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Non-polar halogenated natural products bioaccumulated in marine samples. II. Brominated and mixed halogenated compounds.

Several identified and potential natural brominated bioaccumulative compounds were studied in this work. 4,6-dibromo-2-(2('),4(')-dibromo)phenoxyanisole (BC-2) previously detected in Australian marine mammals and isolated from sponges, was synthesized. Two byproducts (a tetrabromo isomer and a tribromo congener) were investigated as well. The byproducts of the synthesis were not identified in the environmental samples investigated. Previously described natural brominated compounds (BC-1, BC-2, BC-3, BC-10, BC-11, MHC-1) and anthropogenic brominated diphenyl ethers (BDE-47, BDE-99, BDE-100, BDE-154) were detected in a sample of human milk. The sample was from a woman from the Faeroe Islands who frequently consumed fish as well as whale blubber and meat. The most abundant compound originated from the natural tetrabromo phenoxyanisole BC-3 which may have a 3:1 distribution of bromine on the two phenyl units. This sample also accumulated a dibromochloroanisole, as well as a previously unknown mixed halogenated compound (MHC-X) and an unknown, most likely aromatic brominated compound. Co-elutions on a DB-5 column were found for BDE-99 and BC-11 as well as BDE-154 and the unknown brominated compound. This suggests that quantification of these two compounds has to be carried out carefully.Two samples of lower trophic level, namely Baltic cod liver and Mexican mussel tissue, were investigated as well. The cod liver samples contained BDE congeners but also abundant signals for the natural 2,3,3('),4,4('),5,5(')-heptachloro-1(')-methyl-1,2(')-bipyrrole Q1 and tribromoanisole (TBA). The mussel sample contained Q1, TBA, another halogenated anisole, BC-1, BC-2, and BC-3, as well as additional, potential natural brominated compounds in the elution range of tribromophenoxyanisoles.

Animals↗

Effects of alum coagulation on speciation and distribution of trihalomethanes (THMs) and haloacetic acids (HAAs).

The impacts of alum coagulation on the distribution of disinfection by-products (DBPs), trihalomethanes (THMs), and haloacetic acids (HAAs) were evaluated under controlled chlorination conditions using four surface waters. Among the nine HAAs found in waters, dihaloacetic acids (X2AAs) have been found to be the dominant species in all of the raw and alum treated waters. Alum coagulation tends to remove more monohaloacetic acids (XAAs) and trihaloacetic acids (X3AAs) precursors than that of dihaloacetic acids (X2AAs). Alum coagulation treated water had a lower HAA9/TTHM ratio compared with that of the raw water. The increase of THM bromine incorporation factors (BIFalpha) value of alum treated water was statistically significant in comparison with the raw water. On average, BIFalpha increased by 54% after the alum coagulation process in these four different waters. This indicated that THM speciations shifted in favor of the more brominated compounds. However, alum coagulation treatment process had less effect on HAA bromi ne incorporation factors (BIFbeta)than it did on BIFalpha. Bromine incorporation factor (BIF) values decreased with time in the THM and HAA formation processes, especially within the first 10 h of the reaction time. This suggested that brominated THMs or HAAs formed faster than the chlorinated species in the initial period.

Acetates↗

Determination of polybrominated diphenyl ethers and polybrominated dibenzo-p-dioxins/dibenzofurans in marine products.

