Dioxin- and POP-contaminated sites—contemporary and future relevance and challenges

DIOXIN AND POP-CONTAMINATED SITES • CHALLENGES • OVERVIEW

Dioxin- and POP-contaminated sites—contemporaryand future relevance and challengesOverview on background, aims and scope of the series

Roland Weber & Caroline Gaus & Mats Tysklind &

Paul Johnston & Martin Forter & Henner Hollert &Emanuel Heinisch & Ivan Holoubek &

Mariann Lloyd-Smith & Shigeki Masunaga &

Paolo Moccarelli & David Santillo & Nobuyasu Seike &

Robert Symons & Joao Paulo Machado Torres &

Matti Verta & Gerd Varbelow & John Vijgen &

Alan Watson & Pat Costner & Jan Woelz & Peter Wycisk &

Markus Zennegg

Received: 29 April 2008 /Accepted: 10 June 2008 /Published online: 3 July 2008# Springer-Verlag 2008

AbstractBackground, aim and scope Once they have been generat-ed, polychlorinated dibenzo-p-dioxins (PCDDs) and diben-zofurans (PCDFs) and other persistent organic pollutants(POPs) can persist in soils and sediments and in wasterepositories for periods extending from decades to centu-ries. In 1994, the US EPA concluded that contaminated

sites and other reservoirs are likely to become the majorsource of contemporary pollution problems with thesesubstances. With this in mind, this article is the first in anew series in ESPR under the title ‘Case Studies on Dioxinand POP Contaminated Sites—Contemporary and FutureRelevance and Challenges’, which will address thisimportant issue. The series will document various experi-

Environ Sci Pollut Res (2008) 15:363–393DOI 10.1007/s11356-008-0024-1

R. Weber (*)POPs Environmental Consulting,Ulmenstrasse 3,73035 Göppingen, Germanye-mail: [email protected]

C. GausNational Research Centre for Environmental Toxicology (EnTox),39 Kessels Road,Coopers Plains 4108, Australia

M. TysklindDepartment of Chemistry, Umeå University,901 87 Umeå, Sweden

P. Johnston :D. SantilloGreenpeace Research Laboratories,Department of Biological Sciences, University of Exeter,Exeter EX4 4PS, UK

M. ForterUntere Rheingasse 15,4058 Basel, Switzerland

H. Hollert : J. WoelzDepartment of Ecosystem Analysis,Institute for Environmental Research (Biology V),RWTH Aachen University,Worringerweg 1,52074 Aachen, Germany

E. HeinischBayreuther Straße 9,91301 Forchheim, Germany

I. HoloubekRECETOX, National POPs Centre,CR Central and Eastern European Regional POPs Centre,Kamenice 126/6,625 00 Brno, Czech Republic

M. Lloyd-SmithNational Toxics Network Inc.,12 Craig St,East Ballina, New South Wales, Australia 2478

ences from sites contaminated with PCDD/F and otherPOPs. This article provides an overview of the content ofthe articles comprising the series. In addition, it provides areview of the subject in its own right and identifies the keyissues arising from dioxin/POP-contaminated sites. Addi-tionally, it highlights the important conclusions that can bedrawn from these examples. The key aim of this article andof the series as a whole is to provide a comprehensiveoverview of the types of PCDD/F contaminated sites thatexist as a result of historical activities. It details the variousprocesses whereby these sites became contaminated andattempts to evaluate their contemporary relevance assources of PCDD/Fs and other POPs. It also details thevarious strategies used to assess these historical legacies ofcontamination and the concepts developed, or which areunder development, to effect their remediation.Main features Special sessions on ‘Contaminated sites—Cases, remediation, risk and policy’ were held at theDIOXIN conferences in 2006 and 2007, and this themewill be continued at DIOXIN 2008 to be held inBirmingham. Selected cases from the approximately 70contributions made to these sessions, together with someadditional invited case studies are outlined together with thekey issues they raise. By evaluating these cases and addingdetails of experiences published in the current literature, anoverview will be given of the different features andchallenges of dioxin and POP-contaminated sites.

Results This article provides a systematic categorisation oftypes of PCDD/F and POP-contaminated sites. These arecategorised according to the chemical or manufacturingprocess, which generated the PCDD/Fs or POPs and alsoincludes the use and disposal aspects of the product lifecycle in question. The highest historical PCDD/F anddioxin-like polychlorinated biphenyl (PCB) contaminationburdens have arisen as a result of the production of chlorineand of chlorinated organic chemicals. In particular, theproduction of chlorinated pesticides, PCBs and the relatedcontaminated waste streams are identified being responsiblefor historical releases of toxic equivalents (TEQs) at a scaleof many tonnes. Along with such releases, major PCDD/Fcontaminated sites have been created through the applica-tion or improper disposal of contaminated pesticides, PCBsand other organochlorine chemicals, as well through therecycling of wastes and their attempted destruction. In someextreme examples, PCDD/F contaminated sites have alsoresulted from thermal processes such as waste incinerators,secondary metal industries or from the recycling ordeposition of specific waste (e.g. electronic waste or carshredder wastes), which often contain chlorinated orbrominated organic chemicals. The examples of PCDD/Fand dioxin-like PCB contamination of fish in Europeanrivers or the impact of contaminated sites upon fishinggrounds and upon other food resources demonstrate therelevance of these historical problems to current and future

S. MasunagaGraduate School of Environment and Information Sciences,Yokohama National University,79–7 Tokiwadai, Hodogaya-ku,Yokohama-shi, Kanagawa 240-8501, Japan

P. MoccarelliSchool of Medicine, Department of Clinical Biochemistry,Hospital of Desio-Milan, University Milano-Bicocca,Via Mazzini 1,20033 Desio, Italy

N. SeikeOrganochemicals Division, National Institutefor Agro-Environmental Sciences,3-1-3 Kannondai,Tsukuba, Ibaraki 305-8604, Japan

R. SymonsNational Measurement Institute, Dioxin Analysis Unit,P.O. Box 385, Pymble NSW 2073, Australia

J. P. M. TorresInstituto de Biofisica, Federal University of the Rio de Janeiro,21949–900 Rio de Janeiro, Brazil

M. VertaFinnish Environment Institute,P.O. Box 140, 00251 Helsinki, Finland

G. VarbelowFriedrichstrasse 48,76593 Gernsbach, Germany

J. VijgenInternatial HCH and Pesticide Association,Elmevej 14,2840 Holte, Denmark

A. WatsonPublic Interest Consultants,P.O. Box 548, Oakleigh, Wernffrwd,Swansea, Wales, UK

P. CostnerOwltree Environmental Consulting,P.O. Box 548, Eureka Springs, AR, USA

P. WyciskHydro- and Environmental Geology, Martin Luther University,Von-Seckendorff-Platz 3,06120 Halle/Saale, Germany

M. ZenneggLaboratory for Analytical Chemistry,Swiss Federal Laboratories for MaterialsTesting and Research (EMPA),Überlandstrasse 129,8600 Dübendorf, Switzerland

364 Environ Sci Pollut Res (2008) 15:363–393

human generations. Many of the recent food contaminationproblems that have emerged in Europe and elsewheredemonstrate how PCDD/F and dioxin like PCBs fromhistorical sources can directly contaminate human andanimal feedstuffs and indeed highlight their considerablecontemporary relevance in this respect. Accordingly, somekey experiences and lessons learnt regarding the produc-tion, use, disposal and remediation of POPs from thecontaminated sites are summarised.Discussion An important criterion for evaluating the sig-nificance and risks of PCDD/Fs and other POPs atcontaminated sites is their present or future potential formobility. This, in turn, determines to a large degree theirpropensity for off-site transport and environmental accessi-bility. The detailed evaluation of contaminated site casesreveals different site-specific factors, which influence thevaried pathways through which poor water-soluble POPscan be mobilised. Co-contaminants with greater watersolubility are also typically present at such sites. Hence,pumping of groundwater (pump and treat) is often requiredin addition to attempting to physically secure a site. At anincreasing number of contaminated sites, securing measuresare failing after relatively short time spans compared to thetime horizon, which applies to persistent organic pollutantcontamination. Due to the immense costs and challengesassociated with remediation of contaminated sites ‘moni-tored natural attenuation’ is increasingly gaining purchaseas a conceptual remediation approach. However, theseconcepts may well prove limited in their practical applica-tion to contaminated sites containing persistent organicpollutants and other key pollutants like heavy metals.Conclusions It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and futurerelevance. They will continue to represent an environmentalissue for future generations to address. The securing and/orremediation of dioxin/POP-contaminated sites is verycostly, generally in the order of tens or hundreds of millionsof dollars. Secured landfills and secured production sitesneed to be considered as constructions not made for‘eternity’ but built for a finite time scale. Accordingly, theywill need to be controlled, supervised and potentiallyrepaired/renewed. Furthermore, the leachates and ground-water impacted by these sites will require ongoingmonitoring and potential further remediation. These activ-ities result in high maintenance costs, which are accrued fordecades or centuries and should, therefore, be compared tothe fully sustainable option of complete remediation. Thecontaminated site case studies highlight that, while exten-sive policies and established funds for remediation exist inmost of the industrialised western countries, even theserelatively well-regulated and wealthy countries face signif-icant challenges in the implementation of a remediationstrategy. This highlights the fact that ultimately only the

prevention of contaminated sites represents a sustainablesolution for the future and that the Polluter Pays Principleneeds to be applied in a comprehensive way to currentproblems and those which may emerge in the future.Recommendations and perspectives With the continuingshift of industrial activities in developing and transitioneconomies, which often have poor regulation (and weakself-regulation of industries), additional global challengesregarding POPs and other contaminated sites may beexpected. In this respect, a comprehensive application ofthe “polluter pays principle” in these countries will also bea key to facilitate the clean-up of contaminated areas andthe prevention of future contaminated sites. The threats andchallenges of contaminated sites and the high costs ofsecuring/remediating the problems highlight the need for acomprehensive approach based upon integrated pollutionprevention and control. If applied to all polluting (andpotentially polluting) industrial sectors around the globe,such an approach will prove to be both the cheapest andmost sustainable way to underpin the development ofindustries in developing and transition economies.

Keywords Chlorine industry . Chlor-alkali . Contaminatedsites . HCB . Organochlorine industry . PCB . PCDD .

PCDF. Persistent organic chemicals . Pesticides . POPs .

remediation . remediation cost . Stockholm Convention .

Unintentionally produced POPs . UPOPs

1 Introduction

The environmental management and control of polychlori-nated dibenzo-p-dioxins (PCDDs) and dibenzofurans(PCDFs) is addressed at a global level through the Stock-holm Convention. This international treaty, which aims toprotect environmental and human health from adverseeffects associated with exposure to persistent organicpollutants [POPs; Stockholm Convention (SC) 2001,www.pops.int], entered into force on 17 May 2004. Theinitial ‘dirty dozen’ POPs includes the four unintentionallyproduced POP categories1 (UPOPs)—PCDDs, PCDFs,unintentionally produced PCBs and HCB—for reductionand elimination (Article 5/Annex C SC 2001).

Over the last decade and particularly through the recentactivities carried out under the auspices of the Convention,

1 Currently, there are only four unintentionally produced POPs in theStockholm Convention list. However, PentaCBz is currently in thePOPRC and other compounds are proposed or discussed as beingunintentionally produced POPs (see Table 1). Other unintentionallyproduced compound classes are proposed for the evaluation of theTEF concept (Van den Berg et al. 2006) and should to be consideredas UPOPs (see Table 1).

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www.pops.int

a number of national and regional PCDD/F inventorieshave been established (Fiedler 2007; Quaß et al. 2004;UNEP 1999) to establish priorities for source reduction andelimination. The key sources considered in these arepredominantly thermal processes. Open burning of wasteand biomass, the operation of waste incinerators and theactivities of the primary and secondary metal industry forferrous and non-ferrous metals (Fiedler 2007; Quaß et al.2004). Historic PCDD/F releases, however, are not ade-quately addressed in these inventories. Ignoring thesecontaminant reservoirs could create the impression thathistorical sources are no longer relevant and that theelimination of dioxin sources can be achieved solely byaddressing contemporary (thermal) sources.

