Levels and distribution of brominated flame retardants in the soil of Harbin in China

This study reports the presence of brominated flame retardants in the topsoil in and around Harbin, a city in northeastern China. Samples of soil were collected from 17 locations in 2006, and the levels of 9 polybrominated diphenylethers （PBDEs 17, 28, 47, 66, 99, 100, 153, 154, and 183） ranged from 2.45 to 55.9 pg/g dry weight （dw） with a mean of 26.3 pg/g dw. These levels are very low comparing with those for some cities in Europe and USA. BDE 209 and hexabromocyclododecane were the two dominant congeners, with mean concentrations of 520 pg/g dw and 1750 pg/g dw, respectively. The concentrations of the total nine PBDE congeners clearly decreased from urban areas to background, but the compositions of individual congeners differed. Proportions of heavier congeners decreased while those of lighter congeners increased, along urban-rural-background transect, providing evidence for an urban fractionation effect. Correlation analysis indicated similar sources for PBDEs, hexabromocyclododecane, and 1,2-bis（2,4,6-tribromophenoxy）-ethane from urban areas but pentabromoethylbenzene was probably present due to long-range atmospheric transport. Principal component analysis was used to determine the characteristics of the relationships among these brominated flame retardants in the field.

A Simplified Analytical Procedure for Simultaneous Determination of Alkylphenol Ethoxylates and Brominated Flame Retardants in Fish Tissue Samples from Vaal River,South Africa

In this study, the concentration of alkylphenol ethoxylates (APEs) and brominated flame retardants (BFRs) were determined in fish samples, Labeo umbratus and Carp, collected from the Vaal River in South Africa. Ultrasonic-assisted extraction technique was used to extract the organic contaminants from fish samples, and the resulting extract was purified by sulphuric acid lipid removal followed by Strata X-cartridge SPE clean-up. The APEs and BFRs were derivatized using heptafluorobutyric anhydride before analysis with GC-MS. In both types of fish samples, lower oligomers of APEs were more abundant than the higher oligomers, while HBCD, BDE99 and PBB101 were the dominant BFRs. The concentrations of these pollutants ranged from 1.061 ng/g lipids (t-BP) in Labeo umbratus to 11.860 ng/g lipids (HBCD) in Carp.

Exposure Level, Toxicity Effects and Health Risk Assessment of Organophosphorus Flame Retardants in Water Environment

Organophosphorus flame retardants(OPFRs) are gradually replacing brominated flame retardants(BFRs), which are widely used in the world. The increasing output of OPFRs and the increasing detection of OPFRs in environmental media have attracted wide attention of scholars at home and abroad. OPFRs are generally semi-volatile, easy to enter the environment and accumulate in organisms,causing potential hazards to the environment and human health. In this paper, the pollution status and toxic effects of OPFRs in aquatic environment were introduced,and the research progress of human health risk caused by them was summarized.The existing problems were pointed out, and the future research was prospected. In the future, the analytical methods of various environmental and biological media should be improved, and comprehensive and in-depth environmental investigation and ecological and health risk assessment should be carried out. Attention should be paid to the effects of combined pollution on organisms and the study of biological acceptability.

Novel biomonitoring method for determining five classes of legacy and alternative flame retardants in human serum samples

Flame retardants(FRs)are ubiquitous in environment and biota and may pose harm to human health.In recent years,concern regarding legacy and alternative FRs has been intensified due to their widespread production and increasing contamination in environmental and human matrices.In this study,we developed and validated a novel analytical method for simultaneous determination of legacy and alternative FRs,including polychlorinated naphthalenes(PCNs),short-and middle-chain chlorinated paraffins(SCCPs and MCCPs),novel brominated flame retardants(NBFRs),and organophosphate esters(OPEs)in human serum.Serum samples were prepared by liquid-liquid extraction using ethyl acetate,and purified with Oasis®HLB cartridge and Florisil–silica gel columns.Instrumental analyses were carried out using gas chromatography-triple quadrupole mass spectrometry,highresolution gas chromatography coupled with high-resolution mass spectrometry,and gas chromatography coupled with quadrupole time-of-flight mass spectrometry,respectively.The proposed method was validated for linearity,sensitivity,precision,accuracy,and matrix effects.Method detection limits for NBFRs,OPEs,PCNs,SCCPs,and MCCPs were 4.6×10^(–4)–8.6×10^(–2),4.3×10^(–3)–1.3,1.1×10^(–5)–1.0×10^(–4),1.5,and 9.0×10–1 ng/mL,respectively.Matrix spike recoveries ranged from 73%–122%,71%–124%,75%–129%,92%–126%,and 94%–126%for NBFRs,OPEs,PCNs,SCCPs,and MCCPs,respectively.The analytical method was applied for detection of real human serum.CPs were the dominant FRs in serum,indicating CPs were widely presented in human serum and should be pay more attention for their health risk.

