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.

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.

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.

The influence of sewage sludge applications to agricultural land on human exposure to polychlorinated dibenzo-p-dioxins (PCDDs) and -furans (PCDFs).

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) are organic chemicals of suspected extreme toxicity. PCDD/Fs are ubiquitous in the environment and relatively enriched in sewage sludges. The deliberate application of sewage sludge to agricultural land can therefore potentially increase exposure of the human population to these compounds via transfers through the foodchain. This paper presents a protocol for assessing the background human exposure to all seventeen 2,3,7,8-substituted PCDD/Fs for which toxic equivalent factors (TEFs) are available. Background daily human exposure in the UK to 2,3,7,8-T(4)CDD and I-TEQ are calculated to be 0.0239 ng and 0.203 ng, respectively. The potential increases in crop plant and livestock tissue PCDD/F concentrations, and hence in human exposure, following applications of sewage sludge to agricultural land are quantified for different sludge application scenarios. The key role of PCDD/F transfer into livestock via ingestion of sludge adhered to vegetation in determining increases in human exposure is demonstrated.

The relative contribution of individual polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo-p-furans (PCDFs) to toxic equivalent values derived for bulked human adipose tissue samples from Wales, United Kingdom.

Five bulked human adipose tissue samples were analyzed for individual polychlorinated biphenyl (PCB) congeners (including selected non-ortho-substituted compounds) and polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs). Mean sigma PCB and sigma PCDD/F (tetra-through octachlorinated homologues) concentrations were 0.75 microgram/g and 1.22 ng/g adipose tissue respectively. Both the congener patterns and levels detected were similar to those reported by laboratories in other industrialised countries. Each sample comprised of tissue taken from donors within a given locality. However, no obvious relationships were apparent between sampling area, absolute concentrations and congener pattern of PCBs and PCDD/Fs. The contribution of individual PCDD/F and non-ortho-(o), mono-o-, and di-o-substituted PCB congeners to the total calculated toxic equivalent values (sigma TEQ) was assessed for each sample. The main contributions to the sigma TEQ were the mono-o-substituted PCB congeners #118 (TEQ = 42.5 pg/g of lipid), #156 (TEQ = 24.8 pg/g) and #105 (TEQ = 20.7 pg/g), followed by 1,2,3,6,7,8-HxCDD (TEQ = 18.2 pg/g), 2,3,4,7,8-P5CDF (TEQ = 12 pg/g), 1,2,3,7,8-P5CDD (TEQ = 11.5 pg/g), and the non-o-substituted PCB congener #126 (TEQ = 11.3 pg/g). Collectively, these compounds accounted for 80% of the sigma TEQ values. Based on the TEFs proposed by Safe (1990), the overall TEQs calculated for the monitored PCBs, were twice those due to sigma PCDD/Fs.

A source inventory and budget for chlorinated dioxins and furans in the United Kingdom environment.

Polychlorinated dibenzo-p-dioxins (PCDDs) and -furans (PCDFs) are ubiquitous in the environment. This paper estimates the present UK environmental loading of PCDD/Fs in soils, vegetation, air, water and sediments. Greater than 95% of the estimated total PCDD/F loading of 5.7 t in the UK environment is present in surface soils. Annual emissions from known primary sources of PCDDs and PCDFs are estimated. The most important of these include: municipal waste incinerator stack emissions (10.9 kg sigma PCDD/F per annum); industrial (7.7 kg/year) and domestic (5.1 kg/year) combustion of coal; clinical waste incinerators (1.7 kg/year); volatilisation from chlorophenol-treated substrates (1.7 kg/year) and combustion of leaded petrol by motor vehicles (0.7 kg/year). These sources are generally easy to define and reasonably reliable national estimates can be obtained. More difficult to quantify are secondary releases from the large UK stock of pentachlorophenol (PCP) and PCP-treated products, which may represent quantitatively one of the most important sources of total PCDD/Fs to the environment. Estimates of homologue-specific emissions indicate that combustion processes represent a far more significant source of tetra and penta CDD/Fs than do chlorophenols, which in turn constitute a greater source of hepta- and octachlorinated congeners. Direct emission of PCDD/Fs into the atmosphere from combustion processes facilitates their atmospheric transport to remote locations. This, coupled with the diffuse nature of combustion processes, means that the effects of PCDD/F contamination originating from anthropogenic combustion are more widespread than those from the use and disposal of chlorophenols. Contamination from chlorophenols will be more localised, owing to the insignificance of direct atmospheric release pathways for this source. Although there is reasonable agreement between the estimated current annual flux and the present UK environmental loading of PCDDs and PCDFs, a large discrepancy exists between the sum of the annual contributions from primary sources and this annual flux. Whilst the existence of an as yet unidentified source or sources or gross underestimates of known sources cannot be excluded, it is proposed that much of this discrepancy may be accounted for by secondary releases from the use and disposal of chlorophenols and the long-range transport, continued remobilisation and subsequent redeposition of PCDDs and PCDFs already present in the environment. Despite limited evidence for a modest decline in levels of PCDDs and PCDFs in some environmental compartments over the last 20 years, the environmental persistence of these chemicals means that they will remain in the UK environment for the foreseeable future despite recent action to curb primary emissions.