However, the PCDD/F releases from the key historicalsources, largely associated with the chlorine industry andthe onward production and use of chloro-organic chemicals,were substantial in the past2. Data suggest that they haveexceeded by far the documented releases from contempo-rary sources (Weber et al. 2008; see Table 3 in Appendix).This can be illustrated by historical inventories compiledfor Japan and Sweden. PCDD/F contamination from pastpesticide3 use in Japan has been estimated at 460 kg TEQbetween 1950 and 1998 (Masunaga et al. 2001; Seike et al.2003; Weber and Masunaga 2005; Fig. 1). Wood treatment

in Sweden resulted in historical releases of between 205and 250 kg TEQ (Swedish EPA 2005). By comparison,contemporary releases of PCDD/Fs from a total of 55countries where inventories exist have been estimated atapproximately 20 kg TEQ/year (Fiedler 2007). Similarly,these estimated contemporary inventories PCDD/F releasescan be compared to other historic dioxin releases, such asthe release of 378 kg TEQ from a single factory producinghexachlorocyclohexane (HCH) and 2,4,5-trichlorophenoxy-acetic acid (2,4,5-T) in Hamburg. This pesticide factory isthe only plant of this type where a full historical inventoryhas been compiled (University of Bayreuth 1995). Anestimated dioxin release of more than 366 kg TEQ tookplace via the spraying of defoliants in the Vietnam War(Allen 2004; Stellman et al. 2003; Young 2006; Young etal. 2008). Table 3 (see Appendix) details other cases thatwill be featured in this series. In addition, more than10,000 kg TEQ was generated through the manufacture ofPCBs (see below). These incidents have contributedconsiderably to the current TEQ environmental loadings.The large proportion of PCBs still in use, stockpiled or inlandfills, act as reservoirs and secondary sources fromwhich environmental mobilisation will continue in thefuture.

Dioxins and other POPs, emitted from historical sources,can persist in soils, sediments and waste reservoirs overtimeframes ranging from decades to centuries or evenlonger. Accordingly, these legacies will remain of consid-erable contemporary and future relevance and will continueto represent a pollution problem for future generations toaddress. In addition, the potential for these compounds tovolatilise and to be transported through the atmosphere overlong distances provides pathways for their secondaryrelease and wide distribution from historical point sources.Such secondary releases have been only poorly character-

2 For a comprehensive overview on the chlorine industry andemissions from the chlorine industry, see Stringer and Johnston(2001).3 The contemporary release of PCDD/F via pesticide production,however, is not clear. Wenborn et al. (1999) estimated the release ofPCDD/F from pesticide production in Germany alone to be 160 to26,500 g/year. The wide range of the estimation is indicative for thelack of data required for a more clear determination of emissionfactors from chemical production.

Fig. 1 Historic JapanesePCDD/Fs inventory allocatedfrom pesticide application andair emission from thermal sour-ces (WHO TEQ) as well asrelease to the Japanese environ-ment. PCB includes only therelease, not the productionwhich is estimated to 470,000 gTEQ (Takasuga et al. 2005).1958–1995: Estimated emissionby Masunaga (1999). 1997–2006: Governmental emissioninventory yearly compiled bythe Ministry of the EnvironmentJapan (2004 and 2006)


ised and quantified to date. It has been noted, however, thatknown contemporary dioxin sources can only account for aminor portion (perhaps as little as 2−10%) of current annualdeposition of these contaminants (Cooney 1998; Harradand Jones 1992; Eisenberg et al. 1998). Consequently,secondary source releases may be considerably under-estimated, as shown by Baker and Hites (2000), forexample, who suggested that production and release ofPCP, which largely ceased during the 1970s/1980s, stillcontributes to atmospheric PCDD/F deposition. Similarly,the US EPA concluded in 1994 that PCDD/Fs fromcontaminated sites/hot spots would soon become the majorsource of contemporary contamination from these chem-icals (US EPA 1994). Hence, while many sources ofPCDD/Fs are legacies of historical chemical industryactivities, at least in developed countries, they have asignificant contemporary relevance, which is common toother POPs listed in the Stockholm Convention4. TheStockholm Convention stresses this by requiring parties todevelop appropriate strategies to identify sites contaminatedwith PCDD/Fs and other unintentionally and intentionallyformed POPs [Article 6(1)e SC 2001].

To inform this process, a new series in ESPR under thetitle ‘Case Studies on Dioxin and POP Contaminated Sites—Contemporary and Future Relevance and Challenges’ willaddress this important issue. The series will mainly examinethe issue of PCDD/F contaminated sites and will also drawon experiences of sites contaminated with PCBs and otherintentionally and unintentionally produced POPs.

The case studies invited for this series are summarised inTable 3 (see Appendix) and will be published in subsequentESPR issues. The key aims of this series are:

(1) To provide an overview on the types of PCDD/F andPOPs contaminated sites,

(2) To evaluate the contemporary relevance of theselegacies and

(3) To document evaluation strategies and remediationconcepts.

Most of the cases in this series highlight the contempo-rary and future relevance of POP legacies and stress thattheir future impact and risks can only be evaluated byincorporating detailed site-specific information. Addition-ally, it is hoped that this series will help to communicate theexperiences of industrialised countries to the governmentsand other stakeholders in developing/transition countries,which are operating or establishing industries based uponhalogen (chlorine, bromine and fluorine) production andintegrated halogenated chemical synthesis. In many cases,such industries are being established or operated in theabsence of an adequate waste management strategy leadingto the high likelihood that remediation will ultimately berequired. However, securing and/or remediating any subse-quent environmental contamination can lead to significantsocial, economic and environmental costs (see Table 3 inthe Appendix), much above the costs of pollution preven-tion and control measures.

Finally, this series aims to provide information tofacilitate historic PCDD/F inventories on a company-,production-, chemical- (see Table 3 in the Appendix) andcountry-specific basis. The intention is to improve the verylimited quantitative information available to date regardingpollution caused by these historical sources and to allow abroader evaluation of their relevance in today’s environ-ment and food and the pathways, through which they exertany contaminating influence.

2 Global policy and selected country policy/statuson contaminated site remediation

2.1 Stockholm Convention

To date, there is no intergovernmental policy instrumentthat addresses the identification and remediation of con-taminated sites. Countries that have ratified the StockholmConvention (Parties) must endeavour to develop strategiesfor identifying sites contaminated with POPs (Article 6, SC2001). While not explicitly requiring remediation ofcontaminated sites, the Stockholm Convention stipulatesthat any remediation attempts must be carried out in anenvironmentally sound manner (Article 6, SC 2001). In thiscontext, the first POPs remediation project for a contami-nated site (former PCB production facility) has recentlybeen initiated under a United Nations body (UNIDO/UNDP/GEF) in Slovakia (http://www.non-combustion.sk/).

Considering the relatively limited information on exist-ing contaminated sites and the vast number of potentialhotspots from historical and existing facilities where POPscontamination is likely, there is a current need for a broaderapproach to identify sites contaminated with POPs on aglobal scale.

4 The production of the majority of the intentionally produced POPswas stopped in the 1980s, and today, only DDT is produced incommercially significant amounts. Destruction of the remainingstockpiles and wastes, however, is a managerial challenge and afinancial burden. For example, many electrical transformers contain-ing or contaminated with PCBs remain in use, and it is estimated thatabout 4 million tonnes of such equipment will need environmentallysound waste management (OECD 2007) as it is decommissioned.With current total treatment costs of US $2,000 to 5,000 (includingpacking, transport and destruction) this would amount to an estimatedUS $8 to 20 billion to manage transformer-associated PCBs alone. Acomparison to the US $550 million allocated GEF funding for theStockholm Convention from 2003 to 2010 demonstrates the magni-tude of the financial challenge to implement the PCB obligations ofthe Stockholm Convention by the target date of 2028.


http://www.non-combustion.sk/

2.2 Switzerland—regulation requesting completeremediation of persistent landfills

Currently, policies regarding the identification and remedi-ation of contaminated sites vary considerably amongdifferent countries. Switzerland’s regulations are amongthe most stringent and require that landfills that do notdegrade within one generation must be completely reme-diated (Eidgenössisches Department des Innern 1997).Examples of such remediation attempts at large chemicallandfills in Switzerland [Kölliken, approximately 300,000 tchemical waste deposited between 1977 and 1985 (http://www.smdk.ch/), and Bonfol, 114,000 t deposited between1961 and 1976 (http://www.bci-info.ch/; http://w3.jura.ch/dib/); Forter and Walther (2004)] are presented in thisseries. Such complete remediation attempts (completeexcavation and destruction) are associated with enormouscosts. In Bonfol, for example, these costs amount toapproximately $270 million and have to be covered bythe Basel chemical industry (Novartis, Roche, Ciba,Clariant and Syngenta) as the established polluters whoare also operating the landfill. In contrast, in the case ofKölliken, the federal state governments (Kanton Aargauand Kanton Zürich) are responsible for covering most of theremediation costs of approximately 500 million francs(≈$450 million) since the landfills were operated by, andbelong to, the public authorities.

2.3 US Superfund programme

The US Superfund was established to address abandonedhazardous waste sites and is supported by a fund estab-lished under the Comprehensive Environmental Response,Compensation and Liability Act (CERCLA) of 1980. TheSuperfund arose in response to the discovery of toxic wastedumps such as Love Canal and Times Beach in the 1970sand requires the responsible parties to undertake orreimburse the costs of clean-up activities. Over the past25 years or so, thousands of similar hazardous waste siteshave been identified. It has been suggested that the basis ofpast and current remediation strategies and their reportedperformance, sustainable clean-up of these sites in theUSA, is not feasible (Montague 2006). This is largelybecause most remediation strategies in the USA involvedeither leaving waste in place (combined with a cover and/orbarrier of some kind) or excavating the waste and taking itto a licensed landfill. The US regulating agencies failed todevelop permanent cleanup technologies that would destroythe waste or render its toxicity mute. In addition, budgetsallocated for remediation have been considerably reducedunder the current administration. The Superfund is nolonger funded by taxes collected from chemical companiesthat generated/generate hazardous waste. The provision in

the law that provided for this ended in 1995 and was notrenewed by the US Congress. All Superfund money nowused to pay for cleanup in the USA comes from the USgovernment (Rabe and Lester 2005). At the same time, thelist of sites identified as requiring remediation has contin-ued to grow (Sapien 2007). US studies suggest that onlyprevention of contaminated sites in the first place representsa truly sustainable solution and a means to arrest thecontinued development of problems (Montague 2006).

In this series, an update of the Love Canal case in NiagaraFalls, NY, USA (Occidental Petroleum) will be presentedwhere over 21,000 t of industrial waste was buried in alandfill over a 10-year period (1942 to 1952) from HookerChemical Company, including significant quantities ofchlorinated benzenes, phenols, pesticides and PCDD/F.The case reveals the shortcomings of the Superfundapproach, the importance of grassroot NGOs work and therelevance of public awareness and participation in theprocess of addressing and solving contaminated site issues.

2.4 EU regulation and activities on contaminated sites

In the European Union, remediation of contaminated sites,including remediation of POPs, began during the 1980s,especially in densely populated countries such as TheNetherlands, Denmark and Germany. Potentially pollutingactivities are estimated to have occurred at nearly 3 millionsites and investigation is now needed to establish whetherremediation is required. If current investigation outcomescontinue their present trends, the number of sites needingremediation will increase by 50% until 2025 (EuropeanEnvironment Agency 2007). By contrast, only around80,000 sites have been cleaned up in the last 30 years inthe countries for which data on remediation are available.Although the range of polluting activities (and their relativeimportance as localised sources of soil and groundwatercontamination) may vary considerably across Europe,industrial and commercial activities as well as the treatmentand disposal of waste are reported to be the most importantsources. National reports indicate that heavy metals andmineral oil are the most frequent soil contaminants atinvestigated sites, while mineral oil and chlorinated hydro-carbons are the most frequent contaminants found inground water (European Environment Agency 2007).Although considerable efforts have been made already, itwill take decades to clean up the legacy of contamination.The European Union recently adopted a thematic strategyon the protection of soil with an overall objective to protectthe terrestrial environment and future sustainable use ofsoils (EU COM 2006a,b). In addition, the EU WaterFramework Directive (EU WFD 2000; Santillo andJohnston 2006) will be a driving force for the protectionof rivers, lakes and the sea demanding action at the source.


http://www.smdk.ch/

http://www.smdk.ch/

http://www.bci-info.ch/

http://w3.jura.ch/dib/

http://w3.jura.ch/dib/

The costs for these activities are likely to prove enormousand include remediation of not only soil but also groundwater and sediments.

2.5 Fazit of Section 2

These national and regional examples highlight the factthat, while extensive policies and established funds forremediation exist in most of the industrialised westerncountries, even these relatively regulated and wealthycountries face significant challenges in their implementa-tion. In future, the Stockholm Convention can be expectedto place even more focus on POPs and other persistent,bioaccumulative and toxic substances to assure protectionof the environment. This will not only increase the numberof sites earmarked for decontamination but will also requireincreasingly sophisticated remediation strategies to bedeveloped. In addition, with the continuing shift ofindustrial activities to developing and transition countrieswith demonstrably poorer regulation (and concomitantlyweaker self-regulation of industries), additional challengesin relation to contaminated sites may be expected to emergeglobally in the future. In this regard, a more comprehensiveand internationally binding application of the polluter paysprinciple, and an integrated pollution prevention andcontrol approach in industry is required to facilitate theprevention of future contaminated hotspots in developingand industrialised countries, while lessons can also belearned from the OSPAR commitment to cessation ofemissions, discharges and losses of hazardous chemicalsby 2020.

