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

BACKGROUND, AIM AND SCOPE: Once they have been generated, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other persistent organic pollutants (POPs) can persist in soils and sediments and in waste repositories for periods extending from decades to centuries. In 1994, the US EPA concluded that contaminated sites and other reservoirs are likely to become the major source of contemporary pollution problems with these substances. With this in mind, this article is the first in a new series in ESPR under the title 'Case Studies on Dioxin and POP Contaminated Sites--Contemporary and Future Relevance and Challenges', which will address this important issue. The series will document various experiences from sites contaminated with PCDD/F and other POPs. This article provides an overview of the content of the articles comprising the series. In addition, it provides a review of the subject in its own right and identifies the key issues arising from dioxin/POP-contaminated sites. Additionally, it highlights the important conclusions that can be drawn from these examples. The key aim of this article and of the series as a whole is to provide a comprehensive overview of the types of PCDD/F contaminated sites that exist as a result of historical activities. It details the various processes whereby these sites became contaminated and attempts to evaluate their contemporary relevance as sources of PCDD/Fs and other POPs. It also details the various strategies used to assess these historical legacies of contamination and the concepts developed, or which are under development, to effect their remediation. MAIN FEATURES: Special sessions on 'Contaminated sites--Cases, remediation, risk and policy' were held at the DIOXIN conferences in 2006 and 2007, and this theme will be continued at DIOXIN 2008 to be held in Birmingham. Selected cases from the approximately 70 contributions made to these sessions, together with some additional invited case studies are outlined together with the key issues they raise. By evaluating these cases and adding details of experiences published in the current literature, an overview will be given of the different features and challenges of dioxin and POP-contaminated sites. RESULTS: This article provides a systematic categorisation of types of PCDD/F and POP-contaminated sites. These are categorised according to the chemical or manufacturing process, which generated the PCDD/Fs or POPs and also includes the use and disposal aspects of the product life cycle in question. The highest historical PCDD/F and dioxin-like polychlorinated biphenyl (PCB) contamination burdens have arisen as a result of the production of chlorine and of chlorinated organic chemicals. In particular, the production of chlorinated pesticides, PCBs and the related contaminated waste streams are identified being responsible for historical releases of toxic equivalents (TEQs) at a scale of many tonnes. Along with such releases, major PCDD/F contaminated sites have been created through the application or improper disposal of contaminated pesticides, PCBs and other organochlorine chemicals, as well through the recycling of wastes and their attempted destruction. In some extreme examples, PCDD/F contaminated sites have also resulted from thermal processes such as waste incinerators, secondary metal industries or from the recycling or deposition of specific waste (e.g. electronic waste or car shredder wastes), which often contain chlorinated or brominated organic chemicals. The examples of PCDD/F and dioxin-like PCB contamination of fish in European rivers or the impact of contaminated sites upon fishing grounds and upon other food resources demonstrate the relevance of these historical problems to current and future human generations. Many of the recent food contamination problems that have emerged in Europe and elsewhere demonstrate how PCDD/F and dioxin like PCBs from historical sources can directly contaminate human and animal feedstuffs and indeed highlight their considerable contemporary relevance in this respect. Accordingly, some key experiences and lessons learnt regarding the production, use, disposal and remediation of POPs from the contaminated sites are summarised. DISCUSSION: An important criterion for evaluating the significance and risks of PCDD/Fs and other POPs at contaminated sites is their present or future potential for mobility. This, in turn, determines to a large degree their propensity for off-site transport and environmental accessibility. The detailed evaluation of contaminated site cases reveals different site-specific factors, which influence the varied pathways through which poor water-soluble POPs can be mobilised. Co-contaminants with greater water solubility are also typically present at such sites. Hence, pumping of groundwater (pump and treat) is often required in addition to attempting to physically secure a site. At an increasing number of contaminated sites, securing measures are failing after relatively short time spans compared to the time horizon, which applies to persistent organic pollutant contamination. Due to the immense costs and challenges associated with remediation of contaminated sites 'monitored natural attenuation' is increasingly gaining purchase as a conceptual remediation approach. However, these concepts may well prove limited in their practical application to contaminated sites containing persistent organic pollutants and other key pollutants like heavy metals. CONCLUSIONS: It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and future relevance. They will continue to represent an environmental issue for future generations to address. The securing and/or remediation of dioxin/POP-contaminated sites is very costly, generally in the order of tens or hundreds of millions of dollars. Secured landfills and secured production sites need to be considered as constructions not made for 'eternity' but built for a finite time scale. Accordingly, they will need to be controlled, supervised and potentially repaired/renewed. Furthermore, the leachates and groundwater impacted by these sites will require ongoing monitoring and potential further remediation. These activities result in high maintenance costs, which are accrued for decades or centuries and should, therefore, be compared to the fully sustainable option of complete remediation. The contaminated site case studies highlight that, while extensive policies and established funds for remediation exist in most of the industrialised western countries, even these relatively well-regulated and wealthy countries face significant challenges in the implementation of a remediation strategy. This highlights the fact that ultimately only the prevention of contaminated sites represents a sustainable solution for the future and that the Polluter Pays Principle needs to be applied in a comprehensive way to current problems and those which may emerge in the future. RECOMMENDATIONS AND PERSPECTIVES: With the continuing shift of industrial activities in developing and transition economies, which often have poor regulation (and weak self-regulation of industries), additional global challenges regarding POPs and other contaminated sites may be expected. In this respect, a comprehensive application of the "polluter pays principle" in these countries will also be a key to facilitate the clean-up of contaminated areas and the prevention of future contaminated sites. The threats and challenges of contaminated sites and the high costs of securing/remediating the problems highlight the need for a comprehensive approach based upon integrated pollution prevention and control. If applied to all polluting (and potentially polluting) industrial sectors around the globe, such an approach will prove to be both the cheapest and most sustainable way to underpin the development of industries in developing and transition economies.     

