Detection of Dechlorane Plus and brominated flame retardants in marketed fish in Japan

Fish samples purchased from Japanese markets were analyzed for Dechlorane Plus (DP)(syn-, anti-), polybrominated diphenyl ether (PBDE), and hexabromocyclododecane (HBCD)(α, γ). Twenty fish were analyzed using gas chromatography-mass spectrometry for DP and PBDE, and using liquid chromatography-tandem mass spectrometry for HBCD. DP was detected in 18 samples and ∑DP concentrations were <0.2-14.2 pg g⁻¹ wet wt. Among the DP isomers, anti-DP was the dominant residue observed in this study. PBDE was detected in all samples. Concentrations of ∑PBDE ranged from 2.2 to 878 pg g⁻¹ wet wt. HBCD was detected in 18 samples, and ∑HBCD concentrations were <0.02-21.9 ng g⁻¹ wet wt. In fish landed near the East China Sea and the Sea of Japan, we detected relatively high concentrations of DP, PBDE, and HBCD. These results indicate that the seawaters around East Asia are contaminated with flame retardants. This study demonstrates the presence of DP in fish marketed in Japan for the first time.     

A comprehensive evaluation of two sample treatment procedures for the determination of emerging and historical halogenated flame retardants in biota

Environmental Science and Pollution Research - Two different sample preparation protocols for the determination of 37 emerging and historical halogenated flame retardants (HFRs) in marine tissues...     

Organophosphate flame retardants and plasticizers in indoor air

Analytical methods were developed for a broad range of organophosphate flame retardants and plasticizers in indoor air. Screening was performed of various indoor environments at 12 locations in and around Zurich, Switzerland. Method recoveries ranged from 62% for triphenyl phosphate to 100% for tris(2-ethylhexyl) phosphate. Tris(2-chloro-isopropyl) phosphate was found in the highest concentration (260 ng/m(3)) mainly in cars and furniture stores. Tris(2-ethylhexyl) phosphate and triphenyl phosphate, both up to 3.4 ng/m(3), were also detected in quantifiable concentrations at several sites. Tris(1,3-dichloroisopropyl) phosphate, tricresyl phosphate and tri(2-butoxyethyl) phosphate were below the limit of quantification in all samples. The results of the risk assessment indicate that the observed concentrations are below the predicted threshold for human health effects.     

阻燃剂废水的处理及回收利用

采用电化学氧化、电气浮与Fenton强氧化性协同作用的电解Fenton法预处理难降解阻燃剂废水(CODCr=17108mg/L),CODCr去除率达98.34%,色度去除率达74.19%。其适宜操作条件是:pH=2.0～2.6;电流密度10.8～14.3A/dm2;H2O2起始摩尔浓度27～42mmol/L;FeSO4起始质量浓度660～990mg/L;电解5h。处理后取废水50mL,HCl(1∶1)67mL,NaAlO230g,FeCl3·6H2O4g,加热回流反应2h制成聚合氯化铝铁无机高分子絮凝剂(Al2O39.93%、Fe2O30.75%、盐基度68.0%左右)。该絮凝剂在pH=7～9时有良好的絮凝效果。     

Occurrence of alternative flame retardants in indoor dust from New Zealand: indoor sources and human exposure assessment