Superior and safer lithium sulfur batteries realized by robust polysulfides-retarding dam with high flame retardance

The unparalleled energy density has granted lithium-sulfur batteries(LSBs)with attractive usages.Unfortunately,LSBs still face some unsurpassed challenges in industrialization,with polysulfides shuttling,dendrite growth and thermal hazard as the major problems triggering the cycling instability and low safety.With the merit of convenience,the method of designing functional separator has been adapted.Concretely,the carbon aerogel confined with CoS_(2)(CoS_(2)-NCA)is constructed and coated on Celgard separator surface,acquiring CoS_(2)-NCA modified separator(CoS_(2)-NCA@C),which holds the promoted electrolyte affinity and flame retardance.As revealed,CoS_(2)-NCA@C cell gives a high discharge capacity 1536.9 mAh/g at 1st cycle,much higher than that of Celgard cell(987.1 mAh/g).Moreover,the thermal runaway triggering time is dramatically prolonged by 777.4 min,corroborating the promoted thermal safety of cell.Noticeably,the higher coulombic efficiency stability and lower overpotential jointly confirm the efficacy of CoS_(2)-NCA@C in suppressing the lithium dendrite growth.Overall,this work can provide useful inspirations for designing functional separator,coping with the vexing issues of LSBs.

Preparation of Polyurea Elastomer with Flame Retardant, Insulation and Thermal Conductivity Properties

By using 6,6-((sulfonylbis(4,1-phenylene)bis(azanediyl))bis(thiophen-2-ylm-ethylene))bis6H-di-benzo[c,e][1,2]oxaphosphinine 6-oxide(DOPO-N)as phosphorus-nitrogen flame retardant,the polyurea(PUA)with flame retardant properties(PUA/DOPO-N)was prepared.In addition,organically modified montmorillonite(OMMT)and magnesium hydroxide(MH)were used as co-effectors respectively,and the flame retardant PUA(PUA/DOPO-N/OMMT and PUA/DOPO-N/MH)were also prepared.Thermal properties,flame retardant properties,flame retardant mechanism and mechanical properties of PUA/DOPO-N,PUA/DOPO-N/OMMT and PUA/DOPO-N/MH were investigated by thermogravimetric(TG)analysis,limiting oxygen index(LOI),UL 94,cone calorimeter test,scanning electron microscopy(SEM),and tensile test.The results show that the LOI value of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH are 27.1%,27.7%,and 28.3%,respectively,and UL 94 V-0 rating is attained.Compared with PUA,the peak heat release rate(pk-HRR),total heat release(THR)and average effective heat combustion(av-EHC)of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH decrease significantly.SEM results indicate that the residual chars of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH are completer and more compact.The complex of DOPO-N/OMMT and DOPO-N/MH have synergistic flame retardancy.The mechanical properties of PUA can be improved by the addition of DOPO-N,DOPO-N/OMMT and DOPO-N/MH,respectively.The insulation performance test shows that the volume resistivity of PUA/20%DOPO-N is 6.25×10^(16)Ω.cm.Furthermore,by using modified boron nitride(MBN)as heat dissipating material,the complex of PUA/MBN was prepared,and the thermal conductivity of PUA/MBN was investigated.The thermal conductivity of PUA/8%MBN complex coating at room temperature is 0.166 W/(M·K),which is a 163%improvement over pure PUA.