Polybrominated diphenyl ethers (PBDEs) have been widely used as flame retardants in plastics and textile coatings, and these compounds have been recognized as ubiquitous environmental contaminants. Furthermore, it is considered a serious problem that polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/DFs), having toxicities similar to those of chlorinated dioxins, are generated by the manufacture of brominated flame retardants (BFRs) such as PBDEs, and formed by the combustion of substances containing BFRs. Several congeners of PBDD/DFs and PBDEs have been detected in the adipose tissue of the Japanese. Although food is suspected as an exposure source, little information is available regarding the levels of these brominated compounds in food, as compared with information regarding dioxin or polychlorinated biphenyls. It is necessary to investigate the levels of these brominated organic compounds in various foods and to estimate their influence in the case of human exposure. We developed an efficient method of analyzing PBDEs and PBDD/DFs contents in food samples using accelerated solvent extraction and determined the concentrations in several marine products such as raw fish, processed foods, and seaweed purchased in Japan. A recovery test (n = 5) using the method and involving dried fish showed acceptable recoveries of 57.7-78.5% (RSD 5.4-15.9%) for PBDEs and 50.0-56.4% (RSD 1.5-7.9%) for PBDD/DFs. In the analysis of marine product samples, several congeners of PBDEs were detected in raw fish, processed fish, and seaweed; the highest concentration of sigmaPBDEs was detected in yellowtail (1161 pg/g whole basis), followed by mackerel (553.5 pg/g whole basis). The most dominant congener present in these marine samples was 2,2',4,4'-tetraBDE (#47).

Animals↗

Burns caused by bromine and some of its compounds.

Our experience with infrequent and unfamiliar types of injury caused by various compounds of bromine are described and discussed. While bromine containing compounds share some of the characteristics of other common causes of chemical burns, they also have a specific, exclusive mode of affecting the skin. The delay in the appearance of clinical signs and symptoms is an important factor to be considered by those who treat injuries caused by bromine or some of its compounds, or by those who may be the first to see persons who are injured by these agents. As most of the injuries occur at work (92 per cent) it is in these industrial premises that considerable stress should be made of the importance of wearing protective clothing in order to reduce local damage and prevent systemic effects. Prompt first aid, by thorough washing with large volumes of water reduces the extent and depth of the injury.

Accidents, Occupational↗

Formation of PBDD/F from flame-retarded plastic materials under thermal stress.

Thermal treatment of plastics flame retarded with brominated compounds often lead to the formation of PBDD/F, especially if polybrominated diphenyl ethers are used. By the presence of antimony(III) oxide, water and some other metals, the amounts of PBDD/F increase. Even during the production and recycling processes of plastics, PBDD/F can be found in considerable amounts. By the use of flame retardants, which are not direct precursors of PBDD/F, the amounts can significantly be decreased. An incomplete and uncontrolled incineration, occurring in fire accidents in private residences, can form high amounts of PBDD/F, which can endanger the environment and persons in contact with fire residues. Complete and controlled incineration of bromine-containing compounds as usually conducted in municipal waste incinerators, however, show no raised risk. An overview about the formation of PBDD/F primarily during combustion and also during production and recycling processes of flame-retarded plastic materials is given in this paper.

Benzofurans↗

Detection of bromine monoxide in a volcanic plume.

The emission of volcanic gases usually precedes eruptive activity, providing both a warning signal and an indication of the nature of the lava soon to be erupted. Additionally, volcanic emissions are a significant source of gases and particles to the atmosphere, influencing tropospheric and stratospheric trace-gas budgets. Despite some halogen species having been measured in volcanic plumes (mainly HCl and HF), little is known about bromine compounds and, in particular, gas-phase reactive bromine species. Such species are especially important in the stratosphere, as reactive bromine-despite being two orders of magnitude less abundant than chlorine-accounts for about one-third of halogen-catalysed ozone depletion. In the troposphere, bromine-catalysed complete ozone destruction has been observed to occur regularly during spring in the polar boundary layers as well as in the troposphere above the Dead Sea basin. Here we report observations of BrO and SO2 abundances in the plume of the Soufrière Hills volcano (Montserrat) in May 2002 by ground-based multi-axis differential optical absorption spectroscopy. Our estimate of BrO emission leads us to conclude that local ozone depletion and small ozone 'holes' may occur in the vicinity of active volcanoes, and that the amount of bromine emitted from volcanoes might be sufficiently large to play a role not only in the stratosphere, but also in tropospheric chemistry.

Journal Article↗

Analyses of known and new types of polyhalogenated aromatic substances in oven ash from recycled aluminium production.

