Assessment of brominated flame retardants in a small mixed waste electronic and electrical equipment (WEEE) plastic recycling stream in the UK.

Identifying the presence of brominated flame retardants (BFRs) within individual polymer types prior to extrusion has given us a unique perspective on which polymers may be problematic in meeting European Union (EU) low persistent organic pollutant (POP) content limits (LPCLs) and the potential for mixed engineering plastics (MEP) to be used as a viable recycled product. Our findings suggest that careful management of the polymer types within the feed chips prior to extrusion could deliver extruded polymer pellets that meet the EU LPCL values for POP-BFRs (i.e. <1000 mg/kg). Within this study, three fractions of extruded polymer pellets ("light", "medium", and "heavy" MEP) were created using density separation. Each fraction was characterised for 28 legacy and novel BFRs with brominated diphenyl ether-209 (BDE-209) (68-37,000 mg/kg) and tetrabromobisphenol-A (TBBP-A) (17-120,000 mg/kg) both predominant and ubiquitous. Portable X-ray fluorescence (XRF) was utilised to measure Br in 120 individual MEP chips of various polymer types. Those chips that XRF flagged as having high Br concentrations (>2500 mg/kg) were subjected to further evaluation for BFR content via mass spectrometry analysis and the results compared with the XRF Br data. This revealed that in 22% of the 120 chips studied, XRF incorrectly identified the LPCL to be exceeded. Our data also identifies the presence of the novel BFRs decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE) in plastics derived from waste electronic and electrical equipment (WEEE). While the "light-MEP" samples contained POP-BFR concentrations below LPCLs, the "medium-MEP" and "heavy-MEP" fractions exceeded such limits. Management of the polymer chips by colour sorting resulted in significant reductions in concentrations of all BFRs in the clear polymers such that LPCL limits were not exceeded; however, concentration reductions in white polymers were insufficient to meet LPCLs.

Predictors of human PBDE body burdens for a UK cohort.

Human exposure to polybrominated diphenyl ethers (PBDEs) was investigated in a cohort of 20 UK adults along with their anthropometric covariates and relevant properties such as room surveys, lifestyle, diet and activity details. Selected PBDE congeners were measured in matched samples of indoor dust (n = 41), vehicles (n = 8), duplicate diet (n = 24), serum (n = 24) and breast milk (n = 6). Combined exposure estimates via dust and diet revealed total PBDE intakes of 104 to 1,440 pg kg-1 bw d-1 for ΣBDEs3-7 and 1,170 to 17,000 pg kg-1 bw d-1 for BDE-209. These adult intakes are well within health reference doses suggested by the European Food Safety Authority (EFSA) and the US EPA. Diet was the primary source of intake of BDE3-7 congeners for the majority of the cohort, with dust the primary source of BDE-209. Primary sources of PBDE exposure vary between countries and regions with differing fire prevention regulations. Estimated infant exposures (ages 1.5-4.5 years) showed that BDE-99 intake for one of the households did not meet EFSA's recommended margin of exposure, a further two households had borderline PBDE exposures for high level dust and diet intake. Males and those having a lower body fat mass had higher serum BDE-153. Higher meat consumption was significantly correlated with higher BDEs3-7 in serum. A reduction in dietary BDEs3-7 would therefore result in the greatest reduction in BDE-99 exposure. Rooms containing PUF sofas or armchairs over 20 years old had more BDEs3-7 in their dust, and rooms with carpets or rugs of that age had higher dust BDE-209. Dusting rooms more frequently resulted in significantly lower concentrations of all major congeners in their dust. Correlation between BDE-209 body burden and dust or diet exposure was limited by its low bioaccessibility. Although vehicle dust contained the highest concentrations of BDEs3-7 and BDE-209, serum BDEs3-7 correlated most strongly with bedroom dust.

Evidence of bad recycling practices: BFRs in children's toys and food-contact articles.

