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Some heavy metals in farmland soil can be transported into the waterbody, affecting the water quality and sediment at the watershed outlet, which can be used to determine the historical loss pattern. Cd is a typical heavy metal leached from farmland that is related to phosphate fertilizers and carries serious environmental risk. The spatial-vertical pattern of Cd in soil and the vertical trend of Cd in the river sediment core were analyzed, which showed the migration and accumulation of Cd in the watershed. To prevent watershed Cd loss, biochar was employed, and leaching experiments were conducted to investigate the Cd loss from soil depending on the initial concentration. Four rainfall intensities, 1.25 mm/h, 2.50 mm/h, 5.00 mm/h, and 10.00 mm/h, were used to simulate typical rainfall scenarios for the study area. Biochar was prepared from corn straw after pretreatment with ammonium dihydrogen phosphate (ADP) and pyrolysis at 400 °C under anoxic conditions. To identify the effects of biochar amendment on Cd migration, the biochar was mixed with soil for 90 days at concentrations of 0%, 0.5%, 1.0%, 3.0%, and 5.0% soil by weight. The results showed that the Cd leaching load increased as the initial load and rainfall intensity increased and that eluviation caused surface Cd to diffuse to the deep soils. The biochar application caused more of the heavy metals to be immobilized in the amended soil rather than transported into the waterbody. The sorption efficiency of the biochar for Cd increased as the addition level increased to 3%, which showed better performance than the 5% addition level under some initial concentration and rainfall conditions. The research indicated that biochar is a potential material to prevent diffuse heavy metal pollution and that a lower addition makes the application more feasible., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Biochar application has been identified as the effective soil amendment and the materials to control the diffuse herbicide pollution. The atrazine was selected as the typical diffuse herbicide pollutant as the dominant proportion in applications. The biochar treated from four types of crops biomass were added to soil with high organic matter content. The basic sorption characteristics of biocahrs from corn cob (CC), corn stalk (CS), soybean straw (SS), rice straw (RS) and corn stalk paralyzed with 5% of ammonium dihydrogen phosphate (ACS) were analyzed, along with the comparison of the sorption difference of the raw soil and soil amended with biochars at four levels of ratio (0.5%, 1.0%, 3.0% and 5.0%). It was found that the linear distribution isotherm of raw soil was much effective due to the high organic matter background concentration. The addition of five types of biochars under two kinds of initial atrazine concentration (1 mg/L and 20 mg/L) demonstrated the sorption variances. Results showed the soil amended with RS and CS biochar had the biggest removal rate in four regular biochars and the removal rate of the ACS was the biggest. The sorption coefficient and the normalized sorption coefficient from Freundlich modeling presented the isothermal sorption characteristics of atrazine with soil of high organic matter content. The normalized sorption coefficient increased with the equilibrium concentration decreased in the biochar amended soil, which indicated the sorption performance will be better due to the low atrazine concentration in practice. Results showed that biochar amendment is the effective way to prevent leakage of diffuse herbicide loss., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Here we evaluate the excess lifetime cancer risk (ELCR) posed by 10 PAH-contaminated soils using (i) the currently advocated, targeted chemical-specific approach that assumes dose additivity for carcinogenic PAHs and (ii) a bioassay-based approach that employs the in vitro mutagenic activity of the soil fractions to determine levels of benzo[a]pyrene equivalents and, by extension, ELCR. Mutagenic activity results are presented in our companion paper.1 The results show that ELCR values for the PAH-containing fractions, determined using the chemical-specific approach, are generally (i.e., 8 out of 10) greater than those calculated using the bioassay-based approach; most are less than 5-fold greater. Only two chemical-specific ELCR estimates are less than their corresponding bioassay-derived values; differences are less than 10%. The bioassay-based approach, which permits estimation of ELCR without a priori knowledge of mixture composition, proved to be a useful tool to evaluate the chemical-specific approach. The results suggest that ELCR estimates for complex PAH mixtures determined using a targeted, chemical-specific approach are reasonable, albeit conservative. Calculated risk estimates still depend on contentious PEFs and cancer slope factors. Follow-up in vivo mutagenicity assessments will be required to validate the results and their relevance for human health risk assessment of PAH-contaminated soils.

This study employed an in vitro version of the lacZ transgenic rodent mutation assay to assess the mutagenicity of nonpolar neutral and semipolar aromatic soil fractions from 10 PAH-contaminated sites, and evaluated the assumption of dose additivity that is routinely employed to calculate the risk posed by PAH mixtures. Significant mutagenic activity was detected in all nonpolar neutral fractions, and 8 of 10 semipolar aromatic fractions (nonpolar > semipolar). Mutagenic activity of synthetic PAH mixtures that mimic the PAH content of the soils (i.e., 5-PAH or 16-PAH mix) were greater than that of the PAH-containing soil fractions, with 5-PAH mix >16-PAH-mix. Predictions of mutagenic activity, calculated as the sum of the contributions from the mutagenic mixture components, were all within 2-fold of the observed activity of the nonpolar neutral fractions, with one exception. Observed differences in mutagenic activity are likely the result of dynamic metabolic processes, involving a complex interplay of AhR agonsim and saturation of metabolic machinery by competitive inhibition of mixture components. The presence of hitherto unidentified polar compounds present in PAH-contaminated soils may also contribute to overall hazard; however, these compounds are generally not included in current contaminated site risk assessment protocols.

