Biodegradation kinetics of selected brominated flame retardants in aerobic and anaerobic soil

The purpose of the present study was to investigate the biodegradation kinetics in aerobic and anaerobic soil of the following brominated flame retardants: 2,4,4′-tribromodiphenyl ether (BDE 28), decabromodiphenyl ether (BDE 209), tetrabromobisphenol A (TBBPA), 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), 2,4,6-tribromophenol (246BrPh), and hexabromobenzene (HxBrBz). For comparison, the biodegradation of the chlorinated compounds 2,4,4′-trichlorodiphenyl ether (CDE 28), 2,4,6-trichlorophenol (246ClPh), hexachlorobenzene (HxClBz), and 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB 153) was also assessed. In aerobic soil, BDE 209 showed no significant degradation during the test period, but concentrations of the other BFRs declined, with half-lives decreasing in the following order: BDE 28 > TBBPA > TBECH > HxBrBz > 246BrPh. Declines in almost the same order were observed in anaerobic soil: BDE 28, BDE 209 > TBBPA > HxBrBz > TBECH >246BrPh.     

Fate of tetrabromobisphenol A and hexabromocyclododecane brominated flame retardants in soil and uptake by plants

The fate of tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereomers (α-, β-, and γ-HBCD) and uptake by plants (cabbage and radish) was investigated. In a short-term (8 weeks) experiment, sorption to soil matrix resulted in 90% decline in recovery of these compounds in the experimental soil. However, nearly 50% of initial HBCDs recovered in mixed cabbage-radish treatments, which suggested that interspecific plant interactions might enhance the bioavailability of HBCDs. Although both plant species could uptake TBBPA and HBCDs, cabbage showed greater accumulating ability. Up to 3.5-10.0-fold higher HBCD concentrations were observed than TBBPA concentrations in all plant tissues, and the distribution of HBCDs in plant tissues was diastereomer-specific. The predominance of α-HBCD in shoot tissues for both species might be attributed to diastereomer-specific translocation of HBCDs, shift in diastereomer pattern and/or selective metabolization of γ-HBCD within plants. The results showed that strong sorption to soil particles reduced the potential of human exposure to BFRs in the soil. However, plants increased the exposure risk by uptaking these compounds and by enhancing their bioavailability. The results also provide insight into transport mechanisms of TBBPA and HBCD diastereomers in soil-plant systems.     

Emissions of organophosphate and brominated flame retardants from selected consumer products and building materials

The emissions of selected flame retardants were measured in 1- and 0.02-m³ emission test chambers and 0.001-m³ emission test cells. Four product groups were of interest: insulating materials, assembly foam, upholstery/mattresses, and electronics equipment. The experiments were performed under constant environmental conditions (23°C, 50% RH) using a fixed sample surface area and controlled air flow rates. Tris (2-chloro-isopropyl)phosphate (TCPP) was observed to be one of the most commonly emitted organophosphate flame retardants in polyurethane foam applications. Depending on the sample type, area-specific emission rates (SER_a) of TCPP varied between 20 ng m⁻² h⁻¹ and 140 μg m⁻² h⁻¹.The emissions from electronic devices were measured at 60°C to simulate operating conditions. Under these conditions, unit specific emission rates (SER_u) of organophosphates were determined to be 10–85 ng unit⁻¹ h⁻¹. Increasing the temperature increased the emission of several flame retardants by up to a factor of 500. The results presented in this paper indicate that emissions of several brominated and organophosphate flame retardants are measurable. Polybrominated diphenylethers exhibited an SER_a of between 0.2 and 6.6 ng m⁻² h⁻¹ and an SER_u of between 0.6 and 14.2 ng unit⁻¹ h⁻¹. Because of sink effects, i.e., sorption to chamber components, the emission test chambers and cells used in this study have limited utility for substances low vapour pressures, especially the highly brominated compounds; hexabromocyclododecane had an SER_a of between 0.1 and 29 ng m⁻² h⁻¹ and decabromodiphenylether was not detectable at all.     

Levels and sources of brominated flame retardants in human hair from urban, e-waste, and rural areas in South China

Human hair and indoor dust from urban, e-waste, and rural areas in south China were collected and analyzed for brominated flame retardants (BFRs). BFRs concentrations in hair from occupational e-waste recycling workers were higher than those from non-occupational exposed residents in other sampling areas. Polybrominated diphenyl ethers (PBDEs) and decabromodiphenyl ethane (DBDPE) are two major BFRs in hair samples. The PBDE congener profiles in hair from the e-waste area are different from those from urban and rural areas with relatively higher contribution of lower brominated congeners. DBDPE, instead of BDE209, has become the major BFR in non-e-waste recycling areas. Significant correlations were found between hair level and dust level for DBDPE and BTBPE but not for PBDEs. The different PBDE congener profiles between dust and hair may suggest that exogenous exposure to the PBDE adsorbed on dust is not a major source of hair PBDEs.     