Due to worldwide restrictions on polybrominated diphenyl ethers (PBDEs), the demand for alternative flame retardants (AFRs), such as organophosphate flame retardants (OPFRs), novel brominated FRs (NBFRs) and hexabromocyclododecanes (HBCDs), has recently increased. Little is known about human exposure to NBFRs and OPFRs and that their levels in dust have been scarcely evaluated worldwide. To increase the knowledge regarding these chemicals, we measured concentrations of five major NBFRs, ten OPFRs and three HBCD isomers in indoor dust from New Zealand homes. Dust samples were taken from living room floors (n=34) and from mattresses of the same houses (n=16). Concentrations (ngg(-1)) of NBFRs were: 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) (<2-175), decabromodiphenyl ethane (DBDPE) (<5-1430), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) (<2-2285) and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH) (<2-640). For OPFRs, concentrations (ngg(-1)) ranged between: tri-ethyl-phosphate (TEP) (<10-235), tri-n-butyl-phosphate (TnBP) (<20-7545), tris-(2-chloroethyl)-phosphate (TCEP) (<20-7605), tris-(1-chloro-2-propyl) phosphate (TCPP) (20-7615), tri-(2-butoxyethyl)-phosphate (TBEP) (50-27325), tris-(2,3-dichloropropyl)-phosphate (TDCPP) (20-16560), tri-phenyl-phosphate (TPhP) (20-35190), and tri-cresyl-phosphate (TCP) (<50-3760). HBCD concentrations fell in the range <2-4100ngg(-1). BTBPE, DBDPE, TBPH, TBEP, and TnBP showed significant positive correlation (p<0.05) between their concentrations in mattresses and the corresponding floor dust (n=16). These data were used to derive a range of plausible exposure scenarios. Although the estimated exposure is well below the corresponding reference doses (RfDs), caution is needed given the likely future increase in use of these FRs and the currently unknown contribution to human exposure by other pathways such as inhalation and diet.     

Persistent organic pollutants, brominated flame retardants and synthetic musks in fish from remote alpine lakes in Switzerland

Remote alpine lakes do not receive any direct aquatic inputs from anthropogenic activities. Therefore, these ecosystems may receive persistent organic compounds (POPs) by direct atmospheric deposition, only. Consequently, fish dwelling in these ecosystems represent an excellent indicator for the long-term atmospheric input of bioaccumulating and persistent contaminants. In the present study, fish from seven remote alpine lakes, located between 2062 and 2637 m above sea level in south eastern Switzerland (Grisons), were investigated. Lipid-based fish tissue concentrations of pesticides including dichlorodiphenyltrichloroethane (DDT) and its transformation products (2,4'-DDT, 4,4'-DDT, 2,4'-dichlorodiphenyldichloroethane (DDD), 4,4'-DDD, 2,4'-dichlorodiphenyldichloroethene (DDE), 4,4'-DDE), as well as dieldrin, heptachlor exo-epoxide (HPEX), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH), polychlorinated biphenyls (PCB), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), and polybrominated diphenyl ethers (PBDE) were measured. In addition, seven synthetic musk compounds (Crysolide (ADBI), Phantolide (AHMI), Fixolide (AHTN), Traseolide (ATII), Galaxolide (HHCB), musk ketone (MK), and musk xylene (MX)) were determined. Concentrations of PCB, PCDD/F, and PBDE were in the same range as in fish from the major lakes situated in the Swiss plateau, indicating mainly atmospheric input of these persistent compounds. In contrast, concentrations of synthetic musks which are used as fragrances in laundry detergents and cosmetic products were distinctly lower than concentrations in fish from Swiss plateau lakes which receive inputs from waste water treatment plants.     

Conventional and emerging halogenated flame retardants (HFRs) in sediment of Yangtze River Delta (YRD) region,East China

The occurrence and distribution of polybrominated diphenyl ethers (PBDEs) and eleven non-PBDE halogenated flame retardants (HFRs) were investigated through the collection of marine and river sediment from Yangtze River Delta (YRD), East China. Among them, PBDEs, decabromodiphenyl ethane (DBDPE) and 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) were the three predominant HFRs with the highest detection frequencies in the sediment. Significant correlation between PBDEs and DBDPE indicated that they may have the similar emission sources. The production and use of DBDPE is growing rapidly and comparable concentrations between PBDEs and DBDPE in YRD sediment may suggest that DBDPE will likely become one of the major HFRs emerging in the environment in China. Of the seven detected non-PBDE HFRs, this is the first time that TBECH was reported in the Chinese environment and its predominance and prevalence in the YRD may imply its extensive use in these areas.     

Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants in air and seawater of the European Arctic

The spatial distribution of polybrominated diphenyl ethers (PBDEs) and several alternative non-PBDE, non-regulated brominated flame retardants (BFRs) in air and seawater and the air-seawater exchange was investigated in East Greenland Sea using high-volume air and water samples. Total PBDE concentrations (Ó₁₀PBDEs) ranged from 0.09 to 1.8 pg m⁻³ in the atmosphere and from 0.03 to 0.64 pg L⁻¹ in seawater. Two alternative BFRs, Hexabromobenzene (HBB) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), showed similar concentrations and spatial trends as PBDEs. The air-seawater gas exchange was dominated by deposition with fluxes up to −492 and −1044 pg m⁻² day⁻¹ for BDE-47 and DPTE, respectively. This study shows the first occurrence of HBB, DPTE and other alternative flame retardants (e.g., pentabromotoluene (PBT)) in the Arctic atmosphere and seawater indicating that they have a similar long-range atmospheric transport potential (LRAT) as the banned PBDEs.     

Analysis of brominated flame retardants in house dust

The main objective of this study was to create a robust analytical method to analyse the flame retardants decabromodiphenylether (BDE-209), hexabromocyclododecane (HBCD), and tetrabromobisphenol-A (TBBPA) in house dust in order to estimate the degree of contamination of indoor environment. A liquid chromatography method equipped with a UV-detector and electro spray-tandem mass spectrometry was used to achieve this result. Applying an external calibration for BDE-209, an internal calibration for TBBPA, and a standard addition method for HBCD low limits of quantification were obtained. The analytical procedure was carried out under exclusion of UV-light as the target compounds potentially degrade when being exposed to UV-light. Empirical data were obtained in addition to the dust samples to estimate potential influences of apartment characteristics. A weak correlation between the number of electric devices and TBBPA was found.     

Brominated flame retardants and related chlorinated persistent organic pollutants in fish from river Elbe and its main tributary Vltava

Brominated flame retardants (BFRs) are widely used industrial chemicals, residues of which can be nowadays found in all environmental compartments. The widespread presence of BFRs in various environmental compartments and food chain is a consequence of both their broad application area and physico-chemical properties, such as resistance to degradation and high lipophilicity. Alike in the case of other halogenated persistent organic pollutants (POPs), fish can be used as a bioindicator of aquatic environment pollution. In presented study, conducted in the year 2005, altogether 80 samples representing the most abundant fresh water fish species, viz. chub (Leuciscus cephalus), bream (Abramis brama), and perch (Perca fluviatilis) collected in 11 sampling sites located at Elbe and Vltava (Moldau) rivers were examined for levels of major BFRs. Without any exception, BFRs were detected in all fish samples. BDE 47 was the dominating congener in all fish species. This fact was not surprising, since it used to be the main component in various kinds of technical mixtures. With regard to relatively high levels of BDE 47 in fish tissue, as compared to other BFRs, and considering strong correlation with the total PBDEs content, simplified laboratory examination and, consequently, increased samples throughput can be obtained when only this congener is monitored. The potential of comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-TOFMS), to provide more comprehensive information on the bioaccumulating chemicals occurring in fish samples, has been demonstrated in this study.     

Analysis of brominated flame retardants in house dust

The main objective of this study was to create a robust analytical method to analyse the flame retardants decabromodiphenylether (BDE-209), hexabromocyclododecane (HBCD), and tetrabromobisphenol-A (TBBPA) in house dust in order to estimate the degree of contamination of indoor environment. A liquid chromatography method equipped with a UV-detector and electro spray-tandem mass spectrometry was used to achieve this result. Applying an external calibration for BDE-209, an internal calibration for TBBPA, and a standard addition method for HBCD low limits of quantification were obtained. The analytical procedure was carried out under exclusion of UV-light as the target compounds potentially degrade when being exposed to UV-light. Empirical data were obtained in addition to the dust samples to estimate potential influences of apartment characteristics. A weak correlation between the number of electric devices and TBBPA was found.     