Levels of persistent organic pollutant and their predictors among young adults

Exposure to persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs), dichlorodiphenyldichloroethane (p,p′-DDE), and hexachlorobenzene (HCB) continues to be of concern due to their ubiquitous distribution and high persistence. Current toxicant body burden is still a primary concern within the Akwesasne Mohawk Nation since other studies conducted within the community have shown relationships between these POPs and endocrine disruption.In this article we describe the levels of these toxicants in young adults of the Akwesasne Mohawk Nation between the ages of 17 and 21 years of age (mean age 18.1 years), and investigate potential influences of their current body burden. Seventeen congeners in fourteen chromatographic peaks were detected in 50% or more of the individuals sampled (geometric mean [GM] of the sum of these congeners = 0.43 ppb). Congeners 118, 138[+163 + 164] and 153 had the highest rate of detection (?98%) within the Akwesasne young adults. Of the other organochlorines, HCB (GM = 0.04 ppb) and p,p′-DDE (GM = 0.38 ppb) were found in 100% and 99% of the sample respectively.Significantly higher levels of PCBs were found among individuals who were breastfed as infants, were first born, or had consumed local fish within the past year. When compared to levels of p,p′-DDE, HCB, and 13 specific congeners reported by the CDC for youth between the ages of 12 and 19 years, the geometric means of several congeners (CBs 99, 105, 110, and 118) among the Akwesasne were higher than the reported CDC 90th percentile. In contrast, levels of CB 28 in Akwesasne young adults were ∼50% or less than those of the CDC cohort. p,p′-DDE and HCB levels were generally higher in the CDC cohort (GM of 0.516 and 0.065 ppb, respectively for Mohawks vs. 2.51 and 0.123, respectively, for CDC). Concentrations of non-persistent PCBs among this sample of Akwesasne young adults were higher than those reported by the CDC suggesting continued exposure, but lower than those associated with severe contamination.Additional research into the concentration trends of individual PCB congeners within Akwesasne youth and young adults is warranted to further improve our insight into the determinants and influences of organochlorine concentrations within members of the Akwesasne community.     

