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。     

加速溶剂萃取和净化-气相色谱-串联质谱法测定典型污染场地土壤中多氯联苯残留

建立了加速溶剂萃取同步净化-气相色谱-三重四极杆串联质谱法测定污染场地土壤中7种指示性多氯联苯的方法。对加速溶剂萃取、净化、色谱柱、串联质谱离子对、碰撞电压等条件进行了优化。萃取和净化过程合二为一,串联质谱法提高了7种多氯联苯的灵敏度。7种多氯联苯在0.1～100μg/L质量浓度范围内线性良好,线性相关系数为0.999 80～0.999 99,方法检出限为0.004～0.010μg/kg,回收率为84.8%～97.3%,相对标准偏差为2.4%～8.5%。运用网格法采集了华东某典型污染场地土壤中31个土壤样品,分析了该场地7种指示性多氯联苯的残留特征。7种多氯联苯的检出率为100%,检出范围为0.096～3 661μg/kg,各点平均值为307μg/kg。各采样点中多氯联苯的残留程度存在很大差异,局部点位受到了较重污染,与封存点相近的部分点位残留较外围位置高。土壤中多氯联苯同系物以三氯联苯、四氯联苯、五氯联苯为主,占同系物总量的98.2%。该污染场地土壤多氯联苯主要是低氯代联苯污染,土壤中多氯联苯的毒性效应评估处于中等水平,污染以点源污染为主,且已有较大程度扩散。     

超高效液相色谱-三重四极杆质谱法同时分析沉积物中6种溴代阻燃剂

利用超高效液相色谱-三重四极杆质谱建立了沉积物中6种溴代阻燃剂的分析方法,同时进行了采样分析。以正己烷-二氯甲烷(体积比1∶9)为萃取剂,在100℃下用加速溶剂萃取仪提取沉积物样品,循环3次。萃取液浓缩至2.0 m L,转移至净化柱,用150 m L正己烷-二氯甲烷(体积比1∶2)淋洗。将淋洗液浓缩至近干,加入内标物,定容至1 m L后,用液相色谱-三重四极杆准确定量。方法干重检出限为0.01～0.1 ng/g;替代标回收率为75.6%～98.9%,相对标准偏差为12.0%～13.0%;目标物回收率为70.5%～99.2%,相对标准偏差为2.1%～17.0%。研究区域水体沉积物中的三(2,3-二溴丙基)异氰脲酸酯浓度为未检出～0.14 ng/g,(2,4,6-三溴苯氧基)-1,3,5-三嗪浓度为未检出～0.14 ng/g,十溴二苯醚浓度为0.81～4.36 ng/g,六溴苯浓度为未检出～0.08 ng/g,表明沉积物中新型溴代阻燃剂浓度处于较低水平。     

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。     

超高效液相色谱-串联质谱法分析土壤及沉积物中氨基甲酸酯农药

利用超高效液相色谱-串联质谱,建立土壤和沉积物中痕量氨基甲酸酯农药的分析方法。该方法用体积比1:1的二氯甲烷/甲醇对土壤和沉积物样品进行加速溶剂萃取,GCB/PSA固相萃取小柱对萃取液进行净化,内标法定量,用超高效液相色谱-串联质谱法分析土壤和沉积物中20种氨基甲酸酯农药。20种氨基甲酸酯农药在0.02~1.0 μg/mL范围内线性良好(r≥0.99),检测限为0.20~0.60 ng/g。沉积物加标样品(20ng/g)和土壤加标样品(20ng/g)的回收率分别为33.2%~101.9%、38.8%~120.5%,相对标准偏差为6.1%~28.0%、2.3%~16.0%。沉积物加标样品(2.0 ng/g)回收率为43.0%~100.0%,相对标准偏差为2.1%~11.3%。     

三重四极杆质谱技术测定固体废弃物中多氯联苯

以二氯甲烷为萃取剂,采用快速溶剂萃取、凝胶渗透色谱净化、三重四极杆质谱技术测定固体废弃物中7种多氯联苯单体,选择十氯联苯为内标物,2,4,5,6-四氯间二甲苯为替代物。质谱采用MRM扫描,优化了目标物质保留时间、母离子和子离子质量数及碰撞能量等参数。方法在0.050 mg/L～2.00 mg/L范围内线性良好,7种多氯联苯单体的检出限为0.194 ng/g～0.355 ng/g(以称取30 g样品、定容至2.0 mL计),标准样品回收率多在60%～105%之间,空白加标样品测定值的相对标准偏差在8.6%～13.0%之间。     

