The interfaces of perovskite solar cells(PSCs)are well known to be rich in deep-level carrier traps,which serve as non-radiative recombination centers and limit the open-circuit voltage(Voc)and power conversion effici...The interfaces of perovskite solar cells(PSCs)are well known to be rich in deep-level carrier traps,which serve as non-radiative recombination centers and limit the open-circuit voltage(Voc)and power conversion efficiency(PCE)of PSCs.Defect chemistry and surface passivators have been researched extensively and mainly focused on the neutralization of uncoordinated lead or anion defects.Herein,a novel brominated passivator 2-bromophenethylammonium iodide(2-Br-PEAI)is introduced for a multi-functional passivation effect at the perovskite interface.The brominated species readily form 2D perovskite on top of the 3D perovskite and multi-interact with the 3D perovskite surface.Apart from the halide vacancy filling and anion bonding ability,the Br atoms on the benzene ring can interact with the FA cations via strong hydrogen bonding N-H…Br and interact with the[PbI_(6)]^(4−)inorganic framework.The interface defects in the PSCs are well passivated,minimizing non-radiative recombination and enhancing device performance.As a result,a champion PCE of 24.22%was achieved with high V_(oc)and fill factor.In addition,modified devices also showed enhanced operational stability(retention of>95%initial PCE after 400 h)and humidity resistance(>90%initial PCE maintained after 1500 h under~50%RH).展开更多
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 polybromi...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.展开更多
A new brominated phenylpropylaldehyde and its dimethyl acetal together with a new natural brominated phenol were isolated from Rhodomela confervoides. Their structrues were elucidated as 2-methyl-3-(2,3-dibromo-4,5-di...A new brominated phenylpropylaldehyde and its dimethyl acetal together with a new natural brominated phenol were isolated from Rhodomela confervoides. Their structrues were elucidated as 2-methyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)propylaldehyde, 2-methyl-3-(2,3-di-bromo-4,5-dihydroxyphenyl) propylaldehyde dimethyl acetal and 3-bromo-4,5-dihydroxybenzoic acid methyl ester by spectroscopic techniques including IR, HRFABMS, ID and 2DNMR experiments.展开更多
This study describes the development and validation of a sensitive and reliable method for determination of polybrominated diphenyl ethers（PBDEs）in atmospheric particulate matter using selective pressurized liquid e...This study describes the development and validation of a sensitive and reliable method for determination of polybrominated diphenyl ethers（PBDEs）in atmospheric particulate matter using selective pressurized liquid extraction（SPLE）and gas chromatography–mass spectrometry with a negative chemical ionization（GC-NCI-MS）.Extraction and clean-up were performed using PLE with 2 g florisil and 3 g silica placed in the extraction cells.Under optimal conditions,14 PBDEs were extracted at 70℃ using hexane/dichloromethane（50：50,v/v）as solvent.Validation of SPLE returned excellent recoveries for most analytes,with relative standard deviations mostly below20%.Method detection limits ranged from 0.13 to15.38 ng·mL^-1 for the GC-MS analyses.The method was successfully applied to atmospheric particulate matter of Beijing,where analytes were detected in the range of182.79 to 468.99 pg·m^-3.展开更多
Two brominated sesquiterpenes were isolated from the Alga Laurencia majuscula collected from the Xisha Islands in the South China Sea. Compound 1 was first reported, and determined, on spectral evidence, to be 8 bromo...Two brominated sesquiterpenes were isolated from the Alga Laurencia majuscula collected from the Xisha Islands in the South China Sea. Compound 1 was first reported, and determined, on spectral evidence, to be 8 bromo 1 en chamigrene.展开更多
Eight new brominated 2＇（4＇）-nitro-3-hydroxy diphenyl ethers have been designed and synthesized. The structures of new compounds were confirmed by ^1H NMR, IR and HRMS. The bioactivity tests showed that these compo...Eight new brominated 2＇（4＇）-nitro-3-hydroxy diphenyl ethers have been designed and synthesized. The structures of new compounds were confirmed by ^1H NMR, IR and HRMS. The bioactivity tests showed that these compounds possessed antibacterial activities against the tested bacteria. These new compounds cannot be transformed into dioxins when they were manufactured and used.展开更多
