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.     

Evaluation of the thermal/optical reflectance method for quantification of elemental carbon in sediments

The IMPROVE thermal/optical reflectance (TOR) method, commonly used for EC quantification in atmospheric aerosols, is applied to soils and sediments and compared with a thermochemical method commonly applied to these non-atmospheric samples. TOR determines elemental carbon (EC) by an optical method, but it also yields thermally defined EC fractions in a 2% O2/98% He oxidizing atmosphere at 550 degrees C (EC1), 700 degrees C (EC2), and 800 degrees C (EC3). Replicate TOR TC, OC, and EC values exhibited precisions of approximately +/-10% as determined from multiple analyses of the same samples. EC abundances relative to total mass concentrations were within the ranges reported by other methods for diesel exhaust soot, n-hexane soot, wood and rice chars, and coals, as well as for environmental matrices. A direct comparison with the chemothermal (CTO) method of Gustafson et al. for ten soil and sediment samples demonstrated that almost all of the OC and EC1 are eliminated, as is part of the EC2. The CTO soot carbon is bounded by the EC3 and EC2+EC3 fractions of the IMPROVE TOR analysis. It might be possible to adjust these fractions to obtain better agreement between atmospheric aerosol and soil/sediment analysis methods. Given its linking the EC measurement in the atmosphere to sediments, the TOR method will not only provide useful information on the explanation and comparison between different environmental matrices, but also can be used to derive information on global cycling of EC.     

Continuous and filter-based measurements of PM2.5 nitrate and sulfate at the Fresno Supersite

PM(2.5) nitrate [Formula: see text] and sulfate ([Formula: see text]) were measured continuously with R&P8400N and R&P8400S instruments, respectively, and compared with filter-based measurements at the Fresno Supersite from October, 2000 through December, 2005. [Formula: see text] concentrations were higher in winter than summer with a long-term decreasing trend. Correlations between 24-h average continuous and filter-based [Formula: see text] were greater than 0.96 in 4 out of 5 years. Continuous [Formula: see text] was generally lower than filter-based [Formula: see text] although the difference decreased over time, from -52% in 2001 to +13% in 2005. These differences were similar in winter (-23%) and summer (-19%) while the corresponding differences between ambient and instrument temperature were -12 and 0.7 degrees C, respectively. Neither seasonal nor long-term trends in [Formula: see text] can be explained by variations in ambient temperature, the difference between ambient and instrument temperature, or changes in aerosol chemical composition. There were no seasonal or long-term trends in [Formula: see text] concentrations, partially due to low concentrations observed in Fresno. Long-term variability in the performance of R&P8400 [Formula: see text] and [Formula: see text] instruments suggest that collocation with filter measurements is needed for long-term measurements.     

Losses from effluent taxes and quotas under uncertainty

Recent theoretical papers by Adar and Griffin (J. Environ. Econ. Manag.3, 178–188 (1976)), Fishelson (J. Environ. Econ. Manag.3, 189–197 (1976)), and Weitzman (Rev. Econ. Studies41, 477–491 (1974)) show that,different expected social losses arise from using effluent taxes and quotas as alternative control instruments when marginal control costs are uncertain. Key assumptions in these analyses are linear marginal cost and benefit functions and an additive error for the marginal cost function (to reflect uncertainty). In this paper, empirically derived nonlinear functions and more realistic multiplicative error terms are used to estimate expected control and damage costs and to identify (empirically) the mix of control instruments that minimizes expected losses.     

Influence of organic ley–arable management and afforestation in sandy loam to clay loam soils on fluxes of N2O and CH4 in Scotland

Assessment of the sustainability of alternatives to conventional uses of agricultural land, viz. organic systems and afforestation should include consideration of any effects on trace gas budgets. Nitrous oxide (N₂O) and methane (CH₄) fluxes and controlling soil properties were measured in an organic ley–arable rotation in north-east Scotland on a sandy loam. N₂O fluxes were monitored in the ley and arable phases and in organic permanent grass (Lolium perenne) located nearby throughout the 3-year phase duration. Gas fluxes in woodland that had been converted from arable for 1 or 6 years were also measured in both north-east and south-east Scotland on sandy loam to clay loam soils. The climate is maritime and variable with annual rainfall between 800 and 900 mm. Within the organic rotation, differences in N₂O fluxes between the ley and arable phases were less marked than in conventional agriculture. Although this was mainly because grassland emissions were low, some losses from the arable component were also relatively high. Seasonal rainfall had a major influence on cumulative emissions of N₂O, including the first year after conversion from ley to arable. In the short term, changing land use from arable to woodland increased CH₄ oxidation rates and decreased N₂O emissions, though both these rates were also influenced by seasonal weather. Afforestation of agricultural land appears to be more beneficial to trace gas exchange than conversion to organic production.     

