Long-term stability and temporal trends of organic contaminants in four collections of mussel tissue frozen standard reference materials.

The stability of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and chlorinated pesticides in frozen mussel tissue Standard Reference Materials (SRMs) stored at -80 °C was assessed by analyzing samples of SRM 1974, SRM 1974a, and SRM 1974b Organics in Mussel Tissue (Mytilus edulis) periodically over 25 y, 20 y, and 12 y, respectively. The most recent analyses were performed during the certification of the fourth release of this material, SRM 1974c. Results indicate the concentrations of these persistent organic pollutants have not changed during storage at -80 °C. In addition, brominated diphenyl ethers (BDEs) were quantified in each of the materials during this study. The stability information is important for on-going monitoring studies collecting large quantities of samples for future analyses (i.e., formally established specimen banking programs). Since all four mussel tissue SRMs were prepared from mussels collected at the same site in Dorchester Bay, MA, USA, the results provide a temporal trend study for these contaminants over a 17 year period (1987 to 2004).

Blood plasma clinical-chemical parameters as biomarker endpoints for organohalogen contaminant exposure in Norwegian raptor nestlings.

Raptors are exposed to biomagnifying and toxic organohalogenated compounds (OHCs) such as organochlorines, brominated flame retardants and perfluorinated compounds. To investigate how OHC exposure may affect biochemical pathways we collected blood plasma from Norwegian northern goshawk (n=56), golden eagle (n=12) and white-tailed eagle (n=36) nestlings during three consecutive breeding seasons. We found that blood plasma concentrations of calcium, sodium, creatinine, cholesterol, albumin, total protein, urea, inorganic phosphate, protein:creatinine, urea:creatinine and uric acid:creatinine ratios and liver enzymes ALKP and ALAT were positively correlated to PCBs, chlordanes, p,p'-DDE, HCB, PFCs and/or PBDEs. Total bilirubin and glucose were negatively correlated to PCBs while magnesium and potassium were negatively correlated to HCB and p,p'-DDE. In addition, protein:creatinine and ALAT were also negatively correlated to PCBs and PFCs, respectively. The most significant relationships were found for the highly contaminated northern goshawks and white-tailed eagles. The statistical relationships between OHCs and BCCPs indicate that biochemical pathways could be influenced while it is uncertain if such changes have any health effects. The OHC concentrations were below concentrations causing reproductive toxicity in adults of other raptor species but similar to those of concern for endocrine disruption of thyroid hormones in e.g., bald eagles.

Characterization and validation of a Portuguese natural reference soil to be used as substrate for ecotoxicological purposes.

This study describes the first attempt to validate a Portuguese natural soil (PTRS1) to be used as reference soil for ecotoxicological purposes, aimed to both: (i) obtain ecotoxicological data for the derivation of Soil Screening Values (SSVs) with regional relevance, acting as a substrate to be spiked with ranges of concentrations of the chemicals under evaluation and (ii) act as control and as substrate for the dilution of contaminated soils in ecotoxicological assays performed to evaluate the ecotoxicity of contaminated soils, in tier 2 of risk assessment frameworks, applied to contaminated lands. The PTRS1 is a cambisol from a granitic area integrated in the Central Iberian Zone. After chemical characterization of the soil in terms of pseudo-total metals, PAHs, PCBs and pesticide contents, it was possible to perceive that some metals (Ba, Be, Co, Cr and V) surpass the Dutch Target Values (Dtvs) corrected for the percentage of organic matter and clay of the PTRS1. Nevertheless, these metals displayed total concentrations below the background total concentrations described for Portuguese soils in general. The same was observed for aldrin, endosulfan I, endosulfan II, heptachlor epoxide, and heptachlor; however the Dtvs corrected become negligible. The performance of invertebrate and plant species, commonly used in standard ecotoxicological assays, was not compromised by both soil properties and soil metal contents. The results obtained suggest that the PTRS1 can be used as a natural reference soil in ecotoxicological assays carried out under the scope of ecological risk assessment.

Intra- and interspecies variation in bioconcentration potential of polychlorinated biphenyls: are all lipids equal?