3 Human PCDD/F and dioxin-like exposurefrom historic reservoirs

In the general population, more than 95% of humanexposure to PCDD/F and dioxin-like PCBs typically occursvia food (EC 1999a). PCBs contribute, on average, morethan 50% of the uptake of dioxin-like TEQ in the keysources of human nutrition5 (EC 1999b; Scientific Com-mittee on Food 2000; Fiedler et al. 2000). Similarly, dioxin-like PCBs can account for 50% of the total TEQ in humanmilk, however with significant variations between countries(Malisch and van Leeuwen 2003). With respect to PCBs,the sources of food contamination and associated humanexposure are relatively well understood. It is clear that the

estimated 1.3 to 2 million tonnes of PCBs produced asindustrial products in the past (Breivik et al. 2002; DeVoogt and Brinkmann 1989; Fiedler 2001) contribute themajor proportion of PCBs found in food and ingested byhumans. Unintentionally produced PCBs from sources likewaste incineration (Sakurai et al. 2003) or metal production(Grochowalski et al. 2007) only play a minor role andgenerally account for less than 5% of total TEQ in releasesfrom these sources.

In contrast, such source attribution has proven moredifficult for PCDD/Fs. While dioxin inventories have beenestablished in some countries for approximately 20 years(UNEP 1999; Fiedler 2007), the contribution of specificdioxin sources to food and human exposure are not yetresolved. This may be a function of the multitude ofdifferent dioxin sources that exist, coupled with thealteration of PCDD/F congener profiles through environ-mental processes. In particular, the variable bioaccumula-tion efficiencies of the different dioxin congeners (andrelatively rapid metabolisation of non-2,3,7,8-substitutedcongeners), which also vary among species (Hoogenboomet al. 2004; Lenk 2007; Malisch 2000), make it difficult tocorrelate biota contamination patterns directly with thosefrom primary sources.

Similar to PCBs, however, some case studies indicatethat dioxins from reservoir sources represent an importantsource of today’s food contamination and human exposure(see below). For example, the 2,3,7,8-congener patterns ofHxCDDs in contemporary human breast milk from Japan(Tawara et al. 2006) can be correlated with the PCDD/Fimpurities in historical PCP products. Similarly, 1,2,3,7,8-PeCDD and 2,3,7,8-TCDD, which contribute a majorproportion of the TEQ found in human milk in Japan, arecharacteristic of the congener profile of the 100 kg scaleTEQ release attributed to the use of the pesticide chloroni-trophene (CNP; Seike et al. 2003; see Fig. 1). This indicatesthat a considerable proportion of today’s human milkcontamination in the monitored Japanese provinces stemfrom the extensive past use of PCP/CNP in rice paddies6. Inaddition, current PCDD/F levels in human breast milk froma Vietnamese province where Agent Orange and otherdefoliants were sprayed are considerably higher as com-pared to non-sprayed areas (Tawara et al. 2006), demon-strating that today’s generations continue to be exposed todioxins that were emitted 40 years ago.

Similar conclusions have been drawn for PCDD/Fs infood. For example, the German Ministry of Environment

5 For example, the contribution of coplanar PCBs to total TEQ in fish(Scientific Committee on Food 2000), dairy products (Fürst 2001) orbutter (Weiss et al. 2001; Santillo et al. 2003) amount, on average, tomore than 50% in the Northern Hemisphere, while the PCBcontribution to total TEQ is less in the Southern Hemisphere.

6 If the contamination was mainly via food chain to the mothers orstems from exposure of the grandmothers during the decades, PCPwere applied (see Fig. 2) and passed on perinatally warrants furtherevaluation.


has stressed that the PCDD/F contamination of free rangeeggs is predominantly a legacy from historical contamina-tion associated with the chlorine/organochlorine industry(Lahl 2005). Similarly, elevated PCDD/F levels identifiedduring a survey of US beef were considered to stem fromPCP-treated wood used in stables (Huwe et al. 2004), andelevated PCDD/F in today’s fish and other seafood areoften associated with the legacies of the chlorine/organo-chlorine sector together with other industries (Birch et al.2007; Cake et al. 2005; Götz et al. 1998, 2007; Heinisch etal. 2007; Johansen et al. 1996; Kannan et al. 2000; Kang etal. 2000; Micheletti et al. 2007; New South WalesGovernment 2008; Stachel et al. 2007; Wu et al. 2001). Inmany locations (particularly in industrialised countries inthe northern hemisphere), industrially produced PCBscontribute to the major proportion of dioxin-like toxicityin fish (Assmuth and Jalonen 2005; FOEN 2008), whichcan often be associated with a known history of PCBproduction or other PCB point sources (Heinisch et al.2006b; Turrio-Baldassarri et al. 2007). In Switzerland forexample, PCB concentrations in fish from rivers near PCBsources have been recently found to be considerably abovethe EU food regulation (FOEN 2008) and are due to befurther investigated through a national survey that iscurrently underway. An overview of the Swiss survey ofthe impact of PCB contamination of aquatic food resourceswill be presented as part of this series.

Last, but not least, it needs to be highlighted that manyof the recent food and animal feed scandals in Europe,where food and feed are regularly screened for PCDD/Fs toensure compliance with existing regulatory limits (Europe-an Commission 2006a, b), have been caused by legaciesfrom the past production of chlorinated organics andcontaminated sites:

& In 1998, dairy and meat products were contaminatedwith high levels of PCDD/Fs originating from citruspulp made using lime deposits from the chlorine/organochlorine industry (Electrochloro/Solvay Indupa;Fiedler et al. 2000; Malisch 2000; Torres et al. 2008).Details on the origin of this contamination will bedescribed in a paper of this series as an importantexample of the ways whereby materials from contam-inated sites directly reach the human food chain,highlighting the necessity to control contaminantreservoirs and residues and facilitate their destruction.

& In 1999, Belgium chickens, eggs and other animalproducts were contaminated with PCDD/Fs via wastePCB oil that was mixed with old fat and used for animalfeed (Belgium dioxin scandal; Covaci et al. 2002;Fiedler et al. 2000).

& In 2002, an animal feed mixture containing cholinechloride was discovered to contain high levels of

PCDD/Fs, which were later established as originatingfrom PCP via saw mill dust that had been added to themixture (Llerena et al. 2003).

& In 2007, contaminated guar gum from India caused aglobal PCDD/F food scandal. Exported guar gum(widely used as starch for processed food) wascontaminated with PCDD/Fs from PCP. However, it iscurrently not clear if this contamination originated fromold PCP deposits or if PCP, which is still produced inIndia, was added to the guar gum for preservation(Community Reference Laboratory for Dioxins andPCBs in Feed and Food 2007a, b).

These cases further establish that various ‘short-cuts’exist via which reservoir PCDD/Fs and PCBs can reachfood and feed directly, without the normal environmentalbioaccumulation/biomagnification processes (Fig. 2).

The examples above highlight the fact that contemporaryfood contamination and associated human exposureremains closely associated with chlorine7 producing/usingindustries and in particular organochlorine products or theirassociated produced wastes. While local food or humancontamination has been reported for some PCDD/F andPCB contaminated sites (see above and, for example,Balzer et al. 2007; Braga et al. 2002; Chan et al. 2007;Evers et al. 1997; Hauser et al. 2005; Johansen et al. 1996;Karouna-Renier et al. 2007; Mendoza et al. 2006; Perssonet al. 2006; Revich et al. 2004; Revich and Shelepchikov2007; Ruus et al. 2006; Schmid et al. 2003; Turrio-Baldassarri et al. 2007), a comprehensive investigation ofPCDD/F exposure from the numerous reservoir sources viathe food chain and other pathways (see Fig. 2) has not beenundertaken to date. A number of the case studies presenteddemonstrate contamination of humans and food fromreservoir sources. These may prove of use in efforts toinvestigate the role of historical sources of PCDD/Fs anddioxin-like PCBs in contamination of the human andanimal food chain, although this aspect is not a primaryfocus of this series of articles.

4 Categories of PCDD/F-contaminated sites

The most significant historical PCDD/F and dioxin-likePCB contamination incidents have arisen almost exclusive-ly as a result of the industrial production of chlorine and

7 The recent food contamination from PCDD/F resulted from the useof contaminated HCl from Tessenderlo for the production of gelatine(Hoogenboom et al. 2006; Wilm 2007). This case demonstrates thatcontemporary PCDD/F release from the chlorine industry can lead todirect food contamination with PCDD/F and needs to be bettercontrolled.


chlorinated organic chemicals (Weber et al. 2008). Themanufacture of chlorine, chlorinated pesticides, PCBs andthe treatment/disposal of the related contaminated wastestreams have caused particular problems (Table 3 in theAppendix and Table 2; Jürgens and Roth 1989; Kleopfer1985; Massunaga et al. 2001; Stringer and Johnston 2001;Weber et al. 2008). PCDD/F contaminated sites have alsoresulted from processes involving thermal treatment ofhalogenated waste, recyclates or other materials. Hence,waste incinerators, primary and secondary metal smeltersand the processing of electronic waste or shredded scrapvehicles have all been implicated in various contaminationincidents. In turn, such incidents are often attributable to thepresence of chlorinated or brominated chemicals in theprocess. The pre-eminence of the chlorine and chlor-chemical industry with respect to PCDD/F releases andcontaminated sites means that a useful categorisation of

historically contaminated sites can be made. This is simplyachieved on the basis of where in the chlorine production,use and disposal cycle (including product management anddisposal) a given contaminative activity occurs (see Fig. 2).

4.1 PCDD/F contaminated sites from the productionof chlorine

Past experiences from China, Germany, Sweden and theUSA have demonstrated that the chlor-alkali process cangenerate large amounts of PCDD/Fs (Lutz et al. 1991;Rappe et al. 1990, 1991; Wu et al. 2001; Xu et al. 2000; seeTable 3 in the Appendix, and Table 2). Other unintention-ally produced POPs include PCBs, HCB (Lutz et al. 1991)and polychlorinated naphthalenes (PCNs) (Kannan et al.2000). Mercury, together with other inorganic hazardouscontaminants (Lutz et al. 1991; Stringer and Johnston 2001;

Table 1 Chemicals which are unintentionally produced in a range of thermal or chemical processes and which meet or should be evaluated tomeet the POPs criteria

Category Unintentinally produced POPs or unintentionally produced PTS

Listed in the Stockholm Convention PCDDs, PCDFs, PCBs, HCBCurrently in the POPs reviewing committee orsuggested for the reviewing process

Pentachlorobenzenes (PCBz), alpha-HCH, beta-HCH, PCNs, PAHs

Discussed to be evaluated for the TEF concept(Van den Berg et al. 2006)

PBDD,s PBDFs, PXDDs, PXDFs, PBNs, PXNs, PBBs, PXBs

Selection of other unintentionally produced toxicsubstances warrant to be evaluated for UPOPscriteria

Chlorinated PAHs, brominated PAHs, mixed halogenated PAHs, Nitro PAHs,octachlorostyrene, 1,2,3,4-TeCBz, 1,2,3,5-TeCBz, 1,2,4,5-TeCBz, 1,2,3-TrCBz,1,2,4-TrCBz; 1,3,5-TrCBz, HBBz, PentaBBz, TetraBBz, TrBBz, PBP, TeBP, TrBP,PCP, TeCPs, TriCPs, hexachlorbutadien, pentachlorobutadien, tetrachlorobutadien,hexachloroethan, tetrachlorethene, other unintentionally produced chlorinated,brominated and mixed halogenated aromatic or aliphatic compounds

Fig. 2 Sources and reservoirs,environmental transport andmajor human exposure path-ways of PCDD/Fs


UNEP 2002), can also cause significant harm from thisindustrial sector including severe contamination of the envi-ronment, biota and humans (Nishimura and Kumagai 1983).

The use of graphite electrodes has been firmly linkedwith the formation and release of PCDD/F (Otto et al. 2006;Rappe et al. 1990, 1991; Wu et al. 2001; Wilken et al.2006b). Since the 1970s, graphite electrodes have largelybeen superceded by metal electrodes and such releases haveconsequently been greatly reduced in the developed nations(UNEP 2005a). Nonetheless, in some developing andtransition countries, the use of graphite in these applicationsstill persists. For example, according to a Chinese PCDD/Finventory for 2002, the single most significant PCDD/Fsource was the chlor-alkali process with an estimatedrelease of 4.4 tonnes PCDD/Fs, equivalent to 6.6 kg TEQ/year. This represented approximately 50% of the totalestimated release for China in 2002 (Jun et al. 2004).Similar situations are likely to exist in other countries usingolder chlorine production systems.

