Gareth O. Thomas

Different Levels of Polybrominated Diphenyl Ethers (PBDEs) and Chlorinated Compounds in Breast Milk from Two U.K. Regions

Polybrominated diphenyl ether (PBDE) congeners are constituents of flame retardants, and there is growing concern regarding their persistence, bioaccumulation, and toxicity. We collected breast milk samples between late 2001 and early 2003 from 54 U.K.-resident mothers. Of these, 27 originated from southeast England (London), and the other 27 originated from northwest England (Lancaster). Analysis of milk-fat extracts by gas chromatography–mass spectrometry was performed to determine the levels of 15 PBDE congeners, 15 polychlorinated biphenyl (PCB) congeners, and other selected chlorinated compounds. PCB and organochlorine (OC) levels in southeast samples were consistently higher, and significant differences (p < 0.05) were observed. ∑PBDE levels ranged from 0.3 to 69 ng/g lipid (geometric mean, 6.6 ng/g), and PBDE-47 was the most abundant congener. ∑PCB levels ranged from 26 to 530 ng/g lipid (geometric mean, 150 ng/g) and were composed mainly of PCB-153 (26%), PCB-138 (20%), and PCB-180 (13%). OC levels for 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (p,p′-DDT) and its metabolites (∑DDX) ranged from 24 to 2,300 ng/g lipid (geometric mean, 160 ng/g); hexachlorobenzene ranged from nondetectable levels to 180 ng/g lipid (geometric mean, 17 ng/g); and ∑hexachlorocyclohexane levels ranged from 1.2 to 1,500 ng/g lipid (geometric mean, 16 ng/g). Using nuclear magnetic resonance–based metabonomics, samples (n = 7) containing the highest contaminant levels were compared with samples (n = 7) containing the lowest levels. Excellent separation along the first principal component implied that the chemical constituents of the two groups were significantly different. Although reasons for such differences remain obscure, lifestyle factors associated with a more heterogeneous London cohort could be responsible. Identifying primary routes of contaminant exposures and their biologic effects is of great importance.

Persistent organic pollutants in European background air: derivation of temporal and latitudinal trends

Data are presented for polynuclear aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated diphenyls ethers (PBDEs) and selected organochlorine compounds (OCs) in passive air samplers (PAS) along a rural/remote latitudinal transect from southern UK to northern Norway during 2002-2004. This study is part of an ongoing campaign, using semi-permeable membrane devices (SPMDs) as PAS over two year intervals since 1994. Data for PCBs, selected OCs and PBDEs are compared with that from previous campaigns. Absolute sequestered amounts of selected PCB congeners have decreased in a first order fashion between 1994-2004, with an average atmospheric clearance rate of 4.1 +/- 0.6 years and continue to fractionate with latitude. HCB has also declined between 1998-2004, with a clearance rate of 6 +/- 2.4 years. Data on DDT and its breakdown products indicate little fresh release in Europe. Comparison of PBDEs in 2000-02 and 2002-04 indicates site differences, generally with increases at UK sites and decreases in Norway. BDE-28, 47 and 49 decreased with increasing latitude (p < 0.04), while the other congeners did not show any significant latitudinal dependence. Transect data are presented for PAHs the first time. Three- and 4-ringed compounds dominated the mixture present in the SPMD. The PAH composition of the SPMDs at site 3 was compared to the average composition taken by active sampling at the same site. SPMD performance for sampling PAHs leaves many uncertainties, but they can be successfully used to semiquantitatively detect PAHs in the atmosphere. Fluorene and phenanthrene increased with latitude (p > 0.05), while 1-methylphenanthere, fluoranthene, benzo[b]fluoranthene and indeno[123-cd]pyrene decreased. Results are discussed in terms of sources, long-range atmospheric transport, global fractionation and clearance processes.

Occurrence of polychlorinated biphenyls and polybrominated diphenyl ethers in green mussels (Perna viridis) from Singapore, Southeast Asia

The green mussel, Perna viridis, was used in this study to measure levels of polychlorinated biphenyls (PCBs) and, for the first time, polybrominated diphenyl ethers (PBDE) in the marine environment. Samples were collected from eight different locations in the coastal waters of Singapore between April and May 2002. Forty-one PCB and 21 PBDE congeners were quantified by gas chromatography-mass spectrometry and were all positively detected in the mussel tissues. Total concentrations in green mussel tissues ranged from 6.1 to 82 ng/g and 2.0 to 38 ng/g on a dry-weight basis for PCBs and PBDEs, respectively. Such levels reflect the ubiquity of these persistent organic pollutants in a tropical marine environment. Principal component analysis was applied to the PCB data and revealed similarities in the congener composition of mussel tissues to that of the commercial PCB mixture, Aroclor 1254. The PBDE levels, to date, were approximately one order of magnitude greater than the upper concentrations reported for blue mussel (Mytilus edulis) tissues in Europe. At some sampling sites, the congener composition of PBDEs in P. viridis tissues indicated recent exposure to a commercial pentabrominated flame retardant.