Ten-Minute Synthesis of a New Redox-Active Aqueous Binder for Flame-Retardant Li-S Batteries

As a critical role in battery systems,polymer binders have been shown to efficiently suppress the lithium polysulfide shuttling and accommodate volume changes in recent years.However,preparation processes and safety,as the key criterions for Li-S batteries'practical applications,still attract less attention.Herein,an aqueous multifunction binder(named PEI-TIC)is prepared via an easy and fast epoxy-amine ring-opening reaction(10 min),which can not only give the sulfur cathode a stable mechanical property,a strong chemical adsorption and catalytic conversion ability,but also a fire safety improvement.The Li-S batteries based on the PEI-TIC binder display a high discharge capacity(1297.8 mAh g^(-1)),superior rate performance(823.0 mAh g^(-1)at 2 C),and an ultralow capacity decay rate of 0.035%over more than 800 cycles.Even under 7.1 mg cm^(-2)S-loaded,the PEI-TIC electrode can also achieve a high areal capacity of 7.2 mA h g^(-1)and excellent cycling stability,confirming its application potential.Moreover,it is also noted that TG-FTIR test is performed for the first time to explore the flame-retardant mechanism of polymer binders.This work provides an economically and environmentally friendly binder for the practical application and inspires the exploration of the flame-retardant mechanism of all electrode components.

Synthesis of Organic-Inorganic Hybrid Aluminum Hypophosphite Microspheres Flame Retardant and Its Flame Retardant Research on Thermoplastic Polyurethane

Aluminum hypophosphite microspheres(AHP) were synthesized by hydrothermal method using NaH2PO2·H2O and AlCl3·6H2O as raw materials, and then the AHP microspheres were polymerized by surface polymerization of micro-nanospheres with cyclic cross-linked poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol)(PZS). A new organic-inorganic poly(phosphonitrile)-modified aluminum hypophosphite microspheres(PZS-AHP) were synthesized by encapsulation and applied to flame retardant thermoplastic polyurethane(TPU). The microstructure and chemical composition of the PZS-AHP microsphere were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and X-ray spectroscopy. The thermal stability of PZS-AHP microsphere was explored with thermogravimetric analysis. Thermogravimetric data indicate that the PZS-AHP microspheres have excellent thermal stability. The thermal and flame-retarding properties of the TPU composites were evaluated by thermogravimetric(TG), limited oxygen index tests(LOI), and cone calorimeter test(CCT). The TPU composite achieved vertical burning(UL-94) V-0 grade and LOI value reached 29.2% when 10 wt% PZS-AHP was incorporated. Compared with those of pure TPU, the peak heat release rate(pHRR) and total heat release(THR) of TPU/10%PZS-AHP decreased by 82.2% and 42.5%, respectively. The results of CCT indicated that PZS-AHP microsphere could improve the flame retardancy of TPU composites.

Biobased Furfurylated Poplar Wood for Flame-Retardant Modification with Boric Acid and Ammonium Dihydrogen Phosphate

Furfurylated wood exhibits excellent dimensional stability and corrosion resistance,making it a promising material for constructing buildings,but it is highly flammable.Herein,flame-retardant furfurylated poplar wood was produced via a two-step process utilizing boric acid(BA)and ammonium dihydrogen phosphate(ADP)as flame-retardant components,and biomass-derived furfuryl alcohol(FA)as a modifier.The acidity of BA and ADP allowed them to catalyze the polymerization of FA,which formed a cross-linked network that immobilized BA and ADP inside the wood.The addition of BA/ADP substantially delayed the time to ignition from 10 to 385 s and reduced the total heat release and total smoke release by 58.75%and 77.31%,respectively.Analysis of the pyrolysis process showed that the decomposition products of BA and ADP protected the underlying furfurylated wood and diluted combustible gases.This method significantly improved the fire retardancy and smokeless properties of furfurylated wood,providing promising prospects for its application as an engineering material.

