固相萃取-LC-MS/MS测定土壤中多溴联苯醚

采用快速溶剂萃取-固相萃取-液相色谱串联质谱法（LC-MS/MS）测定土壤中8种多溴联苯醚类（PBDEs）化合物,通过优化试验条件,使方法在100 μg/L～1 000 μg/L范围内线性良好,方法检出限为085 μg/kg～125 μg/kg。不同土壤样品的8种多溴联苯醚回收率为68.6%～127%,4次测定结果的RSD为4.8%～27.6%。将该方法用于测定电子废物拆解点周边的土壤样品,结果BDE-209测定值为未检出～168 μg/kg,BDE-183为未检出～560 μg/kg,其余6种BDEs均为未检出。     

加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱测定土壤和沉积物中8种多溴联苯醚

建立了土壤和沉积物中8种多溴联苯醚(PBDEs,BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183和BDE-209)加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱(ASE-GC-MS-MS)的分析方法。通过优化加速溶剂萃取与弗罗里硅土在线净化和串联质谱多反应监测模式的条件,较好地去除基质干扰,并提高了三重四极杆串联质谱定性的准确性及定量的灵敏性。该方法采用改进的色谱柱能同时分析包括高溴代联苯醚BDE-209在内的8种PBDEs,其浓度范围为1～100 ng/mL(BDE-209为10～1 000 ng/mL),线性良好,线性回归系数均大于0.997。方法检出限为0.004～0.1 ng/g,方法回收率为75%～110%,方法精密度为2.4%～15.6%。适于批量处理土壤和沉积物中含有多组分痕量PBDEs的样品。     

分流进样-GC-NCI-MS测定土壤样品中高溴代联苯醚

采用分流进样模式,以GC-NCI-MS法测定土壤样品中7种高溴代联苯醚,对比了分流、不分流2种进样模式下的灵敏度、峰形、回收率、检出限。结果表明,在分流进样模式下,高溴代联苯醚在进样口的热分解率大大降低,色谱峰形尖锐无拖尾,测定结果线性范围宽,7种高溴代联苯醚的基质加标回收率为83.25%~94.71%,RSD为2.91%~7.37%,检出限为0.26~2.71 ng/g,与不分流进样模式相比,该方法灵敏度、检出限更高,适用于环境样品中高溴代联苯醚的检测分析。     

高效液相色谱串联质谱法分析土壤中多溴联苯醚类化合物

建立了一种超高效液相色谱串联质谱法(UPLC-MS/MS)同时测定土壤中8种多溴联苯醚化合物(PBDEs)的方法,采用快速溶剂萃取(ASE)和凝胶净化色谱(GPC),经BEH反相C₁₈色谱柱分离,10 min内完成分离,使用含0.1%氨水的甲醇和水进行梯度洗脱,采用液相色谱-负离子-大气压化学电离(APCI)串联质谱,多反应监测模式(MRM),加入 ¹³C₁₂-BDE-139和¹³C₁₂-BDE-209内标作定量分析。结果表明:在优化的分析条件下,PBDEs的线性相关系数为0.998 8～0.999 5,方法检出限为0.22～0.59 μg/kg,在2个添加水平下,平均回收率为71%～126%,标准偏差为3%～18%,土壤实际质控样测定结果均在允许范围内。适合于土壤中PBDEs的快速分析,特别对于高溴代PBDEs,相比气相色谱质谱方法具有更快的分析速度和更好的稳定性。     

气相色谱法测定空气和废气中8种烃类化合物

建立了针筒采样、大口径毛细管柱分离、气相色谱-氢火焰离子化检测器测定空气和废气中甲烷、乙烷、乙烯、乙炔、丙烷、异丁烷、正丁烷和正戊烷等8种烃类化合物的方法.优化了试验条件,方法线性良好,甲烷、乙烯、乙炔、乙烷、丙烷、异丁烷、正丁烷和正戊烷的检出限分别为0.09 mg/m3、0.20 mg/m3、0.18 mg/m3、0.29 mg/m3、0.28 mg/m3、0.37 mg/m3、0.16 mg/m3和0.56 mg/m3,RSD＜8.0%,加标回收率为80.5%～104%.     