Brominated flame retardants (BFRs) have been used intentionally in a wide range of plastics, but are now found in an even wider range of such materials (including children's toys and food contact articles) as a result of recycling practices that mix BFR-containing waste plastics with "virgin" materials. In this study Br was quantified in toy and food contact samples on the assumption that its concentration can be used as a metric for BFR contamination. Subsequently, compound specific determination of BFRs was performed to evaluate the validity of the aforementioned assumption, crucial to render rapid, inexpensive, in situ Br determination in non-laboratory environments (such as waste handling facilities) a viable option for sorting wastes according to their BFR content. We report semi-quantitative compound specific BFR concentrations to give an overview of the distribution of individual BFRs in the analyzed samples. Finally, we evaluated the correlations between waste electrical and electronic equipment (WEEE) related substances (Ca, Sb and rare earth elements (REEs)) and Br as a proxy for identifying poor sorting practices in different waste streams. 26 samples of toys, food-contact articles and WEEE were analyzed with a suite of different techniques in order to obtain comprehensive information about their elemental and molecular composition. The information obtained from principal component analysis about WEEE-related compounds provides new insights into the influence of sorting practices on the extent of products' contamination and bringing out polymer-related trends in the pollutants' signature. 61% of all samples were Br positive: of these samples, 45% had decaBDE concentrations exceeding the concentration limits for PBDEs and their main constituent polymer was - according to the REE signature of such samples - Acrylonitrile Butadiene Styrene (ABS), uses of which include copying equipment, laptops and computers. The ability to better track chemicals of concern and their trends in products is the main requirement for high-level management and control of material cycles to become non-toxic in the future as proposed in the EU's 7th Environmental Action Plan.

Improving the accuracy of hand-held X-ray fluorescence spectrometers as a tool for monitoring brominated flame retardants in waste polymers.

An optimised method for Br quantification as a metric of brominated flame retardant (BFR) concentrations present in Waste Electrical and Electronic Equipment (WEEE) polymers is proposed as an alternative to the sophisticated, yet time consuming GC-MS methods currently preferred. A hand-held X-ray fluorescence (XRF) spectrometer was validated with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Customized standard materials of specific BFRs in a styrenic polymer were used to perform an external calibration for hand-held XRF ranging from 0.08 to 12 wt% of Br, and cross-checking with LA-ICP-MS having similar LODs (0.0004 wt% for LA-ICP-MS and 0.0011 wt% for XRF). The "thickness calibration" developed here for hand-held XRF and the resulting correction, was applied to 28 real samples and showed excellent (R(2) = 0.9926) accordance with measurements obtained via LA-ICP-MS. This confirms the validity of hand-held XRF as an accurate technique for the determination of Br in WEEE plastics. This is the first use of solid standards to develop a thickness-corrected quantitative XRF measurement of Br in polymers using LA-ICP-MS for method evaluation. Thermal desorption gas chromatography mass spectrometry (TD-GC-MS) was used to confirm the presence of specific BFRs in WEEE polymer samples. We propose that expressing limit values for BFRs in waste materials in terms of Br rather than BFR concentration (based on a conservative assumption about the BFR present), presents a practical solution to the need for an accurate, yet rapid and inexpensive technique capable of monitoring compliance with limit values in situ.

Mass transfer of PBDEs from plastic TV casing to indoor dust via three migration pathways--A test chamber investigation.

Polybrominated diphenyl ethers (PBDEs) are widely detected in humans with substantial exposure thought to occur in indoor environments and particularly via contact with indoor dust. Despite this, knowledge of how PBDEs migrate to indoor dust from products within which they are incorporated is scarce. This study utilises an in-house designed and built test chamber to investigate the relative significance of different mechanisms via which PBDEs transfer from source materials to dust, using a plastic TV casing treated with the Deca-BDE formulation as a model source. Experiments at both room temperature and 60°C revealed no detectable transfer of PBDEs from the TV casing to dust via volatilisation and subsequent partitioning. In contrast, substantial transfer of PBDEs to dust was detected when the TV casing was abraded using a magnetic stirrer bar. Rapid and substantial PBDE transfer to dust was also observed in experiments in which dust was placed in direct contact with the source. Based on these experiments, we suggest that for higher molecular weight PBDEs like BDE-209; direct dust:source contact is the principal pathway via which source-to-dust transfer occurs.

Historical trends of PBDEs and HBCDs in sediment cores from Sydney estuary, Australia.

