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71.
光源和溶剂对十溴联苯醚光降解的影响 总被引:2,自引:0,他引:2
研究了不同光源和溶剂对十溴联苯醚(DecaBDE)光降解特性的影响,并对其降解产物进行了探讨.结果表明,在所试光源和溶剂条件下,DecaBDE均有一定程度的光降解,且都近似符合一级降解动力学.同一光源下,不同溶剂对DecaBDE降解表现出不同的影响.在太阳光照射下,DecaBDE降解速率为甲苯>甲醇>正己烷>正己烷/丙酮>甲醇/水>乙醇/水;在模拟光源照射下,DecaBDE降解速率为甲苯>甲醇>甲醇/水>乙醇/水>正己烷>正己烷/丙酮;在紫外光照射下,DecaBDE降解速率为甲苯>甲醇>正己烷/丙酮>正己烷>甲醇/水>乙醇/水.同一溶剂中,DecaBDE降解速率均为紫外光>太阳光>模拟光源.尽管光源和溶剂对DecaBDE降解速率产生了一定影响,但降解途径基本一致,均为DecaBDE经光解脱溴产生低溴联苯醚. 相似文献
72.
Data on polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) concentrations from Stockholm, Sweden, indoor microenvironments were combined with information from detailed questionnaires regarding the sampling location characteristics, including furnishing and equipment present. These were used to elucidate relationships between possible flame-retarded sources and the contaminant concentrations found in air and dust. Median concentration ranges of ΣPenta-, ΣOcta-, ΣDecaBDE and HBCD from all microenvironments were 19-570, 1.7-280, 29-3200 and < 1.6-2 pg/m3 in air and 22-240, 6.1-80, 330-1400 and 45-340 ng/g in dust, respectively. Significant correlations were found between concentrations of some PBDEs and HBCD in air and/or dust and the presence of electronic/electrical devices, foam furniture, PUF mattresses and synthetic bed pillows in, as well as floor area and construction year of the microenvironment. Car interiors were a source to indoor air in dealership halls. Using median and maximum concentrations of ΣPenta-, ΣOcta-, ΣDecaBDE and HBCD in air and dust, adult and toddler (12-24 months) intakes from inhalation and dust ingestion were estimated. Toddlers had higher estimated intakes of ΣPenta-, ΣDecaBDE and HBCD (7.8, 43, 7.6 ng/d, respectively) from dust ingestion than adults (5.8, 38, 6.0 ng/d, respectively). Air inhalation in offices was also an important exposure pathway for ΣPenta-, ΣOcta- and ΣDecaBDE in adults. For ΣPentaBDE and HBCD, air inhalation and dust ingestion play minor roles when compared to previously published Swedish dietary intakes (median exposures). However, in worst case scenarios using maximum concentrations, dust ingestion may represent 77 and 95% of toddler intake for ΣPentaBDE and HBCD, respectively. 相似文献
73.
Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants in air and seawater of the European Arctic 总被引:3,自引:0,他引:3
Möller A Xie Z Sturm R Ebinghaus R 《Environmental pollution (Barking, Essex : 1987)》2011,159(6):1577-1583
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. 相似文献
74.
Olsman H Hagberg J Kalbin G Julander A van Bavel B Strid A Tysklind M Engwall M 《Environmental science and pollution research international》2006,13(3):161-169
Goal, Scope and Background The use of polybrominated diphenyl ethers (PBDEs) as flame retardants increases the risk for emissions of other brominated
compounds, such as polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). The large homology in structure of PBDD/Fs
and mechanism of toxic action, i.e. the capacity to activate the Ah receptor (AhR) pathway, compared to their well-studied
chlorinated analogues, justifies a raised concern to study the environmental levels and fate of these compounds. Decabromodiphenyl
ether (decaBDE) is the most widely used PBDE today. Studies on photolytic debromination of decaBDE in organic solvents have
shown debromination of decaBDE, as well as formation of PBDFs. However, little is known about the transformation mechanisms
and there are only scarce data on photoproducts and PBDE transformation in environmentally relevant matrices. In this study,
mechanism-specific dioxin bioassays were used to study photolytic formation of AhR agonists in toluene solutions of decaBDE.
In addition, the influence of irradiation time and UV-light wavelength on the formation was studied. PBDE congener patterns
and presence of PBDD/Fs were analysed. Further, AhR agonists were analysed in agricultural soils contaminated with PBDEs.
Soils were also exposed to UV-light to study changes in AhR agonist levels.