The variation among bioconcentration factors (BCFs) available in the literature is commonly ascribed to experimental parameters and metabolic capacity. Though bioconcentration is generally considered to be governed by partitioning processes and therefore to depend on the composition of the partition phases, the effect of lipid composition on BCFs measured for hydrophobic organic chemicals has largely escaped attention. The reason may be that the effect cannot easily be studied separately in a conventional BCF test setup and that any subtle effects will often be obscured by the variation normally observed when working with living organisms. In the present study, this variation was circumvented by substituting biota with biological homogenates, which allowed measuring chemical partitioning in a fashion that has proved successful for many other environmental matrixes (e.g., sediments, soils, carbonaceous materials). The appropriateness of using a homogenate as a representation of the organism from which it was derived was demonstrated by a good agreement between homogenate-water partition coefficients (or necroconcentration factors; NCFs) and actual BCFs for PCBs and aquatic worms. Subsequent experiments focused on the intra- and interspecies differences in lipid-normalized NCFs. Intraspecies variation was studied for aquatic worms and sticklebacks, which were acclimatized at different temperatures (5-24 °C), whereas interspecies variation was investigated by determining NCFs for eight different aquatic species. Although temperature-induced intraspecies differences were subtle (<0.16 log units), interspecies differences among lipid-normalized NCFs were as high as 0.9 log units, with homogenates of "simple" organisms showing a lower sorption capacity than those of the more "complex" species. These results suggest that the variation observed in the literature BCFs may partly be caused by differences in lipid composition and contest the usefulness of the common practice of applying generic BCFs in risk assessment of chemicals.

An integrated approach for bioaccumulation assessment in mussels: towards the development of Environmental Quality Standards for biota.

The possible use of chemical concentrations measured in mussels (Mytillus galloprovincialis) for compliance checking against Environmental Quality Standards (EQS) established for biota is analyzed with the help of an integrated model. The model consists of a 3D planktonic module that provides biomasses in the different compartments, i.e., phytoplankton, zooplankton and bacteria; a 3D fate module that provides the concentrations of contaminants in the water column and in the sediments; and a 3D bioaccumulation module that calculates internal concentrations in relevant biotic compartments. These modules feed a 0D growth and bioaccumulation module for mussels, based on the Dynamic Energy Budget (DEB) approach. The integrated model has been applied to study the bioaccumulation of persistent organic pollutants (POPs) in the Thau lagoon (France). The model correctly predicts the concentrations of polychlorinated biphenyls (PCBs) and polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) in mussels as a function of the concentrations in the water column and in phytoplankton. It also sheds light on the origin of the complexity associated with the use of EQS for biota and their conversion to water column concentrations. The integrated model is potentially useful for regulatory purposes, for example in the context of the European Water Framework (WFD) and Marine Strategy Framework Directives (MSFD).

Characterization of certified reference material for quantification of polychlorinated biphenyls and organochlorine pesticides in fish.

Fish certified reference material (CRM), NMIJ CRM 7404-a, for the analysis of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) was developed by the National Metrology Institute of Japan, part of the National Institute of Advanced Industrial Science and Technology. Fish samples (Japanese seabass) used for the preparation of the CRM were collected from Tokyo Bay, and the edible part was freeze-dried, pulverized, sieved, homogenized, and sterilized by gamma-irradiation. This sample is in the form of a powder comprising approximately 10 g stored in a brown glass bottle. The certification was carried out using multiple analytical methods such as pressurized liquid extraction, Soxhlet extraction, saponification, and homogenization to ensure the reliability of analytical results; the certified values of target PCBs (PCB 28, PCB 70, PCB 105, PCB 153, and PCB 170) and OCPs (trans-nonachlor, dieldrin, p,p'-DDE, p,p'-DDT, and p,p'-DDD) were 1.05-14.0 microg kg(-1) and 1.57-18.0 microg kg(-1) for PCBs and OCPs, respectively. This is the first fish powder CRM in which PCBs and OCPs were determined by isotope dilution mass spectrometry.

pK(a) values of the monohydroxylated polychlorinated biphenyls (OH-PCBs), polybrominated biphenyls (OH-PBBs), polychlorinated diphenyl ethers (OH-PCDEs), and polybrominated diphenyl ethers (OH-PBDEs).