pH affects both soil-water partitioning coefficient (Kd) of polychlorinated biphenyls (PCBs) and dissolved organic matter (DOM), thereby influencing PCBs' leachability from contaminated soils. To explore these incompletely understood interactions, the leachability of 11 selected PCBs in a naturally aged soil was investigated in pH static leaching tests spanning a wide pH range (2 to 9). The K(d) was calculated for each of the PCBs, based on their observed concentrations in the soil and leachates obtained from each test. The concentration and composition of DOM in each leachate were also determined, the latter using FTIR spectroscopy. Correlations between the DOM's FTIR spectra and K(d) values were investigated by orthogonal projections to latent structures. The log K(d)-values varied among the PCB congeners and were most variable at low pH, but the values for all studied congeners decreased with increasing pH, by up to 3 log units (for PCB 187). In the pH 5-7 interval, an abrupt decrease in log K(d) values with increases in pH was observed, although the total organic carbon content remained relatively stable. The FTIR data indicate that fulvic and humic acids in DOM partially deprotonate as the pH rises from 5 to 7., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The influence of soil composition (peat and clay content) on the leachability was investigated in batch leaching experiments for chemically diverse hydrophobic organic compounds (HOCs: PCP, PAHs, HCB, HCHs, PCBs, and TCDD/Fs). An experimental design was applied to generate 8 diverse soil matrices, and the results were evaluated by orthogonal projections to latent structures (OPLS), as well as compound specific response surface models. Overall, the distribution coefficients (logKd) of model HOCs were in the range of approx. 2.0-5.7. The Kd-values of HCHs, phenanthrene and PCP were positively correlated with the peat content. Kd-values of benzo(a)anthracene, HCB, and PCB 47 were positively correlated with both peat and clay content. The Kd-values of 1,3,6,8-TCDD and 1,3,6,8-TCDF were positively correlated with peat content but negatively correlated with clay content, while for PCB 153 and PCB 155 the correlations were reversed. The correlation between the Kd-values and the compounds' Kow-values was linearly for compounds with log Kow <6. For HOCs with log Kow>6, the Kd-values were leveling off, possibly due to small particles in the leachates. Our study demonstrated how complex interaction between both the organic matter and clay components influences the leachability of HOCs in a compound-specific manner., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In 2011, a joint World Health Organization (WHO) and United Nations Environment Programme (UNEP) expert consultation took place, during which the possible inclusion of brominated analogues of the dioxin-like compounds in the WHO Toxicity Equivalency Factor (TEF) scheme was evaluated. The expert panel concluded that polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), and some dioxin-like biphenyls (dl-PBBs) may contribute significantly in daily human background exposure to the total dioxin toxic equivalencies (TEQs). These compounds are also commonly found in the aquatic environment. Available data for fish toxicity were evaluated for possible inclusion in the WHO-UNEP TEF scheme (van den Berg et al., 1998). Because of the limited database, it was decided not to derive specific WHO-UNEP TEFs for fish, but for ecotoxicological risk assessment, the use of specific relative effect potencies (REPs) from fish embryo assays is recommended. Based on the limited mammalian REP database for these brominated compounds, it was concluded that sufficient differentiation from the present TEF values of the chlorinated analogues (van den Berg et al., 2006) was not possible. However, the REPs for PBDDs, PBDFs, and non-ortho dl-PBBs in mammals closely follow those of the chlorinated analogues, at least within one order of magnitude. Therefore, the use of similar interim TEF values for brominated and chlorinated congeners for human risk assessment is recommended, pending more detailed information in the future.

Purpose: Combinatorial bio/chemical approach was applied to investigate dioxin-like contamination of soil and sediment at the petrochemical and organochlorine plant in Pancevo, Serbia, after the destruction of manufacturing facilities that occurred in the spring of 1999 and subsequent remediation actions., Materials and Methods: Soil samples were analyzed for indicator polychlorinated biphenyls (PCBs) by gas chromatography/electron capture detection (GC/ECD). Prioritized soil sample and sediment samples from the waste water channel were analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). Microethoxyresorufin o-deethylase (Micro-EROD) and H4IIE-luciferase bioassays were used for monitoring of dioxin-like compounds (DLC) and for better characterization of dioxin-like activity of soil samples., Results: Bioanalytical results indicated high dioxin-like activity in one localized soil sample, while the chemical analysis confirmed the presence of large quantities of DLC: 3.0 × 10(5) ng/g d.w. of seven-key PCBs, 8.2 ng/g d.w. of PCDD/Fs, and 3.0 × 10(5) ng/g d.w. of planar and mono-ortho PCBs. In the sediment, contaminant concentrations were in the range 2-8 ng/g d.w. of PCDD/Fs and 9-20 ng/g d.w. of PCBs., Conclusions: This study demonstrates the utility of combined application of bioassays and instrumental analysis, especially for developing and transition country which do not have capacity of the expensive instrumental analysis. The results indicate the high contamination of soil in the area of petrochemical plant, and PCDD/Fs contamination of the sediment from the waste water channel originating from the ethylene dichloride production.