气相色谱法同步测定环境空气和废气中甲醇正丁醇叔戊醇

以蒸馏水吸收环境或工业废气中的甲醇正丁醇叔戊醇,用HP-FFAP毛细管柱分离氢火焰离子化检测器检测,样品直接进气相色谱仪测定.方法最低检出质量浓度分别为甲醇0.08 mg/m3、正丁醇0.11mg/m3、叔戊醇0.12mg/m3,相对标准偏差为2%～5%,加标回收率在82%～105%之间.方法简单、灵敏,分离度好、检出限低.     

测量土壤中多溴联苯和多溴联苯醚含量不确定度评定

通过对气相色谱-质谱联用法测定土壤中多溴联苯和多溴联苯醚类化合物含量的不确定度进行评定,分析了测量过程中引入的不确定度来源,求出各不确定度分量,最后合成标准不确定度并计算相对扩展不确定度。结果表明,各化合物最大的不确定度分量是方法回收率,约占50%~90%,方法相对扩展不确定度为0.12~0.20。     

离子色谱法测定空气中氟化氢氯化氢和硫酸

以多孔玻板吸收管采样,采用离子色谱法同时测定作业场所空气中的氟化氢、氯化氢和硫酸,采样效率>92%。氟化氢在0 mg/L～2.00 mg/L、氯化氢在0 mg/L～2.50 mg/L、硫酸在0 mg/L～4.00 mg/L范围内线性良好,检出限分别为0.003 mg/m3、0.02 mg/m3、0.023 mg/m3(按采样体积60 L计),标准溶液平行测定的RSD≤8.0%,两个质量浓度水平加标的平均回收率为92.6%～106%。     

平顶山市大气PM10、PM2.5 污染调查

于2003年12月-2004年11月对平顶山市城区大气PM10、PM2.5污染进行了调查.结果表明,2004年大气PM10、PM2.5质量浓度分别为0.031 mg/m3～0.862 mg/m3、0.019 mg/m3～0.438 mg/m3;年均值分别为0.174 mg/m3、0.114 mg/m3,超标0.74倍、6.60倍.PM10、PM2.5污染的季节变化趋势是以冬季、春季高,秋季次之,夏季最低,细颗粒(PM2.5)约占PM10 65%;As、Pb、Cd、S、Zn、Cu、Mn、Ca等元素是颗粒物中主要污染元素,易在PM2.5中富集.平顶山市大气颗粒物污染的主要来源有煤炭燃烧、汽车尾气、城市基础建设和有色金属冶炼行业.     

GC/MS法测定水中烷基酚聚氧乙烯醚和烷基酚

采用气相色谱/质谱联用测定环境水体中壬基酚、壬基酚一氧乙基醚、壬基酚二氧乙基醚、4-叔辛基酚、4-叔辛基酚一氧乙基醚和4-叔辛基酚二氧乙基醚,用二氯甲烷对水样液液萃取,浓缩后添加BSTFA+ TMCS(体积比为99∶1)在室温下衍生化0.5h.方法在0.001 mg/L～5.00 mg/L范围内线性良好,目标化合物的检出限范围为4.0×10-7 mg/L～8.8×10-7 mg/L,空白加标样品平行测定的RSD为5.1％ ～8.8％,回收率为85.6％～ 110％.     

Investigation of polybrominated diphenyl ethers in old consumer products in India

Polybrominated diphenyl ethers (PBDEs) used extensively over the past 3 decades as flame retardants in most types of polymers, all over the world, have been identified as global pollutants. PBDEs pose various health problems such as thyroid hormone disruption, permanent learning and memory impairment, behavioral changes, hearing deficits, delayed puberty onset, fetal malformations, and possibly cancer. Many measurements of PBDEs in various matrices from Sweden, Holland, Japan, the USA, and elsewhere have been reported, but few measurements are available for India. In this study, a preliminary screening of different congeners of PBDEs has been performed in different old electronic and consumer products with an objective to build capacity in order to analyze PBDEs and BFRs. Six different samples, foam from upholstery, motherboard of a computer, children toy composite sample, old vanishing window blind sample, electrical wire sample, and PVC flooring sample, were collected and analyzed for the presence of the following PBDE congeners: BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, and BDE-209. It was found that three out of six samples were positive for the presence of PBDEs. Three congeners were detected in the samples, i.e., BDE-47, BDE-153, and BDE-209, of which, highest concentration was of BDE-209. Among the samples, motherboard of computer showed the highest concentration of BDE-209 followed by window blind and foam from upholstery. The results of this preliminary investigation indicate that PBDEs are still present in the old consumer products which can be an important additional source of exposure to the population.     

