The global distribution of PCBs and organochlorine pesticides in butter.

In this study we explored the use of butter as a sampling matrix to reflect the regional and global scale distribution of PCBs and selected organochlorine pesticides/metabolites in air. This was because persistent organic pollutants (POPs) concentrate in dairy fats, where concentrations are controlled by feed intake (primarily from pasture/silage), which is in turn primarily controlled by atmospheric deposition. Butter sigmaPCB concentrations varied by a factor of approximately 60 in 63 samples from 23 countries. They were highest in European and North American butter and lowest in southern hemisphere (Australian, New Zealand) samples, consistent with known patterns of historical global usage and estimated emissions. Concentrations in butter reflected differences in the propensity of PCB congeners to undergo long range atmospheric transport from global source regions to remote areas and the relatively even distribution of HCB in the global atmosphere. Concentrations of p,p'-DDT, p,p'-DDE, and HCH isomers all varied over many orders of magnitude in the butter samples, with highest levels in areas of current use (e.g. India and south/central America for DDT; India, China, and Spain for HCH). We conclude that butter is sensitive to local, regional, and global scale spatial and temporal atmospheric trends of many POPs and may therefore provide a useful sampling medium for monitoring purposes. However, to improve the quantitative information derived on air concentrations requires an awareness of climatic and livestock management factors which influence air-milk fat transfer processes.

A congener-specific PCDD/F emissions inventory for the UK: do current estimates account for the measured atmospheric burden?

Considerable effort has been expended in the UK and elsewhere to quantify and rank PCDD/F primary sources and emissions to the environment, principally the atmosphere, so that cost-effective source reduction measures can be taken. Here, we predict a congener-specific emissions inventory for primary and secondary nondioxin-regulated sources to the UK atmosphere, estimated to have ranged from 3 to 22 kg in 1996. The inventory profile is dominated by OCDD (approximately 30-40%), 1,2,3,4,6,7,8-HpCDD (approximately 15-19%) and 1,2,3,4,6,7,8-HpCDF (approximately 14-19%). Congeners 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDD dominate the sigmaTEQ composition. Mass balance modelling suggests that the predicted congener pattern in UK air (based on the emission inventory) is similar to observed measurements, with absolute concentrations being estimated within a factor of 2 for most congeners. Calculations taking into account atmospheric weathering processes and long range (advective) transport suggest that PCDD/F sources to ambient air are primarily ongoing and that atmospheric mixing will mask individual emission source profiles/identities. This supports measured evidence for the consistency of PCDD/F air profiles observed around the UK throughout the year.

A generic model of human lifetime exposure to persistent organic contaminants: development and application to PCB-101.

We have developed a model which successfully reconstructs the lifetime polychlorinated biphenyl (PCB)-101 burden of the UK population for individuals born between 1920 and 1980. It not only follows burdens and clearance of persistent organic contaminants throughout a human lifetime--taking changes in age and body composition into account--but also, importantly, incorporates changing environmental concentrations of the compound of interest. Predicted results agree well with available measured lipid concentrations in human tissues. Its unique construction takes into account both changing environmental concentrations of PCBs in principal food groups and changing dietary habits during the time period. Because environmental burdens of persistent organic contaminants have changed over the last 60 years, residues in food will also have mirrored this change. Critically in this respect, the year in which an individual was born determines the shape and magnitude of their exposure profile for a given compound. Observed trends with age represent an historical legacy of exposure and are not simply a function of equal yearly cumulative inputs. We can demonstrate that the release profile of PCB-101 controls levels in the food supply and ultimately the burden of individuals throughout their life. This effect is expected to be similar for other PCB congeners and persistent organic compounds such as polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs). Models of this type have important applications as predictive tools to estimate the likely impact of source-reduction strategies on human tissue concentrations.

Human exposure to PCDD/Fs in the UK: the development of a modelling approach to give historical and future perspectives.

