been identified. Pollutant R=100 R=20 ROQ (ppm) 19320 19960 Sulfides (ppm) 206 215 Phenols (ppm) 231 244 Mercaptans (ppm) 26070 28960 Oils and fats (ppm) 13080 19200 The plastic segregated of the landfill and residues of oils are using to generate energy too, a great quantity of ash is generated and accumulated in this process; each owner has a piece of land that is closed in which the ash are stored. 96 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs DIGESA has identified and registered people that work in this activity and they are mentioned in the followed table5: Owner Activity Julio Cesar Salas Abanto Produce chemical substances: Zinc sulphate and copper sulphate Edwar Sixto Berrospi Production of blue based in asphalt José Luis Silva Milling of minerals Ventura Meneses Fidencio Smelting activity Carmelo Fernández Smelting activity Abanto Justo Ponciano non ferrous smelting activity This activity has been identified in the industrial zone of Lomas de Carabayllo that is near the landfill. The smelting activity and the incinerators permanently operate and others operate temporally. The residues are stored in the same place for long time (see photos). Therefore, this zone could be vulnerable; the population of this zone claim to authorities to close the landfill and to eradicate the illegal smelting activities. For that reason some environmental studies have been done by DIGESA in order to know about the concentration of particulate material or to do the evaluation of lead level in the population. The 100% of residues come from the same place where different materials are burning. The used oil is the material more used for burning; acid noils are used, too. The acid noils are based in hydrocarbon residues that come from the Conchan refinery. Moreover, batteries are burning in order to recover lead. It is important to mention that the technology that is used in this zone is artisanal and it does not have any security measure. ____________________________ 5 The Information was taken to the Act of inspection of Civil Defence that was done by February 2007, and other information come from the fiscal Act to notify the presence of these smelting activities that was done by June 2007. 97 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Storage of residues The residues or ashes of the incinerators are stored in yards and these residues are exposed to the wind. This is one of the reasons that the ashes are spread by the wind to different communities near the influence zone, and it affects the health of population. Layers of ashes were evidence when the researchers visited the study zone. These layers of ash were located near the artisanal incinerators. The management of these ashes has not been done yet and these materials are in a process of accumulation. The material that is removed when the owner cleans the local is disposed in the garbage dump and in other cases these materials go into the nearest river in this case the Chillon River. As it was mentioned the zone is too arid; there are not superficial and subterranean waters. The wind is one of the factors that spread the ashes and dangerous particles; it happens because wind is very strong and intense. People that are working in the smelting activity are very distrustful; they do not allow people enter into their locals especially if people are strangers in the zone. Therefore, the supervisions have to be done by the competent authority. The main activities in the area of influence of the landfill and waste identified The photo shows in a general way the main activities that are carried out around the Zapallal landfill. The landfill is surrounded by human settlement, artisanal smelting enterprises, and non metallic mining activities. The zone has 54 consolidated urban allotments and it is possible that 30 thousand people could be affected by environmental problems. The distance that separates the landfill from the population is approximately 800 meters. 98 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Access to the landfill and the surrounding To enter into the landfill in an official way it is necessary to have a permission of the Relima enterprise. This enterprise has the concession of the area and it is the responsible of integral management of the landfill. However, there is not surveillance in the area; there is only surveillance in the main entrance for that reason is possible that people enter without any problems by other zones of the landfill. In addition, not all the area has been closed. The enterprise has fulfilled the commitment to establish a life fence, and a barbed wire fence was established to separate the landfill from the population located near. This situation gives opportunity that informal segregators enter into the landfill without any problem. If it is necessary to take samples of ashes, these have to be done in an official way for that reason it is important to request permission to the competent authority such as the Municipality, DIGESA, the prosecution or the organised community. As it was mentioned, there is a serious problem related to the incineration. Therefore, it is important to evaluate the pollutants (dioxin and furan). It is necessary the support of the Carabayllo Municipality and the prosecution for entering into the smelting places of the zone. It is recommended that official samples have to be collected in front of witnesses so that the results can be recognised by all involved people. It possible to say that there are not obstacles for taking samples, but it is necessary to do a bureaucratic process. Moreover, it is necessary to have the presence of competent authorities, and local community to get them. This study has allowed to have actualised information. Moreover, it has been possible to evaluate the actual situation, and it showed that is important to support the local authorities with technical information about the emission problem of pollutants such as dioxin and furan. II. The Cockroach landfill This landfill was abandoned by 2001; none enterprise managed this place. However, emissions of toxic gases were eliminated into the air and the burning appeared in a spontaneous way. Therefore, samples of ashes of this place were taken to be analysed. There was presence of dioxin in the results; it was 0.19 ng-TEQ/g. This landfill is located in the left side of the Chillon River. Nowadays, it has been closed and it does not have any activity of final disposal of solid waste. Moreover, it is not accessible and it is surrounded for human settlements that are very poor. 99 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs III. The Corpac Incinerator The Corpac incinerator was located in the north of the international Jorge Chavez airport. A; all of different kinds of waste generated in the airport and the sanitary products seized have been burned until 2001. The incinerator does not operate these days. The process of incineration of waste had to be undergone by 300 ºC. After this process the ashes went to the landfill. For that reason, samples of this place were taken to analyse; the results showed the presence of 0.36 ng -TEQ/g. According to the health department of the airport and the DISA – Callao, the process of incineration is not carried out in the Corpac incinerator. Nowadays, the waste generated in the airport is previously recycled, then an autoclave