水体中27种有机磷阻燃剂(OPFRs)的检测及风险评价

有机磷阻燃剂(organophosphorus flame retardants,OPFRs)具有致畸、致癌、致突变风险以及神经毒性作用。为了更好地研究其存在水平和健康风险,建立了固相萃取与高效液相色谱-串联质谱仪和气相色谱-质谱联用仪检测水体中27种OPFRs的分析方法,并对OPFRs进行了健康风险评价。20种OPFRs采用MCX固相萃取柱预处理和LC-MS/MS进行检测,以甲醇和含10 mmol·L⁻¹的甲酸水溶液作为流动相进行梯度洗脱,7种OPFRs采用HLB串联Envi-18固相萃取柱进行预处理并利用GC-MS进行检测。检测结果表明,27种OPFRs的检出限为0.02~2.53 ng·L⁻¹;定量限为0.06~8.43 ng·L⁻¹;回收率为65.82%~108.48%。2021年4月份,采集北京市潮白河地表水和地下水8个水样并检测其OPFRs。实测结果表明：除磷酸三(2-异丙基苯)酯、磷酸异癸基二苯酯、磷酸叔丁基苯二苯酯、磷酸二苄酯外,其余23种OPFRs均有不同程度检出,质量浓度为0~973.17 ng·L⁻¹;磷酸三(2-乙基己基)酯、磷酸三乙酯、磷酸三丙酯、磷酸三异丙酯含量相对较高,分别高达973.17、459.90、315.47、298.41 ng·L⁻¹。采用USEPA模型对水样中的OPFRs进行了健康风险评价, 13种OPFRs的非致癌风险值为0~6.17×10⁻⁴,4种OPFRs致癌风险值为1.37×10⁻⁹~1.07×10⁻⁷;在高暴露条件下,OPFRs的非致癌风险值为1.61×10⁻⁵~6.17×10⁻⁴,致癌风险值为1.00×10⁻⁸~1.07×10⁻⁷,均低于风险阈值。上述结果说明,水体中OPFRs产生的健康风险处于较低水平。此次采集的潮白河地表水和地下水水中OPFRs的致癌风险和非致癌风险均处于较低水平。本研究结果可为地表水和地下水水体中OPFRs的检测及风险评价提供参考。     

A chemical and toxicological profile of Dutch North Sea surface sediments

Chemical and toxicological profiles were assessed in surface sediments (fraction <63 μm) from the southern North Sea. In extracts of freeze-dried samples, polybrominated biphenyl (PBB), Irgarol 1051 and phthalate concentrations were below the respective detection limits (except di(2-ethylhexyl)phthalate, which was between 170 and 3300 μg kg⁻¹ dry weight (dw)). Hexabromocyclododecane (HBCD) concentrations were between 0.8 and 6.9 μg kg⁻¹ dw, with highest concentrations at river mouths. Polybrominated diphenylethers (PBDE) concentrations were 0.4–0.6 μg kg⁻¹ dw, decabromodiphenylether (BDE209) 1–32 μg kg⁻¹ dw. The ratio BDE209/PCB153 was used as a tracer for recent emissions, and pointed towards a BDE209 source in the Western Scheldt’s upper estuary. PCBs and PAHs were between 0.19–4.7 and 2.6–200 μg kg⁻¹ dw respectively and generally had highest concentrations at near-shore locations and river mouths.

Responses in the Microtox broad-spectrum and the Mutatox genotoxicity assays were generally low, with near-shore locations giving higher responses. The umu-C genotoxicity and the ER-CALUX assay for estrogenicity showed no response, with the exception of one near-shore location (IJmuiden outer harbour, ER-CALUX).

Highest dioxin-like toxicity (DR-CALUX) was found at near-shore locations, in the outflow of the Rhine/Meuse estuary including a dumping site of harbour sludge. At the Oyster Grounds, DR-CALUX responses appeared to be linked to the occurrence of larger PAHs (4–6 rings). A new, non-destructive clean up procedure resulted in significantly higher DR-CALUX responses than the current protocol. The Dutch legislation on disposal of harbour sludge at sea, dictates the use of the conventional clean up procedure. Our results therefore indicate that probably more dioxin-like toxicity associated with harbour sludge is disposed off at sea than assumed.     