This paper presents the first historical data on the occurrence of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDs) in estuarine sediment from Australia. Sediment cores and surficial sediment samples were collected from four locations within Sydney estuary, Australia. Large increases in concentrations were observed for all compounds between 1980 and 2014, especially for BDE-209 (representative usage of Deca-BDE commercial mixture), which was found in surficial sediment at an average concentration of 42 ng/g dry wt (21-65 ng/g dry wt). PBDE congeners representative of both the Penta- and Octa-BDE commercial mixtures (∑6PBDEs) were also found in their highest concentrations in surficial sediments (average: 1.3 ng/g dry wt; range: 0.65-2.5 ng/g dry wt). PBDE concentrations in surficial sediments were relatively high when compared with those presented in the available literature. This suggests that their input into the Sydney estuary has not decreased since their bans almost a decade earlier. After a sharp increase in the 1990s, HBCD concentrations peaked at an average of 3.5 ng/g dry wt (1.8-5.3 ng/g dry wt) in surficial samples. With global legislation on HBCDs allowing its usage for the next 10 years, it is expected that its input into the estuary is likely to continue.

Test chamber investigation of the volatilization from source materials of brominated flame retardants and their subsequent deposition to indoor dust.

UNLABELLED: Numerous studies have reported elevated concentrations of brominated flame retardants (BFRs) in dust from indoor micro-environments. Limited information is available, however, on the pathways via which BFRs in source materials transfer to indoor dust. The most likely hypothesized pathways are (a) volatilization from the source with subsequent partitioning to dust, (b) abrasion of the treated product, transferring microscopic fibers or particles to the dust (c) direct uptake to dust via contact between source and dust. This study reports the development and application of an in-house test chamber for investigating BFR volatilization from source materials and subsequent partitioning to dust. The performance of the chamber was evaluated against that of a commercially available chamber, and inherent issues with such chambers were investigated, such as loss due to sorption of BFRs to chamber surfaces (so-called sink effects). The partitioning of polybrominated diphenyl ethers to dust, post-volatilization from an artificial source was demonstrated, while analysis in the test chamber of a fabric curtain treated with the hexabromocyclododecane formulation, resulted in dust concentrations exceeding substantially those detected in the dust pre-experiment. These results provide the first experimental evidence of BFR volatilization followed by deposition to dust. PRACTICAL IMPLICATIONS: Brominated flame retardants (BFRs) are ubiquitous in indoor air and dust, leading to human exposure and resultant concerns about their adverse impact on health. Indoor dust has been demonstrated to constitute an important vector of human exposure to BFRs, especially for toddlers. Despite the greater importance of dust contamination in the context of human exposure to BFRs, the mechanisms via which BFRs transfer from source materials to dust have hitherto been subject to only limited research. In this study, a test chamber is utilized to simulate the migration of BFRs to dust via volatilization from source materials and subsequent deposition to dust.

Test chamber and forensic microscopy investigation of the transfer of brominated flame retardants into indoor dust via abrasion of source materials.

Brominated flame retardants (BFRs) have been detected in indoor dust in many studies, at concentrations spanning several orders of magnitude. Limited information is available on the pathways via which BFRs migrate from treated products into dust, yet the different mechanisms hypothesized to date may provide an explanation for the range of reported concentrations. In particular, transfer of BFRs to dust via abrasion of particles or fibers from treated products may explain elevated concentrations (up to 210 mg g(-1)) of low volatility BFRs like decabromodiphenyl ether (BDE-209). In this study, an indoor dust sample containing a low concentration of hexabromocyclododecane, or HBCD, (110 ng g(-1) ΣHBCDs) was placed on the floor of an in-house test chamber. A fabric curtain treated with HBCDs was placed on a mesh shelf 3 cm above the chamber floor and abrasion induced using a stirrer bar. This induced abrasion generated fibers of the curtain, which contaminated the dust, and ΣHBCD concentrations in the dust increased to between 4020 and 52 500 ng g(-1) for four different abrasion experiment times. The highly contaminated dust (ΣHBCD at 52 500 ng g(-1)) together with three archived dust samples from various UK microenvironments, were investigated with forensic microscopy techniques. These techniques included Micro X-ray fluorescent spectroscopy, scanning emission microscopy coupled with an energy dispersive X-ray spectrometer, Fourier transform infrared spectroscopy with further BFR analysis on LC-MS/MS. Using these techniques, fibers or particles abraded from a product treated with BFRs were identified in all dust samples, thereby accounting for the elevated concentrations detected in the original dust (3500 to 88 800 ng g(-1) ΣHBCD and 24 000 to 1,438 000 ng g(-1) for BDE-209). This study shows how test chamber experiments alongside forensic microscopy techniques, can provide valuable insights into the pathways via which BFRs contaminate indoor dust.