The fate of hydrophobic organic compounds (HOCs) in soils and waters in a northern boreal catchment was explored through the development of a chemical fate model in a well-characterised catchment system dominated by two land types: forest and mire. Input was based solely on atmospheric deposition, dominated by accumulation in the winter snowpack. Release from soils was governed by the HOC concentration in soil, the soil organic carbon fraction and soil-water DOC content. The modelled export of selected HOCs in surface waters ranged between 11 and 250 ng day(-1) during the snow covered period, compared to 200 and 9600 ng/d during snow-melt; highlighting the importance of the snow pack as a source of these chemicals. The predicted levels of HOCs in surface water were in reasonable agreement to a limited set of measured values, although the model tended to over predict concentrations of HOCs for the forested sub-catchment, by over an order of magnitude in the case of hexachlorobenzene and PCB 180. This possibly reflects both the heterogeneity of the forest soils and the complicated and changing hydrology experienced between the different seasons., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

The aim of this study was to investigate the potential utility of ethanol washing for remediating soils contaminated with polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), as a cost-efficient alternative to conventional remediation methods of PCDD/F-contaminated soils. Initially, screening experiments were performed with a two-level full factorial design to examine the effects of temperature, extraction time and ethanol concentration on the removal efficiency. The screening experiments showed that the ethanol concentration was the most important parameter. In addition, repeated washing cycles considerably improved the results. Ethanol washing conditions were then selected (10 wash cycles with 75% ethanol at 60 degrees C), and applied to four soils with different soil characteristics and contamination levels to test the robustness of the selected method. Treatment efficiencies of 81% and 85% were obtained for a lightly contaminated sandy-silty soil and a highly contaminated clay soil rich in graphite particles, respectively. Even higher treatment efficiencies (> or = 97%) were obtained for two other highly contaminated soils, one of which contained high amounts of organic matter. PCDD/Fs were found to both dissolve in the solvent and migrate into it as species adsorbed to particles. The relative contributions of these mechanisms and the overall efficiency of the removal seem to depend on contaminant concentration, the types of carbon in the soil matrix and the particle size distribution. The study shows that ethanol washing has effective remediation potential for a variety of PCDD/F-contaminated soils., (2010. Published by Elsevier B.V.)

Two soils with similar contamination levels from wood preservatives containing Chromium (Cr), Copper (Cu) and Arsenic (As) (CCA), were assessed for their general toxicity and genotoxicity. A set of water-based extraction methods, including pressurized liquid extraction (PLE), and batch leaching in milli-Q water and a weak CaCl(2)-solution, was used to produce soil extracts containing available fractions of contaminants. In addition, to obtain indications of the contaminants' bioavailability and toxic potential the genotoxicity of the extracts was estimated by testing their ability to inhibit the growth of wildtype Chinese hamster ovary cells (CHO-cells) and three genetically modified phenotypes that are deficient in different DNA-repair mechanisms. Total extractable arsenic concentrations in the extracts were comparable between the sites. However, the genotoxic potential was clearly higher in soil R extracts. The differences in genotoxic responses were related to differences in inorganic arsenic speciation. The ratio of trivalent arsenic (As(III)) to pentavalent arsenic (As(V)) was higher in all soil extracts from soil R, regardless of the leaching method used. The results of the various combinations of soil extraction techniques and assays using the CHO-cell lines reflected important differences in arsenic speciation in the two soils and possible synergistic effects in CCA-related exposure. They also indicate that speciation and combinatory effects are factors that should be taken into account when assessing risks at former wood impregnation sites contaminated by CCA-agents.

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.

The objective of the present study was to evaluate hazard/risk assessment methods for complex environmental mixtures that involve a targeted, priority chemical approach based on the cumulative hazard/risk of known mixture components or analyses of sufficiently similar mixtures. Ten polycyclic aromatic hydrocarbon (PAH)-contaminated soils were separated into nonpolar and semipolar fractions, and both fractions elicited positive responses on the Salmonella reverse mutation assay. Targeted and nontargeted methods of hazard prediction routinely overestimated mutagenic activities for the nonpolar soil fractions, suggesting nonadditive interactions of PAHs in complex mixtures. This suggests that current risk assessment methods for complex mixtures may provide conservative estimates regarding soils contaminated with priority PAHs alone. Significant underestimations of total risk, however, will be obtained if the soils also contain unidentified PAHs as well as polycyclic aromatic compounds and related compounds that contribute to the total mutagenic activity. Furthermore, estimates of excess lifetime cancer risk associated with the nondietary ingestion of the PAH-contaminated soils studied here indicate that a traditional risk assessment model based on identified priority PAHs and an assumption of additivity generally underestimates the risk associated with the nonpolar soil fractions (in comparison to bioassay-derived risk estimates). Additional cancer risk may be associated with the more polar compounds that also are found at these contaminated sites and that rarely are included in the standard risk assessment methodology.