Persistent aromatic bromine, chlorine and mixed chlorine-bromine compounds were analysed from recycled aluminium smelter (ALS) ashes to explore the impact of brominated flame retardants (BFR) on their formation. Polybrominated diphenyl ethers (PBDE) were the most abundant original BFRs found. Induction furnace ash contained tetra- to octa-BDEs about 2000ng g(-1) in similar congener ratios as the original scrap, but contents of nona- and deca-BDEs were only 25 and 5ng g(-1) indicating their significant degradation in ALS process. In the most non-polar fraction, PCB levels and profiles were similar as earlier ALS ash samples in 1990s. The highest PCB level measured was that of deca-CB (450ng g(-1)) in the induction furnace ash. In this fraction, bromo compounds were non-detectable (<5ng g(-1)). Fraction of the most polar compounds (from reversed toluene elution of carbon column ("dioxin fraction") contained PCDDs, PCDFs and polychlorinated dibenzothiophenes (PCDTs) in similar amounts and congener profiles as earlier investigated ALS ash samples. Bromine-containing dioxin and furan congeners were not detected. From individual PCDDs and PCDFs, octaCDF was the most abundant (205ng g(-1)) in induction furnace ash. In this fraction, the original BFR, tetrabromo-bisphenol-A, was identified. Its level in the induction furnace ash was approximated to be 388ng g(-1). In addition, 12 novel brominated and chlorinated compounds were found as abundant (8-441ng g(-1) in the induction furnace ash) contaminants from the fraction. Four of them were bisphenol derivatives, five biphenylols, then octachlorofluorenone (OCFL) and octachlorobiphenylene (OCBP). Their structures or structure types were deduced from total low-resolution EI mass spectra by theoretical isotope cluster simulation (ICLU) and through known fragmentation rules.

Air Pollutants, Occupational↗

Helium microwave-induced plasma mass spectrometric detection for reversed-phase high-performance liquid chromatography.

Reversed-phase high-performance liquid chromatography (HPLC) is directly coupled to helium microwave-induced plasma mass spectrometry (He MIP-MS) for the element-selective detection of halogenated organic compounds. Absolute detection limits are approximately 50 pg Br for brominated compounds, 1 pg I for iodinated compounds, and 10 ng Cl for chlorinated compounds. The linear dynamic range for Br- and I-containing compounds is 3-4 orders of magnitude. However, the linear range for chlorinated species is severely limited by high background at m/z = 35. The relative standard deviation for repetitive injections is less than 10%. The helium microwave-induced plasma is operated at moderate powers (300-350 W) and with a total helium consumption of 6-8 L/min. The effect of organic solvents on the background mass spectrum is investigated.

Bromides↗

Comparative evaluation of the fate of disinfection byproducts at eight aquifer storage and recovery sites.

Despite the growth in aquifer storage and recovery (ASR) as a technique for the provision of potable water supplies, quantitative data on the fate of disinfection byproducts that may be present in the injected water remain rare. This study evaluates the data from eight ASR sites in Australia and the United States that cover a wide range of source water compositions, hydrogeological environments, and operating conditions. Rates of attenuation and formation of trihalomethanes (THMs) in groundwater were determined using analytical techniques that took dilution effects into account. Half-lives varied by more than 2 orders of magnitude (e.g., <1 to >120 days for total THMs) and were both compound- and site- specific. Chloroform was most persistent, and more highly brominated compounds tended to be less persistent, as has generally been found. For any particular THM compound, much of the variability could be explained by contrasts in geochemical conditions within the aquifer since microbial degradation is the primary mechanism for THM attenuation. As such, bounds on the half-life were defined according to the redox state of the groundwater. In situ formation of some THMs in the aquifer after injection was directly observed at a number of sites, and was predicted to have taken place at all sites. The variance in formation estimates was large between the different methods used. Formation may be more common than previously thought because of the low frequency of groundwater sampling after injection and concomitant attenuation and mixing.

Australia↗

Synthesis and biodistribution of [5-131I]iodotropapride: a potential D2 dopamine receptor imaging agent.