The SPARC software program aqueous pK(a) prediction module was validated against corresponding experimental acidity constants for chlorinated and brominated phenols and the limited experimental aqueous pK(a) data sets for monohydroxylated polychlorinated biphenyls (OH-PCBs), polychlorinated diphenyl ethers (OH-PCDEs), and polybrominated diphenyl ethers (OH-PBDEs). pK(a) values were then estimated for all 837 monohydroxylated mono- through nona-halogenated congeners in each of the OH-PCB, OH-PCDE, and OH-PBDE classes, as well as for the monohydroxylated polybrominated biphenyls (OH-PBBs), giving a total of 3348 compounds. Large intrahomolog pK(a) variation by up to six units is expected within each contaminant class, with pK(a) values ranging from about 4 to 11 dependent on the degree and pattern of halogenation. Increasing halogenation generally decreased the average pK(a) within each homolog group. Significant intrahomolog differences in pK(a) values exist between OH-PCB, OH-PBB, OH-PCDE, and OH-PBDE congeners, including large acidity constant variation between isomers with equivalent halogenation patterns but varying location of the hydroxy moiety. Congener specific pH dependent investigations into the partitioning and degradation behaviors of these compounds are necessary, including greater consideration of analyte ionization effects during their extraction and analysis.

Ambient Air Exposure to PCBs: Regulation and Monitoring at Five Contaminated Sites in EPA Regions 1, 2, 4, and 5.

Existing regulations seek to protect the public from exposure to polychlorinated biphenyls (PCBs) in food, water, and soil. Exposure to PCBs in ambient air has recently been given explicit consideration in the human health risk assessments that form the basis of risk management decisions at contaminated sites. The objective of this paper is to examine how ambient air exposure to PCBs is regulated and monitored at five contaminated sites in the United States. We reviewed online accessible materials (including Environmental Protection Agency-site specific websites, data repositories, and other agency websites). Results indicate that the five sites vary in regard to the measured PCB concentrations in air, the sampling and monitoring methodologies, and the established site-specific guidelines/standards and their basis. We conclude that current practices may not adequately protect those living or working near these sites from airborne PCB exposure and that regulations should include recognition of exposure to indoor sources.

Enantiomer fractions of polychlorinated biphenyls in three selected Standard Reference Materials.

The enantiomer composition of six chiral polychlorinated biphenyls (PCBs) were measured in three different certified Standard Reference Materials (SRMs) from the US National Institute of Standards and Technology (NIST): SRM 1946 (Lake Superior fish tissue), SRM 1939a (PCB Congeners in Hudson River Sediment), and SRM 2978 (organic contaminants in mussel tissue--Raritan Bay, New Jersey) to aid in quality assurance/quality control methodologies in the study of chiral pollutants in sediments and biota. Enantiomer fractions (EFs) of PCBs 91, 95, 136, 149, 174, and 183 were measured using a suite of chiral columns by gas chromatography/mass spectrometry. Concentrations of target analytes were in agreement with certified values. Target analyte EFs in reference materials were measured precisely (<2% relative standard deviation), indicating the utility of SRM in quality assurance/control methodologies for analyses of chiral compounds in environmental samples. Measured EFs were also in agreement with previously published analyses of similar samples, indicating that similar enantioselective processes were taking place in these environmental matrices.

Temporal trends of chlorinated paraffins and polychlorinated biphenyls in Swiss soils.

Persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs), are ubiquitous environmental contaminants that have been targeted by national regulations since the 1970-1980s, followed in 2004 by the worldwide regulation under the Stockholm Convention on POPs. However, concerns are growing regarding the emergence of additional POP-like substances, such as chlorinated paraffins (CPs), which have particularly large production volumes. Whereas short-chain CPs (SCCPs) have recently been restricted in Europe and are currently under evaluation for inclusion into the Stockholm Convention, medium-chain CPs (MCCPs) have received little attention. On the one hand, temporal trends of CPs in the environment have hardly been investigated. On the other hand, the effectiveness of the Stockholm Convention on environmental levels of PCBs is still a matter of debate. Here, we reconstructed temporal trends of SCCPs, MCCPs, and PCBs in archived soil samples from six sampling sites in Switzerland, covering the period 1989-2014 (respectively 1988-2013 for one site). Concentrations of SCCPs have decreased in soil since 1994, which indicates positive effects of the reduction of production of SCCPs in Europe and the increasingly stringent regulation. However, the decline in soil is slow with a halving time of 18 years. Concentrations of MCCPs have continuously increased in soil over the entire period 1989-2014, with a doubling between 2009 and 2014. The concentrations of MCCPs have surpassed those of SCCPs, showing their relevance today, partly as replacements for SCCPs. Soil concentrations of PCBs peaked in 1999, i.e. three decades later than worldwide production and use of PCBs, but earlier than the entry into force of the Stockholm Convention. PCBs follow a decline in soil with a halving time of approx. 8 years. This study shows the usefulness of sample archives for the reconstruction and interpretation of time trends of persistent environmental contaminants.

Using sediment quality guidelines for dredged material management in commercial ports from Spain.

Dredged material contamination was assessed in different commercial ports from Spain: Port of Cádiz and Huelva, South West; Bilbao and Pasajes, North; Cartagena and Barcelona, East; Coruña, North West. Sediment from different locations of these ports was sampled and was characterized following the Spanish recommendations for dredged material management. This characterization included grain size distribution, organic matter content and concentration of the chemical compounds included in the list of pollutants and hazardous substances (As, Cd, Cu, Cr, Hg, Ni, Pb and Zn; PCB congeners IUPAC number 28, 52, 101, 118, 138, 153 and 180; PAHs were also analyzed). The results were compared to the limit values of Spanish Action Levels that define the different categories for assessment and management. A set of empirically derived sediment quality guidelines (SQG) was used to assess the possible toxicity of the dredged materials and to improve the use of the chemical approach to characterize dredged material for its management.

A tiered assessment framework to evaluate human health risk of contaminated sediment.

For sediment contaminated with bioaccumulative pollutants (e.g., PCBs and organochorine pesticides), human consumption of seafood that contain bioaccumulated sediment-derived contaminants is a well-established exposure pathway. Historically, regulation and management of this bioaccumulation pathway has focused on site-specific risk assessment. The state of California (United States) is supporting the development of a consistent and quantitative sediment assessment framework to aid in interpreting a narrative objective to protect human health. The conceptual basis of this framework focuses on 2 key questions: 1) do observed pollutant concentrations in seafood from a given site pose unacceptable health risks to human consumers? and 2) is sediment contamination at a site a significant contributor to seafood contamination? The first question is evaluated by interpreting seafood tissue concentrations at the site, based on health risk calculations. The second question is evaluated by interpreting site-specific sediment chemistry data using a food web bioaccumulation model. The assessment framework includes 3 tiers (screening assessment, site assessment, and refined site assessment), which enables the assessment to match variations in data availability, site complexity, and study objectives. The second and third tiers use a stochastic simulation approach, incorporating information on variability and uncertainty of key parameters, such as seafood contaminant concentration and consumption rate by humans. The framework incorporates site-specific values for sensitive parameters and statewide values for difficult to obtain or less sensitive parameters. The proposed approach advances risk assessment policy by incorporating local data into a consistent region-wide problem formulation, applying best available science in a streamlined fashion.

Waste disposal technologies for polychlorinated biphenyls.

Improper practices in the disposal of polychlorinated biphenyl (PCB) wastes by land burial, chemical means and incineration distribute these chemicals and related compounds such as polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzodioxins (PCDDs) throughout the environment. The complete range of methods for disposal that have been proposed and are in use are examined and analyzed, with emphasis given to the two most commonly used methods: land burial and incineration. The understanding of aquifer contamination caused by migration of PCBs from subsurface burial sites requires a description of the physical, chemical and biological processes governing transport in unsaturated and saturated soils. For this purpose, a model is developed and solved for different soil conditions and external driving functions. The model couples together the fundamental transport phenomena for heat, mass, and moisture flow within the soil. To rehabilitate a contaminated aquifer, contaminated groundwaters are withdrawn through drainage wells, PCBs are extracted with solvents or activated carbon and treated by chemical, photochemical or thermal methods. The chemical and photochemical methods are reviewed, but primary emphasis is devoted to the use of incineration as the preferred method of disposal. After discussing the formation of PCDFs and PCDDs during combustion from chloroaromatic, chloroaliphatic, as well as organic and inorganic chloride precursors, performance characteristics of different thermal destructors are presented and analyzed. To understand how this information can be used, basic design equations are developed from governing heat and mass balances that can be applied to the construction of incinerators capable of more than 99.99% destruction with minimal to nondetectable levels of PCDFs and PCDDs.