A North Sea and Baltic Sea Model Ensemble Eutrophication Assessment

A method to combine observations and an ensemble of ecological models is suggested to produce a eutrophication assessment. Using threshold values and methodology from the Oslo and Paris Commissions (OSPAR) and the Helsinki Commission (HELCOM), four models are combined to assess eutrophication for the Baltic and North Seas for the year 2006. The assessment indicates that the entire southeastern part of the North Sea, the Kattegat, the Danish Straits, the Gulf of Finland, and the Gulf of Riga as well as parts of the Arkona Basin, the Bornholm Basin, and the Baltic proper may be classified as problem areas. The Bothnian Bay and parts of the Baltic proper, the Bornholm Basin, and the Arkona Basin are classified as potential problem areas. This method is a useful tool for the classification of eutrophication; however, the results depend on the threshold values, and further work is needed within both OSPAR and HELCOM to harmonize these values.     

Occurrence and distribution of triclosan in the German Bight (North Sea)

The potential of triclosan (TCS) acting as an endocrine disruptor has led to growing concern about the presence of TCS in the environment. In this study, seawater samples were collected from the German Bight during sampling campaigns conducted with the German research ships Gauss and Ludwig Prandtl. TCS was determined both in the dissolved phase and in the suspended particulate matters with concentrations ranging 0.8-6870 pg L⁻¹ and <1-95 pg L⁻¹, respectively. High concentrations of TCS were present in the estuaries of the Elbe and the Weser, indicating significant input of TCS by the river discharge. The correlation coefficient (R²) between the dissolved concentration and salinity was 0.79 for the data obtained from the Gauss cruise, showing an obvious declining trend from the coast to the open sea.     

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.     

Organochlorines, brominated flame retardants and mercury levels in six seabird species from the Gulf of St. Lawrence (Canada): Relationships with feeding ecology, migration and molt

Concentrations of organochlorines (OCs), brominated flame retardants (BFRs) and mercury (Hg) were measured in eggs of six seabird species breeding in the Gulf of St. Lawrence, Canada. Stable nitrogen (δ¹⁵N) and carbon (δ¹³C) isotopes were used as ecological tracers to measure trophic level and connectivity with benthos, respectively. Concentrations, patterns as well as ecological tracers varied significantly between species. The sum of polychlorinated biphenyls (ΣPCBs) was the most important group measured in all seabird species based on concentration followed generally by the sum of chlorinated pesticides (ΣCPs), the sum of brominated flame retardants (ΣBFRs) and finally total Hg (THg). ΣPCBs, ΣCPs and ΣBFRs increased with trophic level, whereas THg did not. Only ΣBFRs increased with a higher connectivity with the benthos. Seabird species resident to the Great Lakes-St. Lawrence ecosystem showed higher Hg and BFR levels than migratory species. Molt patterns were used to explain variations of contaminant levels.     

Levels and distribution of Dechlorane Plus in coastal sediments of the Yellow Sea, North China

Dechlorane Plus (DP) has been determined in surface sediments from three Chinese coastal bays, e.g. Jiaozhou, Sishili and Taozi Bay in North China. DP concentrations ranged from <1.2 to 187 pg g⁻¹ dry weight (dw) (mean: 24.7 pg g⁻¹ dw) in Jiaozhou Bay, <1.2 to 135 pg g⁻¹ dw (mean 69.9 pg g⁻¹ dw) in Sishili Bay and <1.2 to 66.7 pg g⁻¹ dw (mean: 40.4 pg g⁻¹ dw) in Taozi Bay, respectively. Additionally, two dechlorinated species were quantified, which accounted for 0.6-5.1% of the ∑DP concentration.The f_syn values (syn-isomer/(syn- + anti-isomer)) in sediments from Jiaozhou Bay (mean 0.29) were close to the technical DP mixture (0.2-0.4), probably indicating local inputs of DP. In contrast, sediments in Sishili and Taozi Bay showed much lower f_syn values (mean 0.16). During transportation the DP isomers are subject to stereo selective degradation which partly resulted in the relative enrichment of anti-DP in coastal sediments.     