Due to the potential contamination associated with theproduction of elemental chlorine in the chlor-alkali process,an evaluation of both historical and current productionpractices in this sector could prove useful to the workcarried out under the Stockholm Convention in assessingthe past and present releases of PCDD/Fs attributable to thissector. Lessons learned from contamination caused bychlor-alkali processes could help inform the process ofevaluating this sector on a more global basis. Unfortunately,despite the known problems caused by graphite electrodesludge, involving the situation that little detailed informa-tion exists on appropriate strategies for investigating ofthese facilities, one must consider the overall extent ofassociated contamination or the remedial measures requiredto address the problem. This series will therefore describeseveral cases of contaminated sites impacted by chlor-alkalielectrolysis plants with different contamination patterns(see Table 3 in the Appendix) and provide what details areknown to consider the associated contamination pattern,risk assessments and remediation activities carried out.

Apart from the well-known phenomenon of PCDD/Fformation in the chlor-alkali process, other chlorineproducing processes may have had the potential to causesimilar contamination problems. It has recently beendiscovered that a former soda ash factory using the Leblancprocess and which also produced chlorine and calciumhypochloride (bleaching powder) via the manganese diox-ide process have resulted in high concentrations of heavymetals and PCDD/Fs as key contaminants at the sites(Balzer et al. 2007; see Table 3 in the Appendix). TheLeblanc Process allowed the bulk production of sodiumcarbonate as an important commodity of chemical and theemergence of this process in the late eighteenth century canjustifiably be considered as the birth of the modern

chemical industry (Kiefer 2002; Treue 1967). It was alsothe point at which elemental chlorine was first producedindustrially as a secondary product by reacting hydrogenchloride evolved in the process with manganese dioxideand later by using this gas in the Deacon process, where itwas oxidized via a copper chloride catalyst.

Accordingly, one of the case studies presented will bethat of a Leblanc soda plant, which operated in Germanyfrom 1848–1893 and released somewhere between 1 and10 kg TEQ of PCDD/F at the site. In turn, this led tocontamination of a residential area subsequently developedat the site and remediation is currently being carried out.This has a high degree of contemporary relevance. TheLeblanc process was widely used in Europe until the earlytwentieth century, with more than 15 factories operating inGermany alone. Hence, the recently identified contamina-tion problems may be a problem common to many of theLeblanc and other early chlorine/bleaching powder produc-tion sites. Despite this, such facilities have not beenconsidered as sources of contemporary PCDD/F contami-nation sources up to this point, and to our knowledge, noother evaluations of such sites in respect to PCDD/F havebeen performed.

4.2 PCDD/F and UPOPs contaminated sites associatedwith waste releases from production of organochlorines

As described in the introduction, the highest historicalPCDD/F releases stem from the production of chlorinatedorganics and in particular the chlorinated pesticides (e.g.2,4-D, 2,4,5-T, PCP, CNP and HCH recycling) and PCBs.These releases, which often occurred together with highconcentrations of other chemical residues (see Tables 1 and2), account for a large proportion of known PCDD/Fcontaminated sites (see Table 3 in the Appendix). Inaddition, many of the serious industrial accidents involvingdioxins and human contamination (see Fig. 2) wereassociated with the production of chlorinated organicchemicals (Allen 2004; Dohmeier and Janson 1983;Weidenbach et al. 1984; Weber et al. 2008; Schecter1994). These accidents resulted in contaminated sites suchas that caused by the well-known accident at the ICMESA2,4,5-trichlorophenol production plant in 1976 in Seveso.In this case, up to 30 kg TEQ were estimated to have beenreleased contaminating the population šnd the environment(Mocarelli 2001). An update on ‘Dioxin health effects onhumans 30 years after Seveso’ will also be presented in thisseries of articles.

The quantities and precise character of PCDD/Fs andUPOPs (see Table 1) formed and released from organo-chlorine chemical production is contingent upon theproduction processes themselves together with any purityrequirements imposed by the manufacturers, end-users and


national regulatory authorities. In addition, the wastemanagement policies in force also play an important part.All these aspects need to be considered when industriallycontaminated sites are assessed. Four key modes ofcontaminant release in waste streams can be distinguished.

4.2.1 Discharge to landfills/dumps

Most of the solid residues of chemical industries were/aretypically discharged to landfills and dumps. In industrialcountries, this was a common practice until the 1970/1980swhen hazardous waste incinerators were increasingly usedin hazardous waste management. Many of the chemicalsdumped are persistent. The landfills/dumps were often notadequately secured. In combination, this represents a highrisk of subsequent contaminant release and a considerablechallenge in terms of making the landfills/dumps secureand carrying out remediation. Furthermore, hazardouschemical waste is still dumped/landfilled in many countriestoday, creating similar problems for the future. In thisseries, several cases of chemical landfills and contaminatedproduction (see Table 3 in the Appendix) sites will bepresented covering a wide spectrum of remediation strate-gies, activities and status, including:

& A pesticide factory in Ufa/Russia (Khimprom), wherethe initial evaluation and screening of a contaminatedmegasite is carried out in the absence of strategies forsecuring or remediating the site (this status is represen-tative of most contaminated sites in developing andtransition countries)

& A pesticide factory in Hamburg/Germany (Böhringer),where securing of landfills and the production site aswell as ‘pump and treat’ of ground water has beencarried out and is still ongoing

& A chemical landfill in Amsterdam/The Netherlands(Akzo, Philipps Duphar, Shell), where comprehensivemonitoring is undertaken and extensive funds areavailable for eventually cleaning leachates

& Chemical landfills in Kölliken and Bonfol/Switzerland(Basel Chemical Industry: Novartis, Roche, Ciba,Clariant und Syngenta), where the complete remedia-tion including excavation and destruction (incineration)of chemical waste is being carried out

For the majority of historic cases where PCDD/F releasehas been identified and estimated, only known key productslike chlorophenols have been taken into account (see Table 3in the Appendix, and Table 2). However, dioxin formationand release may occur during the production of numerousother pesticides and other chlorinated organics. This hasbeen recognised by the US EPA, who provide a tentativelist of over 200 pesticides suspected of containing PCDD/Fs or with the high potential of PCDD/F contamination (US

EPA 2003). A similar list was previously published by theGerman Environmental Agency (UBA 1985), and a furtherlist has been compiled by the International POPs Elimina-tion Network (IPEN 2004)8.

Hence, understanding and knowledge of the productportfolio of individual chemical production facilities isextremely important in evaluating the potential for PCDD/Fformation during production and their release in productsand wastes. To exemplify these aspects, one in this series ofarticles will describe the comprehensive evaluation andestimation of historic dioxin releases associated with asignificant part of the production portfolio of the BaselChemical Industries for the years 1961 to 1976. Theseindustries were not associated with the commonly knowndioxin-contaminated products and residues [2,4,5-T, 2,4,5-TCP, PCP or HCH decomposition residues (Table 2)] butproduced a wide range of chlorinated aromatics, some ofwhich were found to be contaminated with PCDD/Fs andunintentionally formed PCBs (Forter 2006).

In the case of the Swiss chemical industry wastes, anassessment of the total quantities of PCDD/Fs disposed tolandfill was undertaken. This evaluation was used todetermine whether safety measures specifically aimed atPCDD/Fs were relevant to the processes involved in the fullremediation of the landfill. The study led to the decisionthat PCDD/Fs were of relevance in assuring worker safetyduring the remediation of the Bonfol chemical landfill. Thecomprehensive strategic approach used in this assessmentof the likelihood of PCDD/F releases was based on thechemical production portfolio of the factories. This methodhas the potential to become a standard approach to estimatehistoric PCDD/F releases from chemical factories.

Another article in this series will describe the evaluationof the considerable polluting legacies of HCH production.The process used to manufacture this pesticide generates amixture of isomers of which only the gamma-isomer showsinsecticidal activity. Common practice was simply to dumpthe 90% of the reaction mixture consisting of other HCHisomers after separation. As a consequence, between 4 and7 million tonnes of wastes of a variety of toxic, persistentand bioaccumulative residues are estimated to have beendumped. This can be considered the largest of the POPs

8 In this respect, it must be emphasised that increased or continued useof chlorinated pesticides is taking place, particularly in developingcountries (Mansour 2004), e.g. Pakistan and India (Sankar et al. 2006;Tariq et al. 2007), leading to increased risk of PCDD/F contaminationof environment and food as, e.g. revealed by the recent PCDD/Fcontamination of guar gum from India by PCP (Community ReferenceLaboratory for Dioxins and PCBs in Feed and Food 2007a, b).Regulations limiting the formation and release of PCDD/Fs fromchlorinated pesticide manufacture and products and concomitantupgrades and control technologies are not applied and/or enforced inall countries (Mansour 2004; Sankar et al. 2006; Tariq et al. 2007).


legacies, with overall quantities similar to the rest of theStockholm Convention POPs combined. The detailedevaluation of HCH production and waste isomer manage-ment serves as an example of how the waste releaseassociated with a particular chemical product can beevaluated on a global scale (Vijgen et al. 2006). Addingto the complexity of the overall picture, waste HCHisomers produced during HCH production were sometimespartially recycled to produce chlorobenzenes using athermal process. This resulted in high PCDD/F releases inthe waste streams. The process residues have been found tocontain PCDD/F in percentage quantities (Jürgens and Roth1989, Bao et al. 1994, Weidenbach et al. 1984; Table 2),while a total PCDD/F release on a scale of tonnes TEQ hasbeen estimated for this practice (Weber et al. 2006a, b).

4.2.2 Discharge into aquatic systems

Heinisch et al. (2004, 2006a, b, 2007) have recentlypublished comprehensive reviews on sources of POPscontamination in European rivers, including the sourcetracking strategies used. These papers highlight the frequentrelease of POPs containing wastes into river systems.Extremely high concentrations of POPs in various environ-mental matrices in some rivers (sediments, fish andsuspended particulates originate to a considerable extentdirectly from chlorine/organochlorine production sites.Similar findings have been described, e.g. for the Baltic

Sea (Isosaari et al. 2000, 2002a, b; Verta et al. 2007), theLaggo Maggiore/Italy (Binelli et al. 2004), the Venicelagoon (Fattore et al. 1997; Guerzoni et al. 2007) andTittabawassee River /USA (Hilscherova et al. 2003; Wilkenet al. 2006a). Examples of such cases addressed in thisseries include the releases from a chlorophenol/chloralkaliproduction facility in Finland, which resulted in contami-nation of the receiving river with approximately 28 kgTEQ, a portion of which ultimately reached the Baltic Sea.In another case, a former pesticide production facility(Union Carbide; 2,4,5-T, PCP) near Sydney, Australiacaused the contamination of a large area of Sydney harbour,resulting in recent bans of commercial and recreationalfishing (Birch et al. 2007; New South Wales Government2008). Another paper will describe the impact and riskassessment of a closed PCP and chlor-alkali factory inTaiwan that has contaminated nearby aquacultural farms.

4.2.3 Disposal via hazardous waste incinerators

From the 1970/1980s, the production wastes associatedwith organochlorine production were increasingly disposedof via hazardous waste incinerators in industrialisedcountries. Together with increasingly stringent regulationsand monitoring of air emissions from the incinerators, thisarguably resulted in considerable reduction of PCDD/Freleases from chemical production wastes. It has to benoted, however, that releases to air and residues from

Table 2 PCDD/Fs concentrations in some contaminated products and residues from chlorinated aromatics, chlor-alkali electrolysis and wasteincineration

Sample Sum PCDD/Fs(μg/kg)

TEQ (μg/kg) Reference

Electrode sludge chor-alkali electrolysis (graphite electrodes) Up to 62,300378,850

Up to 3,900c

21,000Otto et al. 2006;

Xu et al. 2000HCH (product and waste isomers) Up to 87,600 Up to 252 Scholz and Engler 1987HCH decomposer residue 14,000,000 86,300a Juergens and Roth 1989

46,000,000 Weidenbach et al. 198428,000,000 286,000a Weber et al. 2006a, bUp to 160,000,000 Up to 730,000b Bao et al. 1994

Residues 2,4,5-T production Up to 60,000b Weidenbach et al. 1984Up to 2,000,000b Kleopfer 1985

2,4,5-T (product) Up to 7,000b UNEP 2005a,bUp to 100,000b Friege and Klos 1990

Dioxazine dyes and pigments Up to 3,000b

Residues from PCP production 9,015,000 9,580c Friege and Klos 1990PCP (product)PCP Na (product) Up to 6,000,000 Up to 1,300a up to 3,400b Masunaga et al. 2001

Friege and Klos 1990Fly ashes (municipal waste incinerators) 7 to 2,000 0.1–20a Own dataSludge in wet scrubber (municipal waste incinerator) Up to 3,000 Takata 2003

aWHO TEQb I-TEQ NATO/CCMSc TEQ (BGA)


incinerators themselves can lead to contaminated sites,depending on the disposal technologies used, the operationsof these facilities and the management of solid residues.This issue will be addressed by a case study in this seriesdetailing PCDD/F emissions from an incinerator used todispose of chlorophenol production wastes at CoaliteChemicals, Bolsover UK. The operation of the facilitycaused extensive contamination of the surrounding, pre-dominantly agricultural area (see below).