In order to assess the long-term impact of persistent organic contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) it is important to be able to quantify historical exposure. An understanding of past exposure is not only important to place our current body burdens in perspective, but is useful in assessing our potential future exposure. Unfortunately, very few direct measurements of our main source of exposure (i.e., food) over the past decades are available. This study attempts to reconstruct the historical exposure of the UK population to PCDD/Fs using a combination of emission estimates, information on environmental temporal trends derived from sediment cores and archived materials, and environmental/human fate modelling. Predicted adipose and blood lipid concentrations for a typical cross section of the population are derived over time (1920-2000), which is compared with measured data. The approach has been tested with two PCDDs and two PCDFs and showed encouraging agreement with measured data. Certain parts of the modelling methodology have been highlighted where there is still poor understanding of the processes governing fate and behaviour. These areas are discussed and recommendations for future improvements are made. The paper thus represents an initial modelling approach which defines both the historical (1920-present) and future (present-2020) fate of PCDD/Fs in the UK population.

Assessment of organic contaminant fate in waste water treatment plants. I: Selected compounds and physicochemical properties.

An extensive and comprehensive literature review has been conducted for compounds which we hypothesise could be present in sludge and maintain their integrity following application to agricultural land. The following compounds have been selected for review; chlorinated paraffins, quintozene, brominated diphenyl ethers, polychlorinated naphthalenes, polydimethylsiloxanes, chloronitrobenzenes, and a range of biologically active and pharmaceutical compounds. All have received interest as a result of their persistence and/or toxicity in environmental media. Physicochemical property information has also been compiled and/or calculated. In this way, an accompanying paper will attempt to predict compound fate in waste water treatment plants (WWTPs) and assess likely transfers from soil/plants to grazing livestock. These papers describe a first attempt to predict the fate of these classes of compounds in the environment and prioritise those of greatest concern.

Dioxin-like PCBs in the environment-human exposure and the significance of sources.

Dioxin-like PCBs represent an important component of the Sigma-TEQ in many environmental media. Specifically, in animal produce and in fish PCBs dominate the Sigma-TEQ ingested by humans. This in turn leads to high background body burdens in humans with PCB-TEQ greater than that associated with PCDD/Fs. High fish consumers are apparently subject to elevated TEQ exposure from dioxin-like PCBs. This has important implications for exposure assessment studies which have previously only been concerned with PCDDs and PCDFs. Unlike PCDD/Fs, dioxin-like PCBs are not controlled within the food chain. Sources and pathways of exposure are poorly defined. Aroclor formulations and their subsequent usage are considered to be the most important sources in terms of human exposure to some TEF-rated congeners, notably PCB-118, PCB-156 and part of PCB-126. Emissions from combustion sources contribute additional PCB-126. More research is needed to place these compounds in an integrated risk evaluation framework.

Congener specific transfer of PCDD/Fs from air to cows' milk: an evaluation of current modelling approaches.

Three different approaches have been used to model the transfer of individual PCDD/F congeners from the air to cows' milk. These are: (1) an 'Equilibrium Partitioning' approach, (2) a 'Deposition Velocity' approach and (3) a 'Scavenging' approach. Air-leaf transfers and livestock feed-milk transfers, the two most critical components of the food chain exposure model, are discussed. A representative database for measured PCDD/Fs in UK air, herbage and milk is presented and the performance of each predicted model concentration against this measured dataset is assessed. Weaknesses and uncertainties associated with modelling the complex transfer processes involved are highlighted.

Persistence and fate of polychlorinated biphenyls (PCBs) in sewage sludge-amended agricultural soils.

Four metal enriched sewage sludges containing different concentrations of polychlorinated biphenyls (PCBs) were applied to two field soils in the UK in 1968. Samples of the sludges, sludge-amended soils and soils from untreated control plots were stored and analysed retrospectively. Sludge concentrations ranged from 1 to 7 mg SigmaPCB kg(-1). The pattern of PCBs was similar in three of the four sludges, with congeners 14, 18, 28 and 52 present at the highest concentrations. The fourth sludge contained higher amounts of congeners 149, 153, 138 and 180. SigmaPCB concentrations in control plot soil have declined over the last 20 years, indicating a reduction in atmospheric deposition inputs of PCBs to the soil. SigmaPCB concentrations also declined on the sludge-amended plots, reaching control plot concentrations (30-60 microg SigmaPCB kg(-1)) in the late-1980s. Half-lives ranged from < 1 to 8.5 years for congeners 18, 28 and SigmaPCB. Biodegradation and/or the formation of reversibly sorbed soil PCB residues could not account for the losses observed. Volatilisation is implicated as the most important loss process on both the control and sludge-amended plots. Using the fugacity approach, congener concentrations in soils at Luddington were predicted still to have not reached equilibrium with the air. Further losses to the atmosphere are likely.