Thermal degradation of a FR-4 type printed circuit board, PCB, containing brominated flame retardant has been studied both in inert and oxidative atmosphere for the emission control of harmful brominated compounds. Th...Thermal degradation of a FR-4 type printed circuit board, PCB, containing brominated flame retardant has been studied both in inert and oxidative atmosphere for the emission control of harmful brominated compounds. The presence of oxygen in atmosphere resulted in the reduction of the yield of hydrogen bromide, one of the major brominated compounds in thermal treatment, and in the enhancement of the formation of bromine and hypobromous acid. The intentional addition of zinc oxide to the PCB powder sample gave rise to the fixation of Br as zinc bromide. It also resulted in the promotion of the release of brominated compounds in comparison to the case of pure PCB. Thus, the addition of the oxide can be a benefit with respect to the bromine fixation and the kinetics of thermal treatment of PCB as well as metal recovery.展开更多
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. Ultras...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.展开更多
To elucidate the mechanism of brominated natural rubber(BNR), eight BNR samples with different bromine content were prepared from latex in different bromination time, and the microstructures were characterized by Four...To elucidate the mechanism of brominated natural rubber(BNR), eight BNR samples with different bromine content were prepared from latex in different bromination time, and the microstructures were characterized by Fourier transform infrared spectroscopy(FTIR) and ~1H-NMR spectroscopy, respectively. The hardness of BNR increased and its nature transformed from elastomer to resin with the increase of bromine content. Unlike chlorinated natural rubber(CNR), FTIR showed that there were no carbonyl groups on the molecular chains of BNR. ~1H-NMR spectroscopy revealed that the reaction activity of bromine and the secondary hydrogen atom of BNR were much higher than those of the primary one. The brominated substitution took place in the hydrogen atom of CH_3 and CH_2 groups firstly, then in the late period of bromination the bond of C=C was transferred to the saturated bond of C-C due to the Markovnikov addition of hydrogen bromide. Based on these findings, the mechanism of BNR from latex could be deduced as a free radical reaction and the detailed bromination process was presented.展开更多
The apparent solubility (S), concentration-average diffusivity (D), and permeability (P), for C0_2, CH_4 and N_2 through PPO and aryl-brominated PPO at 35℃ for pressure ranging from 1 to 26 atm are reported. It is fo...The apparent solubility (S), concentration-average diffusivity (D), and permeability (P), for C0_2, CH_4 and N_2 through PPO and aryl-brominated PPO at 35℃ for pressure ranging from 1 to 26 atm are reported. It is found that P, D, and S of the membranes to all the three gases vary with the extent of bromination. S increases with the increase of the percent of bromine in each case, but D to CO_2 increases remarkably only at higher degree of brominafion, and therefore, P to CO_2 is increased by more than 100% over a wide range ofpressure in the case. The solubility data are well described by the dual mode sorption model. It is found that the gas molecules sorbed by the Langmuir mode are relatively more immobilized and the contribution of the nonequilibrinm character of the polymer to gas permeation increases obviously for CO_2 and is hardly changed for CH_4 with increasing bromine content. These observations are interpreted in terms of changes in specific free volume (SFV)and the cohesive energy density (CED) of the polymers.展开更多
With the B3LYP calculation method of density functional theory（DFT）and the 6-31G＊ basis set,full optimization calculation was made for phenoxathiin10-oxide（PTO）and 135 polybromine phenoxathiin 10-oxides（PBPTOs）...With the B3LYP calculation method of density functional theory（DFT）and the 6-31G＊ basis set,full optimization calculation was made for phenoxathiin10-oxide（PTO）and 135 polybromine phenoxathiin 10-oxides（PBPTOs）with the Gaussian 03 program and molar heat capacity in constant volume（CVθ）value of each molecule in the standard state was obtained.The relation between CVθ and the substitution position and number of bromine atom（NPBS）was studied,and the results indicated good correlation（R2 = 1.000）between CVθ and NPBS of PBPTO compounds.Based on the output file of Gaussian 03 program,molar heat capacity at constant pressure（Cp,m）of PBPTO compounds from 200 to 1,000 K was calculated with the statistical thermodynamics program,and the correlation equation between Cp,m and temperature（T,T-1 and T-2）was obtained with the least-squares method,and the correlation coefficient of the correlation equation（R2）was 1.000.In addition,based on the partition function of each molecule calculated by vibration analysis,the relative rate constant of formation of each molecule was calculated.展开更多