Distribution and levels of brominated flame retardants in sewage sludge

One hundred and sixteen sewage sludge samples from 22 municipal wastewater treatment plants in Sweden were analysed for brominated flame retardants. Polybrominated diphenyl ethers (PBDEs) were in the range n.d.-450 ng/g wet weight, tetrabromobisphenol A (TBBPA) varied between n.d. and 220 ng/g wet weight, 2,4,6-tribromophenol was in the range n.d.-0.9 ng/g wet weight and polybrominated biphenyls were not detected (except for a possible analytical interference). There was a significant variation in the samples among plants. Influence from industries and other local sources can therefore be assumed. The correlation pattern indicated contribution from three different types of technical products; composed of either low-brominated PBDEs, decaBDE or TBBPA.     

Levels and trends of brominated flame retardants in the Arctic

Polybrominated diphenyl ethers (PBDEs) containing two to seven bromines are ubiquitous in Arctic biotic and abiotic samples (from zooplankton to polar bears (Ursus maritimus) and humans; air, soil, sediments). The fully brominated decabromodiphenyl ether (BDE-209), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA) and polybrominated biphenyls (PBBs) are also present in biotic and abiotic samples. Spatial trends of PBDEs and HBCD in top predators are similar to those seen for polychlorinated biphenyls (PCBs) and indicate western Europe and eastern North America as source regions. Concentrations of tetra- to heptaBDEs have increased significantly in North American and Greenlandic Arctic biota and in Greenland freshwater sediments paralleling trends seen further south. For BDE-209, increasing concentrations in Greenlandic peregrine falcons (Falco peregrinus) and in dated lake sediment cores in the Canadian Arctic have been seen during the 1990s. BDE-47, -99, -100 and -153 are observed to biomagnify in Arctic food webs. summation operatorPBDE concentrations in Arctic samples are lower than in similar sample types from more southerly regions and are one or more orders of magnitude lower than summation operatorPCB concentrations except for some levels for air. Air and harbor sediment results for PBDEs indicate that there are local sources near highly populated areas within the Arctic. Findings of PBBs on moss and TBBPA on an air filter, and that both are found in biota at high trophic levels indicates that these compounds may also reach the Arctic by long-range atmospheric transport. Based on the evidence of their presence in the Arctic and indications that most if not all are undergoing long-range transport, these brominated flame retardants (BFRs) have characteristics that qualify them as POPs according to the Stockholm Convention.     

Anaerobic degradation of brominated flame retardants in sewage sludge

Tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), and decabromodiphenyl ether (DecaBDE) are high production volume chemicals used as flame retardants in plastics for products such as electronic equipment, insulation panels, and textiles. The environmental safety of brominated flame retardants, especially their persistence, bioaccumulation, and toxicity is a controversial topic. Here, we studied and compared the degradation of TBBPA, HBCD, and DecaBDE under anaerobic conditions in digested sewage sludge. The half-lives of TBBPA and a technical HBCD mixture were 0.59 and 0.66 d, respectively. The fact that (+/-)-alpha-HBCD exhibited an almost doubled half-life compared to (+/-)-beta-HBCD and (+/-)-gamma-HBCD is an important finding with respect to the discussion on the persistence of individual HBCD stereoisomers and the recent reports on strong relative enrichment of alpha-HBCD in biota. We found no statistically significant enantioselective degradation of alpha-, beta-, or gamma-HBCD. Half-lives of TBBPA and a technical HBCD mixture were not dependent on the presence of additional nutrients or primers. Concentrations of TBBPA and a technical HBCD mixture decreased also in sterile control samples, however, at a rate that was more than a factor of 50 smaller than in incubations under non-sterile conditions. Compared to TBBPA and a technical HBCD mixture, DecaBDE exhibited a much longer half-life of 7 x 10(2)d in the same system. Pseudo-first-order degradation rate constants decreased according to the following sequence: TBBPA congruent with(+/-)-gamma-HBCD congruent with(+/-)-beta-HBCD>(+/-)-alpha-HBCD>DecaBDE. Preliminary investigations suggest that degradation of TBBPA, HBCD, and DecaBDE occurs in full-scale anaerobic digesters, as well.     