Research Progress in Flame Retardant in Flame Retardant Coatings

Flame retardant coatings are functional materials that can serve as decorative and protec-tive substrates in the event of a fire.Flame retardant coatings generally consist of two parts:a base material and a flame retardant agent.A detailed introduction was given to the development of flame retardant coatings in recent years and the flame retardants used in flame retardant coatings.Flame retardants mainly include halogen flame retar-dants,phosphorus nitrogen flame retardants,expansion flame retardants,biomass flame retardants,and graphene flame retardants.The application of flame retardant coatings in the fields of epoxy resin,polyurethane,etc.was elaborated.In addition,the application of new biomass flame retardants and graphene flame retardants was introduced,and the future development of flame retardant coatings and flame retardants was described.

Comparisons of indoor active and passive air sampling methods for emerging and legacy halogenated flame retardants in Beijing, China offices

One active and two passive air sampling configurations were deployed simultaneously in three offices in Beijing,China to test their comparability for sampling emerging and legacy halogenated flame retardants spanning a large range of octanoleair partition coefficients(KOA).Sampling in each office was carried out for three consecutive 28-day periods in the spring-summer of 2013.The active sampler was run for 2.5 h at different times every day for 28 days to parallel the passive samplers and sample a total volume comparable to that sampled by the passive samplers(~20 m^3).At the end of each 28-day sampling period,a separate active air sample was taken by running the sampler pump continuously for about 2.5 days.The comparability of measured concentrations varied between the air sampling configurations and for different compounds.The predominant compound measured in nearly all samples was BDE-209,a compound known to have heavy use in China.Several emerging flame retardants were also detected including DBE-DBCH,PBT,HBB,DDC-CO,and DBDPE.Very little of the tetra-hexabrominated BDEs associated with the technical PentaBDE product was observed.

A review of polybrominated diphenyl ethers and alternative brominated flame retardants in wildlife from China:Levels,trends,and bioaccumulation characteristics

Accelerated industrialization and urbanization,and unregulated disposal of waste of electric and electronic equipment（e-waste） in China have caused environmental pollution of brominated flame retardants（BFRs）.This review summarized the levels,trends,and bioaccumulation characteristics of polybrominated diphenyl ethers（PBDEs） and other potential alternative BFRs including hexabromocyclododecanes（HBCDs）,1,2-bis（2,4,6-dibromophenoxy） ethane（BTBPE） and decabromodiphenylethane（DBDPE） in wildlife from China.PBDE levels in wildlife from China were generally higher than those from other parts in Asia,and were comparable to those from Europe but were lower than those from North America.However,wildlife from the e-waste recycling sites in South China and East China contained much higher PBDEs compared to other reports around the world,suggesting the heavy contamination of PBDEs in these regions.The alternative BFRs were also detected in wildlife,revealing that the animals are exposed to these chemicals,in addition to PBDEs.Temporal trends indicated by levels in marine mammals from South China suggested that PBDE levels increased from the beginning of 1990s to 2000s,but decreased from the middle of 2000s,followed by relatively steady levels.In contrast,HBCDs were found to be continuously increasing from 1997 to 2007,indicating the increasing usage of HBCDs in China in recent years.Compared to PBDE profiles found in other parts,aquatic species and birds from China contained relatively higher contributions of BDE28 and 209,respectively,suggesting the possible different usage pattern of PBDEs.Future works including keeping monitoring at a reasonable scale and frequency to make sure levels near urban centers indicative of population do not increase are needed.Additionally,focus effort on e-waste recycling regions to look for impacts and to determine if regulation/controls are resulting in lower environmental contamination,and incorporation of sentinel species in monitoring efforts are recommended.

Concentrations and distribution of novel brominated flame retardants in the atmosphere and soil of Ny-Alesund and London Island,Svalbard,Arctic