Self-healing anticorrosive coatings in extreme environment have attracted considerable interest from researchers.In this work,4-tert-butylpyridine(TBP)was incorporated into brominated butyl rubber(BIIR)polymer network...Self-healing anticorrosive coatings in extreme environment have attracted considerable interest from researchers.In this work,4-tert-butylpyridine(TBP)was incorporated into brominated butyl rubber(BIIR)polymer networks to form a reversible ionic bond with the highly reactive bromine anion.Based on the low glass transition temperature of the BIIR polymer and the electrostatic effects,a robust self-healing anticorrosive coating of TBP-BIIR was prepared.TBP-BIIR coating showed a maximum protection efficiency(PE)of more than 94%(TBP-BIIR-acid,94.37%;TBP-BIIR-alkali,94.95%;TBP-BIIR-salt,95.49%)when treated with a strong acid(HNO_(3),pH=2),strong base(NaOH,pH=12)and high salt solution(3.5 wt%NaCl).In addition,the PE of coating repaired exceed 89%,and the maximum PE value was approximately 95%in different solutions,which demonstrated its extinguished self-healing abilities.These results indicated that the TBP-BIIR anticorrosive coating could provide excellent safety and durability in special environment,which would be extremely beneficial to improve the working life of metal parts used in aviation and shipping,oil and gas and related industries.展开更多
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...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.展开更多
Decabromodiphenyl ether （BDE209） is the primary component in a commonly used flame retardant. Previous studies had proved that BDE209 itself was not toxic, while its metabolites including debrominated diphenyl ethe...Decabromodiphenyl ether （BDE209） is the primary component in a commonly used flame retardant. Previous studies had proved that BDE209 itself was not toxic, while its metabolites including debrominated diphenyl ethers （De-BDEs） and methoxylated brominated diphenyl ethers （MeO-BDEs） posed a potential threat to organisms. Many studies had indicated that BDE209 could metabolize quickly in mammals, but lacking in the basic data about the metabolism of BDE209 in fish. In the present study, two replicate treatment groups of rainbow trout （Oncorhynchus rnykiss） were exposed to BDE209 via a single intraperitoneal injection approximately 100 and 500 ng/g, respectively. Muscle, liver and blood samples were collected to analyze the specific metabolites on day 1 and day 28 post injection. The highest concentration of BDE209 was detected in muscle tissues, from 796.1 ng/g wet weight （day 1） to 687.1 ng/g wet weight （day 28） in high dose group, suggesting that BDE209 could accumulate slightly in muscle tissues. However, BDE209 was not detected in the blood for all treatments. Most congeners of De-BDEs were found in muscle and liver tissues, with the highest concentration in the liver. The main De-BDEs were nona-, octa-, hepta- and penta-De-BDEs. A total of seven MeO-BDE metabolites were observed among different fish tissues. Blood had the highest contribution of the MeO-BDE metabolites. Each MeO-BDE congener increased over the 28 days. These results in contrast to other studies suggested possible species-specific differences in metabolic abilities.展开更多
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(B...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.展开更多
Brominated phenols （BPs）, a widely used group of emerging flame retardants, are important environmental contaminants and exhibit endocrine disrupting potential. Method for simultaneous determination of tetrabromobis...Brominated phenols （BPs）, a widely used group of emerging flame retardants, are important environmental contaminants and exhibit endocrine disrupting potential. Method for simultaneous determination of tetrabromobisphenol A （TBBPA）, tribromophenol （TBP）, dibromophenols （DBPs） and monobromophenols （MBPs） in soils using gas chromatography-mass spectrometry analysis （GC/MS） was successfully developed. Cleanup methods for soil extracts including several solid-phase extraction cartridges and different elution solvents were compared and optimized. Florisil cartridge with dichloromethane as the elution reagent was selected for sample cleanup owing to its high and reproducible recoveries of the target analytes in soils. Derivatization conditions were tested and the optimal conditions were obtained with 20 μL silylation reagent at room temperature. The chromatographic separation was optimized with different columns and DB-XLB column was selected for its excellent separation of the analytes. The limits of detection for the target compounds were from 0.04 to 0.19 ng/g. Mean recoveries of the compounds from spiked soils exceeded 84% with a good reproducibility, excepting that the recovery of 2-bromophenol was relatively poor （lower than 55%） due to its instability. The developed method was applied to the determination of the BPs in the soils collected from e-waste sites. The contents of BPs in the soils were at ng/g levels with TBBPA and TBP the most frequently detected. To our knowledge, this is the first report for the simultaneous determination of TBBPA, TBP, DBPs and MBPs in soils.展开更多
