Martin Rose

A novel abbreviation standard for organobromine, organochlorine and organophosphorus flame retardants and some characteristics of the chemicals

Ever since the interest in organic environmental contaminants first emerged 50years ago, there has been a need to present discussion of such chemicals and their transformation products using simple abbreviations so as to avoid the repetitive use of long chemical names. As the number of chemicals of concern has increased, the number of abbreviations has also increased dramatically, sometimes resulting in the use of different abbreviations for the same chemical. In this article, we propose abbreviations for flame retardants (FRs) substituted with bromine or chlorine atoms or including a functional group containing phosphorus, i.e. BFRs, CFRs and PFRs, respectively. Due to the large number of halogenated and organophosphorus FRs, it has become increasingly important to develop a strategy for abbreviating the chemical names of FRs. In this paper, a two step procedure is proposed for deriving practical abbreviations (PRABs) for the chemicals discussed. In the first step, structural abbreviations (STABs) are developed using specific STAB criteria based on the FR structure. However, since several of the derived STABs are complicated and long, we propose instead the use of PRABs. These are, commonly, an extract of the most essential part of the STAB, while also considering abbreviations previously used in the literature. We indicate how these can be used to develop an abbreviation that can be generally accepted by scientists and other professionals involved in FR related work. Tables with PRABs and STABs for BFRs, CFRs and PFRs are presented, including CAS (Chemical Abstract Service) numbers, notes of abbreviations that have been used previously, CA (Chemical Abstract) name, common names and trade names, as well as some fundamental physico-chemical constants.

Brominated Organic Micropollutants—Igniting the Flame Retardant Issue

There is increasing concern over the toxicity and environmental distribution of a number of classes of brominated compounds such as polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) used as flame retardants as well as brominated and mixed bromochloro dibenzo-p-dioxins and dibenzofurans (PBDD/Fs and PBrClDD/Fs). Observed ubiquity and bio-accumulative characteristics coupled with dioxin-like toxicity have led to some of these compounds being classified as POPs. Unlike chlorinated dioxins the levels of brominated compounds in the environment shows an increasing trend. The main pathway to observed human exposure is probably through food. The European Commission has reviewed the use of some of these compounds and has recommended a ban on some commercial mixtures. There is corresponding legislation in individual countries against production and usage. This article reviews the ecological and environmental impact of the use of PBDEs, PBBs and other brominated flame retardants. Attention is given to the properties of individual PBDE and PBB congeners as well as the more toxic PBDD/Fs and PBrClDD/Fs. Occurrence, source, fate, toxicology, exposure, analysis and future work required is assessed for each class of brominated organic micropollutant (BOM) outlined.

Dietary exposure to metals and other elements in the 2006 UK Total Diet Study and some trends over the last 30 years.

Concentrations of 24 elements including metals in the 2006 UK Total Diet Study (TDS) were measured and dietary exposures estimated. Composite samples for the 20 TDS food groups (bread, fish, fruit, etc.) were collected from 24 UK towns and analysed for their levels of aluminium, antimony, arsenic, barium, bismuth, cadmium, chromium, copper, germanium, indium, lead, manganese, mercury, molybdenum, nickel, palladium, platinum, rhodium, ruthenium, selenium, strontium, thallium, tin, and zinc. Concentrations of each of the elements in the food groups were lower than or similar to those reported in the previous TDS survey, conducted in 2000, with the exception of aluminium, barium, and manganese. Dietary exposures to the 24 elements were estimated for UK consumers and compared with previous estimates made over the last 30 years in order to examine any trends in exposure to these elements in the typical UK diet. Population exposures to the elements have generally declined over time, and exposures to most of these elements remain at low levels. The independent UK Government scientific Committee on Toxicity of Chemicals in Food, Consumer Products and the Environment (COT) commented on the estimated dietary exposures, taking into account their previous evaluations (in 2003 and 2008), and identified no major concerns for the health of consumers, but did advise that there was a need for more information on aluminium and barium, and also commented that dietary exposure to inorganic arsenic and to lead should continue to be reduced.

Brominated and chlorinated dioxins, PCBs and brominated flame retardants in Scottish shellfish: Methodology, occurrence and human dietary exposure