An equilibrium and recirculation column test for hydrophobic organic chemicals (ER-H test) was used to study the leaching behaviour of chlorophenols (CPs), polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) from contaminated soil. A 50% increase in the pore water velocity was shown to have little or no effect on the mobility of CPs, PCDEs, PCDFs and PCDDs. The standard deviations of truly dissolved compounds, CPs, were between 19% and 65% between the tests. However, the repeatability of the ER-H test decreased with increases in the hydrophobicity of the studied compounds; the standard deviations for PCDEs, PCDFs and PCDDs ranged from 53% to 110%, 57% to 77% and 110% to 130%, respectively. The influence of colloids on the release of these compounds was also examined. Up to 30% of the CPs in the soil were leached, of which 1-3% were associated with colloids. The PCDEs, PCDFs and PCDDs were found to be preferably associated with the particulate fraction of the leachate, and less than 0.2% of these compounds were mobilised.

In this study, we investigated how the chemical degradability of polycyclic aromatic hydrocarbons (PAHs) in aged soil samples from various contaminated sites is influenced by soil characteristics and by PAH physico-chemical properties. The results were evaluated using the multivariate statistical tool, partial least squares projections to latent structures (PLS). The PAH-contaminated soil samples were characterised (by pH, conductivity, organic matter content, oxide content, particle size, specific surface area, and the time elapsed since the contamination events, i.e. age), and subjected to relatively mild, slurry-phase Fenton's reaction conditions. In general, low molecular weight PAHs were degraded to a greater extent than large, highly hydrophobic variants. Anthracene, benzo(a)pyrene, and pyrene were more susceptible to degradation than other, structurally similar, PAHs; an effect attributed to the known susceptibility of these compounds to reactions with hydroxyl radicals. The presence of organic matter and the specific surface area of the soil were clearly negatively correlated with the degradation of bi- and tri-cyclic PAHs, whereas the amount of degraded organic matter correlated positively with the degradation of PAHs with five or six fused rings. This was explained by enhanced availability of the larger PAHs, which were released from the organic matter as it degraded. Our study shows that sorption of PAHs is influenced by a combination of soil characteristics and physico-chemical properties of individual PAHs. Multivariate statistical tools have great potential for assessing the relative importance of these parameters.

This paper summarizes recent studies on the environmental fate of chloroaromatic compounds in chlorophenol (CP)-contaminated soil and groundwater at Swedish sawmill sites. Relative proportions of CPs, polychlorinated phenoxy phenols (PCPPs), polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) were determined in preservatives, particulate organic matter (POM), dissolved organic matter (DOM), groundwater, and particles filtered from groundwater. All compound classes were found in the different compartments. The fraction of PCPPs, PCDEs, PCDDs, and PCDFs had increased in the soil samples relative to the proportions in the preservatives. This increase showed correlation with the hydrophobicity, that is, PCDDs had the largest increase. Similar correlation was found between hydrophobicity and the importance of partitioning to POM over DOM. The more water soluble compound group, CP, was found equally distributed between POM and DOM. For PCPPs, PCDEs, PCDDs, and PCDFs, the relative partitioning to POM increased with increased hydrophobicity. Despite the relative partitioning towards POM, compared with DOM, cotransport with DOM and suspended colloidal fractions was found to substantially increase the transport of these compounds in the groundwater samples.

In this paper we show that oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) are important cocontaminants that should be taken into account during risk assessment and remediation of sites with high levels of PAHs. The presented data, which have been collected both from our own research and the published literature, demonstrate that oxy-PAHs are abundant but neglected contaminants at these sites. The oxy-PAHs show relatively high persistency and because they are formed through transformation of PAHs, their concentrations in the environment may even increase as the sites are remediated by methods that promote PAH degradation. Furthermore, we show that oxy-PAHs are toxic to both humans and the environment, although the toxicity seems to be manifested through other effects than those known to be important for polycyclic aromatic compounds in general, that is, mutagenicity and carcinogenicity. Finally, we present data that support the hypothesis that oxy-PAHs are more mobile in the environment than PAHs, due to their polarity, and thus have a higher tendency to spread from contaminated sites via surface water and groundwater. We believe that oxy-PAHs should be included in monitoring programs at PAH-contaminated sites, even if a number of other toxicologically relevant compounds that may also be present, such as nitro-PAHs and azaarenes, are not monitored. This is because oxy-PAH levels are difficult to predict from the PAH levels, because their environmental behavior differs substantially from that of PAHs, and oxy-PAHs may be formed as PAHs are degraded.