The brominated products, formed in chlorination treatment of benzophenone-4 in the presence of bromide ions, were identified, and the formation pathways were proposed.Under disinfection conditions, benzophenone-4 woul...The brominated products, formed in chlorination treatment of benzophenone-4 in the presence of bromide ions, were identified, and the formation pathways were proposed.Under disinfection conditions, benzophenone-4 would undertake electrophilic substitution generating mono- or di-halogenated products, which would be oxidized to esters and further hydrolyzed to phenol derivatives. The generated catechol intermediate would be transformed into furan-like heterocyclic product. The product species were p H-dependent,while benzophenone-4 elimination was chlorine dose-dependent. When the chlorination treatment was performed on ambient water spiked with benzophenone-4 and bromide ions, most of brominated byproducts could be detected, and the acute toxicity significantly increased as well.展开更多
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 2014–2...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.展开更多
Here, we examined the incineration of extruded polystyrene containing hexabromocyclododecane（HBCD） in a pilot-scale incinerator under various combustion temperatures（800–950℃） and flue gas residence times（2–8 ...Here, we examined the incineration of extruded polystyrene containing hexabromocyclododecane（HBCD） in a pilot-scale incinerator under various combustion temperatures（800–950℃） and flue gas residence times（2–8 sec）. Rates of HBCD decomposition ranged from 99.996%（800℃, 2 sec） to 99.9999%（950℃, 8 sec）; the decomposition of HBCD, except during the initial stage of combustion（flue gas residence time 〈 2 sec）, followed a pseudo-first-order kinetics model. An Arrhenius plot revealed that the activation energy and frequency factor of the decomposition of HBCD by combustion were 14.2 kJ/mol and 1.69 sec^（-1）,respectively. During combustion, 11 brominated polycyclic aromatic hydrocarbons（BrPAHs）were detected as unintentional by-products. Of the 11 BrPAHs detected, 2-bromoanthracene and 1-bromopyrene were detected at the highest concentrations. The mutagenic and carcinogenic BrPAHs 1,5-dibromoanthracene and 1-bromopyrene were most frequently detected in the flue gases analyzed. The total concentration of BrPAHs exponentially increased（range,87.8–2,040,000 ng/m^3） with increasing flue gas residence time. Results from a qualitative analysis using gas chromatography/high-resolution mass spectrometry suggest that bromofluorene and bromopyrene（or fluoranthene） congeners were also produced during the combustion.展开更多
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 ether...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.展开更多
基金supported by the National Natural Science Foundation of China(21872080)State Key Laboratory of Power System and Generation Equipment(No.SKLD21Z03,SKLD20M03)China Postdoctoral Science Foundation(No.043240004).
文摘The interfaces of perovskite solar cells(PSCs)are well known to be rich in deep-level carrier traps,which serve as non-radiative recombination centers and limit the open-circuit voltage(Voc)and power conversion efficiency(PCE)of PSCs.Defect chemistry and surface passivators have been researched extensively and mainly focused on the neutralization of uncoordinated lead or anion defects.Herein,a novel brominated passivator 2-bromophenethylammonium iodide(2-Br-PEAI)is introduced for a multi-functional passivation effect at the perovskite interface.The brominated species readily form 2D perovskite on top of the 3D perovskite and multi-interact with the 3D perovskite surface.Apart from the halide vacancy filling and anion bonding ability,the Br atoms on the benzene ring can interact with the FA cations via strong hydrogen bonding N-H…Br and interact with the[PbI_(6)]^(4−)inorganic framework.The interface defects in the PSCs are well passivated,minimizing non-radiative recombination and enhancing device performance.As a result,a champion PCE of 24.22%was achieved with high V_(oc)and fill factor.In addition,modified devices also showed enhanced operational stability(retention of>95%initial PCE after 400 h)and humidity resistance(>90%initial PCE maintained after 1500 h under~50%RH).
基金supported by the Heilongjiang Province Postdoctoral Research Funding (No. AUGA41001074)
文摘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.
基金support from the NSF(Grant No.99-929-01-26)national“863”program(Grant No.2001AA620403).
文摘A new brominated phenylpropylaldehyde and its dimethyl acetal together with a new natural brominated phenol were isolated from Rhodomela confervoides. Their structrues were elucidated as 2-methyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)propylaldehyde, 2-methyl-3-(2,3-di-bromo-4,5-dihydroxyphenyl) propylaldehyde dimethyl acetal and 3-bromo-4,5-dihydroxybenzoic acid methyl ester by spectroscopic techniques including IR, HRFABMS, ID and 2DNMR experiments.