Studies into the formation of PBDEs and PBDD/Fs in the iron ore sintering process.

Polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and furans (PBDD/Fs) were detected in stack emissions from UK sinter plants. The sum of 36 PBDE congeners was measured at a mean concentration of 295 ng/N m(3) with a standard deviation of 96 ng/N m(3). The mean PBDD/F concentrations were 0.14 ng WHO-TEQ/m(3) (range=0.03-0.39). PBDD/F emission concentrations were approximately ten times lower than their PCDD/F homologues. To understand the possible formation mechanisms of brominated organic species in iron ore sintering, both full-scale and laboratory experiments using an experimental sintering process were carried out. A complete PBDE mass balance was undertaken for a full scale sinter plant showing that PBDEs were already present in the raw materials such as iron ores and coke breeze and that a significant proportion of the PBDE inputs were actually destroyed during the process. A number of controlled experiments were conducted using a laboratory-scale sintering apparatus (sinter pot). These were designed to investigate: (a) mass balance of PBDEs during sintering, (b) the relationship between the availability of bromide (as KBr) and PBDE emissions, and (c) the influence of the availability of both bromide and PBDEs on PBDD/F formation. As observed in the full scale plant, the PBDEs already present in the raw materials were mostly destroyed during the process (79-96%) for all sinter pot experiments. Increasing amounts of KBr in the raw sinter mix did not result in a significant increase in PBDE formation suggesting that there was no PBDE formation in sintering via de novo synthesis. No relationship was observed between PBDE inputs and PBDD/F emissions indicating that PBDEs did not act as precursors for PBDD/Fs formation. Finally, PBDD/F formation was enhanced substantially with increasing amounts of KBr suggesting that their formation mechanism was similar to that of PCDD/Fs via de novo synthesis.

Versatility of a new bioinorganic catalyst: palladized cells of Desulfovibrio desulfuricans and application to dehalogenation of flame retardant materials.

The versatility and reaction specificity of a novel bioinorganic catalyst is demonstrated in various reactions. Palladized cells (bioPd) of the sulphate-reducing bacterium Desulfovibrio desulfuricans showed an increased product selectivity and a catalytic activity comparable to a commercial Pd catalyst in several industrially relevant hydrogenations and hydrogenolyses (reductive dehalogenations). The ability of palladized cells to promote the reductive debromination of a polybrominated diphenyl ether (PBDE #47) is demonstrated, although chemically reduced Pd(II) and commercial Pd(0) were more effective debromination agents. Polybrominated diphenyl ethers are being supplanted as flame retardants by other compounds, e.g. tris(chloroisopropyl)phosphate (TCPP), the concentration of which was seen to increase approximately 10-fold in groundwater samples between 2000 and 2004. BioPd dechlorinated TCPP in groundwater samples with >90% recovery of free chloride ion, and was five times more effective than using commercial Pd(0) catalyst. Examination of the spent groundwater using 31P NMR showed a phosphorus species novel to the bioPd-treated solution, which was not evident in a commercial reference sample of TCPP.

Concentrations and chiral signatures of POPs in soils and sediments: a comparative urban versus rural study in Canada and UK.