Rapid screening methods can improve the cost effectiveness, throughput, and quality of risk assessments of contaminated sites. In the present case study, the objective was to evaluate a combination of pressurized liquid extraction and 2 in vitro bioassays for the hazard assessment of surface soil sampled from 46 points across a pyrotechnical industrial site. Pressurized liquid extraction was used to rapidly produce soil-water extracts compatible with 2 high-capacity bioassays. Hazard assessment using combined toxicological and chemical screening revealed zones with relatively high potential risks of metal pollution. Multivariate data analysis provided indications that significant inhibition in the bioassays was correlated with levels of metals in the extracts, suggesting an elevated toxic potential from certain metals. Low pH and high concentrations of dissolved organic carbon were associated with increased cytotoxicity of extracts, indicating that these factors influence metal bioavailability. The cytotoxicity observed was more strongly correlated to metal concentrations in the extracts than in the soil, suggesting that measurements of total metal concentrations in soils do not provide good indications of the soil's potential toxicity.

The retention and mobility of hydrophobic organic contaminants (HOCs) in soil is mainly determined by hydrophobic partitioning to dissolved and particulate organic matter (DOM and POM, respectively). The aqueous phase, DOM, and POM fractions were extracted and separated from soils at three sites contaminated with technical chlorophenol formulations. Concentrations of chlorophenols (CP), polychlorinated phenoxyphenols (PCPP), polychlorinated diphenyl ethers (PCDE) and polychlorinated dibenzo-p-dioxins and furans (PCDD/F) were determined. The partitioning to POM, in relation to DOM, increased in all three soils with increasing hydrophobicity in the order CP < PCPP ~ PCDE ~ PCDF < PCDD. Differences in partitioning to DOM (logK(DOC)) and POM (logK(POC)) could not be explained by differences in gross organic C chemistry. Black carbon did not contribute significantly to the sorption of PCDDs, whereas >70% wood fibre in one soil resulted in a decrease of logK(POC) of 0.5 units for CPs and PCDDs. We conclude that logK(OC) for both DOM and POM need to be explicitly determined when the retention and mobility of HOCs is described and modelled in soils.

Recent survey results for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, dioxins) in Baltic Sea sediments from Finland, Sweden and Denmark were merged with previously published Baltic Sea data. Regional distribution of concentration levels, differences in congener patterns, and temporal changes in sediment profiles were examined. One of the main objectives was to study if any major point sources for different PCDD/F congeners could be identified on a regional scale, based on sediment records. The survey confirmed the impact of chlorophenol production derived highly chlorinated PCDF-congeners on the total toxicity in sediments in the Gulf of Finland near the Kymijoki river estuary. Signatures of other point sources or combined point sources pertinent to specific industry branches or particular production processes (such as pulp bleaching, vinyl chloride production, thermal processes) may be discerned. However, the findings did not support any of the known point sources significantly influencing those congeners that are most abundant in Baltic herring and salmon. Instead, regional distributions in the Baltic Sea indicate that atmospheric deposition may act as a major source for those congeners and especially for 2,3,4,7,8-PeCDF. There were clear indications of declines in levels in sediment in some areas, but generally the levels of highly chlorinated PCDD/Fs on the northern coast of the Gulf of Finland were still high when compared with other areas of the Baltic Sea. Major areas with data gaps cover the south-eastern and eastern coastal regions of the Baltic Proper and the southern Gulf of Finland.

Soil samples from five contaminated sawmill sites in Sweden were characterized with respect to chlorophenols (CP), chlorinated phenoxy phenols (PCPP, hydroxylated chlorinated diphenyl ethers), chlorinated diphenyl ethers (PCDE), chlorinated dibenzofurans (PCDF) and chlorinated dibenzo-p-dioxins (PCDD). The composition of chlorinated compounds in the soil samples was compared to the composition of two preservatives commonly used in the Scandinavian wood impregnation industry: the 2,3,4,6-tetrachlorophenol preservative called Ky-5 and the pentachlorophenol preservative Dowicide G. The levels of CPs in the soil samples ranged from 0.1 to 4500 mgkg-1 d.w., PCPPs from <0.15 to 940 mgkg-1 d.w., PCDEs from <38 to 6800 microgkg-1 d.w., PCDFs from 7.4 to 18000 microgkg-1 d.w. and PCDDs from 9.9 to 35000 microgkg-1 d.w. The resulting WHO-TEQ of PCDD/Fs in the soil samples ranged from 0.14 to 3000 microgkg-1 d.w. Despite a wide range of concentrations the congener compositions were similar within tetrachlorophenate and pentachlorophenate contaminated soils respectively. The contamination at each sawmill site may be linked to the use of either a tetrachlorphenol preservative, e.g. Ky-5, or a pentachlorophenol preservative, e.g. Dowicide G. Best-fit calculations were used to compare the chlorinated phenol contents of the preservatives to those of the soil samples. This revealed a positive correlation between the hydrophobicity (logKow) of contaminants and the ratio of their levels in soil to preservatives. The relative abundance of the chlorinated compounds varied greatly between the five sites studied, suggesting that their transport parameters differ substantially.