Validation of a passive atmospheric deposition sampler for polybrominated diphenyl ethers

An atmospheric deposition sampler was validated with respect to polybrominated diphenyl ethers (PBDEs), a compound group that is widely used as flame retardants in many types of consumer products. The deposition sampler consists of an adsorption cartridge that is connected to a glass funnel. Extraction tests with spiked cartridges using soxhlet extraction with acetone revealed recoveries of >80% for all of the investigated PBDEs. Once adsorbed, PBDEs are stable, as proven by extractions of spiked cartridges that were stored outdoors and collected after different periods of time, up to 84 days. High recoveries indicate that degradation of adsorbed PBDEs does not play a role under realistic field conditions. Bulk deposition rates of PBDEs were determined in a field test with 3 replicates, and a possible breakthrough of target compounds was assessed in the field using a second adsorption cartridge in series. No breakthrough of target compounds could be observed within a sampling period of 61 days, and a bulk deposition rate of approximately 1 ng m(-2) day(-1) for the sum of all analysed PBDEs was measured. The highest deposition rates were measured for octa-brominated congeners, followed by BDEs 99, 183, 153, and 47. Overall, the sampler was successfully validated regarding the atmospheric deposition of PBDEs.     

Dehalogenation of polychlorinated biphenyls and polybrominated diphenyl ethers using a hybrid bioinorganic catalyst

The environmentally prevalent polybrominated diphenyl ether (PBDE) #47 and polychlorinated biphenyls (PCBs) #28 and #118 were challenged for 24 hours with a novel biomass-supported Pd catalyst (Bio-Pd(0)). Analysis of the products via GC-MS revealed the Bio-Pd(0) to cause the challenged compounds to undergo stepwise dehalogenation with preferential loss of the least sterically hindered halogen atom. A mass balance for PCB #28 showed that it is degraded to three dichlorobiphenyls (33.9%), two monochlorobiphenyls (12%), and biphenyl (30.7%). The remaining mass was starting material. In contrast, while PCB #118 underwent degradation to yield five tetra- and five trichlorinated biphenyls, no less chlorinated products or biphenyl were detected, and the total mass of degraded products was 0.3%. Although the Bio-Pd(0) material was developed for treatment of PCBs, a mass balance for PBDE #47 showed that the biocatalyst could prove a potentially useful method for treatment of PBDEs. Specifically, 10% of PBDE #47 was converted to identifiable lower brominated congeners, predominantly the tribrominated PBDE #17 and the dibrominated PBDE #4, 75% remained intact, while 15% of the starting mass was unaccounted for.     

Polybrominated diphenyl ethers and organochlorine pesticides in human breast milk from Massachusetts, USA

Concentrations of polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs; DDTs, HCHs, CHLs, and HCB) were measured in human breast milk samples collected across Massachusetts, USA, in 2004. Seventeen PBDE congeners were found in the samples, ranging in concentration from 0.06 to 1910 ng g(-1) lipid wt. BDE-47 (2,2',4,4'-tetraBDE), BDE-99 (2,2',4,4',5-pentaBDE), and BDE-100 (2,2',4,4',6-pentaBDE) were the major congeners detected in breast milk samples. Overall mean (+/-SD) concentrations of DDTs, HCHs, CHLs, and HCB were 64.5 +/- 75, 18.9 +/- 19, 32.4 +/- 36, and 2.3 +/- 2.2 ng g(-1) lipid wt, respectively. Concentrations of PBDEs were strongly correlated with concentrations of OCPs in the samples. Based on the concentrations of organohalogens and the intake rates of breast milk by infants in the United States, daily ingestion rates of contaminants were calculated. The median ingestion rates for PBDEs, HCHs, DDTs, CHLs, and HCB were 4.0, 212, 141, 44, and 5.79 ng kg(-1) body wt day(-1), respectively. The estimated daily intake of organohalogens by infants was compared with threshold reference values suggested by the United States Environmental Protection Agency (USEPA) and the Agency for Toxic Substances and Disease Registry (ATSDR), for calculation of hazard quotients (HQs). HQs for individual organohalogens and the sum of HQ for all organohalogens were calculated as HQ indices (HQI). The results suggest that one or more of the contaminants analyzed in this study exceeded the threshold reference values in at least 26% of the breast milk samples.     