Novel brominated flame retardants(NBFRs)were investigated in Arctic air and soil samples collected from Ny-?lesund and London Island,Svalbard,during Chinese scientific research expeditions to the Arctic during 2014–2015.The concentrations of 9 NBFRs in the Arctic air and soil were 4.9–8.7 pg/m3(average 6.8 pg/m3)and 101–201 pg/g dw(average 150 pg/g dw),respectively.The atmospheric concentration of hexabromobenzene(HBB)was significantly correlated with that of pentabromotoluene(PBT)and pentabromobenzene(PBBz),suggesting similar source and environmental fate in the Arctic air.No significant spatial difference was observed among the different sampling sites,both for air and soil samples,indicating that the effects of the scientific research stations on the occurrence of NBFRs in the Arctic were minor.The fugacities from soil to air of pentabromoethylbenzene(PBEB),2,3-dibromopropyl 2,4,6-tribromophenyl ether(DPTE),and decabromodiphenylethane 1,2-bis(pentabromophenyl)ethane(DBDPE)were lower than the equilibrium value,indicating a nonequilibrium state of these compounds between air and soil,the dominant impact of deposition and the net transport from air to soil.The correlation analysis between the measured and predicted soil-atmosphere coefficients based on the absorption model showed that the impact of the soil organic matter on the distribution of NBFRs in the Arctic region was minor.To the best of our knowledge,this work is one of the limited reports on atmospheric NBFRs in the Arctic and the first study to investigate the occurrence and fate of NBFRs in the Arctic soil.

Presence of organophosphate flame retardants(OPEs)in different functional areas in residential homes in Beijing,China

The production and application of organophosphate esters(OPEs)have dramatically increased in recent years due to their use as a replacement for brominated flame retardants.In this study,13 OPEs(∑_(13)OPEs)were analyzed in indoor air samples from kitchens and living rooms in 14 residential homes in Beijing,China.The concentrations of ∑_(13)OPEs in kitchen air samples(mean:13 ng/m^(3))were significantly(p<0.05)higher than in living room air samples(5.0 ng/m^(3)).In addition,paired window surface organic film samples were collected and analyzed to investigate film-air partitioning,exhibiting a mean concentration of ∑_(13)OPEs of 4100 ng/m^(2).The congener profiles showed that tris(2-chloroisopropyl)phosphate(TCPP)was the predominant compound in both window film samples(48%)and the corresponding indoor air sample(56%).The estimated daily intakes(EDI)of OPEs via indoor air inhalation were 2.8 and 1.4 ng/kg/day for infants and adults,respectively,both of which are below the reference dose values(RfDs).Overall,these findings indicate that OPEs in the indoor air environment of residential homes in Beijing are not likely to pose a health risk to the general population.

The presence and partitioning behavior of flame retardants in waste,leachate,and air particles from Norwegian waste-handling facilities

Flame retardants in commercial products eventually make their way into the waste stream.Herein the presence of flame retardants in Norwegian landfills, incineration facilities and recycling sorting/defragmenting facilities is investigated. These facilities handled waste electrical and electronic equipment（WEEE）, vehicles, digestate, glass, combustibles, bottom ash and fly ash. The flame retardants considered included polybrominated diphenyl ethers（∑BDE-10） as well as dechlorane plus, polybrominated biphenyls, hexabromobenzene,pentabromotoluene and pentabromoethylbenzene（collectively referred to as ∑FR-7）. Plastic,WEEE and vehicles contained the largest amount of flame retardants（∑BDE-10： 45,000–210,000 μg/kg; ∑FR-7： 300–13,000 μg/kg）. It was hypothesized leachate and air concentrations from facilities that sort/defragment WEEE and vehicles would be the highest. This was supported for total air phase concentrations（∑BDE-10： 9000–195,000 pg/m^3 WEEE/vehicle facilities, 80–900 pg/m^3 in incineration/sorting and landfill sites）, but not for water leachate concentrations（e.g., ∑BDE-10： 15–3500 ng/L in WEEE/Vehicle facilities and 1–250 ng/L in landfill sites）. Landfill leachate exhibited similar concentrations as WEEE/vehicle sorting and defragmenting facility leachate. To better account for concentrations in leachates at the different facilities, waste-water partitioning coefficients, Kwastewere measured（for the first time to our knowledge for flame retardants）. WEEE and plastic waste had elevated Kwastecompared to other wastes, likely because flame retardants are directly added to these materials. The results of this study have implications for the development of strategies to reduce exposure and environmental emissions of flame retardants in waste and recycled products through improved waste management practices.