Respiratory uptake kinetics of neutral hydrophobic organic chemicals in a marine benthic fish, Pseudopleuronectes yokohamae

We investigated the respiratory uptake kinetics of polychlorinated biphenyls (PCBs), organohalogen pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and 2,2′,4,4′-tetrabrominated diphenyl ether (BDE #47) in a marine benthic fish, Pseudopleuronectes yokohamae. The respiratory uptake efficiencies (E_W) of the chemicals, of which there have been no reports for the majority of persistent organic pollutants (POPs), were obtained by measuring the respiratory uptake rate constants (k₁) and the oxygen consumption rates of fish. Fish were exposed to water in which these chemicals were dissolved at environmentally relevant concentrations for 28 d, followed by 168 d of depuration in clean seawater. The k₁ and E_W values for 99 compounds were obtained, and they ranged from 2000 to 42 000 L kg-lipid⁻¹ d⁻¹ and from 0.060 to 1.3, respectively. The E_W values of the chemicals, except for PAHs, tended to increase with increasing values of the log octanol–water partition coefficients (K_OW) of the chemicals up to a log K_OW of 5. For log K_OW in the range 3–5, the E_W values in this study were much lower than those in a published study (about one-third). As a result of analysis by a two-phase resistance model, the resistance of transport rates to the lipid phase in this study was lower than was the case in the published study. These findings indicate that the E_W predicted by the published study for log K_OW in the range 3–5 may differ among fish species and water temperature, and further study is needed.     

Determination of levels of polychlorinated biphenyl in transformers oil from some selected transformers in parts of the Greater Accra Region of Ghana

Although polychlorinated biphenyls have never been manufactured in Ghana, it has been used extensively as dielectric fluid in electric transformers and capacitors. However, very little is known of its health and environmental impacts by both managers of these transformers and capacitors and also the general public. This work therefore seeks to explore INAA as a possible alternative to screening transformer oils for PCBs by determining the total chlorine content. The total chlorine content of transformer oil samples from Ghana that tested positive and some randomly selected samples that tested negative from screening using CLOR-N-OIL test kits, have had their total chlorine estimated. INAA using the Research Reactor located at the Ghana Atomic Energy Commission was used to estimate the total chlorine content of the oil samples. Neutron Activation and gamma ray spectroscopy using HPGe detector coupled to MAESTRO 32 software was used to determine the total chlorine content by integrating the peak area of the spectrum into a simplified program that was developed from the activation equation. Instrumental Neutron Activation Analysis was able to validate the result obtained from the test kits screening with accuracy 7.5%.The minimum total chlorine content of the positive samples determined by NAA was 71.34 μg g⁻¹.     

On enumeration of congeners of common persistent organic pollutants

Congeners are molecules based on the same carbon skeleton but different by the number of substituents and/or a substitution pattern. Various Persistent Organic Pollutants (POPs) exist in the environment as families of halogen substituted congeners and/or their hydroxyl and methoxy substituted derivatives. Numbers of possible congeners resulting from substitution of a parent POP molecule with only one type of chemical group are generally available. At the same time, numbers of mixed-substituent congeners have not been counted and presented yet, although there is an increasing interest in such as is the increasing number of research articles presenting results on already identified Cl−/Br−mixed type congeners and/or their HO-/CH₃O-mixed metabolites. We have enumerated and counted possible mixed-substituent congeners of common POPs. This article presents the obtained numbers for congener families of benzene, naphthalene, biphenyl, diphenyl ether, dibenzo-p-dioxin, dibenzofuran, anthracene, pyrene and others and obtained by substitution of up to five chemical group types.     

Rate of hexabromocyclododecane decomposition and production of brominated polycyclic aromatic hydrocarbons during combustion in a pilot-scale incinerator

Here, we examined the incineration of extruded polystyrene containing hexabromocyclododecane(HBCD) in a pilot-scale incinerator under various combustion temperatures(800–950℃) and flue gas residence times(2–8 sec). Rates of HBCD decomposition ranged from 99.996%(800℃, 2 sec) to 99.9999%(950℃, 8 sec); the decomposition of HBCD, except during the initial stage of combustion(flue gas residence time 2 sec), followed a pseudo-first-order kinetics model. An Arrhenius plot revealed that the activation energy and frequency factor of the decomposition of HBCD by combustion were 14.2 kJ/mol and 1.69 sec~(-1),respectively. During combustion, 11 brominated polycyclic aromatic hydrocarbons(BrPAHs)were detected as unintentional by-products. Of the 11 BrPAHs detected, 2-bromoanthracene and 1-bromopyrene were detected at the highest concentrations. The mutagenic and carcinogenic BrPAHs 1,5-dibromoanthracene and 1-bromopyrene were most frequently detected in the flue gases analyzed. The total concentration of BrPAHs exponentially increased(range,87.8–2,040,000 ng/m~3) with increasing flue gas residence time. Results from a qualitative analysis using gas chromatography/high-resolution mass spectrometry suggest that bromofluorene and bromopyrene(or fluoranthene) congeners were also produced during the combustion.     