A national probabilistic study of polybrominated diphenyl ethers in fish from US lakes and reservoirs

Polybrominated diphenyl ethers (PBDEs) are persistent, bioaccumulative, and toxic chemicals that are present in air, water, soil, sediment, and biota (including fish). Most previous studies of PBDEs in fish were spatially focused on targeted waterbodies. National estimates were developed for PBDEs in fish from lakes and reservoirs of the conterminous US (excluding the Laurentian Great Lakes) using an unequal probability design. Predator (fillet) and bottom-dweller (whole-body) composites were collected during 2003 from 166 lakes selected randomly from the target population of 147,343 lakes. Both composite types comprised nationally representative samples that were extrapolated to the sampled population of 76,559 and 46,190 lakes for predators and bottom dwellers, respectively. Fish were analyzed for 34 individual PBDE congeners and six co-eluting congener pairs representing a total of 46 PBDEs. All samples contained detectable levels of PBDEs, and BDE-47 predominated. The maximum aggregated sums of congeners ranged from 38.3 ng/g (predators) to 125 ng/g (bottom dwellers). Maximum concentrations in fish from this national probabilistic study exceeded those reported from recent targeted studies of US inland lakes, but were lower than those from Great Lakes studies. The probabilistic design allowed the development of cumulative distribution functions to quantify PBDE concentrations versus the cumulative number of US lakes from the sampled population.     

Polybrominated diphenyl ethers (PBDEs) in freshwater mussels and fish from Flanders, Belgium

The levels and distribution of PBDEs in zebra mussels and several freshwater fish species (eel, carp and gibel carp) were investigated for different sites in Flanders, Belgium. In parallel, other organohalogenated contaminants, such as polychlorinated biphenyls (PCBs), p,p[prime or minute]-DDE and hexachlorobenzene (HCB) were also measured and their relationship with PBDEs was investigated. At most sites, individual PBDE congeners were present at detectable levels in mussel tissue, with the mean [summation operator]PBDE concentration ranging from 0.15 to 1.8 ng g(-1) wet weight (ww). The PCB concentrations in mussels ranged from 6.2 to 102 ng g(-1) ww. HCB and p,p[prime or minute]-DDE could be measured in mussels from most sites, mean values ranging from below the limit of quantification (LOQ) to 0.58 ng g(-1) ww and from 0.66 to 6.5 ng g(-1) ww, respectively. Except for one site (Blokkersdijk, Antwerp) where PBDEs were below the LOQ in carp muscle, all fish samples from other sites contained detectable PBDE levels, with the highest concentrations (14 +/- 14 ng g(-1) ww) being measured in eel liver from Watersportbaan (Ghent). The sampled sites covered a broad concentration range of organohalogenated pollutants with the highest values being consistently measured in eel liver. With few exceptions, all correlations between PBDEs and organochlorine pollutants for each species were low (r < 0.50) and most were statistically not significant (p > 0.05). This suggests that the exposure to contaminants arises from local sources possessing different signatures of PBDEs and organochlorine pollutants.     