Surface soils and sediments were collected in Toronto, Canada to investigate the concentrations and enantiomeric signatures of urban versus rural locations. Samples were analyzed for polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs) and organochlorine pesticides (OCs). In soils, the sum of 10 PCB congeners (Sigma PCB 28, 52, 95, 101, 118, 136, 138, 149, 153, 180) and 15 PAHs (Sigma PAHs) ranged from 0.76-58 to 58-3200 ng g(-1), respectively. The most abundant OCs detected were DDTs, followed by chlordanes and endosulfans. Sigma PAHs exhibited an urban-rural gradient of up to 60 times but a gradient was not observed for Sigma PCBs and OCs which may reflect local sources of these chemicals. In sediments, Sigma PCBs and Sigma PAHs ranged from 0.03-23 ng g(-1) to 42-3300 ng g(-1), respectively. Sigma PCBs, Sigma PAHs, chlordanes and DDTs exhibited weak urban-rural gradients. Chiral signatures of PCB 95, 136, 149, trans-chlordane (TC), cis-chlordane (CC) and o,p-DDT were characterized to study the enantiomeric degradation in urban versus rural areas and its relation to contaminant levels. Supplementary to these data, we also report on the chiral signatures of PCBs in UK lake sediments from a variety of urban and rural locations. The extent of enantiomeric degradation was expressed as the enantiomeric excess (EE%) which is defined as 100x(E1-E2)/(E1+E2), where E1 is always the most abundant enantiomer and E2 is the least abundant enantiomer. The EE% of PCB 149 in the UK sediments was negatively correlated (p<0.05) with Sigma PAHs suggesting either more recent emissions of this PCB congener in the more contaminated urban locations and hence a more racemic signature or less enantiomeric degradation of the congener in more contaminated urban soils. However, no significant correlation was observed between EE% of any of the chiral chemicals and contaminant levels in the Toronto soils.

Dehalogenation of chlorinated aromatic compounds using a hybrid bioinorganic catalyst on cells of Desulfovibrio desulfuricans.

A novel bioinorganic catalyst was obtained via reduction of Pd(II) to Pd0 on to the surface of cells of Desulfovibrio desulfuricans at the expense of H2. Palladised biomass, supplied with formate or H2 as an electron donor, catalysed the dehalogenation of 2-chlorophenol and polychlorinated biphenyls. In the example of 2,3,4,5-tetrachlorobiphenyl, the bioinorganic catalyst promoted a rate of chloride release of 9.33 +/- 0.17 nmol min(-1) mg (-1) and only approximately 5% of this value was obtained using chemically reduced or commercially available Pd0. In the case of 2,2',4,4',6,6'-hexachlorobiphenyl the rate was more than four orders of magnitude faster than the degradation reported using a sulfidogenic culture. Negligible chloride release occurred from any of the chloroaromatic compounds using biomass alone, or from palladised biomass challenged with hexane carrier solvent only. Analysis of the spent solution showed that in addition to catalysis of reductive dehalogenation the new material was able to remove very effectively the organic residua, with neither any PCB nor any breakdown products identifiable by GC/MS.

Temporal trends, temperature dependence, and relative reactivity of atmospheric polycyclic aromatic hydrocarbons.

Atmospheric polycyclic aromatic hydrocarbon (PAH) concentrations have declined appreciably between 1992 and 1997 at an urban background site in Birmingham, U.K. In contrast, no decline is evident in the city center between 1994 and 1997. Although most PAHs display statistically significant negative correlation with temperature, so does NOx, for which traffic (a nonseasonal activity) is the major source, and for which the negative correlation with temperature reflects seasonal boundary layer depth variations. When concentrations of PAHs divided by NOx were plotted against temperature, no significant relationship was detected for any PAH, except fluorene, phenanthrene, and fluoranthene. For these PAHs, the relationship was positive, suggesting volatilization from surfaces may be appreciable. For samples collected simultaneously at the city center and urban background sites, greater negative temperature-dependence was observed at the latter location. Although this may be partly due to the fact that the enhanced reactivity of PAHs at higher temperatures exerts a greater influence at sites more distant from emissions; the dichotomy in temperature-dependent behavior and temporal trends may also be due to city center concentrations being "buffered" by volatilization from surfaces to a greater extent than those at the urban background site.

Concentrations and sources of VOCs in urban domestic and public microenvironments.

Concentrations of 15 VOCs including 1,3-butadiene, benzene, and styrene were measured in a wide range of urban microenvironments, viz: homes, offices, restaurants, pubs, department stores, coach and train stations, cinemas, libraries, laboratories, perfume shops, heavily trafficked roadside locations, buses, trains, and automobiles. For most target VOCs-including 1,3-butadiene and benzene-mean concentrations at heavily trafficked roadside locations were exceeded by those in automobiles and were comparable to those in pubs and train stations. With regard to indoor-outdoor relationships in homes, this study revealed higher mean indoor concentrations, no correlation between simultaneously measured indoor and outdoor concentrations, and significantly different patterns of diurnal variation. Thus-in poorly ventilated buildings-indoor emission source strength is considered a more significant influence on VOC concentrations than infiltration of outdoor air. In the six smoking homes studied, environmental tobacco smoke (ETS) was found to make a substantial contribution to concentrations of 1,3-butadiene. This finding was based on the significantly higher concentrations detected in smoking compared to nonsmoking homes, the significant correlation between 1,3-butadiene concentrations and those of 3-ethenylpyridine (an ETS marker), factor analysis, and the results of a source apportionment exercise based on ratios of 1,3-butadiene to 3-ethenylpyridine.