Seasonal variations of polybrominated flame retardants bound to car dust under Mediterranean climate

Polybrominated diphenyl ethers（PBDEs） are commercial flame retardants that have been commonly used in vehicle interior to reduce fire-related hazards. Due to high temperatures and intense insolation that can be attained inside cars parked in the sun, additive PBDEs are prone to leach out and attach to in-vehicle dust, as well as to photo-debrominate. This study examines seasonal variations of concentrations of three common PBDE congeners（BDE-47, BDE-99 and BDE-209） in car dust in Israel. The overall concentrations of these BDEs ranged from 1 to 29 μg/g, and were higher in the summer than in the winter（average of 10.2 and5.3 μg/g, respectively）. Congener-specific concentrations showed distinct seasonal pattern,representing the interplay between leaching, evaporation and photodebromination. Photolysis of the three congeners, while adsorbed on glass filters and exposed to solar radiation, revealed first order kinetics with debromination rates on the order of 10-2/min. Hence, seasonal variations of the meteorological conditions were found to affect the in-vehicle PBDE concentrations, and are therefore expected also to affect the exposure of passengers to PBDEs.

Occurrence of emerging flame retardants from e-waste recycling activities in the northern part of Vietnam

This study investigated the contamination status of 21 emerging flame retardants(FRs)in soils(n=32)and river sediments(n=8)from an e-waste recycling(EWR)site in the northern part of Vietnam.Among analyzed FRs,higher levels of decabromodiphenyl ethane(DBDPE)(NDe4200 ng/g dw),1,2-bis-(2,4,6-tribromophenoxy)ethane(BTBPE)(NDe350 ng/g dw)and Dechlorane Plus isomers(DPs)(NDe65 ng/g dw)were found in soils near EWR workshops and open burning places.The highest concentrations of DBDPE(20 ng/g dw),BTBPE(5.7 ng/g dw)and DPs(6.7 ng/g dw)were also detected in sediments collected from the middle of the EWR site.The levels decreased concomitantly with increasing distance from the EWR site.These results indicate that these FRs were released to the surrounding environment from improper recycling activities,such as manual dismantling of devices and open burning of e-wastes.Moreover,the estimated daily intakes of those FRs via soil ingestion were approximately ten times higher for children than adults.To our knowledge,this is a first comprehensive study on characterization of soil and sediment contamination by a series of emerging FRs at an EWR site in Vietnam.

Detection of novel brominated flame retardants (NBFRs) in the urban soils of Melbourne, Australia

A range of brominated flame retardants(BFRs)have been incorporated into polymeric materials like plastics,electronic equipment,foams and textiles to prevent fires.The most common of these,polybrominated diphenyl ethers(PBDEs),have been subject to legislated bans and voluntary withdrawal by manufacturers in North America,Europe and Australia over the past decade due to long-range atmospheric transport,persistence in the environment,and toxicity.Evidence has shown that replacement novel brominated flame retardants(NBFRs)are released to the environment by the same mechanisms as PBDEs and share similar hazardous properties.The objective of the current research was to characterize soil contamination by NBFRs in the urban soils of Melbourne,Australia.A variety of industrial and nonindustrial land-uses were investigated with the secondary objective of determining likely point sources of pollution.Six NBFRs;pentabromotoluene(PBT),pentabromoethylbenzene(PBEB),hexabromobenzene(HBB),2-ethylhexyl-2,3,4,5-tetrabromobenzoate(EH-TBB),1,2-bis(2,4,6-tribromophenoxy)ethane(BTBPE)and decabromodiphenyl ethane(DBDPE)were measured in 30 soil samples using selective pressurized liquid extraction(S-PLE)and gas chromatography coupled to triple quadrupole mass spectrometry(GC-MS/MS).NBFRs were detected in 24/30 soil samples with S5NBFR concentrations ranging from nd-385 ng/g dw.HBB was the most frequently detected compound(14/30),while the highest concentrations were observed for DBDPE,followed by BTBPE.Electronic waste recycling and polymer manufacturing appear to be key contributors to NBFR soil contamination in the city of Melbourne.A significant positive correlation between S8PBDEs and S5NBFR soil concentrations was observed at waste disposal sites to suggest that both BFR classes are present in Melbourne's waste streams,while no association was determined among manufacturing sites.This research provides the first account of NBFRs in Australian soils and indicates that these emerging contaminants possess a similar potential to contaminate Melbourne soils as PBDEs.