Methods Toluene solutions of decaBDE were irradiated using three different spectra of UV-light, simulating UV-A (320-400 nm), UV-AB
(280-400 nm), and UV-ABC (250-400 nm). Additionally, decaBDE solutions were exposed to narrow wavelength intervals (10 nm
bandwidth) with the central wavelengths 280, 290, 300, 310, 320, 330, 340, 350, 360 nm. AhR agonists in decaBDE solutions
were analysed with two different bioassays, the chick embryo liver-cell assay for dioxins (Celcad) and the dioxin responsive,
chemically activated luciferase expression assay (DR-Calux). Also, the decaBDE solutions were analysed with LRGC-LRMS to obtain
PBDE congener patterns for breakdown of decaBDE, and with HRGC-HRMS, for presence of PBDD/Fs. Four soils were exposed to UV-AB
light, under both dry and moist conditions. Levels of AhR agonists in soil extract fractions, before and after UV-exposure,
were analysed with the DR-Calux.
Results and Discussion Significant levels of photoproducts able to activate the AhR pathway, up to 31 ng bio-TEQ/ml, were formed in UV-exposed decaBDE
solutions. The transformation yield of decaBDE into AhR agonists was estimated to be at the 0.1%-level, on a molar basis.
The net formation was highly dependent on wavelength, with the sample irradiated at 330 nm showing the highest level of dioxin-like
activity. No activity was detected in controls. PBDE analysis confirmed decaBDE degradation and a clear time-dependent pattern
for debromination of PBDE congeners. AhR agonist effect in the recalcitrant fractions of the soils corresponded to the levels
of chemically derived TEQs, based only on chlorinated dioxin-like compounds in an earlier study. It was concluded that no
significant levels of other AhR agonists, e.g. PBDFs, were accumulated in the soil. UV-light caused changes in AhR-mediated
activity in the more polar and less persistent fractions of the soils, but it is not known which compounds are responsible
for this.
Recommendations and Perspective . The laboratory experiments in this study show that high levels of AhR agonists can be formed as photoproducts of decaBDE
and it is important to elucidate if and under which conditions this might occur in nature. However, soil analysis indicates
that photoproducts of PBDE do not contribute to the accumulated levels of persistent dioxin-like compounds in agricultural
soil. Still, more data is needed to fully estimate the environmental importance of PBDE photolysis and occurrence of its photoproducts
in other environmental compartments. Analysis with dioxin bioassays enabled us to gather information about photoproducts formed
from decaBDE even though the exact identities of these compounds were not known.
Conclusion Bioassays are valuable for studying environmental transformation processes like this, where chemical analysis and subsequent
toxicological evaluation requires available standard compounds and information on toxicological potency. The use of bioassays
allows a rapid evaluation of toxicological relevance. 相似文献
75.
Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs) 总被引:1,自引:0,他引:1
Moreira Bastos P Eriksson J Vidarson J Bergman A 《Environmental science and pollution research international》2008,15(7):606-613
BACKGROUND, AIM, AND SCOPE: The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. MATERIALS AND METHODS: PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. RESULTS: The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are indications that further reactions of OH-PBDEs, e.g., methylation to the MeO-PBDEs, decrease the oxidation rates, and thereby generate more persistent substances. DISCUSSION: The resistance of PBDEs to oxidation, a major degradation pathway in air, should be further investigated, since these compounds do undergo long range transport. With slight modifications, the original method has been adapted to include a larger variety of chemical substances, and preliminary data are now available on the oxidative transformation rates for PBDEs and of OH-PBDEs. CONCLUSIONS: The original oxidation degradation method can now include non-water soluble compounds. This modification, using low concentrations of test chemicals, allows us to measure oxidative transformation rates, for some of the lower brominated DEs, data that can be used to assess their persistence in future model calculations. Oxidative transformation rates for PBDEs are slow compared to those for the OH-PBDEs. This suggests that OH-PBDEs, when released into the environment, undergo faster oxidative metabolism and excretion than the PBDEs. RECOMMENDATIONS AND PERSPECTIVES: To evaluate the modified method, more degradation reactions with non-water soluble compounds should be investigated. Recent studies show that OH-PBDEs are present in rats and in humans and, because of their activity as endocrine disruptors, determining their subsequent environmental fate is of importance. The resistance of PBDEs to oxidative degradation should be acknowledged as of possible future concern. Several other compound classes (such as polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), and pharmaceuticals) need to be subjected to this screening method to increase the database of transformation rates that can be used with this model. 相似文献
76.
77.