[5-131I]Iodotropapride is a benzamidic compound which displays high affinity and selectivity for dopaminergic receptors. It was prepared from the corresponding brominated compound by a nucleophilic substitution with [131I]iodine (t1/2 = 8.02 days, E gamma = 364 keV) based on the use of Cu(I) as catalyst and high specific activity of [131I]NaI. After i.v. injection in rats the tracer crosses the blood-brain barrier (0.42 +/- 0.06% of injected dose in the total brain) and demonstrates a high affinity binding to the striatum. The striatum-to-cerebellum ratio increases with time and reaches values of 9 and 22 at 30 and 120 min after injection, respectively. This specific uptake in the striatum is saturable and can be blocked by pretreatment with different D2 antagonists. When labeled with 123I (t1/2 = 13 h, E1 = 159 keV), the corresponding [123I]iodotropapride may be useful for the investigation of the D2 dopamine receptors in humans with single photon emission computer tomography (SPECT).

Animals↗

Global biomonitoring of perfluorinated organics.

The environmental distribution of fluorinated organic compounds (FOCs) has been less well described than the other halogenated hydrocarbons such as chlorinated and brominated compounds. This is despite the fact that FOCs have been used in a wide variety of products and applications for more than 50 years. FOCs are resistant to hydrolysis, photolysis, microbial degradation, or metabolism by vertebrates due to the high energy of carbon-fluorine bond. In particular, perfluorinated (fully fluorinated) compounds (PFCs) have the potential to persist in the environment. But, until recently, the extent and magnitude of environmental distribution of PFCs was unknown. Recent development of an analytical technique for PFCs using high performance liquid chromatography-negative ion electrospray tandem mass spectrometry (HPLC-ESMSMS) permitted the survey of PFCs in livers and blood plasma of wildlife on a global scale.

Animals↗

An overview of commercially used brominated flame retardants, their applications, their use patterns in different countries/regions and possible modes of release.

Brominated flame retardants (BFRs) are used in a variety of consumer products and several of those are produced in large quantities. These compounds have been detected in environmental samples, which can be attributed to the anthropogenic uses of these compounds. Brominated flame retardants are produced via direct bromination of organic molecules or via addition of bromine to alkenes; hence, an overview of the production and usage of bromine over the past three decades is covered. Production, application, and environmental occurrence of high production brominated flame retardants including Tetrabromobisphenol A, polybrominated biphenyls, Penta-, Octa-, Deca-brominated diphenyl ether (oxide) formulation and hexabromocyclododecane are discussed.

Bromine↗

Monobromoisophakellin, a new bromopyrrole alkaloid from the Caribbean sponge Agelas sp.

A detailed analysis of the chemical constituents of a Caribbean specimen of Agelas sp. was carried out. Four brominated compounds (1-4) were isolated and one of them was identified as a new bromopyrrole metabolite, monobromoisophakellin (1). The structure of 1 was determined using spectroscopic methods. All compounds were tested for their antifeedant activity against the Caribbean reef fish Thalassoma bifasciatum in an aquarium assay.

Alkaloids↗

Lipophilic organic contaminants in the Rhine river, Germany.

Detailed gas chromatographic-mass spectrometric analyses applied to eight Rhine river water samples constituted a comprehensive characterization of the low molecular weight organic contamination. Within the group of predominant anthropogenic contaminants, only a few compounds were characterized as frequently detected or priority pollutants. Numerous compounds exhibiting physiological or ecotoxicological properties are only rarely reported or still unnoticed riverine contaminants. Information on environmental behaviour or ecotoxicological effects is still limited for most of these substances. In particular, several brominated compounds (mono- and dibrominated (methoxyphenyl)propionic acids and hydroxymethylacetophenones) were identified for the first time as environmental contaminants. Quantitative analyses differentiated five groups of pollutants with respect to their concentration profiles. The spatial distribution and the intensity of emission sources on the one hand and the environmental stability as well as the tendency to adsorb on the particulate matter on the other hand determined the quantitative occurrence of individual compounds.

Acetophenones↗

Toxic equivalency factors of polybrominated dibenzo-p-dioxin, dibenzofuran, biphenyl, and polyhalogenated diphenyl ether congeners based on rainbow trout early life stage mortality.