基金supported by the National Natural Science Foundation of China(41325010)
文摘This study describes the development and validation of a sensitive and reliable method for determination of polybrominated diphenyl ethers（PBDEs）in atmospheric particulate matter using selective pressurized liquid extraction（SPLE）and gas chromatography–mass spectrometry with a negative chemical ionization（GC-NCI-MS）.Extraction and clean-up were performed using PLE with 2 g florisil and 3 g silica placed in the extraction cells.Under optimal conditions,14 PBDEs were extracted at 70℃ using hexane/dichloromethane（50：50,v/v）as solvent.Validation of SPLE returned excellent recoveries for most analytes,with relative standard deviations mostly below20%.Method detection limits ranged from 0.13 to15.38 ng·mL^-1 for the GC-MS analyses.The method was successfully applied to atmospheric particulate matter of Beijing,where analytes were detected in the range of182.79 to 468.99 pg·m^-3.
文摘Two brominated sesquiterpenes were isolated from the Alga Laurencia majuscula collected from the Xisha Islands in the South China Sea. Compound 1 was first reported, and determined, on spectral evidence, to be 8 bromo 1 en chamigrene.
文摘Eight new brominated 2＇（4＇）-nitro-3-hydroxy diphenyl ethers have been designed and synthesized. The structures of new compounds were confirmed by ^1H NMR, IR and HRMS. The bioactivity tests showed that these compounds possessed antibacterial activities against the tested bacteria. These new compounds cannot be transformed into dioxins when they were manufactured and used.
文摘Thermal degradation of a FR-4 type printed circuit board, PCB, containing brominated flame retardant has been studied both in inert and oxidative atmosphere for the emission control of harmful brominated compounds. The presence of oxygen in atmosphere resulted in the reduction of the yield of hydrogen bromide, one of the major brominated compounds in thermal treatment, and in the enhancement of the formation of bromine and hypobromous acid. The intentional addition of zinc oxide to the PCB powder sample gave rise to the fixation of Br as zinc bromide. It also resulted in the promotion of the release of brominated compounds in comparison to the case of pure PCB. Thus, the addition of the oxide can be a benefit with respect to the bromine fixation and the kinetics of thermal treatment of PCB as well as metal recovery.
基金The authors are indebted to Rand Water for providing the technical environment and funding for this project which is part of Mr.Chokwe’s doctoral degree and Tshwane University of Technology for support
文摘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.
基金Funded by the National Natural Science Foundation of China(No.21264006)National Scholarship Fund of China(No.201308460040)
文摘To elucidate the mechanism of brominated natural rubber(BNR), eight BNR samples with different bromine content were prepared from latex in different bromination time, and the microstructures were characterized by Fourier transform infrared spectroscopy(FTIR) and ~1H-NMR spectroscopy, respectively. The hardness of BNR increased and its nature transformed from elastomer to resin with the increase of bromine content. Unlike chlorinated natural rubber(CNR), FTIR showed that there were no carbonyl groups on the molecular chains of BNR. ~1H-NMR spectroscopy revealed that the reaction activity of bromine and the secondary hydrogen atom of BNR were much higher than those of the primary one. The brominated substitution took place in the hydrogen atom of CH_3 and CH_2 groups firstly, then in the late period of bromination the bond of C=C was transferred to the saturated bond of C-C due to the Markovnikov addition of hydrogen bromide. Based on these findings, the mechanism of BNR from latex could be deduced as a free radical reaction and the detailed bromination process was presented.
文摘The apparent solubility (S), concentration-average diffusivity (D), and permeability (P), for C0_2, CH_4 and N_2 through PPO and aryl-brominated PPO at 35℃ for pressure ranging from 1 to 26 atm are reported. It is found that P, D, and S of the membranes to all the three gases vary with the extent of bromination. S increases with the increase of the percent of bromine in each case, but D to CO_2 increases remarkably only at higher degree of brominafion, and therefore, P to CO_2 is increased by more than 100% over a wide range ofpressure in the case. The solubility data are well described by the dual mode sorption model. It is found that the gas molecules sorbed by the Langmuir mode are relatively more immobilized and the contribution of the nonequilibrinm character of the polymer to gas permeation increases obviously for CO_2 and is hardly changed for CH_4 with increasing bromine content. These observations are interpreted in terms of changes in specific free volume (SFV)and the cohesive energy density (CED) of the polymers.