The aim of this study was to evaluate different techniques for assessing the availability of polycyclic aromatic hydrocarbons (PAHs) in soil. This was done by comparing the amounts (total and relative) taken up by the earthworm Eisenia fetida with the amounts extracted by solid-phase microextraction (SPME), semi-permeable membrane devices (SPMDs), leaching with various solvent mixtures, leaching using additives, and sequential leaching. Bioconcentration factors of PAHs in the earthworms based on equilibrium partitioning theory resulted in poor correlations to observed values. This was most notable for PAHs with high concentrations in the studied soil. Evaluation by principal component analysis (PCA) showed distinct differences between the evaluated techniques and, generally, there were larger proportions of carcinogenic PAHs (4-6 fused rings) in the earthworms. These results suggest that it may be difficult to develop a chemical method that is capable of mimicking biological uptake, and thus estimating the bioavailability of PAHs.

We determined the distribution of hydrophobic organic contaminants (HOCs) to fractions of natural organic matter in a soil contaminated by chlorophenol wood preservatives more than 30 years ago. The concentration of dissolved organic matter (DOM) was enhanced in soil suspensions by raising pH to 6.8-9.1. After 48 h of desorption/equilibration, the DOM fraction was separated from the particulate organic matter (POM) of the soil by filtration. In the next step, DOM was flocculated by Al-nitrate, and free concentrations of HOCs were determined in the aqueous phase. The HOCs associated with DOM and POM were extracted with toluene. No significant differences in gross carbon chemistry were detected between DOM and POM, using X-ray photoelectron spectroscopy (XPS). Normalized to organic C, chlorophenols (CPs) showed a similar degree of partitioning between DOM and POM, whereas the partitioning of polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzo-p-dioxins, and furans (PCDD/Fs) was highly shifted toward POM. The partitioning to POM, relative to DOM, increased in the order PCDE < PCDF < PCDD, reflecting the hydrophobicity of the compounds.

Polychlorinated dibenzo-p-dioxins (PCDDs) of high concentrations in a ball clay deposit from the Mississippi Embayment were found to be consistent with a natural abiotic and non-pyrogenic origin by investigation with bulk radiocarbon analysis, compound-specific chlorine isotope analysis (CSIA-delta37Cl) of octachlorodibenzo-p-dioxin (OCDD), and black carbon (BC) analysis. The conventional radiocarbon date of total organic carbon from a depth of approximately 10 m in three parallel cores ranged from 14 700 years to >48 000 years, indicating that the strata with elevated levels of PCDDs have remained isolated from recent anthropogenic input in these >40 Ma old clay sediments. The CSIA-delta37Cl of OCDD yielded a delta37Cl of -0.2 per thousandth, which is significantly higher than the postulated range for biotic chlorination by chloroperoxidase enzymes, -11 to -10 per thousandth, and falls within the known range for abiotic organochlorines, -6 to +3 per thousandth. The absence of correlations between concentrations of PCDDs and corresponding pyrogenic black carbon (BC), together with estimations of BC sorptive loadings and the absence of polychlorinated dibenzofurans (PCDFs), suggest that vegetation fires did not form these ball-clay PCDDs. Results from this study indicate that the high levels of the toxic and carcinogenic PCDDs found in kaolinite-bearing clays may result from natural abiotic formation via in situ surface-promoted reactions on the clay mineral, including a so-far unknown organic precursor, rather than being the result of anthropogenic contamination.