超高效液相色谱-串联质谱法测定土壤中多种全氟化合物

采用超声提取、固相萃取法处理土壤,用超高效液相色谱-电喷雾串联三重四极杆质谱测定样品中11种全氟化合物,通过优化测定条件,使方法在0.100μg/L~150μg/L范围内线性良好(r~20.995)。当取样量为2.0 g时,方法检出限为0.1 ng/g~0.4 ng/g。实际土壤样品的加标回收率为67.2%~106%,测定6次结果的RSD为6.6%~17.3%。     

三重串联四极杆气相质谱联用仪测定饮用水源地水体中的多氯联苯

建立了以液-液萃取、三重串联四极杆气相质谱多反应监测法同时测定饮用水源地水体中18种多氯联苯的方法,给出了测量线性范围,线性关系良好,相关系数大于0.998。水中加标浓度为1.00、5.00、10.0ng/L时,平均加标回收率分别为75.6%～96.0%、90.6%～105%和92.4%～102%,相对标准偏差分别为19.8%～11.8%、4.2%～12.9%和4.3%～9.9%,检出限为0.29～0.57ng/L。结果表明,在测定水体中痕量多氯联苯方面,三重串联四极杆气相质谱相对于气相色谱-电子捕获检测和气相色谱质谱-选择离子检测具有更高的灵敏度和准确度,具有更广泛的应用。     

太滆运河表层沉积物中的酞酸酯类增塑剂和溴系、有机磷系阻燃剂残留特征初探

分别采用微波萃取-气相色谱/质谱法、加速溶剂萃取提取-液相色谱/质谱法对采自太滆运河5个沉积物样品中的6种邻苯二甲酸酯类(PAEs)、13种多溴联苯醚(PBDEs)和9种有机磷酸酯(OPEs)的质量比及分布进行研究。结果表明,所有样品中均检测到PAEs、PBDEs和OPEs(以总量计),其总质量比分别为1.99~6.90μg/g,47~572和17.1~69.7 ng/g;十溴联苯醚(BDE-209)和磷酸三异辛酯(TEHP)分别是质量比最高的PBDEs和OPEs;对于PAEs,入太湖点位处邻苯二甲酸二(2-乙基己基)酯(DEHP)质量比较高,其余点位则是邻苯二甲酸二正丁酯(DBP)质量比较高;ω(PAEs)、ω(PBDEs)和ω(OPEs)两两间线性相关性较好,指示其来源相同;下游沉积物中污染物的质量比均高于上游,沿岸生产、生活中增塑剂和阻燃剂对太湖的污染应引起更多关注。     

凝胶渗透色谱-硅胶柱-气相色谱-负化学离子源质谱测定生物介质中49种BFRs类化合物

建立了生物介质内22种多溴联苯(PBBs)和27种多溴联苯醚(PBDEs)的净化和分析方法。通过分析不同时间段凝胶渗透色谱(GPC)洗脱液中49种化合物含量,得出不同化合物凝胶色谱洗脱曲线。样品经过凝胶渗透色谱-混合硅胶柱净化后,再使用GC-(NCI)/MS对样品进行检测。实验结果表明,PBBs和PBDEs检出限分别为0.02~0.88 pg/g和0.01~74.00 pg/g。对实验过程进行验证发现,样品不同浓度加标回收率为80%~120%,相对标准偏差小于20%。该方法具有良好的净化效果、准确度和精密度,拥有良好的线性范围及检出限,满足生物介质中溴代阻燃剂的检测分析实际要求。     

Occurrence, distribution, and source of polybrominated diphenyl ethers in soil and leaves from Shenzhen Special Economic Zone, China