The fate and persistence of polychlorinated biphenyls in soil.

The fate and persistence of PCBs 28, 52, 101, 138, and 180 artificially introduced into three soils was studied under a variety of field conditions for up to 415 d following initial contamination. A relationship was detected between ln Koa (octanol/air partition coefficient) and the experimentally observed first-order loss rate constant that was statistically significant at at least the 90% level in all but one instance. In nearly all experiments, PCB persistence was greater in soils of higher organic carbon content. Soil temperature and moisture content were also indicated as important influences on persistence. Significantly longer half-lives were observed in a soil in which initial PCB contamination had occurred ca. 1 year previously. A mass balance showed the most likely mechanism of loss to be volatilisation. Losses attributable to aerobic biodegradation could not be ruled out, but those due to leaching, uptake by biota, and soil erosion were demonstrated to be negligible. First-order rate constants (Kv) were determined for volatilisation of the same congeners from soil under a variety of controlled laboratory scenarios. Multiple linear regression analysis (MLRA) showed the most important influences on kv to be ln Koa (adjusted for soil temperature) and soil organic carbon content. Limited evidence was observed for a relationship between kv and soil moisture content, but not water flux. When tested against field measurements, the MLRA-derived relationship between kv and independent variables predicted to within a factor of 2.5, the persistence of PCBs 28, 52, and 101, However, it did not account for the influence of the age of contaminant association with the soil, soil moisture content or water flux, and failed to function for soils of high organic content, or where ln Koa exceeds ca. 23.

Field evaluation of a mathematical model of PCB transfer through the freshwater aquatic food chain.

A mathematical model of the transfer of PCBs through the freshwater aquatic food chain is described. The model predicts concentrations of 11 selected individual PCB congeners in forage fish and pike, from source terms of atmospheric deposition and watershed soil concentrations. Model performance has been evaluated using data from a field study conducted in a section of the River Severn near Birmingham, UK. Results demonstrate that with the exception of congener 52, overall model predictions of individual PCB concentrations in both forage fish and pike underestimate measured concentrations by factors of between approximately 3 and 25 for individual congeners. Closer examination suggests that whilst model equations contribute to these underestimations, a significant factor is the lack of knowledge of additional PCB inputs to the waterbody.

Evaluation of a terrestrial food chain model for estimating foodstuff concentrations of PCDD/Fs.

A terrestrial food chain model designed to predict foodstuff concentrations of PCDD/Fs from observed air and soil concentrations is described, and its efficacy evaluated by comparison of predicted and observed concentrations in specific foodstuffs and estimates of daily human exposure. The limitations of the model are discussed and future research requirements identified.

Bioaccumulation factors (BAFs) and biota to sediment accumulation factors (BSAFs) for PCBs in pike and eels.

"Freely-dissolved" aqueous concentrations of 9 trichlorothrough heptachlorobiphenyls are reported, alongside those in sediments and fish from the R. Severn. For most congeners, BSAFs and lipid-normalised BAFs for pike exceed those for eels. Whilst R. Severn BSAFs are comparable with those for L. Ontario trout and New Bedford Harbour flounder, R. Severn BAFs are 1-2 orders of magnitude lower. This discrepancy may be due to inter-species variability, as well as inter-laboratory differences between operational definitions of "freely-dissolved" aqueous PCB, underlining that the same operational definition must be employed if R. Severn BAFs are extrapolated elsewhere. For eels, correlation of Log K(ow) with Log BAF is better (R(2) = 0.66) than with BSAF (R(2) = 0.13), whilst similar correlation coefficients (R(2) = 0.81 and 0.82) were observed for pike. When Log K(ow) is plotted against BSAF and Log BAF for both species combined, better correlation is observed for Log BAF (R(2) = 0.65), than BSAF (R(2) = 0.36). For both species combined, the observed relationship between Log BAF and Log K(ow) for trichloro-through heptachlorobiphenyls is: Log BAF = 0.96 * Log K(ow) -0.24.