Goal, Scope and Background: The use of polybrominated diphenyl ethers (PBDEs) as flame retardants increases the risk for emissions of other brominated compounds, such as polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). The large homology in structure of PBDD/Fs and mechanism of toxic action, i.e. the capacity to activate the Ah receptor (AhR) pathway, compared to their well-studied chlorinated analogues, justifies a raised concern to study the environmental levels and fate of these compounds. Decabromodiphenyl ether (decaBDE) is the most widely used PBDE today. Studies on photolytic debromination of decaBDE in organic solvents have shown debromination of decaBDE, as well as formation of PBDFs. However, little is known about the transformation mechanisms and there are only scarce data on photoproducts and PBDE transformation in environmentally relevant matrices. In this study, mechanism-specific dioxin bioassays were used to study photolytic formation of AhR agonists in toluene solutions of decaBDE. In addition, the influence of irradiation time and UV-light wavelength on the formation was studied. PBDE congener patterns and presence of PBDD/Fs were analysed. Further, AhR agonists were analysed in agricultural soils contaminated with PBDEs. Soils were also exposed to UV-light to study changes in AhR agonist levels., Methods: Toluene solutions of decaBDE were irradiated using three different spectra of UV-light, simulating UV-A (320-400 nm), UV-AB (280-400 nm), and UV-ABC (250-400 nm). Additionally, decaBDE solutions were exposed to narrow wavelength intervals (10 nm bandwidth) with the central wavelengths 280, 290, 300, 310, 320, 330, 340, 350, 360 nm. AhR agonists in decaBDE solutions were analysed with two different bioassays, the chick embryo liver-cell assay for dioxins (Celcad) and the dioxin responsive, chemically activated luciferase expression assay (DR-Calux). Also, the decaBDE solutions were analysed with LRGC-LRMS to obtain PBDE congener patterns for breakdown of decaBDE, and with HRGC-HRMS, for presence of PBDD/Fs. Four soils were exposed to UV-AB light, under both dry and moist conditions. Levels of AhR agonists in soil extract fractions, before and after UV-exposure, were analysed with the DR-Calux., Results and Discussion: Significant levels of photoproducts able to activate the AhR pathway, up to 31 ng bio-TEQ/ml, were formed in UV-exposed decaBDE solutions. The transformation yield of decaBDE into AhR agonists was estimated to be at the 0.1%-level, on a molar basis. The net formation was highly dependent on wavelength, with the sample irradiated at 330 nm showing the highest level of dioxin-like activity. No activity was detected in controls. PBDE analysis confirmed decaBDE degradation and a clear time-dependent pattern for debromination of PBDE congeners. AhR agonist effect in the recalcitrant fractions of the soils corresponded to the levels of chemically derived TEQs, based only on chlorinated dioxin-like compounds in an earlier study. It was concluded that no significant levels of other AhR agonists, e.g. PBDFs, were accumulated in the soil. UV-light caused changes in AhR-mediated activity in the more polar and less persistent fractions of the soils, but it is not known which compounds are responsible for this., Recommendations and Perspectives: The laboratory experiments in this study show that high levels of AhR agonists can be formed as photoproducts of decaBDE and it is important to elucidate if and under which conditions this might occur in nature. However, soil analysis indicates that photoproducts of PBDE do not contribute to the accumulated levels of persistent dioxin-like compounds in agricultural soil. Still, more data is needed to fully estimate the environmental importance of PBDE photolysis and occurrence of its photoproducts in other environmental compartments. Analysis with dioxin bioassays enabled us to gather information about photoproducts formed from decaBDE even though the exact identities of these compounds were not known., Conclusion: Bioassays are valuable for studying environmental transformation processes like this, where chemical analysis and subsequent toxicological evaluation requires available standard compounds and information on toxicological potency. The use of bioassays allows a rapid evaluation of toxicological relevance.

Polybrominated diphenyl ethers (PBDEs), including octa-decaBDEs, were found in soil and earthworm samples collected in 2000 from three research stations (reference plots and sewage-sludge-amended plots) and two farms (reference and amended/flooded soils) in Sweden. Sewage-sludge amendment at the research stations increased concentrations of all BDE congeners 2- to 13-fold, with the highest increases for BDE-209. Concentrations 100-to 1000-fold higher were seen in contaminated soils at both farms. BDE-209 was the predominant congener in all soils. sigmaPBDE concentrations in worms ranged from 3.1 to 38 000 ng/g lipid weight and were correlated to soil concentrations, including the octa-decaBDEs. Biota-soil accumulation factors declined in the following order: TeBDE > PeBDE > HxBDE > OcBDE > NoBDE > DeBDE, and ranged from 0.3 to 2 for the octa-decaBDEs. Thus, higher-brominated PBDEs, including BDE-209, are bioavailable from soils and accumulate in earthworms, presenting an exposure pathway into the terrestrial food web. High levels found at one farm 20 years after the last use of PBDEs indicate high persistence of PBDEs in soils, including BDE-209. No evidence of photolytic debromination of BDE-209 in soils was seen.

In this study, we report the PCDD and mineralogical results from the analyses of 27 different samples from three ball clay cores from different locations in Kentucky and Tennessee. One goal of this study was to determine if there is a correlation between the mineralogy of the ball clay samples and the PCDD concentrations and/or homologue profiles in each sample. Samples from each of the three cores exhibited the natural formation profile with extremely high PCDD concentrations with low and mostly undetectable levels of polychlorinated dibenzofurans (PCDFs). The maximum toxic equivalents (TEQs) for Cores C-E were 2500, 440, and 15,000 pg WHO-TEQ/g, respectively. Although there does not seem to be a direct correlation between mineralogy and PCDD concentrations or homologue profiles, the mineralogy of Core C is substantially different than that of Cores D and E, which may in part explain the differences in congener patterns we observed among the three cores.

This study was designed to assess the availability of polycyclic aromatic hydrocarbons (PAHs) present at a gasworks site to different soil remediation techniques. The study examined the effect on PAH availability of using different organic solvents, the degree of pretreatment, and the extraction time. In total, 25 PAHs (with two to six fused rings) and five carbonyl derivatives were measured. The results indicated that the PAHs and their derivatives were bound loosely to the surface of the studied soil and that there were no significant kinetic boundaries associated with the extraction of the PAHs. Furthermore, it was concluded that the studied soil was not suitable for bioremediation, as the concentration of PAHs with low molecular weight were limited. However, pressurized liquid extraction (PLE) with methanol as the solvent extracted 97% of all PAHs and PAH-derivatives, indicating that extraction may be effective as part of a soil remediation technique for old gasworks soils.