Metabolism and body-burden of PCBs in lactating dairy cows.

This paper uses data from a detailed 4 month PCB mass balance study on lactating cows fed a naturally contaminated background diet to quantify the metabolism and body-burdens of a range of PCB congeners. Dietary intake fluxes and milk and faecal output fluxes reported previously are combined with subcutaneous fat and blood PCB concentrations and with data from tissue/organ samples from a slaughtered animal to estimate the degree of metabolism within the cow. A total body burden is derived, showing that fat deposits account for approximately 98% of total PCB present in the lactating cow. The daily intake through feed (ng day-1) accounted for between 0.9 and 1.5% of the total body burden for persistent congeners (e.g. PCB 153) and up to 43% for those congeners which are readily metabolised (e.g. PCB 52). Detailed balances for a range of tri- to octa-chlorinated PCBs are presented and clearly demonstrate that many congeners are metabolised effectively by lactating dairy cows (e.g. PCB 149) whilst others are efficiently transferred to human dairy food products. An approach to predicting the degree of metabolism for individual PCB congeners is presented which gives good agreement with observations.

Polychlorinated biphenyls, DDT, polybrominated diphenyl ethers, and organic pesticides in United Kingdom harbor seals (Phoca vitulina)—mixed exposures and thyroid homeostasis

Polychlorinated biphenyls, DDT and its metabolites, polybrominated diphenyl ethers, and selected organochlorine pesticide concentrations were measured in blubber samples from 60 free-living harbor seals in 2003 from five sites around the United Kingdom coast. Significant regional differences among contaminant levels were found, with seals on Islay and Jura (southwest Scotland) having the highest levels of polychlorinated biphenyls and seals in the Wash (eastern England) having the highest polybrominated diphenyl ether levels. Animals from the north and northeast of Scotland (Orkney and the Moray Firth) had the lowest levels of all the contaminant groups studied. Congener-specific profiles of polychlorinated biphenyls and polybrominated diphenyl ethers showed relatively higher levels of the lower chlorinated and brominated compounds at the more northerly sites, with the lowest total levels of both chemical groups. Significant positive relationships between blubber contaminants and total triiodothyronine (TT3) concentrations were found after controlling for the potential effects of confounding because of sex, mass, and season. Increased serum TT3 levels were significantly related to higher blubber contaminant concentrations in the following order: sum of all contaminants > polybrominated diphenyl ethers > polychlorinated biphenyls > DDT. Serum TT3 levels in the harbor seals with the highest exposures might be indicative of a T3 thyrotoxicosis, but without information on free T3 and circulating thyroid-stimulating hormone levels, it is difficult to determine the importance of this observation for the health of the individuals or populations. However, the mixture of contaminants to which United Kingdom harbor seals are exposed has changed over the last few decades, and the toxicological and epidemiological importance of adding the brominated compounds to the classical organochlorine and heavy metal mixture is not known.

Further studies of the air–pasture transfer of polychlorinated biphenyls

Abstract Field survey and field experimental data are presented and interpreted in the context of the factors controlling the supply of polychlorinated biphenyls (PCBs) to the pasture sward. The field experimental data show that an air (gas phase)–pasture equilibrium was approached rapidly, within a few days, with a similar equilibrium attained between different grass species studied ( Lolium perenne , Holcus lanatus , Festuca ovina ). A mass balance model for a typical UK air–pasture–soil system is presented and used to estimate the distribution and rates of air–surface exchange and sequestration of PCBs into freshly growing plant biomass. A soil–air–vegetation model developed by Trapp and Matthies (1997 , Environmental Science and Technology 31, 71–74) and other information is used to consider the possible influence of soil outgassing and sequestration versus the supply of PCBs from the bulk air to the pasture. It is hypothesised that a rapid approach to air–pasture equilibrium conditions could occur because PCBs are supplied from both the bulk air and by volatilisation from the underlying pastureland soil.

A reexamination of the negative assortative mating phenomenon and its underlying mechanism inDrosophila melanogaster

Averhoff and Richardson [(1974)Behav. Genet.4:207–225] reported a trend toward negative assortative mating inDrosophila melanogaster during the course of inbreeding. These authors proposed that the underlying mechanism was based on pheromone polymorphism and male selection. Mass mating experiments were carried out to verify their hypothesis, detailed behavior observations were made to identify the underlying mechanism, and sex pheromone composition and variation were examined by using gas chromatography-mass spectrometry analysis. The results showed that negative assortative mating is not a general phenomenon. Although male pheromones are probably polymorphic, female pheromones are not. We found no evidence for male selection as predicted by Averhoff and Richardson. It is argued that the most parsimonious mechanism underlying negative assortative mating is similar to one proposed by Bryant [(1979)Behav. Genet.9:249–256], which was based on interstrain differences in female reluctancy and male vigor.