The most commonly consumed shellfish species produced in Scotland - mussels, oysters and scallops - were investigated for the occurrence of a range of brominated and chlorinated contaminants in order to establish current levels and estimate human dietary exposure. Flesh from individual sub-samples was representatively pooled and 35 composites were analysed for brominated and chlorinated dioxins (PBDD/Fs, PCDD/Fs), brominated and chlorinated biphenyls (PBBs, PCBs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs) and tetrabromobisphenol A (TBBPA). The analytical methodology used (13)C(12) labelled surrogates of the target compounds, with GC coupled to (usually) high resolution MS, and LC-MS/MS for HBCD and TBBPA analysis. Positive identifications were made in the majority of samples for most analytes with the exception of TBBPA and most PBDD congeners measured. None of the levels detected for PCDD/F and PCB were above the maximum permitted levels specified in European Union regulations. The levels of brominated furans predominated over brominated dioxins, reflecting the environmental distribution and source emission profiles of these contaminants, and relatively high levels of the tri-brominated congeners were observed. Levels of the flame retardant chemicals reflected current and legacy use, with appreciable concentrations of PBDEs and HBCDs (predominantly alpha-HBCD) but far lower levels of PBBs. TBBPA was not detected in any of the species. In general, mussels and oysters displayed relatively higher levels of contamination than scallops, although the gonad tissue of the latter showed significant levels of brominated dioxins. The estimated adult dietary intakes of PCDD/Fs and PCBs arising from the consumption of a typical portion of these foods in combination with an otherwise average UK diet were in the range 0.5-0.6 pg World Health Organisation (WHO)-toxic equivalent (TEQ)(2005)/kg bodyweight per day. These estimated dietary intakes are well within the Tolerable Daily Intake for dioxins and dioxin-like PCBs of 2 pg WHO-TEQ(2005)/kg bodyweight/day endorsed by the independent expert Committee on Toxicology of Chemicals in Food, Consumer Products and the Environment. The corresponding intakes for sumPBDEs and sumHBCDs were 5.6-6.1 and 5.9-7.9 ng/kg bodyweight/day respectively.

Polybrominated Dibenzo-p-Dioxins, Dibenzofurans, and Biphenyls: Inclusion in the Toxicity Equivalency Factor Concept for Dioxin-Like Compounds

In 2011, a joint World Health Organization (WHO) and United Nations Environment Programme (UNEP) expert consultation took place, during which the possible inclusion of brominated analogues of the dioxin-like compounds in the WHO Toxicity Equivalency Factor (TEF) scheme was evaluated. The expert panel concluded that polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), and some dioxin-like biphenyls (dl-PBBs) may contribute significantly in daily human background exposure to the total dioxin toxic equivalencies (TEQs). These compounds are also commonly found in the aquatic environment. Available data for fish toxicity were evaluated for possible inclusion in the WHO-UNEP TEF scheme (van den Berg et al., 1998). Because of the limited database, it was decided not to derive specific WHO-UNEP TEFs for fish, but for ecotoxicological risk assessment, the use of specific relative effect potencies (REPs) from fish embryo assays is recommended. Based on the limited mammalian REP database for these brominated compounds, it was concluded that sufficient differentiation from the present TEF values of the chlorinated analogues (van den Berg et al., 2006) was not possible. However, the REPs for PBDDs, PBDFs, and non-ortho dl-PBBs in mammals closely follow those of the chlorinated analogues, at least within one order of magnitude. Therefore, the use of similar interim TEF values for brominated and chlorinated congeners for human risk assessment is recommended, pending more detailed information in the future.

Simultaneous determination of PCDDs, PCDFs, PCBs and PBDEs in food.

Established and comprehensively validated methodology for the analysis of PCDDs, PCDFs and polychlorinated biphenyls (PCBs) in food, animal feed and other matrices is presented. The method achieves the analytical standards of EU protocols (2002/69/EC and 2002/70/EC) that are used to determine the compliance of food and animal feed to maximum permissible levels of chlorinated dioxins in these commodities. The methodology provides WHO-TEQ data for dioxins and PCBs as well as individual concentrations for toxic PCDD/F congeners and >50 commonly occurring PCBs. In addition, the methodology allows the simultaneous determination of individual polybrominated diphenylether (PBDE) congeners. A wide range of (13)Carbon -labelled surrogates allow accurate internal standardisation, and measurements are carried out using high resolution GC coupled to high resolution mass spectrometry except for mono-, tetra, ortho-substituted PCBs where unit resolution mass spectrometry can be used instead. Evidence of internal as well as external validation through the frequent use of reference materials, and successful participation in international inter-comparison exercises over many years is presented. A large number of different food types have been analysed for dioxins and PCBs using this methodology over several years and typical congener profiles for various food matrices are discussed.

Bromine and iodine in 1997 UK total diet study samples

Concentrations of bromine and iodine were analysed in samples from the 1997 UK Total Diet Study (TDS) using ICP-MS. The data has been used to estimate dietary exposures of UK consumers to these elements from the typical UK diet. Samples for the 20 TDS food groups were obtained from 20 towns in the UK in 1997 and analysed in 1998/99 for total bromine and total iodine concentrations. These samples were also analysed for 12 other elements. The UK regulatory authority had considered iodine recently, but had not considered bromine before. This survey provides up-to-data baseline data for those two elements. Iodine concentrations are similar to those found in recent surveys. Levels of bromine were consistent with previous data where available. Dietary exposures to bromine and iodine were calculated to see if there were any risks to health from the levels of these elements found in the UK diet. The estimated population average exposure to iodine was 0.25 mg d-1, which is within the range of previous estimates (1995, 0.21 mg d-1; 1991, 0.17 mg d-1; 1985, 0.28 mg d-1). The estimated population average exposure to bromine was 3.6 mg d-1.