Polybrominated diphenyl ethers (PBDEs) were measured in soil and three plant species samples taken at different land use areas in Shenzhen China. The concentrations of ??₇BDEs (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, and BDE-183) and BDE-209 in the surface soils ranged from 0.23 to 271 and 8.9 to 5,956 ng/g dry weight (dw), respectively. These figures are comparable to that in the soils of electronic waste dismantling sites. BDE-209 was the predominant congener (contributes 85?C99% of ??₈PBDEs (??₇PBDEs plus BDE-209)) in soils. The regression slopes of total organic carbon and individual BDE congeners were rather gentle, indicating that factors other than soil organic matter regulated the soil concentrations. Proximity to sources of deposition processes might be the major factors. In the plant leaves, ??₇BDEs and BDE-209 concentrations ranged from 1.29 to 5.91 and 5.49 to 28.2 ng/g dw, respectively. BDE-209 is also the dominant component, but the contribution was much lower compared with that in soils. Bauhinia purpurea Linn. and Michelia alba DC. show some similarities on the uptake of PBDEs, while Ficus microcarpa var. pusillifolia is different from them. The correlations between plant leaf concentrations and predicted gaseous concentrations were moderate, indicating that gaseous concentration did not influence the leaf concentration significantly.     

Levels and congener profiles of polybrominated diphenyl ethers (PBDEs) in primipara breast milk from Shenzhen and exposure risk for breast-fed infants

This study aimed at revealing the levels of polybrominated diphenyl ethers (PBDEs) in breast milk from primipara in Shenzhen (China), and estimating daily intake of PBDEs for breast-fed infants. Concentrations of 7 PBDEs were measured in 60 breast milk samples by isotope dilution HRGC/HRMS (high-resolution gas chromatography/high-resolution mass spectrometry). The intake of PBDEs for breast-fed infants was estimated based on the infant's daily milk consumption. The range of total concentration of 7 PBDEs congeners in samples was 2.6-188.6 ng g(-1) lipid (mean: 14.8 ng g(-1) lipid; median: 7.2 ng g(-1) lipid). The mean estimated daily intake of PBDEs by breast-fed infants ranged from 9.9 to 335.9 ng kg(-1) body weight (bw) per day (mean: 52.5 ng kg(-1) bw per day; median: 28.6 ng kg(-1) bw per day). The levels of PBDEs body burden in the recruited mothers of Shenzhen were higher than those reported previously for the general population from other areas in China. No significant correlations were found between the body burden of PBDEs and the mothers' age, pre-pregnancy BMI, dietary habits, duration of residence in Shenzhen, weight and length of the newborns. BDE-47 and BDE-153 were major PBDE congeners in milk samples, while the congeners of BDE-183 and BDE-28 were also high in Shenzhen. The situation may be attributed to the special economic pattern including electronic production in Shenzhen in the past three decades. Continuous surveillance on PBDEs levels in human milk is needed in order to accurately evaluate the environmental impact of PBDEs to human health in Shenzhen.     

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.     

PBDE,HBCD, and novel brominated flame retardant contamination in sediments from Lake Maggiore (Northern Italy)

The reduction in the use of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) has opened the way for the introduction of novel brominated flame retardants (NBFRs) in place of the banned formulations. Important representatives of this group are decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), hexabromobenzene (HBB), and pentabromoethylbenzene (PBEB). In this study, the contamination due to NBRFs was investigated for the first time in Italy in the sediments of Lake Maggiore. The aim of the research was to characterize in detail the possible presence of temporal trends and/or to identify potential sources of contamination. The study also considered the PBDE and HBCD lake sediment’s current contamination. The analytical results showed that sediments in Lake Maggiore and its tributary rivers had weak concentrations of PBEB, HBB, and BTBPE, but they did not have a negligible/insignificant contamination of HBCD (up to 23.7 ng/g dry weight (d.w.)). The determination of PBDEs in sediments showed that BDE-209 was the predominant congener (up to 217 and 28 ng/g d.w. in river and lake sediments, respectively). DBDPE was detected in the sediments with relevant concentrations (up to 280 ng/g d.w in the River Boesio sediments). The positive correlation of DBDPE with BDE-209 confirmed the wide and important use of this compound in the Lake Maggiore basin and the hypothesis that this compound will soon become one of the most important NBFRs used in Northern Italy. The contamination of Lake Maggiore sediments due to PBDEs, HBCD, and NBFRs were comparable to other worldwide situations.     