Organochlorines and polybrominated diphenyl ethers in four geographically separated populations of Atlantic salmon (Salmo salar)

Atlantic salmon (Salmon salar) populations from four locations, two from isolated Swedish lake systems, one of the Baltic Sea and one of the North Atlantic, were analyzed to determine the concentrations and spatial variations of polybrominated diphenyl ethers (PBDEs) and organochlorines (DDT, PCB and HCH). Levels in both liver and muscle were in the same range as previously reported in Atlantic salmon, except for elevated concentrations found per lipid weight (lw) in the muscle samples of salmon from the North Atlantic ( summation PBDE 263 ng g(-1) lw, summation PCB 3262 ng g(-1) lw, summation DDT 4063 ng g(-1) lw summation HCH 131 ng g(-1)). In general, elevated concentrations in the muscles compared to the liver were observed, especially in lipid depleted migrating salmon, possibly caused by a faster lipid depletion compared with the redistribution of PBDEs, PCBs and DDTs. These findings indicated that the life stage and thereby the lipid dynamics of the fish must be considered prior to comparison based on lipid weight, especially as Atlantic salmon experience large variations in lipid content during periods of migration. The dominating PBDE congener was BDE-47, representing more than 25% in all fish. The PBDE pattern changed between locations, with a significant separation of the fish from the freshwater and marine environment when analyzed using principal component analysis.     

Detection of polybrominated diphenyl ethers in tilapia (Oreochromis mossambicus) from O'ahu, Hawai;i

Polybrominated diphenyl ethers (PBDEs) have been detected for the first time at a range from 231.58 to 685.61 ng g(-1) lipid weight in the muscles of tilapia (Oreochromis mossambicus) collected from O'ahu, an island of the geographically isolated Hawaiian archipelago.     

Polybrominated diphenyl ethers (PBDEs) in the riverine and marine sediments of the Laizhou Bay area, North China

62 riverine and marine sediments were collected from the Laizhou Bay area, where the largest manufacturing base of brominated flame retardants (BFRs) in Asia is located. Eight polybrominated diphenyl ethers (PBDEs) were analyzed to investigate the impact of rapidly-developed bromine industries on the regional aquatic system. PBDE concentrations varied largely in riverine sediments. Σ(7)PBDEs (including BDE 28, 47, 99, 100, 153, 154 and 183) and BDE 209 ranged from 0.01 to 53 ng g(-1) dw and from 0.74 to 285 ng g(-1) dw with a mean value of 4.5 ng g(-1) dw and 54 ng g(-1) dw, respectively, indicating a strong influence of direct pollution discharges from local factories. In marine sediments, Σ(7)PBDEs and BDE 209 ranged from not detected (nd) to 0.66 ng g(-1) dw and from 0.66 to 12 ng g(-1) dw with a mean value of 0.32 ng g(-1) dw and 5.1 ng g(-1) dw, respectively. PBDE concentrations were mostly <10 ng g(-1) dw for Σ(7)PBDEs and <50 ng g(-1) dw for BDE 209, which are at a relatively low level for monitored riverine and coastal sediments around the world. Even at the most contaminated sites in Laizhou Bay area, PBDE concentrations were not among the highest concentrations reported in the literature. Congener compositions were dominated by BDE 209 (57.2-99.9% of the sum of BDE congeners), with minor contributions from penta- and octa-BDE products. Tri- to octa-BDE congeners were well correlated among each other (r > 0.75) and thus sources from similar mixing of penta- and octa-BDE products were suggested in this area. Compared with riverine sediments, a much better correlation between PBDE concentrations with TOC was observed in marine environment. The congener pattern changed and their correlation coefficients among each other were remarkably reduced. Contributions of BDE 28, 47 and 99 to Σ(7)PBDEs were generally the same in almost all the marine sites, while it was distinctively higher for BDE 153. These are probably attributable to several reasons, such as contributions by atmospheric deposition and/or redistribution between particles of various sizes during and/or after fluvial transportation combined with the difference of physiochemical properties of BDE congeners.     

Preliminary assessment of polybrominated diphenyl ethers (PBDEs) in the Scottish aquatic environment, including the Firth of Clyde

This paper presents preliminary data on polybrominated diphenyl ethers (PBDEs) in the Scottish aquatic environment. Sediment and biota (fish liver, fish muscle and mussels) from a number of locations around Scotland were analysed for PBDEs with samples being from both remote and from potentially contaminated areas such as the former sewage sludge dump site at Garroch Head in the Clyde. PBDEs were measured in both cultivated, rope grown mussels and wild mussels collected from 5 sites around Scotland in 2006. Total PBDE concentrations (sum of tri- to hepta-BDEs) ranged from 相似文献