An input-output balance study for PCBs in humans.

Polychlorinated biphenyl (PCB) input-output balance studies were performed on five male volunteers, aged between 24 and 30, for periods of 8-14 days in 1998. Dietary exposure was quantified by the duplicate meals method and varied between 220 and 460 ng of sigmaPCB (sum of 20 congeners) per day for each of the five individuals over the study period. Dietary intake was dominated by congeners 118, 138, 153 and 180. Average faecal outputs for the five volunteers were 50-290 ng of sigmaPCB (sum of 20 congeners) per day for each of the five individuals over the same period and was dominated by the same four congeners. Whilst the total PCB fluxes were therefore into the body (i.e., accumulation), important differences were noted for different individual congeners. PCBs 44, 47, 49, 52, 60, 66, 101, 105, 110, 118, 149, 151 and 183 all showed net absorption for all five volunteers. Some congeners showed a net absorption in some of the individuals but net excretion in others, as seen by other workers. These congeners (PCBs 138, 153, 180, 187 and 194) are all higher chlorinated congeners and lack meta-para-vicinal hydrogen atoms. There were differences in the net absorption/excretion between individuals, which appeared to be a function of body fat index (BFI). The volunteers with the lowest BFIs showed net excretion for the greatest number of congeners, whilst the individual with the highest BFI was a net absorber of all the congeners studied. The problems in determining and interpreting absorption efficiency values for use in quantitative exposure assessments are discussed. Various factors that influence net absorption of PCBs and other persistent organic pollutants are identified. These include compound properties (including susceptibility to metabolism), the individuals fat status and balance, exposure history and diet.

Methods for the analysis of PCBs in human food, faeces and serum.

A method was developed to determine trace concentrations of a range of individual PCB congeners in biological samples (serum, food and faeces) using GC-MS, to prepare a mass balance of PCBs in humans. A simple method for the analysis of PCBs in human serum, which excluded an extraction step, was first employed. Results indicated that the recoveries of 13C12 PCB spikes were variable. A soxhlet extraction step was added and was found to be efficient and reproducible. A quality control routine and method validation results are presented. In batch tests of the methods presented it was found that the serum analysis method gave within batch mean 13C12 spike recoveries of 98-120% and standard deviations between 6 and 20%. The food/faeces analysis method gave within-batch mean 13C12 spike recoveries of 88-100%, and within batch standard deviations between 4 and 12%. The batch to batch mean recovery for serum analysis was 100%, with an RSD of 9% for high spikes and 10% for low spikes. For food/faeces analysis the batch to batch average recovery was 110%, with an RSD of 5% for high spikes and 9% for low spikes.

Dual actions of lindane (γ-hexachlorocyclohexane) on calcium homeostasis and exocytosis in rat PC12 cells.

The persistent organochlorine pesticide lindane is still abundantly found in the environment and in human and animal tissue samples. Lindane induces a wide range of adverse health effects, which are at least partially mediated via the known inhibition of GABA(A) and glycine receptors. Additionally, lindane has been reported to increase the basal intracellular Ca(2+) concentration ([Ca(2+)](i)). As Ca(2+) triggers many cellular processes, including cell death and vesicular neurotransmitter release (exocytosis), we investigated whether lindane affects exocytosis, Ca(2+) homeostasis, production of reactive oxygen species (ROS) and cytotoxicity in neuroendocrine PC12 cells. Amperometric recordings and [Ca(2+)](i) imaging experiments with fura-2 demonstrated that lindane (≥ 10 μM) rapidly increases basal exocytosis and basal [Ca(2+)](i). Additional imaging and electrophysiological recordings revealed that this increase was largely due to a lindane-induced membrane depolarization and subsequent opening of N- and P/Q-type voltage-gated Ca(2+) channels (VGCC). On the other hand, lindane (≥ 3 μM) induced a concentration-dependent but non-specific inhibition of VGCCs, thereby limiting the lindane-induced increase in basal [Ca(2+)](i) and exocytosis. Importantly, the non-specific inhibition of VGCCs also reduced stimulation-evoked exocytosis and Ca(2+) influx. Though lindane exposure concentration-dependently increased ROS production, cell viability was not affected indicating that the used concentrations were not acute cytotoxic. These combined findings indicate that lindane has two, partly counteracting effects. Lindane causes membrane depolarization, thereby increasing basal [Ca(2+)](i) and exocytosis. In parallel, lindane inhibits VGCCs, thereby limiting the basal effects and reducing stimulation-evoked [Ca(2+)](i) and exocytosis. This study further underlines the need to consider presynaptic, non-receptor-mediated effects in human risk assessment.