4.2.4 Storing of chemical waste

Inadequate waste management policies, lack of auditingand/or disposal capacities can result in situations wherewastes from facilities producing organochlorines and otherchemicals are stored inadequately and ‘unnoticed’. Theglobal dimension of sites contaminated as a result of storingPCB transformers and POP pesticide stockpiles, whichresulted in thousands of POPs contaminated sites, isdemonstrated in the National Implementation Plan reportsof countries that have ratified the Stockholm Convention(www.pops.int). Selected cases will be presented in thisseries.

One well-known case of stored ‘unintentionally pro-duced HCB waste9 is that of Orica Australia Pty. Ltd(formerly ICI Australia) in Sydney (Orica TransformationProject 2008). This site has recently received much publicattention and will be discussed as part of this series.Australia does not permit the operation of hazardous wasteincinerators and has only limited alternative disposalcapacity. The HCB (with hexachlorobutadiene, hexachlor-oethene, etc.) was produced as a by-product of themanufacture of chlorinated solvents [carbon tetrachloride,perchloroethylene (PER)], ethylene dichloride (EDC) andvinylchloride (VCM). Over time, around 10,000 tonnes ofconcentrated HCB waste were accumulated with a further1,000 tonnes of wastes held in storage tanks. Attempts toexport these wastes for disposal failed due to permittingissues. In addition, an estimated 45,000 m3 of contaminatedsoils have been isolated on the site.

A similar situation exists with HCB waste generatedfrom PER manufacture as detailed in the National Imple-mentation Plan of Ukraine. In this case, a HCB stockpile ofmore than 11,000 tonnes exists as a result of carbon-tetrachloride/PER manufacture in the town of Kalush in theIvano-Frankivsk region of the Ukraine (Antonov et al.2007). In another case, in the Czech Republic, around

80,000 drums of HCB-containing waste were deposited in alandfill at Chabařovice near Ústí n. L. These wastesoriginated from the production activities of SpolchemieÚstí (Heinisch 2006a, 2007).

These three cases illustrate the dimension for theunintentional production of POPs during the manufactureof organochlorine chemicals and can be expected in manyorganochlorine factories where no destruction capacities forthe production residues exist.

For the evaluation and identification of sites contami-nated due to storage of chemical waste, it is important tounderstand and consider the various waste managementstrategies and practices used over the time of operation.Typically, a given chemical manufacturer might have aproduction history extending over decades and a spectrumof products during these time waste management strategiesevolved and changed in response to a variety of factors.These included the development of technologies such ashazardous waste incinerators, pressure on landfill capacityand availability, new legal and regulatory frameworks, newproduction methods and changes in the production portfo-lio. In addition, pressure from other stakeholders (e.g.neighbours or fisheries), such triggers and associatedchanges in waste management, have been researched anddocumented by Forter (2000) for the Basel ChemicalIndustry over a production period in excess of 100 years.The work in this series of articles will feature.

4.3 PCDD/F contaminated sites associated with applicationof contaminated pesticides, wood preservatives, PCBsand other chlorinated chemicals

In addition to releases of PCDD/Fs via waste streamsassociated with chemical production, PCDD/Fs and otherunintentionally produced POPs may also remain in thechemical product. The resulting levels and patterns ofPCDD/Fs and other UPOP impurities in pesticides, pig-ments, HCl or PVC, etc. depend on the productionprocesses employed (e.g. formation route, temperature,reagents and catalysts used) and can therefore vary betweencompanies, batches and product types. Depending on theproduction process, the PCDD/F contamination may remainpredominantly in the product as an impurity or be dis-charged with the production residue (e.g. by distillation ofthe product).

Before the availability of PCDD/F analysis, PCDD/Fand dioxin-like contamination in organochlorine chemicalswere commonly ‘monitored’ indirectly through the preva-lence of chloracne in factory workers. Chloracne was aknown factor associated with organochlorine chemicalproductions from the early beginnings of chloronaphthaleneproduction in 1918 (Braun 1955) until 2,4,5-T productionduring the 1950s to 1970s (Dohmeier and Janson 1983;

9 Unintentionally produced POPs (PCDD, PCDF, PCB and HCB) arenormally formed in parallel in thermal and chemical processes (Weberet al. 2001; Kannan et al. 2000), and therefore, unintentionallyproduced HCB waste can be expected to contain also the otherunintentionally produced PCDDs, PCDFs and PCBs.


http://www.pops.int

Weidenbach et al. 1984). In some companies, chloracneinduced in the ears of rabbits exposed to the products andproduction processes was used to indicate the need to takesteps to limit dioxin-like releases and exposures.

Analytical capabilities for PCDD/Fs were developed insome companies during the 1960s. Increased publicawareness of PCDD/F developed particularly after theSeveso accident of 1976 resulting in the development of atrace analytical method for PCDD/F (Buser 1978). As aresult, organochlorine production processes generally im-proved in relation to the PCDD/F formation and releasefrom the 1960s to 1980s. Hence, pesticides and associatedwastes produced during the early operations of theorganochlorine industry can generally be considered tocontain significantly higher PCDD/F levels. Decreases inPCDD/F impurity levels have been shown, for example, forCNP from the 1970s to the 1980s in Japan (Masunaga et al.2001). The historical trend of PCDD/Fs in Japanese ricepaddy soil reflect this decreasing PCDD/F contaminationlevel in the applied pesticides over time (Seike et al. 2007).

To reduce PCDD/F release through their presence asimpurities in pesticides, many industrialised countries havebanned or strictly regulated such pesticides. In parallel withthese regulatory activities, however, the production and useof these pesticides has gradually shifted from industrialisedto developing countries with increasingly intensive agricul-tural sectors. These countries often do not require and/orimpose regulation and monitoring for PCDD/F and otherimpurities (Mansour 2004; Sankar et al. 2006; Tariq et al.2007). Even so, some still produce and use pesticidesnotorious for PCDD/F impurities (e.g. PCP) and due to thedeficient regulatory and control regimes in place, whichprovide relatively little information according to thatavailable regarding the PCDD/F levels in pesticidesproduced after the 1980s (Wenborn et al. 1999). Presently,the levels of PCDD/Fs are being investigated in historicaland current use agrochemical formulations used in Aus-tralia. Preliminary results show that both current use andredundant pesticides used in this country contain PCDD/Fsat a wide range of concentrations (low ppt to low ppm) and,after compilation, will be presented in this series.

To provide data to support evaluation of the current scaleof the problem, case studies from the countries wheredetailed information on widespread PCDD/F contaminationfrom pesticide use exists, namely Japan, Sweden andVietnam, will be included in this series. In Vietnam,spraying of the defoliant Agent Orange and other 2,4,5-T/2,4-D containing agents (contaminated with an estimatedlevel of 366 kg TEQ) during 1963−1970 caused extensiveenvironmental contamination and associated exposure toboth local populations and personnel engaged in spraying(Allen 2004; Young 2006; Young et al. 2008; Dohmeierand Janson 1983; Schecter 1994; Stellmann et al. 2003;

Weidenbach et al. 1984). This series will, therefore, alsopresent an overview of related contaminated sites inVietnam and the current remediation activities. In addition,the contemporary fate and extent of PCDD/F contamination(with a total estimated release of 460 kg TEQ) as a result ofPCP and CNP application on Japanese rice paddies, as wellas first remediation attempts, will be described. A third casestudy from Sweden will provide specific informationrelevant to the 400 to 500 contaminated sites resultingfrom wood treatment processes. This amounts to a total ofaround 5−50 kg TEQ. Around 200 kg TEQ remained in thetreated wood itself (Swedish Environmental ProtectionAgency 2005). These examples from three differentcountries give an insight into how chlorinated pesticideuse contributes to global PCDD/F contamination andreveals the current challenges associated with the legaciesof decades of contaminated pesticide application.

Total dioxin-like toxicity associated with a contamina-tion of manufactured PCBs has to date only been estimatedfor products from Japan (approximately 59,000 tonnes) andis estimated at 112 to 941 kg TEQ (mean: 473 kg TEQ;Takasuga et al. 2005). Assuming that a similar averageTEQ for loading applies to manufactured PCBs fromelsewhere (approximately 1.3 to 2 million tonnes), so thata resulting, in rough estimate of 10,400 to 16,000 kg TEQfor total PCBs produced can be made, which can beconsidered a lower estimate, since a key PCB product fromMonsanto, producer of nearly 50% of global PCBs, had ahigher TEQ compared to the average Japanese Kanechlor(compare Johnson et al. 2008 and Takasuga et al. 2005).This estimate, however, excludes any increase in TEQ as aresult of PCB transformation/degradation to PCDF10 duringuse (Masuda et al. 1986), transformer fires (Mehag andOsborn 1995) or through incomplete destruction. This canresult in worst case scenarios in a TEQ increase of up to4,500% (Weber et al. 2002; Weber 2007a). Accordingly,sites used for the production, storage and use of PCBs,together with the sites of fires or disposal activitiesinvolving PCBs, are likely to prove one of the mostfrequently encountered and significant examples of PCDD/F and dioxin-like TEQ contaminated sites.

Further PCB contaminated building (sealants, condens-ers in lamps and paints) are of high concern for humancontamination. Here, the efforts and cost of remediation ofPCB contaminated buildings should be a warning for the

10 The relevance of PCB conversion to PCDF can be seen, forexample in the Belgium food crises (Covaci et al. 2002) and also forthe Yusho and Yucheng incidents of high human exposure viacontaminated oil in which PCDF from PCB contamination accountedfor more than 50% of TEQ and today account for approximately 90%of the TEQ burdens of these populations (Masuda et al. 1986;Kajiwara et al. 2007).


use of New-POPs [e.g. chlorinated paraffins, fluorinatedsurfactants, brominated flame retardants (BFRs), etc.] inconstruction. The potential high restoration costs of futureremediation and together with the current exposure risks—and particularly hazards associated with exposure of infantsand children in, for example, schools and kindergartens—should be considered when choosing construction materialswith POPs like characteristics.

4.4 PCDD/Fs from use or generation of chlorine or otherchlorinating agents in specific industrial processes

Large quantities of chlorine were used historically in theproduction of bleached pulp and paper. In most industri-alised countries, the pulp and paper industry was animportant historic source of PCDD/Fs, which were gener-ated by the chlorination of phenolic compounds naturallypresent in the wood used in the mills and which weredischarged in the wastewaters and sludges (Rappe et al.1991; UNEP 2005a; Verta et al. 2007). Today, the use ofelemental chlorine for bleaching has been discontinued inthe majority of industrialized countries. Nonetheless, thehistorical PCDD/F contamination resulting from theseactivities remains in the form of contaminated sedimentsin water bodies into which the industry’s wastewater hasbeen discharged.

Elemental chlorine continues in use as a bleaching agentin developing and transition economy countries, anddischarges from these industries can be expected, therefore,to release the associated PCDD/Fs to the environment(Thacker et al. 2007). The scale of chlorine use for pulpbleaching may be proportionately quite high. In 1995 forexample, the Indian pulp and paper industry was reportedlythe largest single chlorine user in the country, with a 26%share of chlorine use as compared to PVC (22%) orchlorinated paraffins (12%), for example, in the country(UNIDO 2006).

Chlorine is also used during the production of inorganicchemicals, whether it remains in the final product (NaOCl,ClO2 or metal chlorides) or is simply used in the process(e.g. titanium dioxide, magnesium or silicon; Secretariat ofthe Stockholm Convention 2006; Stringer and Johnston2001). It is known, for example, that PCDD/F formationand release can occur via electrolysis of magnesiumchloride during magnesium metal production (Oehme etal. 1989). In one well-documented case, a magnesiumsmelter in Norway contaminated several fjords and associ-ated food webs with PCDD/Fs (Persson et al. 2006; Ruus etal. 2006) with an estimated release between 50 and over100 kg TEQ (Knutzen and Oehme 1989). Similarly, it hasbeen suggested that magnesium production at the industrialcomplex in Bitterfeld, Germany (a case included in thisseries) has contributed significantly to the PCDD/F contam-

ination of sediments and associated floodplains of the riversMulde and Elbe (Götz et al. 1998, 2007; Bunge et al. 2007).

More recently, it was discovered that the production oftitanium dioxide using the chlorine process can alsogenerate PCDD/F in significant amounts (in the range ofkilograms; Cake et al. 2005; Secretariat of the StockholmConvention 2006; Wenborn et al. 1999). One of thecontributions in this series will provide an insight intoPCDD/Fs release from the TiO2 industry.

In a study of PCDD/F releases to water from industrialprocesses in Japan, Kawamoto (2002) discovered that anintermediate step involving nitrosyl chloride (NOCl) duringthe production of nylon results in the formation ofenvironmentally relevant amounts of PCDD/Fs. This studyalso listed several other processes (e.g. production ofacetylene, dioxazine pigments, monochlorobenzene andalumina fibres) that are current PCDD/F sources. Thesemore recent discoveries of PCDD/F generation, as part ofcurrent industrial processes, highlight the need for system-atic PCDD/F [and other UPOPs (see Table 1)] screening inany process using chlorine or bromine, oxidizing processesin the presence of HCl/chlorides, HBr/bromides or otherchlorinating or brominating reagents. In this respect, theInternational POPs Elimination Network has proposed astrategy for PCDD/F source tracking in their comments foran improvement of the UNEP Standardized Toolkit forIdentification and Quantification of Dioxin and FuranReleases (UNEP 2005a; IPEN 2004).