基金supported by the National Natural Science Foundation of China (41071319,20977046 and 20737001)
文摘With the B3LYP calculation method of density functional theory（DFT）and the 6-31G＊ basis set,full optimization calculation was made for phenoxathiin10-oxide（PTO）and 135 polybromine phenoxathiin 10-oxides（PBPTOs）with the Gaussian 03 program and molar heat capacity in constant volume（CVθ）value of each molecule in the standard state was obtained.The relation between CVθ and the substitution position and number of bromine atom（NPBS）was studied,and the results indicated good correlation（R2 = 1.000）between CVθ and NPBS of PBPTO compounds.Based on the output file of Gaussian 03 program,molar heat capacity at constant pressure（Cp,m）of PBPTO compounds from 200 to 1,000 K was calculated with the statistical thermodynamics program,and the correlation equation between Cp,m and temperature（T,T-1 and T-2）was obtained with the least-squares method,and the correlation coefficient of the correlation equation（R2）was 1.000.In addition,based on the partition function of each molecule calculated by vibration analysis,the relative rate constant of formation of each molecule was calculated.
基金the National Natural Science Foundation of China(No.51873133)Material Corrosion and Protection Key Laboratory of Sichuan province(No.2022CL12).
文摘Self-healing anticorrosive coatings in extreme environment have attracted considerable interest from researchers.In this work,4-tert-butylpyridine(TBP)was incorporated into brominated butyl rubber(BIIR)polymer networks to form a reversible ionic bond with the highly reactive bromine anion.Based on the low glass transition temperature of the BIIR polymer and the electrostatic effects,a robust self-healing anticorrosive coating of TBP-BIIR was prepared.TBP-BIIR coating showed a maximum protection efficiency(PE)of more than 94%(TBP-BIIR-acid,94.37%;TBP-BIIR-alkali,94.95%;TBP-BIIR-salt,95.49%)when treated with a strong acid(HNO_(3),pH=2),strong base(NaOH,pH=12)and high salt solution(3.5 wt%NaCl).In addition,the PE of coating repaired exceed 89%,and the maximum PE value was approximately 95%in different solutions,which demonstrated its extinguished self-healing abilities.These results indicated that the TBP-BIIR anticorrosive coating could provide excellent safety and durability in special environment,which would be extremely beneficial to improve the working life of metal parts used in aviation and shipping,oil and gas and related industries.
基金supported by the National Natural Science Foundation of China (No. 41103054,40821003,41073081)the Earmarked Fund of the State Key Laboratory of Organic Geochemistry (No. OGL-200905)
文摘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.
基金supported by the National Basic Research Program (973) of China (No. 2009CB421605)the National Natural Science Foundation of China (No.20877089,20737003)
文摘Decabromodiphenyl ether （BDE209） is the primary component in a commonly used flame retardant. Previous studies had proved that BDE209 itself was not toxic, while its metabolites including debrominated diphenyl ethers （De-BDEs） and methoxylated brominated diphenyl ethers （MeO-BDEs） posed a potential threat to organisms. Many studies had indicated that BDE209 could metabolize quickly in mammals, but lacking in the basic data about the metabolism of BDE209 in fish. In the present study, two replicate treatment groups of rainbow trout （Oncorhynchus rnykiss） were exposed to BDE209 via a single intraperitoneal injection approximately 100 and 500 ng/g, respectively. Muscle, liver and blood samples were collected to analyze the specific metabolites on day 1 and day 28 post injection. The highest concentration of BDE209 was detected in muscle tissues, from 796.1 ng/g wet weight （day 1） to 687.1 ng/g wet weight （day 28） in high dose group, suggesting that BDE209 could accumulate slightly in muscle tissues. However, BDE209 was not detected in the blood for all treatments. Most congeners of De-BDEs were found in muscle and liver tissues, with the highest concentration in the liver. The main De-BDEs were nona-, octa-, hepta- and penta-De-BDEs. A total of seven MeO-BDE metabolites were observed among different fish tissues. Blood had the highest contribution of the MeO-BDE metabolites. Each MeO-BDE congener increased over the 28 days. These results in contrast to other studies suggested possible species-specific differences in metabolic abilities.
基金Royal Golden Jubilee Ph.D.Program(RGJ-Ph.D.Program)scholarship of Thailand Research Fund(PHD/0129/2559)to carry out this work.