Occurrence of persistent organic pollutants in sediments and biota from Portugal versus European incidence: A critical overview

Persistent organic pollutants (POPs) are widespread compounds, such as organohalogenated compounds, polycyclic aromatic hydrocarbons (PAHs) and pesticides, which can be found in all types of environmental compartments. Their presence in the aquatic environment is a worldwide problem, with emphasis on sediments which act as depository and consequently as a source of hydrophobic, recalcitrant and harmful compounds. Besides, these pollutants might affect the reproduction and mortality of living organisms, diverging in their potential to bioaccumulate in tissues. The present paper aims to review the occurrence of POPs in sediments and biota from the coastal, estuarine and river areas of Portugal. The list of the studied compounds comprises organohalogenated compounds, PAHs, organometallic compounds, pesticides, sterols, fatty acids and pharmaceutical compounds. The contamination of sediments by various pollutants is presented, such as PAHs up to 7,350 ng g^?1 found in Sado estuary and polychlorinated biphenyls up to 62.2 ng g^?1 in the case of sediments collected in Ria de Aveiro. The occurrence of these persistent toxic substances in sediments demonstrates aquatic contamination from agricultural, industrial and urban discharges and the concern about the potential risks to aquatic organisms, wildlife and humans. In fact, several classes of POPs have also been found in biota, such as polychlorinated biphenyls up to 810.9 ng g^?1 in sentinel fish from the Douro River estuary and pesticides in bivalves from the Sado River estuary. The importance of further systematic research on sediments and biota is here highlighted to compare the contamination of these two reservoirs; to assess their spatial and temporal variation; and to determine other classes of POPs that were not investigated yet (e.g., industrial compounds, estrogens and many classes of pharmaceuticals).     

抚顺市二噁英类持久性有机污染物污染现状调查分析

对抚顺市二噁英类持久性有机污染物污染状况进行深入调查,进一步明确污染源和排放情况.     

重庆市空气污染持续过程特征及其气象成因分析

利用空气质量日报数据分析了重庆市主城区空气质量的总体概况以及持续空气污染过程的特征,并着重探讨了2005年11月29日至12月31日期间的空气污染指数API变化及其与主要气象条件的相关关系.结果显示,一年中主城区出现连续3 d以上空气污染指数API超过100的持续污染过程10次,累计污染超标日为61 d,占全年总超标天数的61.6%;持续污染过程的气象条件往往有着共同的特点,即平均风速小,无降水或降水稀少,大气层结稳定,混合层高度较低.     

Effects of hydrodynamics on the distribution of trace persistent organic pollutants and macrobenthic communities in Bohai Bay

In recent years, the rapid economic development along Bohai Bay, has brought out continuous increasing of the pollution loads in the Bohai Sea, especially by the large coastal reclamation project, Tianjin Binhai New Area. In the period of 2007-2009, we collected the sediments of the main rivers, estuaries, intertidal zone, and near-shore area of Bohai Bay, and Macrobenthos associated with the marine sediments to assess the influence of hydrodynamics in the coastal environment on the pattern of trace contaminants and the macrobenthic community. Based on data derived from these samples, the levels of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) in sediments followed the order PAHs > OCPs > PCBs > PBDEs. The higher concentrations of PCBs, OCPs, PAHs and PBDEs were found in the estuarine and near-shore environment of the Dagu Drainage River. The spatial distribution of OCPs was different to that of PCBs due to the direction of the velocity field of Bohai Bay in its old and new topography, and the higher water-solubility of OCPs than that of PCBs. The results of the Pearson correlation and the PCA indicate that the medium diameter (MD) of sediments was the predominant factor influencing the distribution of PCBs and OCPs, most sampling sites were characterized mainly by TOC of sediments and biomass of macrobenthos. The results indicate that the distribution of trace contaminants and macrobenthic community in Bohai Bay are mainly affected by the hydrodynamic conditions.