Spatial mapping of city-wide PBDE levels using an exponential decay model

Passive air samplers (PAS) consisting of polyurethane foam (PUF) disks were deployed at 6 outdoor air monitoring stations in different land use categories (commercial, industrial, residential and semi-rural) to assess the spatial distribution of polybrominated diphenyl ethers (PBDEs) in the Brisbane airshed. Air monitoring sites covered an area of ~1143 km(2) and PAS were allowed to accumulate PBDEs in the city's airshed over three consecutive seasons commencing in the winter of 2008. The average sum of five (∑(5)) PBDEs (BDEs 28, 47, 99, 100 and 209) levels were highest at the commercial and industrial sites (12.7 ± 5.2 ng PUF(-1)), which were relatively close to the city center and were a factor of 8 times higher than residential and semi-rural sites located in outer Brisbane. To estimate the magnitude of the urban 'plume' an empirical exponential decay model was used to fit PAS data vs. distance from the CBD, with the best correlation observed when the particulate bound BDE-209 was not included (∑(5)-209) (r(2) = 0.99), rather than ∑(5) (r(2) = 0.84). At 95% confidence intervals the model predicts that regardless of site characterization, ∑(5)-209 concentrations in a PAS sample taken between 4-10 km from the city centre would be half that from a sample taken from the city centre and reach a baseline or plateau (0.6 to 1.3 ng PUF(-1)), approximately 30 km from the CBD. The observed exponential decay in ∑(5)-209 levels over distance corresponded with Brisbane's decreasing population density (persons/km(2)) from the city center. The residual error associated with the model increased significantly when including BDE-209 levels, primarily due to the highest level (11.4 ± 1.8 ng PUF(-1)) being consistently detected at the industrial site, indicating a potential primary source at this site. Active air samples collected alongside the PAS at the industrial air monitoring site (B) indicated BDE-209 dominated congener composition and was entirely associated with the particulate phase. This study demonstrates that PAS are effective tools for monitoring citywide regional differences however, interpretation of spatial trends for POPs which are predominantly associated with the particulate phase such as BDE-209, may be restricted to identifying 'hotspots' rather than broad spatial trends.     

New evidences in the complexity of contamination of the lagoon of Venice: polybrominated diphenyl ethers (PBDEs) pollution

This study presents the first evaluation of the current pollution by polybrominated diphenyl ethers (PBDEs) of surface sediments from the Lagoon of Venice. We focused the research on tri-to hepta-BDEs, the main components of penta- and octa-mixtures, which are considered to be the most toxic for the biocoenosis. The results pointed out a quite homogeneous contamination of this keystone European transitional environment, with ∑ ₁₃PBDEs values ra nging from 0.39 to 6.78 ng/g dry weight; these values reflect low to moderate pollution levels, which is in conformity to other coastal European ecosystems. The average PBDE profile of the lagoon sediments follows this decreasing trend of congeners: BDE-47>BDE-99> >BDE-190>BDE-28>BDE-153>BDE-154>BDE-138, BDE-183, and BDE-17, which is similar to the worldwide distribution pattern. BDE-47 and BDE-99 revealed a recent use of a penta-BDE mixture, while the presence of hepta-BDEs (BDE-183 and BDE-190) in all of the sites can indicate the actual use of a deca-BDE formulation, because these congeners are considered to be debrominated byproducts of BDE-209 degradation.     

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.     

Temporal trend studies on polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in ringed seals from east Greenland

The concentrations of polybrominated diphenyl ethers (PBDEs) 17, 28, 47, 49, 66, 85, 99, 100, 153, 154, and 183 were determined in ringed seal blubber from central East Greenland collected in 1986, 1994, 1999 and during the period 2001 to 2004. The trend of PBDEs was compared with the trends of polychlorinated biphenyls (PCBs) 28, 31, 52, 101, 105, 118, 138, 153, 156, and 180 during the same period. The levels of sigmaPBDE in East Greenland ringed seals ranged from 21.8 ng g(-1) lipid weight (1w) in 1986 to 39.3 ng g(-1) lw in 2001 and are among the highest observed in ringed seal from the Arctic. The dominating congeners were BDE-47 (75.4%) and BDE-99 (9.7%). The concentrations of PBDEs and PCBs increased with the age of the seals, and therefore only young seals < or =4 years old) were included in the temporal trend analyses. No significant trend (p > 0.14) was observed in sigmaPBDE or the congeners BDE 28, 47 and, 99 during the period while sigmaPCB decreased significantly (p = 0.004) over the period from 1986 to 2004 with an estimated annual rate of 4.3%.     

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.