Soils from five agricultural sites, three research sites, and two privately owned farms were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and polybronimated diphenylethers (PBDEs). In soils that had not been treated with sludge (reference soils), the international toxic equivalents (I-TEQs) were 0.6 to 1.5 pg/g dry matter (D.M) for the PCDD/Fs. which are low compared to generally reported background soil levels in Europe. The concentrations of sum of six penta- and hexa-PCBs were 450 to 1,400 pg/g DM. The PBDEs 47 and 99 dominated among the tri- to hepta-PBDEs analyzed (8-80 pg/g DM). The impact of adding 1 to 3 tonnes of sludge (DM) per hectare per year on the concentrations was studied at the three research sites by calculating ratios of the compounds in sludge-treated soil to reference soil (S/R ratio). The concentrations of I-TEQs did not increase in the sludge-treated soil, whereas the S/R ratios for PBDEs were greater than one. Also, although the PCB contents were higher in the sludge-treated soils, the background sources were more important for the concentrations of PCBs than of PBDEs. The largest increase in the S/R ratios was found at a private farm where large amounts of sludge had been used in the past. Accumulation of the compounds in earthworms from the sites also was investigated. The biota-soil accumulation factors (BSAFs) of the tested compounds declined in the following order: ortho-PCBs approximately PBDEs > non-ortho-PCBs > 2.3,7,8-substituted PCDD/Fs. The average BSAF for ortho-PCBs was five (organic matter/lipids), and the lowest BSAFs (0.1-0.8) found were for octachlorodibenzo-p-dioxin. To our knowledge, accumulation of PBDEs in earthworms has not been published previously.

Accumulation and elimination of different polycyclic aromatic compounds (PACs) were studied in earthworms (Eisenia fetida) exposed to contaminated soil from an old gasworks site. In total, 12 polycyclic aromatic hydrocarbons (PAHs), two N- and S-heterocyclic PACs, and two PAC-quinones were included in the study. Peak-shaped accumulation curves were found for many of the compounds. After 19 d of exposure, the ratio between concentrations in worm lipids and soil organic matter was 0.02 on average. The half-lives of the PACs were relatively long, between 2 and 11 d. The elimination rate constants, k2, correlated both with literature-derived octanol-water partition coefficients (Kow) for PAHs (r2 = 0.93) and the computed polarizability (r2 = 0.88) of all the compounds. The elimination rate constants of PAHs are comparable to those of PCBs found in earlier studies, and the linear regression coefficient, r2, of k2 against Kow for PAHs and PCBs together was 0.93.

The reliability and efficiency of the pressurised liquid extraction technique (PLE) for extracting polycyclic aromatic hydrocarbons (PAHs) from contaminated soil has been investigated. Experimental design was used to study the influence of seven extraction variables (sample load, solvents used, solvent ratios, pressure, temperature, extraction time, and rinse volume). The results show that large sample loads in combination with small solvent volumes may result in low extraction efficiency. They also indicate that the recovery of low-molecular-mass PAHs is reduced by low extraction temperatures. The exact settings of the other variables are, however, less significant for the extraction efficiency. Repeated extractions at optimised settings of the tested variables show that PLE is an exhaustive extraction technique that generally results in high yields. In addition, extraction of a certified reference material (CRM 103-100) revealed that the method is both accurate and precise. Another finding was that adding the internal standard on top of the soil in the extraction cell causes considerable over-estimation of the concentrations when large samples are extracted with small solvent volumes. This is because the PLE-cell resembles a chromatographic column, so compounds added to the top of the soil layer have a longer distance to travel through the soil compared to the average distance of the native compounds, which are distributed evenly throughout the column. We therefore recommend that the internal standard should be added to the extract immediately after the extraction or, alternatively, carefully mixed with the sample prior to extraction.

An expert meeting was organized by the World Health Organization (WHO) and held in Stockholm on 15-18 June 1997. The objective of this meeting was to derive consensus toxic equivalency factors (TEFs) for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and dioxinlike polychlorinated biphenyls (PCBs) for both human, fish, and wildlife risk assessment. Based on existing literature data, TEFs were (re)evaluated and either revised (mammals) or established (fish and birds). A few mammalian WHO-TEFs were revised, including 1,2,3,7,8-pentachlorinated DD, octachlorinated DD, octachlorinated DF, and PCB 77. These mammalian TEFs are also considered applicable for humans and wild mammalian species. Furthermore, it was concluded that there was insufficient in vivo evidence to continue the use of TEFs for some di-ortho PCBs, as suggested earlier by Ahlborg et al. [Chemosphere 28:1049-1067 (1994)]. In addition, TEFs for fish and birds were determined. The WHO working group attempted to harmonize TEFs across different taxa to the extent possible. However, total synchronization of TEFs was not feasible, as there were orders of a magnitude difference in TEFs between taxa for some compounds. In this respect, the absent or very low response of fish to mono-ortho PCBs is most noticeable compared to mammals and birds. Uncertainties that could compromise the TEF concept were also reviewed, including nonadditive interactions, differences in shape of the dose-response curve, and species responsiveness. In spite of these uncertainties, it was concluded that the TEF concept is still the most plausible and feasible approach for risk assessment of halogenated aromatic hydrocarbons with dioxinlike properties.