is using to sterilise and the residues are milling. Finally the waste of this process goes to the landfill. Therefore, there are not ashes with this kind of process. Acknowledgment My thanks to Mr. Carlos Ascarza that belongs to the promoter group of the association of the concentrated development plan of Lomas de Carabayllo and to engineer Kathia Fuertes Espinoza of the Municipal Agency of Lomas de Carabayllo for the supporting for the elaboration of this report. References PNI-COP PROJECT, 2006: National Inventory of the sources and emissions of dioxin and furan, executed by CONAM, SENASA, DIGESA and sponsored by GEF/PNUMA CESIP, 2004: Child working in Lomas of Carabayllo: looking at the situation of children working in the recycling of garbage, sponsored by Terre des Hommes Netherlands. Health Ministry – DIGESA, 2008. Report Nº 001551-2008/DEPAAPCCA/DIGESA: Monitoring air quality in the human settlement of Lomas de Carabayllo. Fiscal Act, 2007: Authorization for the Carabayllo Municipality to closed and to eradicate the smelting activities, according to the Art 49 of the LOM No 27972 and the material law. 100 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Civil Defence, 2007: Visiting Act for inspection of Civil Defence to different illegal places dedicated to smelt and recycle materials. Gomero L y Velásquez H, 2001: Dioxin evaluation in samples of ashes of incinerators and landfills of urban waste. Executed by RAAA and sponsored by Japan Offspring Fund (JOF) Carrasco M., Ore J.: Treatment of acid noils produced in the manufacture of lubricating base type LCT at the Talara refinery. 101 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Appendix B Map of Zapallal and sampling points 102 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 103 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs 104 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Appendix C Photos from the field study at Zapallal, Peru (taken by Viktor Sjöblom, SLU, Umeå, Sweden) Picture 1. Welcome to Zapallal. 105 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 2. Arid climate at Zapallal, it is windy and lots of dust in the air. Picture 3. Within the waste site, there are at least 100 industrial allotments. Most of the activities involve recycling. Other activities are production of chemicals and zinc powder and burning. Burning of waste took place at one of the four allotments that were visited during the field sam-pling. 106 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 4. The area is quite large, and there were even official and non official burning of waste outside the area. The main area (the hot spot) was ~1 km2, even though burning did not take place everywhere. Picture 5. Recycling of copper from copper cable. Ash sample 1. 107 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 6. This road started where the industrial allotments ended. Soil samples 1-3 and plant samples 1-4 were taken along the road. Picture 7. This part of a small village is situated 1.5 km east of Zapallal. Soil and plant samples 5. 108 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 8. This area is situated 4 km east of Zapallal. There are some agricultural activities here (cultivation of plants and vegetables) Soil and plant samples 6. Picture 9. Cable burning for recycling of cupper. 109 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 10. Furnace for cable burning. 110 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 11. Ash from cable burning. Ash sample 1. Picture 12. Area for burning of plastic film for recycling of cellulose. Ash sample 2. People are living here, and the area with the industrial allotments begins in the background. Egg sample 3 was taken downside this place. 111 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 13. Ash from burning of lead batteries. Ash sample 3. 112 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 14. Sediment sampling in Chillon river, 2-3 km south of Zapallal. Sediment 1. The wet season is between October and April, but water is not necessarily flowing in the River the whole rainy season. During the visit it was completely dry. 113 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 15. Daily disposal of waste in Chillon River. During the visit we saw traces from dumping of ash. Picture 16. Sediment sampling at the reference site at Trapiche, some 20-30 km upstream sediment sample 1. Sediment sample 2. 114 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 17. Area with free range chickens. Egg sample 1. 115 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 18. Area with free range ducks. Egg sample 2. Picture 19. Aloe Vera, plant sample 1:1,1:2 and 1:4. 116 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 20. Plant sample 2. 117 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 21. Plant sample 3. 118 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 22. Plant sample 4. Picture 23. Site of reference soil sample Soil 7. 119 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 24. Site of reference soil sample Soil 7. Picture 25. Site of reference sample Soil 9 120 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Appendix D Photos from field study at the incinerator plant in Phuket, Thailand (taken by Lars Lundmark, Umeå University, Sweden) Picture 1. Ash sampling from open area. Picture 2. Ash deposit at pond. 121 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 3. Bottom ash sampling. Picture 4. Untreated waste deposit. 122 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 5. Water sampling. Picture 6. Waste water sampling (out to channel). Picture 7. Pond outside plant. 123 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 8. Sediment ash store. Picture 9. Grey ash without graphite injection. Picture 10. Some part of the ash store was covered by a thick layer of some plastic material. 124 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 11. Sediment from pond (fisherman). Picture 12. Fisherman on the other side. Picture 13. Buying fish samples. 125 SWEDISH ENVIRONMENTAL PROTECTION AGENCY REPORT 6418 • Low POP Content Limit for PCDD/Fs Picture 14. Reference sample (Paton Beach town). 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Consequently, the management of such waste is of major concern considering its potential toxic impact on the environment and human health. In this report a science-based Low POP Content Limit for PCDD/F in waste is developed based on case studies including improper waste management resulting in contamination of soil and human food chains. Direct contact with contaminated waste is also of great concern from a human health risk perspective. Setting of Low POP Content Limits is a complex issue and involves political, technical and economic perspectives as well. It should however always be focused on finding a limit value that protects the environment and human health. Swedish EPA SE-106 48 Stockholm. Visiting address: Stockholm - Valhallavägen 195, Östersund - Forskarens väg 5 hus Ub, Kiruna - Kaserngatan 14. Tel: +46 8-698 10 00, fax: +46 8-20 29 25, e-mail: [email protected] Internet: www.naturvardsverket.se Orders Ordertel: +46 8-505 933 40, orderfax: +46 8-505 933 99, e-mail: [email protected] Address: CM Gruppen, Box 110 93, SE-161 11 Bromma. Internet: www.naturvardsverket.se/bokhandeln
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