An overview of brominated flame retardants in the environment

The presence of brominated flame retardant (BFR) chemicals, and particularly polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD), has become of increasing concern to scientists over the past decade. Environmental studies conducted primarily in Europe, Japan and North America indicate that these chemicals are ubiquitous in sediment and biota. The levels of PBDEs seem to be increasing, and several trends, including in humans, indicate that this increase may be rapid. The occurrence of high concentrations of certain PBDE isomers may be sufficient to elicit adverse effects in some wildlife. There is also concern that levels could cause adverse effects in sensitive human populations such as young children, indigenous peoples, and fish consumers. However, our knowledge about these chemicals, their sources, environmental behavior, and toxicity is limited, making risk assessment difficult. In this paper, the current state of knowledge is reviewed and areas for further research recommended to improve future monitoring and risk assessment efforts.     

Characterization of polychlorinated biphenyls and brominated flame retardants in sludge,sediment and fish from municipal dumpsite at Surabaya,Indonesia

We investigated the PCBs, PBDEs and HBCDs contamination in sludge, sediments and fish from various locations including raw leachate pond, leachate treatment plans (LTPs), control wells and reference site at open landfill of municipal dumpsite, Surabaya City, Indonesia. 62 PCBs and 14 PBDEs congeners, and 3 HBCDs isomers were identified and quantified using GC–MS and LC–MS/MS, respectively. Concentration ranges and median (value in parentheses) of PCBs, PBDEs and HBCDs were from not detected (ND) to 60 (3.9) ng g⁻¹ dw, 0.0075 to 45 (4.5) ng g⁻¹ dw and ND to 2.8 (0.052) ng g⁻¹ dw in sludge and sediments, respectively. While in two polled of fish samples were 30–55 ng g⁻¹ lw, 6.6–11 ng g⁻¹ lw and 1.6–3.3 ng g⁻¹ lw, respectively. Among the sampling sites, the highest level of PCBs and PBDEs were detected in sludge from raw leachate pond. However, PCBs and PBDEs levels were showing decreased in LTP-1 that could be due to the bacterial degradation but not in LTP-2, HBCDs were more stable in both LTPs. Levels of PCBs and BFRs in sludge at the present study were lower than those reported in sewage sludge reported from some other countries. PCBs profiles were mainly composed in that order by CB-138, -153, -180, -101, -118 and -28, while by BDE-47, -99, -100, -153, -154 and -28 for PBDEs in sludge, sediments and fish. Profiles of HBCDs were predominantly composed by γ- and α-isomers in sludge and fish, respectively. Debromination, dechlorination, commercial formulations used and congener-specific accumulation of those contaminants are the factors influenced the profiles.     

Concentrations and specific loads of brominated flame retardants in sewage sludge

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. The present study focuses on two classes of brominated flame retardants: polybrominated diphenyl ethers (BDE28, BDE47, BDE49, BDE66, BDE85, BDE99, BDE100, BDE119, BDE138, BDE153, BDE154, BDE183, BDE209) and hexabromocyclododecane (HBCD) detected in sewage sludge collected from a monitoring network in Switzerland. Mean concentrations (n=16 wastewater treatment plants) were 310, 149, 95 and 17microg per kg dry matter for decaBDE, HBCD, penta- and octaBDE, respectively. These numbers correspond well with other studies from European countries. DecaBDE, HBCD, penta- and octaBDE showed average specific loads (load per connected inhabitant per year) in sludge of 6.1, 3.3, 2.0 and 0.3mgcap(-1)yr(-1), respectively. This is in line with consumption and storage of the compounds in the environment and the anthroposphere. Discrepancies observed for octaBDE and HBCD can be explained by the release from materials where these compounds are incorporated in and/or their degradation during anaerobic sludge treatment. Loads from different types of monitoring sites showed that brominated flame retardants ending up in sewage sludge originate mainly from surface runoff, industrial and domestic wastewater.     