2,2',4,4'-四溴联苯醚高效好氧降解菌的鉴定及其降解路径 总被引:1,自引:0,他引:1
2,2',4,4'-四溴联苯醚(BDE-47)是环境和生物体中普遍检出且生物毒性较大的一种多溴联苯醚同系物.本研究从广东省贵屿镇电子垃圾拆解厂周边采集的农田土壤中分离出一株BDE-47的高效好氧降解菌GYP1,考察了其对BDE-47的降解性能、降解路径及不同的环境因素对菌株降解BDE-47的影响.根据菌株形态特征、16S r DNA基因序列及系统发育树分析,将该菌鉴定为伯克霍尔德菌(Burkholderia cepacia).结果表明,菌株GYP1在好氧条件下能够利用BDE-47为唯一碳源生长,在BDE-47初始质量浓度为1 mg·L~(-1)、温度为30℃、摇床转速为150r·min~(-1)的条件下避光培养4 d,该菌株对BDE-47的降解率可达到82.4%.菌株GYP1在15~35℃和p H=4.0~7.0的环境条件范围内对BDE-47均能保持良好的降解性能,但外加蔗糖、酵母粉、联苯醚等碳源会明显抑制其对BDE-47的降解.在菌株GYP1对BDE-47的降解过程中检测到6-OH-BDE-47、5-OH-BDE-47、4'-OH-BDE-17、2'-OH-BDE-3这4种羟基多溴联苯醚及2,4-二溴苯酚,证明菌株GYP1对BDE-47的好氧降解机理主要是羟基化过程. 相似文献
78.
铜绿假单胞菌胞内酶粗提液对十溴联苯醚的降解 总被引:4,自引:3,他引:1
探讨了铜绿假单胞菌粗酶液对十溴联苯醚(BDE-209)的降解特性,结果表明,该菌株胞内酶在12 h内对1 mg.L-1的BDE-209降解率达到了69.22%,温度、pH值、酶蛋白浓度及底物BDE-209浓度均会影响胞内酶粗提液对BDE-209的降解效率.当BDE-209浓度为1 mg.L-1时,BDE-209适宜的酶促降解条件为:温度30℃,反应pH值7.5,且降解率随着酶浓度的增加而增大.胞内酶对BDE-209的降解过程符合一级动力学反应模型,底物浓度为1 mg.L-1时降解速率最快,半衰期为6.9 h.胞内酶降解BDE-209符合高浓度底物抑制的酶促反应类型,其基本降解动力学参数为rmax=0.133 mg.(L.h)-1,Km=0.642mg.L-1,Ki=1.558 mg.L-1. 相似文献
79.
青海省西宁市与天峻县大气中得克隆与十溴联苯醚的水平与来源 总被引:2,自引:1,他引:1
十溴联苯醚(BDE-209)与得克隆(DP)是两种常见的添加型卤代阻燃剂,被广泛应用于各种电子产品中.由于其普遍存在于多种环境介质中,现已成为一种广泛存在的污染物,可能会对人体及生态系统产生潜在的危害.本研究测定了青海省西宁市与海西蒙古族藏族自治州天峻县夏、冬两季大气中BDE-209与DP的水平.结果表明,青海省西宁市夏、冬两季大气中BDE-209的平均水平分别为370 pg·m-3、470 pg·m-3,天峻县为220 pg·m-3、390 pg·m-3,与其他城市和地区相比,属于水平较高的地区.而西宁市大气中DP的平均水平为0.85 pg·m-3、0.25 pg·m-3,天峻县为0.24 pg·m-3、0.16 pg·m-3,西宁市水平高于天峻县,夏季水平高于冬季,与其他地区相比,青海省DP整体水平较低.西宁市与天峻县DP的同分异构体中,anti-DP所占比例分别是0.66±0.04与0.68±0.06,在时间与时空上的变化均不明显.青海省BDE-209与DP呈现弱的负相关性,说明两种污染物在青海省可能没有相同的本地源. 相似文献
80.
2,2',4,4'-四溴联苯醚的好氧微生物降解 总被引:1,自引:0,他引:1
从北京高碑店污水处理厂活性污泥中筛选出1株能好氧降解2,2’,4,4’-四溴联苯醚(BDE-47)的细菌,并对其降解特性及有关蛋白质进行分析,目的是了解好氧条件下BDE-47的微生物降解机制.BDE-47降解菌通过平板划线法获得,其16S rDNA与不动杆菌(Acintobacter sp.)的相似度最大,为90%.采用250 mL锥形瓶研究了所得菌对BDE-47的降解情况,在BDE-47初试浓度为146μg.L-1的条件下,经过63 d的培养,所得菌降解了45.44%的BDE-47,降解产物主要为4-OH-联苯醚,菌量增加了7倍左右.分别以BDE-47和酵母提取物为碳源培养所得菌2周,然后各自提取蛋白质,通过蛋白质双向电泳及质谱检测,发现了与BDE-47降解有关的一些特异蛋白质.本研究表明,在好氧条件下,细菌可以BDE-47为碳源生长,其过程涉及多种蛋白质的作用. 相似文献