Seasonal and spatial variation of solvent extractable organic compounds in fine suspended particulate matter in Hong Kong

The results of a 12-month study of more than 100 solvent extractable organic compounds (SEOC) in particulate matter (PM) less than or equal to 2.5 microm (PM2.5) collected at three air monitoring stations located at roadside, urban, and rural sites in Hong Kong are reported. The total yield of SEOC that accounts for approximately 8-18% of organic carbon (OC) determined by a thermal optical transmittance method was 125-2060 ng/m3, which included 14.6-128 ng/m3 resolved aliphatic hydrocarbons, 39.4-1380 ng/m3 unresolved complex mixtures, 0.6-17.2 ng/m3 polycyclic aromatic hydrocarbons, 41.6-520 ng/m3 fatty acids, and < 0.1-12.1 ng/m3 alkanols. Distinct seasonal variations (summer/winter differences) were observed with higher concentrations of the total and each class of SEOC in the winter and lower concentrations in the summer. Spatial variations are also obvious, with the roadside samples having the highest concentrations of SEOC and the rural samples having the lowest concentrations in all seasons. Characteristic ratios of petroleum hydrocarbons, such as carbon preference index, unresolved to resolved components, and carbon number with maximum concentration, suggest that PM2.5 carbon in Hong Kong originates from both biogenic and anthropogenic sources. The proportion of SEOC in PM2.5 from anthropogenic sources is estimated.     

Removal process estimation of population size for a population with a known sex ratio

A removal model for estimating population size which uses the known population sex ratio is studied. A maximum likelihood estimate and an optimal martingale estimate of the population size are proposed. Their standard errors and large sample properties are obtained. Simulation studies are reported, and the performance of the proposed estimators are compared with the standard maximum likelihood estimator which ignores the sex ratio information. An example on a capture study of deer mice is given.     

Assessment of prey vulnerability through analysis of wolf movements and kill sites.

Within predator-prey systems behavior can heavily influence spatial dynamics, and accordingly, the theoretical study of how spatial dynamics relate to stability within these systems has a rich history. However, our understanding of these behaviors in large mammalian systems is poorly developed. To address the relationship between predator selection patterns, prey density, and prey vulnerability, we quantified selection patterns for two fine-scale behaviors of a recovering wolf (Canis lupus) population in Yellowstone National Park, Wyoming, USA. Wolf spatial data were collected between November and May from 1998-1999 until 2001-2002. Over four winters, 244 aerial locations, 522 ground-based telemetry locations, 1287 km of movement data from snow tracking, and the locations of 279 wolf kill sites were recorded. There was evidence that elk (Cervus elaphus) and bison (Bison bison) densities had a weak effect on the sites where wolves traveled and made kills. Wolf movements showed a strong selection for geothermal areas, meadows, and areas near various types of habitat edges. Proximity to edge and habitat class also had a strong influence on the locations where elk were most vulnerable to predation. There was little evidence that wolf kill sites differed from the places where wolves traveled, indicating that elk vulnerability influenced where wolves selected to travel. Our results indicate that elk are more vulnerable to wolves under certain conditions and that wolves are capable of selecting for these conditions. As such, vulnerability plays a central role in predator-prey behavioral games and can potentially impact the systems to which they relate.     

Quantifying the relative irreplaceability of important bird and biodiversity areas

World governments have committed to increase the global protected areas coverage by 2020, but the effectiveness of this commitment for protecting biodiversity depends on where new protected areas are located. Threshold‐ and complementarity‐based approaches have been independently used to identify important sites for biodiversity. We brought together these approaches by performing a complementarity‐based analysis of irreplaceability in important bird and biodiversity areas (IBAs), which are sites identified using a threshold‐based approach. We determined whether irreplaceability values are higher inside than outside IBAs and whether any observed difference depends on known characteristics of the IBAs. We focused on 3 regions with comprehensive IBA inventories and bird distribution atlases: Australia, southern Africa, and Europe. Irreplaceability values were significantly higher inside than outside IBAs, although differences were much smaller in Europe than elsewhere. Higher irreplaceability values in IBAs were associated with the presence and number of restricted‐range species; number of criteria under which the site was identified; and mean geographic range size of the species for which the site was identified (trigger species). In addition, IBAs were characterized by higher irreplaceability values when using proportional species representation targets, rather than fixed targets. There were broadly comparable results when measuring irreplaceability for trigger species and when considering all bird species, which indicates a good surrogacy effect of the former. Recently, the International Union for Conservation of Nature has convened a consultation to consolidate global standards for the identification of key biodiversity areas (KBAs), building from existing approaches such as IBAs. Our results informed this consultation, and in particular a proposed irreplaceability criterion that will allow the new KBA standard to draw on the strengths of both threshold‐ and complementarity‐based approaches.