文摘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.
基金supported by the National Basic Research(973)Program of China(No.2014CB441102)the National Natural Science Foundation of China(No.21177139)
文摘Brominated phenols （BPs）, a widely used group of emerging flame retardants, are important environmental contaminants and exhibit endocrine disrupting potential. Method for simultaneous determination of tetrabromobisphenol A （TBBPA）, tribromophenol （TBP）, dibromophenols （DBPs） and monobromophenols （MBPs） in soils using gas chromatography-mass spectrometry analysis （GC/MS） was successfully developed. Cleanup methods for soil extracts including several solid-phase extraction cartridges and different elution solvents were compared and optimized. Florisil cartridge with dichloromethane as the elution reagent was selected for sample cleanup owing to its high and reproducible recoveries of the target analytes in soils. Derivatization conditions were tested and the optimal conditions were obtained with 20 μL silylation reagent at room temperature. The chromatographic separation was optimized with different columns and DB-XLB column was selected for its excellent separation of the analytes. The limits of detection for the target compounds were from 0.04 to 0.19 ng/g. Mean recoveries of the compounds from spiked soils exceeded 84% with a good reproducibility, excepting that the recovery of 2-bromophenol was relatively poor （lower than 55%） due to its instability. The developed method was applied to the determination of the BPs in the soils collected from e-waste sites. The contents of BPs in the soils were at ng/g levels with TBBPA and TBP the most frequently detected. To our knowledge, this is the first report for the simultaneous determination of TBBPA, TBP, DBPs and MBPs in soils.
基金supported by the National Natural Science Foundation of China(Nos.20877090,21077123,21377143)
文摘The brominated products, formed in chlorination treatment of benzophenone-4 in the presence of bromide ions, were identified, and the formation pathways were proposed.Under disinfection conditions, benzophenone-4 would undertake electrophilic substitution generating mono- or di-halogenated products, which would be oxidized to esters and further hydrolyzed to phenol derivatives. The generated catechol intermediate would be transformed into furan-like heterocyclic product. The product species were p H-dependent,while benzophenone-4 elimination was chlorine dose-dependent. When the chlorination treatment was performed on ambient water spiked with benzophenone-4 and bromide ions, most of brominated byproducts could be detected, and the acute toxicity significantly increased as well.
基金supported by National Key Research and Development Program of China(No.2018YFC0830802)National Natural Science Foundation of China(Nos.21477155 and 91743206)+2 种基金the Sanming Project of Medicine in Shenzhen(No.SZSM201811070)the support of Chinese Arctic and Antarctic AdministrationPolar Research Institute of China。
文摘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.
基金supported by a Grant-in-Aid for Scientific Research (KAKENHI) from the Japan Society for the Promotion of Science (No. JP16H05891)the Steel Foundation for Environmental Protection Technology+1 种基金the Environment Research and Technology Development Fund (No. 3K153003) of the Ministry of the Environment, Japana Health and Labor Sciences Research Grant of the Ministry of Health, Labor and Welfare, Japan
文摘Here, we examined the incineration of extruded polystyrene containing hexabromocyclododecane（HBCD） in a pilot-scale incinerator under various combustion temperatures（800–950℃） and flue gas residence times（2–8 sec）. Rates of HBCD decomposition ranged from 99.996%（800℃, 2 sec） to 99.9999%（950℃, 8 sec）; the decomposition of HBCD, except during the initial stage of combustion（flue gas residence time 〈 2 sec）, followed a pseudo-first-order kinetics model. An Arrhenius plot revealed that the activation energy and frequency factor of the decomposition of HBCD by combustion were 14.2 kJ/mol and 1.69 sec^（-1）,respectively. During combustion, 11 brominated polycyclic aromatic hydrocarbons（BrPAHs）were detected as unintentional by-products. Of the 11 BrPAHs detected, 2-bromoanthracene and 1-bromopyrene were detected at the highest concentrations. The mutagenic and carcinogenic BrPAHs 1,5-dibromoanthracene and 1-bromopyrene were most frequently detected in the flue gases analyzed. The total concentration of BrPAHs exponentially increased（range,87.8–2,040,000 ng/m^3） with increasing flue gas residence time. Results from a qualitative analysis using gas chromatography/high-resolution mass spectrometry suggest that bromofluorene and bromopyrene（or fluoranthene） congeners were also produced during the combustion.
文摘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.