Validation of a congener specific method for ortho and non-ortho substituted polychlorinated biphenyls in fruit and vegetable samples.

An on-line procedure has been developed and validated for the clean-up and fractionation of ortho and non-ortho-PCBs in fruit and vegetable samples. The procedure combines silica/acid and carbon/glass fibre columns with gas chromatography-mass spectrometry. Chromatography on carbon/glass fibre allowed collection of mono-ortho/di-ortho and non-ortho-PCB fractions, which were determined separately by GC-MS. The method was validated by replicate analyses and by inter-laboratory comparison of data for PCB congeners determined in fruit and vegetable samples collected in South Wales. The concurrent determination of ortho and non-ortho substituted PCBs is reported with recoveries ranging from 55-95% and a mean intra-laboratory precision (%COV) of 9.5% for apple extracts.

Method development and implementation for co-planar polychlorinated biphenyls (PCBs).

The Emission Measurement Center (EMC) in the Environmental Protection Agency's Office of Air Quality Planning and Standards was directed to conduct an emissions test program at a sewage sludge incinerator in support of a Maximum Achievable Control Technology (MACT) standard. One pollutant category of concern at these facilities was polychlorinated biphenyls, or PCBs. An objective of the test program was to measure co-planar PCBs in the incinerator emissions, the sewage sludge introduced to the incinerator, and the scrubber water effluent used in controlling the incinerator emissions. Co-planar PCB congeners are those having four or more chlorine atoms with only a few substitutions in the ortho positions, i.e. positions designated 2, 2', 6, and 6'. Thirteen PCB compounds are sometimes referred to as the "WHO PCBs," because the World Health Organization (WHO) has derived toxic equivalency factors for these congeners. Studies have shown that these dioxin-like compounds can react with the aryl hydrocarbon receptor. This same reaction is believed to initiate adverse health effects for dioxin and furan congeners. In order to conduct the co-planer PCB testing, the EMC had to develop analytical methods that could measure the 13 co-planar PCBs. The purpose of the test program was to develop, evaluate, and implement analytical test methods capable of measuring co-planar PCBs in three matrices: incinerator stack gases, sewage sludge, and scrubber water effluents. The paper summarizes the initial development work that was performed in preparation of analytical test protocols that could measure co-planar PCBs in air, water, and sludge matrices. Following the method development, a MACT emissions test program was conducted at a sewage sludge facility in July 1999 and these data are also summarized in the paper.

Concentrations of halogenated natural products versus PCB 153 in bivalves from the North and Baltic Seas.

Different halogenated natural products (HNPs) have been reported to occur in marine wildlife, particularly from regions with comparably little contamination with anthropogenic pollutants. The North Sea and the Baltic Sea have been known as a marine site heavily polluted with organohalogen compounds, and especially with polychlorinated biphenyls (PCBs). In this study we wished to determine the current abundance of HNPs in comparison with 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153), i.e. the major PCB congener in marine biota. For this purpose, forty blue mussels (Mytilus edulis) and oysters (Crassostrea gigas) from seven sites were analyzed on HNPs and PCB 153. Most of the samples contained HNPs in the form of polyhalogenated 1'-methyl-1,2'-bipyrroles (PMBPs including Q1) and the mixed halogenated compound MHC-1. In addition we determined several polyhalogenated 1,1'-dimethyl-2,2'-bipyrroles (PDBPs), 2,3,4,5-tetrabromo-N-methylpyrrole and several novel homologs, as well as polybrominated N-methylindoles. The occurrence of these HNP groups were considerably different in the samples from different regions with varying sum concentrations up to 1930 µg/kg lipids in blue mussels from Heligoland (North Sea) and much lower concentrations in samples from the Baltic Sea (up to 13 µg/kg lipids). The concentrations of HNPs varied by two orders of magnitude, compared to a factor of 10 for PCB 153, suggesting that HNPs are more spatially (and perhaps temporally) variant than POPs. In the North Sea region Heligoland, HNPs were more abundant than PCB 153.