4.5 PCDD/F contaminated sites from waste deposits, wasterecycling and waste incineration

As outlined above, current inventories predominantlyhighlight sources of PCDD/Fs, which originate fromthermal processes. (e.g. waste incineration, open burning,sinter plants, secondary metal production, etc.; Fiedler2007). While these represent contemporary sources, thereare only few cases documented of sites contaminated by thehistorical operations of incinerators or the metal industry.This is due to the far higher PCDD/F levels in residuesfrom chlorine making and typically using industries severalorders of magnitude higher than those of incineratorresidues (see Table 2; UNEP 2005a) and the widespreaddistribution and associated dilution of air emissions fromthermal sources.

4.5.1 PCDD/F and UPOPs contaminated sites from wasteincineration

Hazardous waste incinerators (and other thermal processes)that include high proportions of products from theorganochlorine industry, especially PCDD/F precursors(PCBs, chlorophenols, chlorobenzenes and other chlorinat-


ed aromatics)11, can result in high emissions of PCDD/Fswith considerable impacts on the local environment(Goovaerts et al. 2008; Holmes et al. 1994, 1998; Kim etal. 2006; Lovett et al. 1998). For example, the use of achemical waste incinerator at the Coalite Chemicals’ worksat Bolsover (UK) for destruction of chlorinated phenolwastes resulted in elevated PCDD/F levels in cow’s milk(Holmes et al. 1994, 1998) and other foods (Malisch et al.1999), demonstrating that the PCDD/F emissions from athermal source can enter the food chain. Similar findingshave been reported for a range of other cases related tothermal facilities (incinerators and metal plants), whichhave resulted in the contamination of milk, eggs orvegetables in the surroundings (Schmid et al. 2003;DiGangi and Petrlík 2005). The Coalite case study will becompiled and updated for this series. These areas can alsobe highly contaminated from the spill of the hazardouschemicals treated/destroyed in these facilities (e.g. PCBs;Lovett et al. 1998).

Municipal waste incinerators can also generate elevatedlevels of PCDD/Fs, and these can contaminate theenvironment if the releases are not controlled. One suchdocumented case is the Byker municipal incinerator inNewcastle (UK) where ash (a mixture of fly and bottomash) were used to construct footpaths and added to the soilsof allotment gardens (Pless-Mulloli et al. 2000, 2001 citedby Watson 2001), resulting in elevated PCDD/F levels infood (eggs and vegetables). This case is included in thisseries and focuses on the importance of public participationin addressing and following such cases. The series will alsoexamine the first case of a remediation project related tocontamination of a site by operations of a municipal wasteincinerator near Osaka (Japan; Ishi and Furuchi 2005). Inthis case, contaminated water from the wet scrubber wassprayed onto the soil in the vicinity of the incinerator over anumber of years, resulting in a PCDD/F-contaminated site.

The above three examples illustrate that releases fromincinerators via all three release vectors—air, solids andwater—can lead to PCDD/F-contaminated sites if notappropriately managed and controlled.

4.5.2 Contaminated sites from waste management,deposition and recycling

The production/application peak of chlorinated aromaticcompounds in industrialised countries from the 1940s

through to the 1980s (see, e.g. Fig. 1) is often reflected inthe PCDD/F time trends of sediment cores (Hagenmaier etal. 1986; Kjeller and Rappe 1995; Zennegg et al. 2007).During this period, waste streams including municipalwaste, sewage sludge and compost were generally contam-inated with elevated levels of PCDD/Fs and PCBs (Lahl etal. 1991). These waste streams, or their components,including the PCDD/Fs, were often applied to soil ordeposited in landfills thereby further mobilising or creatingreservoirs (see Fig. 2).

Some waste types, such as electronic waste (e-waste) orcar shredder waste material, were and continue to be highlycontaminated with compounds such as PCBs, brominatedflame retardants, brominated dibenzodioxins and dibenzo-furans (PBDD/Fs) as well as toxic heavy metals (Meyer etal. 1993; Olsman et al. 2006; Secretariat StockholmConvention 2006; Tasaki et al. 2004; Five Winds 2001;US EPA 1991; UNEP 2005b; Weber and Kuch 2003; Wonget al. 2007). As a result, the associated disposal sites andrecycling areas can become highly contaminated if theseactivities are carried out without appropriate regulation andcontrol.

This series, therefore, includes a case representing thefirst complete remediation of a large dump site containinge-waste, car shredder and other waste types (contaminatedwith approximately 1.5 kg TEQ) on Teshima Island (Japan;see Table 3 in the Appendix). The site required remediationdue to leaching, which was spreading contamination intothe wider environment. This example may represent aprecedent setting case of the complete remediation of sucha hazardous landfill.

Recent studies have also revealed that the human milk ofwomen living near open dump sites in South East Asiacontains elevated PCDD/F and PCB levels, suggesting thatsignificant PCDD/F contamination exists around these sites(Kunisue et al. 2004, 2006).

Another example is the large-scale low-tech recycling ofe-waste in China, which has resulted in a contaminatedmegasite, including contamination of drinking watersupplies as well as other exposures of local populations(Chan et al. 2007). Such e-waste recycling sites existpredominantly in developing and transition countries andare contaminated with a wide range of compounds includingheavy metals, PCDD/Fs and PBDD/Fs from the openburning of the PVC, as well as BFR- and PCB-containinge-waste (Leung et al. 2007; Li et al. 2007; Shen et al. 2008;Wong et al. 2007). Due to the complex contaminationpattern of this mixed halogenated waste (e.g. chlorinated,brominated and mixed halogenated dioxins, furans, biphen-yls contain 10,000 s of halogenated aromatics), a combina-tion of instrumental- and bioassay-based assessment isnecessary for an adequate estimation of dioxin-like toxicity(Yu et al. 2008) and will be presented in a case study.

11 Another important contemporary waste management challenge witha high risk of PCDD/F release is the destruction of global POPsstockpiles (PCB and POPs pesticides) as required under theframework of the Stockholm Convention (www.pops.int). Thedestruction of such high chlorine and dioxin precursor containingwaste will require comprehensive monitoring with respect to PCDD/Fformation and emission from destruction facilities (Weber 2007b).


http://www.pops.int

4.6 PCDD/F contaminated sites from the metal industries

Only a few cases of PCDD/F contaminated sites associatedwith the various metal industry processes have beendocumented. Typically, toxic heavy metals represent thekey contaminants for sites associated with these industries,while PCDD/Fs are generally regarded as rather minor by-products. One case from Germany highlights that releasesfrom primary metal production processes can cause PCDD/F contaminated sites via the distribution of metal industryslag. In this case, more than 400,000 tonnes of slag(‘Kieselrot’) from a specific12 primary copper productionprocess, which was highly contaminated with PCDD/F(10,000 to 100,000 ng TEQ/kg), was used as surface coverfor more than 1,000 sports fields, playgrounds and pave-ments in Germany and neighbouring countries (Ballschmiterand Bacher 1996; Theisen et al. 1993). After the problemwas identified most of these contaminated sites weresubsequently covered over or closed to public access.

The secondary metal industry, in particular plantsrecycling aluminium, copper, iron, lead and zinc, have alsobeen identified as sources of PCDD/Fs and other POPs.These plants recycle scrap metals, which may be contam-inated with PVC, BFR-containing plastic, PCBs andchlorinated paraffin containing oils. Moreover, during theheating, melting and cooling phases of metal recyclingprocesses, PCDD/Fs and other UPOPs (see Table 1) can beformed and emitted (UNEP 2005a; Grochowalski et al.2007). This series will document contaminated sites arisingfrom secondary metal smelters in Germany (Hagenmaier etal. 1992), which have contaminated the nearby environmentincluding residential areas over decades via air emissions ofPCDD/Fs and heavy metals as well as heavy metal releasesinto the groundwater. The article will detail the remediationactivities undertaken at these sites.

4.7 PCDD/F contamination during demolitionof contaminated buildings

Demolition wastes from incinerators, secondary metalplants and chemical factories can be highly contaminatedwith PCDD/Fs. This can result in the considerable exposureof personnel involved in the demolition and remediation atsuch sites. This has occurred following accidents in 2,4,5-T-and 2,4,5-TCP-producing factories. Exposures resulted inchloracne occurring in not only the remediation staff butalso in their family members due to PCDD/F transfer viawork clothes (Weidenbach et al. 1984; Degler andUentzelmann 1984). Similarly, workers demolishing acontaminated incinerator in Nose/Japan showed highly

elevated PCDD/F concentration in their blood (up to806 pg I-TEQ/g fat), although no acute impacts on healthwere observed (Kitamura et al. 2000; Takata 2003). Thesecases highlight that the demolition of contaminated facili-ties presents challenges to the health and safety ofassociated workers in addition to those posed by thesubsequent treatment of the wastes generated. This chal-lenge will be addressed in the context of this series as partof case studies documenting the demolition of both a 2,4,5-T production facility and a metal recycling facilities inGermany.

5 Mobility or other off-site transport of PCDD/Fsand other hydrophobic POPs at contaminatedsites and evaluation of necessity for remediationand securing measures

An important criterion for evaluating the significance andrisks of POPs at contaminated sites is their present or futurepotential for off-site transport and accessibility. Due to theirhigh affinity for organic matter and low water solubility,PCDD/Fs and other highly lipophilic POPs are generallyconsidered relatively non-mobile. However, experiencesfrom former organochlorine production and application sitesas well as landfills receiving POPs wastes have revealed thatsuch compounds can also leach from landfills into ground-water (Schnittger 2001; Götz 1986; Tysklind et al. 2006;Persson et al. 2008; Hofmann and Wendelborn 2007).

Several case studies presented in this series describe thedifferent aspects of PCDD/F and POP mobility/accessibilityat contaminated sites, and the resulting remediation orsecuring measures required to negate the associated risks.

5.1 Increased mobility of PCDD/Fs via co-contaminantfacilitated transport

One key factor influencing the mobility of PCDD/Fs atcontaminated sites is the presence of other, co-depositedwaste materials. Dense non-aqueous phase liquids(DNAPLs13; e.g. pesticides, organic solvents, creosote,coal tar and many other chemicals commonly used/dis-charged in industry) are known for their potential tofacilitate the vertical transport of otherwise poorly mobileorganic compounds. The US EPA, for example, hasestimated that 70% of all superfund sites with groundwatercontamination contain DNAPLs (Gordon 1996). Otherubiquitous chemicals, which may considerably increase

12 In this process, 8% sodium chloride was added before roasting.

13 A good overview on DNAPLs topics can be found on the websiteof the DNAPL group at Sheffield University http://www.dnapl.group.shef.ac.uk/main.htm


http://www.dnapl.group.shef.ac.uk/main.htm

http://www.dnapl.group.shef.ac.uk/main.htm

the apparent solubility of poorly mobile chemicals whenpresent at high concentrations (i.e. by allowing theformation of micelles), include the anionic and non-ionicsurfactants, commonly used as adjuvants in pesticideformulations.

Despite the ubiquitous occurrence of such chemicals atcontaminated sites, in landfills and at pesticide production,formulation, mixing and application sites, only relativelylimited published documentation exists regarding theassociated leaching potential of PCDD/F to ground water.One relatively well-known case is a former pesticideproduction site in Hamburg and its related landfill. At thissite, high concentrations of chlorinated and other organicchemicals have facilitated leaching of PCDD/Fs to ground-water where concentrations of 2,3,7,8-TCDD up to75,000 ng/kg have been detected (Götz 1986; Schnittger2001). This case, which will be documented in detail in thisseries, highlights that sites where particular co-contaminantsoccur have to be carefully evaluated and monitored for thepotential vertical movement of PCDD/F and other poorlymobile chemicals.

5.2 Mobility of PCDD/F via colloidal transport

Increased movement of chemicals such as PCDD/Fs andPCBs to groundwater has also been shown to occur in thepresence of colloids, such as dissolved organic matter(Tysklind et al. 2006; Persson et al. 2008; Frankki et al.2007; Hofmann and Wendelborn 2007). This mechanism isthought to involve the movement of chemicals withrelatively low water solubility through adsorption on tocolloidal particles. They can thereby reach ground water andother water bodies. The interaction, however, betweencolloids and low mobility contaminants is complex and notfully understood to date. This series will include a case studyregarding colloidal transport of PCDD/Fs at contaminatedsaw mill sites in Sweden (Persson et al. 2008). Historicalsaw mill sites are considered the largest PCDD/F reservoirin Sweden [approximately 5 to 50 kg TEQ involving some400 to 500 sites (Swedish Environmental Protection Agency2005)] and will be similarly relevant in other countries withpast history of the treatment of timber with PCP.