Polybrominated and polychlorinated biphenyls (PBBs/PCBs), dibenzo-p-dioxins (PBDDs/PCDDs), dibenzofurans (PBDFs/PCDFs), and diphenyl ethers (PBDEs/PCDEs) are persistent, lipophilic environmental contaminants that may pose a risk to fish early life stage survival. To determine this potential risk, a rainbow trout early life stage mortality bioassay was used in which the potency of individual polybrominated chemicals was compared to the potency of the most potent polychlorinated chemical in these classes, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). Following injection of newly fertilized rainbow trout eggs, fish-specific toxic equivalency factors (TEFs) were calculated as the molar ratio of TCDD LD50 to brominated compound LD50. Signs of toxicity were identical to those produced by polychlorinated TCDD-like chemicals and included yolk sac edema, pericardial edema, multifocal hemorrhages, reduced growth, and craniofacial malformations. Polybrominated dibenzo-p-dioxins, dibenzofurans, and biphenyls exhibited decreased potency with increased bromine substitution. Only 2,3,7,8-TBDD was more potent than 2,3,7,8-TCDD, whereas other polybrominated dibenzo-p-dioxins were equipotent or less potent than identically substituted polychlorinated dibenzo-p-dioxins in this assay. Although two PBDF congeners were equipotent to identically substituted PCDFs, 2,3,7,8-TBDF was 9-fold more potent than 2,3,7,8-TCDF. Both 3,3',4,4'-TBB and 3,3',4,4',5,5'-HxBB were 10-fold more potent than identically substituted polychlorinated biphenyls. The halogenated diphenyl ethers and di-ortho polybrominated biphenyls were inactive in this assay. Thus, in this in vivo assay the polybrominated and polychlorinated TCDD-like chemicals were not always equally potent. To assess the risk posed by mixtures of these chemicals to feral fish populations, fish-specific TEFs for both polybrominated and polychlorinated chemicals should be used.

Animals↗

The determination and fate of disinfection by-products from ozonation of polluted raw water.

The major disinfection by-products (DBPs) resulting from ozone treatment of polluted surface water were investigated. By-products of either health concern or which may contribute to biological instability of treated drinking water were investigated. The major DBPs were analyzed in two fractions: carbonyl compounds and brominated organic compounds. The natural organic matter (NOM) was also isolated and fractionated from polluted water for subsequent ozonation and DBPs identification under conditions of typical drinking treatment. The main identified carbonyl compounds were low molecular weight carboxylic acids, benzoic compounds, aliphatic aldehydes and odorous aldehydes, respectively. Brominated organics were also found in ozonated water, including bromoform (CHBr3), monobromoacetic acid (MBAA), dibromoacetic acid (DBAA), 2,4-dibromophenol (2,4-DBP) and dibromoacetonitrile (DBAN), respectively. It was also found that the characteristic of organic precursors have significant influences on brominated organic by-products formation. Humic acid demonstrated the highest CHBr3, DBAA and 2,4-DBP formations, whereas hydrophilic neutral produced less CHBr3 and 2,4-DBP than the rest of the organic fractions but produced the highest amount of DBAN. In addition to the other target compounds, a total of 59 different organic compounds were detected by means of gas chromatograph/high-resolution electron-impact mass spectrometry (GC/EI-MS) detection and tentatively identified using mass spectral library searching, mainly aromatics, acids/esters, alcohols, aldehydes, phthalates and amines/amino acids were analyzed. The percentage of elimination or formation levels reached during ozonation is also discussed in this study.

Carboxylic Acids↗

Synthesis of new fluorescent nucleosides, 3-beta-D-ribofuranosylpyrazolo (3,2-i) purine derivatives and their cytotoxic activities.

The novel nucleosides 3-beta-D-ribofuranosylpyrazolo(3,2-i) purine (8) and their 9-substituted bromo, nitro and amino compounds (3, 6 and 11) have been prepared from a fully protected 3-beta-D-ribofuranosyl(3,2-i)purine-9-carboxyamide 1 by bromodeamidation (ipso bromination). Compounds 3, 8 and 11 exhibited antileukemic activity against mouse leukemia L5178Y cells in culture, while the 9-substituted nitro, ester and amide compounds (6, 12 and 13) showed no cytotoxicity.

Animals↗