Exposure assessment of French women and their newborn to brominated flame retardants: determination of tri- to deca- polybromodiphenylethers (PBDE) in maternal adipose tissue, serum, breast milk and cord serum

In the frame of a French monitoring program, tri- to deca- polybromodiphenylethers (PBDE) have been measured in maternal and cord serum, adipose tissue, and breast milk samples, collected from 93 volunteer women during caesarean deliveries. The seven major tri- to heptaBDE (BDE-28, 47, 99, 100, 153, 154, and 183) were detected in adipose tissue and breast milk with cumulated median values of 2.59 and 2.51 ng g⁻¹ l w. Nine highly brominated octa- to decaBDE (BDE-196, 197, 201, 202, 203, 206, 207, 208 and 209) was performed in the same samples, with cumulated median values of 2.73 and 3.39 ng g⁻¹ l w in adipose tissue and breast milk, respectively. At this opposite, median levels of octa- to decaBDE in maternal and cord serum appeared significantly higher than the levels of tri- to heptaBDE in the same matrices, i.e. 8.85 and 12.34 versus 0.98 and 0.69 ng g⁻¹ l w, respectively.     

Levels and distribution of organophosphorus flame retardants and plasticizers in fishes from Manila Bay, the Philippines

Organophosphorus compounds (OPCs) and stable isotope ratios (δ¹³C and δ¹⁵N) were determined in 58 fishes belonging to 20 species collected from Manila Bay, the Philippines. OPCs were detected in most of the samples and found up to μg/g lw (lipid weight) level, suggesting their ubiquitous presence in the coastal marine environment of the Philippines. Higher levels (>1000 ng/g lw) of total OPCs were determined in yellowstriped goatfish, silver sillago, tripletail wrasse and bumpnose trevally indicates either their active uptake from ambient water or lower metabolic capacity of these species. Levels of triphenyl phosphate (TPhP) in demersal species showed a positive correlation with δ¹⁵N, indicating that TPhP was adsorbed onto the particle, settled down to the bottom sediment and accumulated through the benthic food web rather than the pelagic. Estimated dietary intake of OPCs in Manila Bay fishes were four to five orders of magnitude lower than the proposed reference dose (RfD).     

Organophosphorus flame retardants in house dust from the Philippines: occurrence and assessment of human exposure

The use of organophosphorus flame retardants (PFRs) as flame retardants and plasticizers has increased due to the ban on common polybrominated diphenyl ether mixtures. However, only limited information on PFR contamination is available so far from Southeast Asia. In the present study, residual levels of PFRs in house dust and exposure through dust ingestion were investigated in the Philippines. House dust samples (n?=?37) were collected from Malate (residential area) and Payatas (municipal dumping area) in the Philippines and analyzed using ultra-high-performance liquid chromatography coupled with tandem mass spectrometry. Among the targeted seven PFRs, triphenyl phosphate (TPP) was the predominant compound. Median levels of ΣPFRs in Malate (530 ng/g) were two times higher (p?<?0.05) than in Payatas (240 ng/g). The estimated daily intake of PFRs in the Philippines (of areas studied) via house dust ingestion was below the guideline values. House dust may be an important contributor in the overall exposure of humans to TPP even when considering dietary sources. To our knowledge, this is a first report on PFR contamination in house dust from developing country. PFRs were ubiquitously detected in the home environments in the Philippines. Although estimated exposure levels through dust ingestion were below the guideline, it was suggested that toddlers are at higher risk. Therefore, further investigations to understand the behavior of PFRs in house and other microenvironments and overall exposure pathways for the country’s populace to PFRs are necessary.     

"Novel" brominated flame retardants in Belgian and UK indoor dust: implications for human exposure