5.3 The mobility of contaminated sediments and associatedevaluation regarding remediation requirements

Due to their inherent capacity to absorb contaminants,aquatic sediments are regarded as particularly sensitive toanthropogenic impacts (Chapman and Hollert 2006) Oncecontaminated, sediments may serve as sinks and secondarysources for many persistent chemicals (Hollert et al. 2007a).To protect the aquatic life community, various bioanalyticalmethods for assessing the severity of sediment contamina-

tion have been introduced over the past decades (e.g.Kosmehl et al. 2007; Seiler et al. 2006; Weber et al. 2006a,b; Keiter et al. 2006).

As noted above, a large proportion of the historicproduction residues from chemical industries includingPCDD/Fs and other POPs were directly released into riversor into marine environments (Forter 2000; Heinisch et al.2004, 2006a, b, 2007; Isosaari et al. 2002a, b; Sundqvist etal. 2006; Verta et al. 2007). The waste discharges of thechemical industrial complex at Bitterfeld, which causedand, due to their persistence, continues to cause PCDD/Fcontamination of the rivers Mulde and Elbe (and ultimatelyalso the North Sea), represents a well-documented case(Götz et al. 1998, 2007; Wilken et al. 1994; Bunge et al.2007). The key issues associated with such cases are thecontemporary and future environmental significance of thecontaminated sediments and, therefore, whether these sedi-ments need to be removed. While historical PCDD/Fs andother POPs are generally buried in sediments and thereforelargely considered not currently bioavailable, such contam-inants can be mobilised during floods, long-term construc-tion activities, dredging or during remediation activities.During such activities, historical contaminants from deepersediments re-enter the aquatic ecosystem and into aquaticfood chains (Hollert et al. 2003, 2007a, b), Gerbersdorf etal. 2007; Schwartz et al. 2006; Westrich and Förstner 2005;Wölz et al. 2008).

To illustrate the potential for remobilisation of PCDD/Fsfrom contaminated sediments, an increase in TEQ insuspended solids during a flood event involving two Germanrivers will be detailed in this series. Such events are commonin wet tropical countries and are also expected to increase infrequency and intensity in other regions due to climatechange. Another case study will present the related exampleof the impact of construction activities on POPs remobilisa-tion in water ways in Berlin. The series will also includedetails of a comprehensive risk assessment carried out on thesignificance and potential mobility of PCDDs/Fs andmercury from sediments contaminated by an estimated28 kg TEQ from chlorophenol manufacture (Ky5), as wellas by the emission of mercury from the associated chlor-alkali plant in one of the largest cases of its kind known fromFinland and the Baltic Sea (Isosaari 2002a, b).

In case of sediment remediation/dredging activities,contaminated sediments need to be disposed off in anenvironmentally sound manner to avoid contamination ofdeposition areas (in particular agricultural and grazing areas).

5.4 The run-off from PCDD/F contaminated soil

PCDD/Fs can contaminate soils through the application ofcontaminated pesticides, land spreading of contaminatedsewage sludge and the open burning of wastes and


remaining residues. In addition, deposition from theatmosphere can play an important role (see Fig. 2). Theexample of PCP and CNP applied to Japanese agriculturalland (as described above) contributed to around 70% of thetotal TEQ estimated in the Japanese inventory of historicalsources (Masunaga et al. 2001; Weber and Masunaga 2005;see Fig. 1). PCDD/F in soil is mobile to some extent andcan migrate for decades: A mass balance for the Tokyo baycatchment estimated that approximately 20% of the PCDD/Fs emitted to land over the past five decades havemeanwhile been transported to Tokyo Bay (Masunaga2004), where they have been deposited. This case ispresented in one paper of the series and also provides aview into the pilot project being conducted to prevent themobilisation of particle-bound PCDD/Fs from rice fieldsinto surrounding watersheds.

5.5 Contamination of groundwater and drinking watersources with relatively water soluble chemicals at landfillscontaining PCDD/Fs and other POPs/UPOPs

A consideration critical to environmental protection is thatthe movement in water of many chlorinated aromatic andaliphatic compounds, including the chemicals with higherwater solubility than PCDD/Fs, typically occurs relativelyslowly (over a time frame of years to decades). Therefore,the potential for contamination of groundwater or offsitetransport via leaching is likely to be identified only by acomprehensive and long-term monitoring programme orpredicted by a suitably focussed model. This needs to takeinto account the nature of the contaminant mixture andinteractions of its components. In this series, considerablegroundwater migration of the lower chlorinated benzenesand phenols will be described for the former HCH/2,4,5-Tproduction site in Hamburg. This contamination triggeredthe closure of a major waterworks supplying the city.

The series of articles will also include information on theleaching of water-soluble chemicals and the associatedremediation requirements as part of a case study on theBasel Chemical Industry landfills described earlier in thisarticle. This contamination requires full and completeremediation due to the presence of a range of relativelywater soluble persistent pollutants (hexachlorobutadiene,hexachloroethane, perchloroethylene, tetrachloroethane, tri-chloroethene, dichloroaniline chlorobenzene, barbiturates,etc.). These contaminants are present in landfill leachatesand pose a threat to the groundwater and other drinkingwater resources supplying Basel and its suburbs (200,000inhabitants). The contamination resulted in the discontinueduse of the water supply in a nearby local area (Forter 2007;Matter 2007; Bühler and Hauswirth 2007). PCDD/Fs werenot detected in the groundwater at significant concentra-tions. As noted above, however, the total TEQ content at

the Bonfol site has been estimated to be up to 100 kgtogether with 1 tonne of unintentionally formed PCBs. ThePCDD/Fs in this landfill are distributed as hotspots amongthe 114,000 t of heterogeneous chemical waste. Therefore,the case of the Swiss chemical landfills demonstrates thateven the non-mobile deposited PCDD/Fs become a neces-sary consideration to human health during remediationactivities, which, for example, were required based on themore water soluble contaminants.

5.6 Modelling of groundwater contamination as a key toolfor decision making in remediation and securing activities

The above-described cases of contamination as a result ofthe mobility of contaminating chemicals (including poorlywater soluble compounds) show that evaluation of theactual and potential future groundwater contamination isone of the key assessment requirements in evaluating therisks associated with contaminated sites. A holistic evalu-ation is necessary, taking into account locally relevantprocesses and the contaminant mixtures which are actuallypresent. Another paper in the series will describe thecomprehensive groundwater modelling approach developedfor Bitterfeld. This is one of the largest contaminatedmegasites in Germany with a complex hydrological regimeand which has been impacted by releases of industrialchemical and by open-pit lignite mining (Wycisk et al.2005). This process-orientated approach will be presentedin this series with a focus on HCH contamination and canbe regarded as a potential standard tool to facilitate decisionmaking of remediation strategies for contaminated mega-sites in respect to ground water contamination.

6 Securing and monitoring of contaminated sites: riskmanagement strategies and transgenerational transferof responsibilities

The majority of landfill and other sites contaminated withPOPs and other hazardous chemicals over the last 100 yearsor so were not secure facilities. Over the last 30 years,many remediation concepts have been devised for suchsites and have been applied and tested. However, the highcosts of comprehensive remediation mean that manycontaminated sites are often only made secure, rather thanbeing fully remediated. The approaches to site containmenthave evolved and developed markedly in recent years, buteven so, a full accounting of the costs involved inimplementing site-specific strategies designed to preventmigration of contamination off-site in the long-term remainelusive.

Since more water-soluble co-contaminants are typicallypresent at such sites and given that even poorly water-


soluble POPs can be mobilised depending upon sitespecific factors, the pumping of groundwater (pump andtreat) is often required in addition to attempting tophysically secure a site. Such treatment is resource andenergy intensive and requires ongoing monitoring efforts todetect the leaching of chemicals. One example of how themanagement of these risks has been attempted throughestablishing funding mechanisms and strategic approaches,coupled with a comprehensive monitoring programme, isdescribed for a Dutch chemical landfill containing POPsand PCDD/Fs in this series. In addition, the monitoringconcept during a remediation project of a former pesticide(2,4,5-T, DDT, HCH) factory in the Czech Republic(Spolana) is also described.

In many cases, securing measures are carried out usinggeotextile barriers made from inter alia high-densitypolyethylene and by the construction of slurry walls. Whilethese are thought likely to last for more than 30 and50 years, respectively (albeit with manufacturers’ guaran-tees generally of less than 10 years), they representrelatively short-term measures when considered on thetimescale of the persistence of POPs. POPs can persist forsome centuries if not permanently (e.g. PCDD/Fs andheavy metal contamination from the soda-ash production inGermany described above, for example, occurred around150 years ago and has not shown significant signs ofnatural attenuation).

The question of future containment of contaminated sitesis not simply an abstract one. As an increasing number ofsites securing measures are failing after relatively short timespans. This series examines this issue in the context ofseveral documented failures of securing measures, includ-ing two chemical landfills in Switzerland (Kölliken andBonfol), a case from Australia (Orica) and one hazardouswaste landfill from Germany (see Table 3 in the Appendix).For the chemical landfills, Bonfol and Kölliken, it wasrecently decided that complete remediation (excavation anddestruction) is required as noted earlier.

Due to the immense costs and challenges associated withremediation of contaminated sites, ‘monitored naturalattenuation’ (MNA) is increasingly gaining purchase as aconceptual remediation approach (TNO 1999). However,these concepts might come to their limit for contaminatedsites containing persistent organic pollutants and otherpollutants such as heavy metals. This becomes apparent inthe construction of remediation targets, time frames forremediation, evaluation of proofs and/or lines of evidencefor MNA and comparison to other remediation alternatives,which are all necessary for the full assessment of MNA(Rügner et al. 2006). This series includes an example of

historical PCDD/F and arsenic contamination caused by aLeblanc factory operating during the nineteenth century.This case demonstrates that PCDD/Fs and arsenic (in itstoxic and bioavailable form) remain present at high concen-trations in the soil and residues of the estate, even afterapproximately 150 years of deposition. The case thereforeillustrates that the time frame of natural degradation requiredfor persistent organic pollutants renders the MNA remedi-ation approach unfeasible for these compound groups (seealso Renner 2006). While this may seem evident based ontheir persistent nature, POPs have been included for MNAapproaches in the past, failing to meet basic risk or qualitycriteria (Schwartz et al. 2006; Renner 2006).

While this particular topic is not a focus of this series,the negative impact of ‘natural attenuation’ on chlorinatedorganics will nonetheless be described for the Hamburgpesticide production plant referred to earlier in this article.The ‘natural attenuation’ of chlorinated organics in this caseenhanced the mobility of contaminants. This occurred as aresult of the production of degradation products, whichwere actually more water soluble. Yet, another case profiledin this series will report on a PAH-contaminated site wherebioremediation resulted in increased PAH toxicity andgenotoxicity (monitored through with bioassay), althoughthe target PAHs decreased. These two examples highlightthe fact that, for ‘soft’ remediation approaches like naturalattenuation or bioremediation, the identification screeningand monitoring of degradation products becomes a neces-sity. A reliable hazard and risk assessment of soils, SPMand sediments require both the detection of adverse effectsand the identification of the chemicals causing the effects.This can be done by combining physicochemical fraction-ation, biological testing (genotoxicity, mutagenicity andendocrine effects) and chemical analysis. One approach iseffect-directed analyses (Brack 2003; Brack et al. 2005,2007; Gustavsson et al. 2007; Olsmann et al. 2007; Keiteret al. 2008; Schwab and Brack 2007; Wölz et al. 2008).Effect-directed fractionation and analysis were applied inseveral studies to characterize and identify the toxicants thatcause toxic effects.

7 Conclusions

Contamination caused by PCDD/Fs and chlorinated POPsis often considered as solely an historical problem Thecases outlined here and later described in detail in thisseries highlight the fact that the POP legacies of thechlorine/organochlorine industrial sector and some otherindustries still represent contemporary and, more seriously,


future concerns. These concerns are global in scale.Sustainable solutions to this issue need to be devised andimplemented. The concentrated efforts required will dependfor their success upon the transfer of knowledge amonginternational stakeholders regarding the identification,evaluation and remediation of contaminated sites.

Active contribution to this process and the support of thekey polluting industries responsible is required. Theseexperienced stakeholders also carry a large responsibilityfor remediation effort. Furthermore, it needs to be acknowl-edged that, while POPs must be addressed on a globalscale, there are vast differences in production, use anddisposal of POPs among countries worldwide. This is alsotrue of contaminated site management. Some of thecompounds that are considered entirely an issue of the pastfrom the perspective of industrialised countries (e.g. DDT,HCH, PCP, 2,4,5-TCP) are still produced either intention-ally or otherwise, or are still in use in developing countries.This is particularly true of countries and regions with weakregulatory and monitoring practices.