Contamination of fish in UK fresh water systems: Risk assessment for human consumption

There is growing evidence that more people in the UK are consuming fish taken from inland waterways. This may be partly due to the increased numbers of migrants from Eastern Europe where this is part of traditional culture and partly because of a desire to try new foods encouraged by celebrity chefs. Fish can bioaccumulate environmental contaminants and so could contribute a significant amount to dietary exposure to these chemicals. This study examined the changing habits of anglers and consumers and characterised a range of existing and emerging contaminants in freshwater fish species with a view to determining current levels of occurrence and possible risk from consumption. The project was conducted in two stages. The first stage included (a) a study that identified freshwater systems that are contaminated either by anthropogenic activity or as a result of the geology of the area; and (b) socioeconomic research to assess the consumption habits of the public, particularly anglers, with respect to fish and shellfish from unmanaged inland waterways. Based on the outcome from the first stage, specific rivers and other inland waterways were chosen for investigation, along with the range of contaminants to be included in the analytical programme. Predicted contamination levels and prevalence of anglers were among the factors taken into consideration. The second stage of the project involved sampling and analysis of fish taken from selected locations on the chosen waterways. A range of fish species from a variety of inland water habitats were obtained. These were analysed for the following contaminants: heavy metals, chlorinated dioxins (PCDD/Fs), polybrominated biphenyls (PBBs), polychlorinated biphenyls (PCBs), brominated dioxins (PBDD/Fs), polychlorinated naphthalenes (PCNs), polybrominated diphenylethers (PBDEs), OC pesticides, organotin compounds and organo-fluorine compounds. Legal limits for contaminants apply only to food traded commercially, but some samples were in excess of the regulatory limits for PCDD/Fs and PCBs in such fish. The maximum detected WHO-TEQ (1998) for PCDD/Fs plus PCBs was over 32ngkg(-1) on a whole weight basis for a sample of barbel from the River Don, and 6 other samples were also above the 8ngkg(-1) limit.

Investigation into the formation of PAHs in foods prepared in the home to determine the effects of frying, grilling, barbecuing, toasting and roasting

The effects of frying, grilling, barbecuing, toasting and roasting on the formation of 27 different PAHs in foods were investigated. A total of 256 samples from in-house cooking experiments were produced. There was little evidence of PAH formation during the grilling, frying, roasting and toasting experiments. Comparison with the raw materials used in the experiments showed little or no increase in PAH concentrations for all of the sample types, regardless of distances from the heat source, cooking mediums and intensity of cooking conditions. Barbecuing with charcoal plus wood chips however resulted in the formation of benzo[a]pyrene in most foods; for beef burgers only, barbecuing over charcoal (without the use of wood chips) gave the highest levels. In general PAH levels increased when the food was barbequed closer to the heat source. For sausages cooked over briquettes, and for beef burgers, beef and salmon cooked over charcoal, the concentration of PAHs was lower when the food was closer to the heat source. Cooking time may result in a moderate increase of PAHs in some foods, although concentrations in beef burgers appeared to fall when cooking time was extended by 50-100%.

Polybrominated diphenylethers (PBDEs) and brominated dioxins (PBDD/Fs) in Irish food of animal origin.

Brominated dioxins (PBDD/Fs) and 17 polybrominated diphenylether (PBDE) congeners including BDE-209 were analysed in 100 composite samples of commonly consumed foods of animal origin, prepared from ten to 40 individual subsamples of each type. These included 30 samples of milk from farms; eggs from chickens; fat from cows, pigs, sheep, and poultry; and liver from cows, pigs, sheep, horses, and poultry. The ISO 17025-accredited analytical methodology used, follows similar guidelines as given for chlorinated dioxins and polychlorinated biphenyls (PCBs) in European Commission Directive 2002/69/EC. Apart from some samples of milk, PBDD/Fs and PBDEs were detected in all food types. Concentrations ranged from 0.31 µg kg−1 Σ17 PBDEs for a sample of milk to 37.5 µg kg−1 Σ17 PBDEs for a sample of liver. The corresponding range for the PBDD/F toxicity (computed using analogous PCDD/F toxic equivalency factors (TEFs)) was 0.09 ng TEQ kg−1 to approximately 3.5 ng TEQ kg−1. The detection of these compounds, in particular PBDD/Fs, is consistent with the increased use and disposal of brominated organic compounds.