Current-use halogenated and organophosphorous flame retardants:A review of their presence in Arctic ecosystems

Since the ban of polybrominated diphenyl ethers(PBDEs)and hexabromocyclododecane(HBCDD),other flame retardants may be increasingly used.Thirty-one current-use halogenated(HFRs)and 24 organophosphorous flame retardants(PFRs)have been sought in Arctic ecosystems so far.Air measurements provide evidence of long-range atmospheric transport for the majority of these compounds,with much higher concentrations for PFRs than for HFRs.Some HFRs,i.e.bis(2-ethylhexyl)-tetrabromophthalate(BEH-TEBP),2-ethylhexyl-2,3,4,5-tetrabromobenzoate(EH-TBB)and hexabromobenzene(HBBz),had air concentrations comparable to those of PBDEs in some studies.Complementary data for seawater and ice indicate dry deposition of HFRs,while net volatilization from seawater was observed for some PFRs.Studies in the marine environment indicate a wide presence of HFRs in marine biota,but generally at low levels,i.e.typically lower than those of PBDEs.Exceptions exist,namely 2,4,6-tribromophenyl 2,3-dibromopropyl ether(TBP-DBPE)and decabromodiphenyl ethane(DBDPE),which were found in concentrations comparable to PBDEs in some species.The same was the case for 2,4,6-tribromophenyl allyl ether(TBP-AE)in a study from the terrestrial environment.PFRs generally had low concentrations in biota,probably due to metabolic transformation of PFR triesters,as suggested by in vitro studies.Elevated PFR concentrations occurred in some individuals,generally indicating a larger variability of PFRs in biota than found for HFRs.The commercially important tetrabromobisphenol A(TBBPA)was only detected sporadically,and only in abiotic matrices.

Temporal trends in concentrations of legacy and novel brominated flame retardants in house dust from Birmingham in the United Kingdom

Concentrations of polybrominated diphenyl ethers(PBDEs),hexabromocyclododecane(HBCDD),tetrabromobisphenol-A(TBBPA)and two potential replacements decabromodiphenylethane(DBDPE)and 1,2-bis(2,4,6-tribromophenoxy)ethane(BTBPE)were measured in dust samples collected from 14 homes across Birmingham(UK).Concentrations were compared with those from the same city in previous studies to ascertain any temporal changes and to assess the effects of legislative restrictions.The average PHBCDDs concentration(46,000 ng/g;median=280 ng/g)included the highest dust concentration recorded globally(570,000 ng/g).This is despite the listing of HBCDD under the Stockholm Convention in 2013,demonstrating that decreases in indoor contamination will likely be slow as existing sources are gradually discarded.In contrast,concentrations of BDE-47(mean=5.7 ng/g;median=0.93 ng/g)and BDE-99(mean=11 ng/g;median=2.9 ng/g)were significantly lower than in all previous(p<0.01)studies in the same city since 2006,suggesting restrictions on the Penta-BDE formulation have been effective.The average BDE-209 concentration(4800 ng/g;median=1600 ng/g)is lower than the peak average concentration,which was observed in 2007(280,000 ng/g),however this is not a significant decline,probably due to the later imposition of Deca-BDE restrictions compared to those on Penta-BDE.Decreases in PBDE concentrations have coincided with a significant(p<0.01)increase in DBDPE concentrations(average=1500 ng/g;median=660 ng/g)since 2014,suggesting its use as a replacement flame retardant for Deca-BDE.While no significant change was detected for BTBPE(average 11 ng/g;median=0.84 ng/g in this study);concentrations of TBBPA(average=34 ng/g;median=35 ng/g)were significantly lower(p<0.05)than in 2007(average 62 ng/g).The decreases observed in PBDE concentrations,demonstrates that legislation has been effective in reducing the commercial use of PBDEs,however this has coincided with increases of alternative flame retardants such as DBDPE.