Hence, the past and present experiences in the produc-tion, use and disposal of chemicals and approaches to theremediation in industrialised countries can also provideimportant information to minimise the recurrence of similarissues elsewhere. Finally, public awareness of theseexperiences may also facilitate better management of newchemicals, which may include compounds that result insimilar challenges in the future. Some of the key experi-ences and lessons learnt regarding the production, use,disposal and remediation of POPs from the case studiespresented in this series can be summarised as follows:

& Detailed and transparent information regarding chemi-cal products, production processes, volumes and asso-ciated waste disposal methods and locations areimportant for evaluation of risks and risk managementstrategies.

& For the implementation of risk management strategies,close cooperation of the production industry and nation-al/state/local authorities as well as the public and NGOsprovides the best basis for sustainable solutions.

& The location of landfills and contaminated areas needsto be identified and documented in order to minimisefuture environmental and human exposure.

& Evaluation of the potential risks associated with land-fills and contaminated areas need to be based on site-specific information and characteristics including theextent and type (full screening and toxicologicalassessment) of contamination, the geological condi-tions, the contamination and potential for contamination

of groundwater as well as the current and potentialfuture potential for off-site migration of contaminants.

& The extent and type of PCDD/Fs (PBDD/Fs and otherUPOPs) in chemical production residues and at pro-duction sites/buildings and associated landfills of anyorganochlorine and organobromine industry need to beincluded in the risk assessments.

& Engineering offices with expertise in the specific fieldof remediation should be consulted. The approachestypically require high creativity, since the solutions areoften not achievable using standard engineering techni-ques and may require rather unique methods, dependingon the site.

& Specific safety guidelines for the protection of remedi-ation personnel are inevitable and require specialconsiderations.

& Comprehensive evaluation of available remediationtechnologies need to be carried out, since the wrongchoice of technologies can lead to enormous costs andproject delays.

& Timely environmental impact assessments and promptremedial and securing actions can considerably mini-mize the ultimate damage and costs.

& Secured landfills and secured production sites need tobe considered as constructions not made for ‘eternity’but built for a limited time, which need to be controlled,supervised and potentially repaired/renewed. Further-more, the leachates and groundwater require ongoingmonitoring and potential further remediation. Theseactivities result in high maintenance costs, which areaccrued for decades or centuries and should becompared to the sustainable option of completeremediation.

& Chemical landfills and other contaminated sites withcomplex contaminant mixtures require careful evalu-ation regarding whether total remediation of the areais necessary. Complex mixtures require a comprehen-sive screening of contaminants and degradationproducts and should include comprehensive toxico-logical evaluations.

& Even the most industrialized countries face significantchallenges in coping with contaminated sites, highlight-ing that ultimately only the prevention of contaminatedsites represents a sustainable solution. Therefore, anintegrated pollution prevention and control process needto be stipulated and enforced for the polluting industriesincluding the use of Best Available Technology andBest Environmental Practice.

& The Polluter Pays Principle needs to be applied in amore comprehensive way.


Appendix

Table 3 Overview on the contaminated site cases to be presented within this series. (The cases are compiled according to the chronology of the‘chlorine cycle’ and/or the origin of contamination)

Case location(company)

Contamination source Main contaminants Specific issues of thecase

Total TEQa

(approx.)Approx. cost ofremediation orsecuring (US $)

Contaminated sites from production of chlorine and organochlorinesGermany,Lampertheim(Chemische FabrikNeuschloß)

Leblanc soda productionand associatedchlorine production(1840s to 1893)

Heavy metals PCDD/Fs,PAHs

Oldest type of industrialPCDD/F contaminatedmegasite; start ofchlorine production;remediation ofhousing estates.

1–10 kg 100 million(securing andremediation)

Germany,Rheinfelden(GriesheimElektron; DynamitNobel; Hüls)

Chlor-alkali process(1898–1985); PCPproduction(1972–1986)

PCDD/Fs, PCNs, AOX,Heavy metals

Migration of residuesdue to constructionactivities and resultingcontamination oflarger areas of theinner city; historicinvestigation and wellmanaged remediationby city.

8.5 kg (chlor-alkali)+7.7 kg (PCPresidues)

35 million(securing andremediation)

Taiwan, Tainnan city(CPDC An-ShunSite)

Chlor-alkali process(1942–1977); PCPproduction(1964–1979)

Mercury, PCDD/PCDF,pentachlorophenol

Contaminatedsediments; impactedaquatic farms; healthrisk assessment; socialaspects; remediationand redevelopmentplan.

30–150 million(securing,remediationand/or re-development)

Sweden Chlor-alkali processes Mercury, PCDD/Fs,PCN, AOX

Contaminated sedimentsand contaminated soil.

1–2.5 kg Ongoing

Finland, KymijokiRiver

Chlor-alkali process;chlorophenolproduction (Ky5:TetraCP, PCP, TriCP1940–1984)

Mercury, PCDD/Fschlorinateddiphenylethers(PCDE)

Contamination of riverand Baltic Sea;mobility ofcontaminants in riversediments;comprehensive riskassessment.

28 kg Phase ofevaluation8.7–13 million(hot spot only)

Germany, Hamburg(Böhringer)

HCH production/recycling; 2,4,5-Tproduction(1951–1984)

PCDD/Fs, HCH,chlorobenzenes,chlorophenols

Inventory of pollutantsin soil of pesticideproduction site; groundwater contamination;movement of PCDD/Fswith DINAPLs; closureof drinking water well.

378 kgHamburg+moreexported toexternallandfills

Ca. 200 million(securing) and >800 million forsecuring oflandfills

Russian Federation,Ufa (Khimpromplant)

2,4,5-T production(1965–1976), 2,4,5-Trichlorophenol(till 1987) 2,4-Dproduction; chlor-alkali process

PCDD/Fs, chlorinatedorganics

Industrial PCDD/Fscontaminatedmegasites;contamination of largerareas of the inner city.

10–200 kg Phase ofevaluation(estimation 850million)

Czech Republic(Spolana)

Chlor-alkal-process(since 1949);production of 2,4,5-T,HCH, DDT

PCDD/Fs, HCH, DDT,mercury

Air monitoring conceptduring remediation.

N.E.Yb 110 millionRemediation oftwo productionbuildings


Table 3 (continued)



Total TEQa


Germany, Bitterfeld(IG FarbenElektochemischesKombinatBitterfeld)

Production ofchlorinated organics,chlor-alkali process(from 1890s);magnesiumproduction, inorganicchemicals

HCH, PCDD/Fs, DDT,organochlorinesorganotin compounds,mercury, arsenic

Comprehensivemodelling ofgroundwater for riskassessment andremediation strategy;exposure routeassessment of HCHgroundwater pollution.

N.E.Y b Ongoing

Italy, Seveso(ICMESA)

2,4,5-trichlorphenolproduction

2,3,7,8-TCDD 30 year Seveso accident. 30 kg Securing

Australia, HomebushBay, Port Jackson,Sydney Harbour(Timbrol Ltd,Union Carbide)

2,4-D; 2,4,5-Tproduction; chlor-alkali production;chlorobenzenes;chlorophenols, DDT,aniline nitrobenzene;coal tars (PAHs)xanthate (timberpreservative);bisphenol A (DPP)

PCDD/Fs DDT,chlorobenzenes,chlorophenolsincluding PCP

Contamination ofSydney harbour area;stop of fisheries (since2005); exposure offishermen to elevatedPCDD/F levels.105,000 tonnes soil/sediment requiringtreatment usingdirectly heated thermaldesorption.

N.E.Yb

(540,000 tof soil;46,500 tsediment

contaminated)

95 millionAustralia, Sydney(Orica, formerlyICI Australia)

Production ofchlorinated solvents;carbon tetrachloride,perchloroethylene(PER); ethylenedichloride (EDC);vinyl chloridemonomer(VCM)

Unintentionallyproducedhexachlorobenzene(HCB),hexachlorobutadiene(HCBD),trichloroethylene(TCE)

Unintentionallyproduced POPs wastefrom production ofchlorinated organics;POPs waste export;shallow and deepgroundwater plumes;challenges withencapsulated waste.

20,000 t HCBwaste

Ongoing

Global HCH HCH waste isomers;HCH recycling

HCH isomers PCDD/Fs Global status; largestPOPs legacy (4.8 to7.2 million tons).

tons Ongoing

Brazil, Sao Paolo(Electrochloro,now SolvayIndupa)

Chlor-alkali process(since 1940s); EDC,VCM, PVC

PCDD/Fs, HCB, PCB,mercury

PCDD/Fs contaminatedlime resulting incontamination of citruspulp sold as feed in theEuropean market.

N.E.Yb Evaluation

Switzerland,Feldrebengrube(and 15 other sitesin the regionBasel), Bonfol,Kölliken (Novartis;Syngenta Clariant,Ciba, Roche)

Chemical landfills(region Basel, 16 sites:1945–1961; Bonfol:1961–1976; Kölliken:1977–1986) fromproduction ofpesticides, pigments,dyes, plastics andpharmaceuticals(since 1890s)

Organics (chlorinatedand non-chlorinated),PCDD/Fs, PCB,Triclosan, chloranil,Mitin LA (Sandoz,Geigy, Ciba, Ciba-Geigy), 2,4,5-T(Roche)

Complete remediationof chemical landfills;drinking andgroundwatercontamination; dioxinand PCB inventoryfrom production.

Several 10 sto 100 s kgPCDD/Fs;1 t of PCB(total)

Bonfol 280million,Kölliken 450million, regionBasel:estimated 800Mio. Franken,full remediation

Love Canal, NiagaraFalls, NY(OccidentalPetroleum)

Dumping of chemicalwaste (21,000 t; 1942–1952) including wastefrom organochlorineproduction

Chlorinated benzenes,phenols, pesticides;PCDD/F

30 years Love Canalfollow-up; over 900families evacuated;creation of USSuperfund; grassroots

N.E.Yb 230 millionSecuring


Table 3 (continued)



Total TEQa


environmentalmovement.

Netherlands(Philipps Dufar,Akzo, Shell)

Chemical landfillsproduction oforganochlorines(waste 2,4,5-Tproduction,pesticides); mixedwith household waste

Chlorinated organicsPCDD/Fs

Long term monitoringstrategy; funds forcleaning of leachates ifsite starts to leach.

N.E.Yb Monitoring

Germany and China,selected rivers

Historicallycontaminatedsediments (mainlyindustrial sources)

PCDD/Fs, PCB, dioxin-like activity, POPs

Remobilisation ofcontaminants byflooding events andconstruction measures.

N.E.Y b

Contaminated sites from application of organochlorinesVietnam/South EastAsia (most 2,4,5-Tproducers)

Defoliant spray (AgentOrange et al. 1961–1971)

PCDD/Fs 2,4-D, 2,4,5-T Impact on large area;contaminated hot spots.

366 kgsprayed

Ongoing

Japan, rice Fields Pesticide application(PCP, Chlornitrofen(CNP))(1950s to1980s)

PCDD/Fs Large area ofcontaminated soil; run-off over decades;contaminatedsediments; initialremediation strategy.

460 kg Ongoing

Sweden Chlorophenol basedwood preservatives

PCDD/Fs, PCDEs Movement of PCDD/Fson colloids; 400 to500 contaminatedsites; largestinventoried dioxinsource in Sweden.

5–50 kg insoil; 200 kgapplied towood

Ongoing

Germany, PCBs inbuilding

PCBs in sealants andpaints

PCBs Remediation andrestoration of PCBcontaminated building(sealants, paints).

Sweden PAH from industrialactivities

PAH Bioremediation; effectdirected screening forevaluation of totalPAH toxicity

Contaminated sites from waste recycling, destruction and disposalJapan, TeshimaIsland

Dumping of shredderresidues (car shredder,electronic waste,industrial sludge)

Heavy metals, PCBs,PCDD/Fs

Contaminated site fromdeposition of mainlyhazardous municipalwaste; completeremediation.

1.6 kg 450 million

Switzerland, VariousRivers

Historic PCB depositsand contamination ofrivers

PCB; dioxin-like PCB Survey of PCBcontamination of riversand fishes for a country.

N.E.Yb

China, Guiyu E-waste (mainlyexported from U.S.)manual recycling withlowest technologystandards

Heavy metals PCDD/Fs,PBDD/PBDF

Contaminated site fromrecycling activities;chlorinated andbrominated PXDD/PXDF; bio-assayapproach to determinetotal dioxin liketoxicity.

N.E.Yb Not started


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Table 3 (continued)



Total TEQa


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Industrial wasteincinerator; production/destruction ofchlorophenols

PCDD/Fs Dioxin contaminatedsite from industrialwaste incineration(chlorophenols andothers); contaminationriver, land, milk.

N.E.Yb

United Kingdom,Byker incinerator

Municipal wasteincinerator

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N.E.Yb

Japan, Nose-Osaka Municipal wasteincinerator

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N.E.Yb Ongoing 70million(remediationand securing)

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N.E.Yb Evaluation

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Dioxin- and POP-contaminated sites—contemporary and future relevance and challenges

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