Monitoring micropollutants in marine waters, can quality standards be met?

The environmental risks of 33 micropollutants occurring in Belgian coastal zone were assessed as single-substances and as mixtures. Water and sediment samples were taken in harbors, coastal waters and the Scheldt estuary during 2007-2009. Measured environmental concentrations were compared to quality standards such as Predicted No Effect Concentrations (PNECs), Environmental Quality Standards (EQSs), and Ecotoxicological Assessment Criteria (EAC). Out of a total of 2547 samples analyzed, 232 and 126 samples exceeded the EQS and EAC, respectively. Highest risks were observed for TBT, PBDEs, PCBs and the PAHs anthracene, indeno(1,2,3-cd)pyrene, benzo(g,h,i)perylene, benzo(k)fluoranthene, and benzo(b)fluoranthene in the water compartment and for TBT and PCBs in the sediment compartment. Samples taken at all stations during the April 2008 campaign indicate a potential risk of the contaminant mixtures to the aquatic environment (except W06 station). This study argues the need to revise quality standards when appropriate and hence the overall regulatory implication of these standards.

Revised relative potency values for PCDDs, PCDFs, and non-ortho-substituted PCBs for the optimized H4IIE-luc in vitro bioassay.

While the World Health Organization 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalency factors are useful estimates of relative potencies of mixtures when conducting risk assessments, they are not useful when comparing the results of bioassays such as the H4IIE-luc to concentrations of TCDD equivalents calculated from instrumental analyses. Since there are thousands of dioxin-like compounds (DLCs), one use of screening assays is to determine if all of the aryl hydrocarbon receptor (AhR) active DLCs in a mixture have been accounted for in instrumental analyses. For this purpose, bioassay-specific relative potency (ReP) values are needed. RePs of 21 polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls that exhibit effects mediated through the AhR were determined by use of the H4IIE-luc assay. Different values of RePs are derived, depending on the statistical, curve-fitting methods used to derive them from the dose-response relationships. Here, we discuss the various methods for deriving RePs from in vitro data and their assumptions and effects on values of RePs. Full dose-response curves of 2,3,7,8-TCDD and other representative DLCs were used to estimate effective concentrations at multiple points (e.g., EC20-50-80), which were then used to estimate ReP of each DLC to 2,3,7,8-TCDD.

Body burden of metals and persistent organic pollutants among Inuit in the Canadian Arctic.

Inuit living in the Arctic are exposed to elevated levels of environmental contaminants primarily due to long-range atmospheric transport. Blood sampling and contaminant biomonitoring was conducted as part of the International Polar Year Inuit Health Survey in 2007-2008. The body burden of metals (e.g. Cd, Pb) and persistent organic pollutants (e.g. PCBs, DDT & DDE, toxaphene, chlordane, PBDEs) were measured for Inuit participants (n=2172) from 36 communities in Nunavut, Nunatsiavut, and the Inuvialuit Settlement Region, in Canada. The geometric mean of blood concentrations for Cd, Pb, PCBs, DDE & DDT, toxaphene, and chlordane were higher than those in the Canadian general population. A total of 9% of study participants exceeded the intervention guideline of 100µgL(-1) for Pb, 11% of participants exceeded the trigger guideline of 5µgL(-1) for Cd, and 1% exceeded the intervention guideline of 100µgL(-1) for PCBs. Also, 3% of women of child-bearing age exceeded blood Pb of 100µgL(-1) while 28% of women of child-bearing age exceeded 5µgL(-1) of PCBs. This work showed that most Inuit Health Survey participants were below blood contaminant guidelines set by Health Canada but that metal and POP body burdens commonly exceed exposures observed in the general population of Canada.