Levels and trends of brominated flame retardants in the European environment

In this paper, we review those data which have recently become available for brominated flame retardants (particularly the brominated diphenyl ethers (BDEs) and hexabromocyclododecane (HBCD)) in samples from the European environment. Environmental compartments studied comprise the atmosphere, sediments and soils, sewage sludges, and a variety of biological samples and food chains. This is currently a very active research area, and we cite over 70 studies reported in the literature during 2003-04. Findings include that the input of BDEs (especially BDE209) to the Baltic Sea by atmospheric deposition now exceeds that of PCBs by a factor of almost 40 times. Sewage sludge samples from both industrial and background locations show concentrations of BDEs, HBCD and tetrabromobisphenol-A (TBBP-A) that are of a similar order, indicating that the major source is from diffuse leaching from products into wastewater streams from users, households and industries generally. Point-sources from industries using BFRs (e.g. the textile industry) also generate local hot-spots. Sediment core studies identified the presence of two of the three PBDE formulations. The penta-mix formulation was clearly present from the beginning of the 1970s, but the deca-mix only appeared in the late 1970s. BDE183, BDE209 and HBCD were detected in peregrine falcons from Sweden and other birds feeding on terrestrial food chains. BDEs are found widely distributed in fish, including those from high mountain lakes in Europe, as a consequence of long-range atmospheric transport and deposition. A temporal trend study in archived freeze-dried mussels from the Seine estuary, France, indicated an exponential increase in BDE concentrations during the period 1982-1993, which levelled off in 1999 and 2001 and then began to decline after 2002. HBCD was detected in liver and blubber samples from harbour seals and harbour porpoises from the Wadden and North Seas, though very few animals yielded positive values for TBBP-A. There are difficulties in comparing data on summation operatorBDE from studies in which different suites of BDE congeners have been determined, and we suggest a common suite which will allow the study of all three commercial PBDE formulations.     

Brominated flame retardants and other organobromines in Norwegian predatory bird eggs

A set of 62 unhatched eggs was collected from six different predatory bird species throughout Norway after incubation period was completed. They were analysed for PBDE, PBB, TBBP A and naturally occurring halogenated compounds. BDE 47, 99 and 153 were the dominating congeners, with species dependent PBDE patterns. BDE 153 was observed as the most abundant congener in eggs of peregrine falcon, golden eagle and merlin. The highest PBDE level (sum of nine congeners) was found in eggs of white-tailed sea eagle with up to 800ng/gww (median sumPBDE: 184ng/gww), followed by eggs of peregrine falcon and osprey (median sumPBDE: 155 and 105ng/gww, respectively). Golden eagle eggs showed the lowest concentration of all species (median sumPBDE: 3ng/gww). The levels in the peregrine falcon are similar to those found earlier in the Baltic region [Lindberg, P., Sellstrom, U., Haggberg, L., de Wit, C.A., 2004. Higher brominated diphenyl ethers and hexabromocyclododecane found in eggs of peregrine falcons (Falco peregrinus) breeding in Sweden. Environmental Science & Technology. 38 (1), 93-96]. The differences between species are not fully explainable, due to lack of data from the major food species. BB 101 and 153 were found in eggs of all investigated bird species. Especially in samples of white-tailed sea eagle, peregrine falcon and goshawk additional unknown penta- and hexabrominated biphenyls were detected. TBBP A was detected in all of eight eggs analysed sampled from four different bird of prey species. The naturally occurring halogenated compounds Q1, the dibromotrichloro monoterpene MHC-1, and 2,4,6-tribromoanisole (TBA) were detected in all of seven analysed samples except for one peregrine falcon egg.