PCDD/Fs and non-o-PCBs in digested U.K. sewage sludges.

Twelve digested sewage sludges from rural and urban waste water treatment works in the north-west of England were analysed for PCDD/Fs and non-o-PCBs. The PCDD/F analysis of eight samples was repeated using high-resolution mass spectrometry, which enabled detection of the lower chlorinated congeners and calculation of TE values. sigma TEQ values for these eight samples ranged from 19-206 ng/kg with the higher values detected in the samples from urban/industrial areas. Examination of the congener/homologue profiles for the more contaminated samples suggests a major input from the use of pentachlorophenol. Archived sewage sludge samples collected and stored from one sewage treatment works in the south of England between 1942 and 1960 were analyzed to gain some insight into temporal trends and possible variations in source inputs. These provide some evidence of changing sources of PCDD/Fs over time and a decline in sigma TEQs since the 1950s.

Polychlorinated biphenyls (PCBs) in the British environment: sinks, sources and temporal trends.

This paper estimates the present UK environmental loading of polychlorinated biphenyls (PCBs). Of the estimated approximately 40,000 t SigmaPCB sold in the UK since 1954, only an estimated 1% (400 t) are now present in the UK environment. Comparisons of estimated production and current environmental loadings of congeners 28, 52, 101, 138, 153 and 180 suggest that PCB persistence broadly increases with increasing chlorination. Those PCBs that are not now present in the UK environment are considered to have been destroyed--by natural or anthropogenic mechanisms, to be still in use, to reside in landfills or to have undergone atmospheric and/or pelagic transport from the UK. The dramatic fall in PCB levels in archived UK soils and vegetation between the mid-1960s and the present is evidence that the latter mechanism is the most important and that a significant proportion of PCBs released into the UK environment in the 1960s have subsequently undergone environmental transport away from the UK. The bulk (93.1%) of the estimated contemporary UK environmental burden of SigmaPCBs is associated with soils, with the rest found in seawater (3.5%) and marine sediments (2.1%). Freshwater sediments, vegetation, humans and sewage sludge combined account for 1.4% of the present burden, whilst PCB loadings in air and freshwater are insignificant. Although consideration of individual congeners does not reveal any major deviations from the relative partitioning of Sigma PCBs, the importance of sinks other than soils is enhanced for individual congeners, particularly 138 and 180. In particular, around 2% of the total UK burden of congener 180 is present in humans, implying that biodata as a whole may constitute an important sink for the higher chlorinated congeners. The contemporary flux of SigmaPCBs to the UK surface is estimated at 19 t yr(-1), compared with an estimated annual flux to the atmosphere of 44-46 t. This implies that the major sources of PCBs to the UK atmosphere have been identified and that there is currently a net loss of these compounds from the UK. These sources are: volatilisation from soils (88.1%), leaks from large capacitors (8.5%), the production of refuse-derived fuel (RDF) (2.2%), leaks from transformers (0.6%), the recovery of contaminated scrap metal (0.5%) and volatilisation from sewage sludge-amended land (0.2%). Interestingly, whilst large excesses of estimated annual fluxes to the atmosphere over deposition fluxes for individual congeners exist for congeners 28, 52 and 101, estimates of fluxes in both directions across the soil-atmosphere interface agree closely for congeners 138, 153 and 180. This suggests that lower chlorinated congeners are more susceptible to both long-range environmental transport beyond the UK and to atmospheric degradation. Retrospective analysis of dated sediment cores, vegetation and soils indicates that environmental transport from North America and continental Europe introduced PCBs into the British environment well before the onset of their commercial production in the UK in 1954. Since that time, the input of PCBs to the UK environment has essentially reflected temporal trends in UK use. After peaking in the 1960s they declined rapidly through the 1970s following restrictions on PCB use. Recent evidence, however, is that the rate of decrease has diminished and that further significant reductions in fresh environmental input will take some time to occur. Such reductions will be especially slow for humans and other biota with long life-spans. This stems partly from cross-generational transfer from parents to offspring and also because the persistence of PCBs in biota means that present body burdens will reflect past as well as current exposure.