Concentrations of several “novel” brominated flame retardants (NBFRs) are reported in indoor dust samples from Belgian houses (n = 39) and offices (n = 6) and from day-care centers and schools in the West Midlands of the UK (n = 36). Using a GC-ECNI/MS method, the following NBFRs were quantified: decabromodiphenyl ethane (DBDPE) (range <20-2470 ng g⁻¹), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) (range <0.5-1740 ng g⁻¹), tetrabromobisphenol A-bis(2,3-dibromopropylether) (TBBPA-DBPE) (range <20-9960 ng g⁻¹), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) (range <2-436 ng g⁻¹) and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH) (range <2-6175 ng g⁻¹). Hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO), another NBFR, was below the detection limit of 2 ng g⁻¹ dust in all dust samples. No correlation was detected between concentrations of NBFRs and PBDEs. The ratio of TBB:TBPH in the dust samples ranged from 0.01 to 4.77 (average 0.42), compared to the ratio present in the commercial flame retardant product FM 550 (TBB:TBPH = 4:1). Furthermore, no correlation was detected between concentrations in dust of TBB and TBPH. This may suggest different sources of these NBFRs, or similar sources but compound-specific differences in their indoor fate and transport. Exposure via dust ingestion was estimated for both adults and toddlers under low-end (5th percentile), typical (median), and high-end (95th percentile concentrations) scenarios. These were calculated assuming 100% absorption of intake dust and using mean dust ingestion (adults = 20 mg d⁻¹; for toddlers = 50 mg d⁻¹) and high dust ingestion (adults = 50 mg d⁻¹; for toddlers = 200 mg d⁻¹). Typical exposure with high dust ingestion estimates for adults were 0.01, 0.2, 0.01, 0.02 and 0.08 ng kg⁻¹ bw d⁻¹ and for toddlers 0.05, 1.9, 0.08, 0.4 and 1.12 ng kg⁻¹ bw d⁻¹ for BTBPE, DBDPE, TBB, TBPH and TBBPA-DBPE, respectively. Our results showed that, similar to PBDEs, toddlers have higher exposure to NBFRs than adults. This study documents the presence of NBFRs in indoor environments, and emphasizes the need to evaluate the health implications of exposure to such chemicals.     

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.     

Emerging pollutants in sewage, surface and drinking water in Galicia (NW Spain)

A monitoring programme was carried out on wastewater, surface and drinking water on the NW area of Spain during the four seasons of a year period (November 2007-September 2008). This study covered a series of emerging pollutants of different classes, including pharmaceuticals, neutral and acidic organophosphorus flame retardant/plasticizers (OPs), triclosan, phenoxy-herbicides, insect repellents and UV filters. From the total set of 53 compounds, 19 were found in raw wastewater with median concentrations higher than 0.1 μg L⁻¹. Among them, salicylic acid, ibuprofen and the UV filter benzophenone-4 (BP-4) were the most concentrated, exceeding the 1 μg L⁻¹ median value. Subsequently, 11 of these contaminants are not efficiently enough removed in the small WWTPs tested and their median concentrations in effluents still surpassed the 0.1 μg L⁻¹, so that they can spread through surface water. These chemicals are the pharmaceuticals naproxen, diclofenac and atenolol; the OPs tri(2-chloroethyl) phosphate (TCEP), tri(chloropropyl) phosphate (TCPP), tri-n-butyl phosphate (TnBP), diphenyl phosphate (DPhP) and diethylhexyl phosphate (DEHP); and the sulphonate UV filters BP-4 and 2-phenylbenzimidazole-5-sulphonic acid (PBSA). These OPs were then the dominant emerging pollutants occurring in surface and drinking water, where they are detected in the 20-200 ng L⁻¹ range. Pharmaceuticals and UV filters are typically below the 10 ng L⁻¹ level. Finally, herbicides were only detected in the last sampling campaign under the 100 ng L⁻¹ drinking water European Union limit.     

Visions for the North Sea: The Societal Dilemma Behind Specifying Good Environmental Status

We augment discussions about the Good Environmental Status of the North Sea by developing two extreme visions and assessing their societal benefits. One vision (‘Then’) assumes restoration of benthic functioning; we contend that trawling had already degraded the southern North Sea a century ago. Available information is used to speculate about benthic functioning in a relatively undisturbed southern North Sea. The second vision (‘Now’) draws on recent benthic functioning. The supply of five ecosystem services, supported by benthic functioning, is discussed. ‘Then’ offers confidence in the sustainable supply of diverse services but restoration of past function is uncertain and likely to be paired with costs, notably trawling restraints. ‘Now’ delivers known and valued services but sustained delivery is threatened by, for example, climate change. We do not advocate either vision. Our purpose is to stimulate debate about what society wants, and might receive, from the future southern North Sea.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-014-0536-5) contains supplementary material, which is available to authorized users.     

Estimation of the impact of prevailing weather conditions on the occurrence of oil-contaminated dead birds on the German North Sea coast

Chronic oil pollution by illegal oil dumping in the North Sea is difficult to quantify. Beached, oil-contaminated sea birds, however, may be used as an indirect indicator. Reconstructing the drift of oil slicks and sea bird corpses in the southern North Sea for the period 1992-2003 by means of a two-dimensional numerical transport model driven by re-analysed weather data, we show with an example of two common sea bird species that the variability observed within the number of corpses registered during beached bird surveys for the German coast primarily reflects the inter-annual variability of prevailing weather conditions. This should be taken into account when interpreting the data. We propose normalisation of beached bird survey data based on numerical drift simulations to improve the recognition of trends in the level of chronic oil pollution.