首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 296 毫秒
1.
This study presents a time‐ and solvent‐saving method, pressurized liquid extraction (PLE), to extract polybrominated diphenyl ethers (PBDEs) in sediment samples. The effects of various operating parameters (i.e., extraction solution, temperature, pressure, static/dynamic extraction times) for the quantitative extraction of PBDEs by home‐made PLE were systematically investigated and optimized. The analytes were then identified and quantitated by gas chromatography‐mass spectrometry (GC‐MS) in selected ion monitoring (SIM) mode. The 16 PBDE congeners (from tri‐ to deca‐BDE) can be completely extracted by dichloromethane: n‐hexane (3/2, v/v) at 100 °C and 100 atm combined with 15 min static and then 15 min dynamic extraction steps. Recovery of PBDEs in spiked sediment samples ranged from 52 to 104% with 2‐16% RSD, except for BDE‐206. Limits of quantitation (LOQ) were established between 4 and 400 pg/g (dry weight) in 10 g of sediment sample. The extraction efficiency of the PLE was also compared with the traditional Soxhlet extraction method. The total contents of PBDEs ranged from 8.0 to 37.9 ng/g (dry weight) in various river and coastal sediment samples in Taiwan. Deca‐BDE (BDE‐209) was the major PBDE detected in these sediment samples.  相似文献   

2.
An efficient microwave-assisted extraction (MAE) method has been developed and evaluated for the quantification of eight major polybrominated diphenylethers (PBDEs) in sewage sludge. The PBDEs were extracted from wet and dry sludge in a microwave extraction unit using a hexane/acetone mixture for 35 min at a controlled temperature of 130 °C. The extract was concentrated, cleaned up on a silica gel column, and analyzed by gas chromatography/mass spectrometry (GC/MS) in the negative chemical ionization (NCI) mode. The MAE procedure exhibited higher extraction efficiency, specifically for BDE (brominated diphenylether) 209, than the conventional Soxhlet extraction. The test congeners were clearly separated under specific instrumental operating conditions, at a source temperature of 230 °C and a column length of 20 m. The present analytical method showed recovery efficiencies ranging from 80 to 110% when applied to the PBDE-free sludge spiked with eight PBDE congeners. The efficiency of the MAE method was confirmed using sludge obtained from four sewage treatment plants (STPs). The results indicate that BDE 47, 99, and 209 are the most abundant congeners present in these sewage sludges, which is consistent with previous reports.  相似文献   

3.
Polybrominated diphenyl ethers (PBDEs) are flame retardants. As a consequence of their widespread use, they have been released into the environment. PBDEs are lipophilic organic contaminants that enter wastewater treatment plants (WWTPs) from urban, agricultural and industrial discharges. Because of their low aqueous solubility and resistance to biodegradation, up to 90% of the PBDEs are accumulated in the sewage sludge during the wastewater treatment. To assess the possibilities for sludge re-use, a reliable determination of the concentrations of these PBDEs is of crucial importance. Six PBDE congeners (BDE 28, BDE 47, BDE 99, BDE 100, BDE 153 and BDE 154) are listed as priority substances under the EU Water Framework Directive. In the present work a simple analytical method with minimal sample-preparation steps was developed for a sensitive and reliable determination of the six PBDEs in sewage sludge by the use of gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS). For this purpose an extraction procedure was optimised. Different extracting agents (methanol (MeOH), acetic acid (AcOH)/MeOH mixture (3:1) and 0.1 mol L−1 hydrochloric acid (HCl) in MeOH) followed by the addition of a Tris-citrate buffer (co-extracting agent) and iso-octane were applied under different modes of extraction (mechanical shaking, microwave- and ultrasound-assisted extraction). Mechanical shaking or the microwave-assisted extraction of sewage sludge with 0.1 mol L−1 HCl in MeOH and the subsequent addition of the Tris-citrate buffer and the iso-octane extracted the PBDEs from the complex sludge matrix most effectively. However, due to easier sample manipulation during the extraction step, mechanical shaking was used. The PBDEs in the organic phase were quantified with GC-ICP-MS by applying a standard addition calibration method. The spike recovery test (recoveries between 95 and 104%) and comparative analyses with the species-specific isotope-dilution (ID) GC-ICP-MS confirmed the accuracy of the developed analytical procedure. The procedure is sensitive (limits of detection (LODs) for PBDEs congeners between 0.2 and 0.3 ng g−1), repeatable and reproducible (RSDs 2.2–5.7%) and was applied for the determination of PBDEs in sewage sludge samples collected three times at the municipal WWTP over a period of 16 years.  相似文献   

4.
A rapid analytical method has been developed for the determination of polybrominated diphenyl ethers (PBDEs) in human hair. PBDEs were determined by gas chromatography with electron ionization mass spectrometric detection in the selected ion monitoring mode (GC-MS-SIM). A 200 mg amount of hair samples was overnight digested in 3N HCl and then PBDEs extracted with n-hexane. After clean up of extracts in a Florisil column, PBDEs were analyzed by GC-MS. The method has been validated by spiking human hair at five concentration levels, in the range from 5 to 25 ng/g for most compounds, and PBDEs were quantified using labelled compounds as internal standards. Recoveries of PBDEs were higher than 90%, repeatability was equal or lower than 12.5%, and reproducibility lower than 14%, expressed as relative standard deviation (RSD). Limits of detection (LOD) were in the range 0.08-0.9 ng/g and limits of quantification (LOQ) were between 0.27 and 3.0 ng/g. This method was applied to the determination of PBDEs in hair samples from 16 individuals and 5 PBDE congeners were detected in most of the samples. BDE-209 was the dominant compound found, followed by BDE-47, BDE-99, BDE-100, and BDE-190. BDE-209 was found in 12 out of 16 hair samples, and the total levels of PBDEs ranged from 1.4 to 19.9 ng/g.  相似文献   

5.
鱼肉组织中多溴联苯醚的定量分析   总被引:9,自引:0,他引:9  
多溴联苯醚(PBDEs)是一类广泛用于家用电器、电子产品、塑料泡沫、家居装饰材料等行业的添加型阻燃剂[1],使用量最多的是五溴联苯醚(penta-BDE),八溴联苯醚(octa-BDE)和十溴联苯醚(deca-BDE)3种[2]。最近的研究表明[4-6],多溴联苯醚已广泛地存在于各种环境介质、生物体及人体中  相似文献   

6.
A method for the determination of 27 polycyclic aromatic hydrocarbons (PAHs) in sludge from wastewater treatment plants (WWTPs) located in urban, industrial or rural zones is presented. PAHs were extracted by matrix solid-phase dispersion (MSPD) assisted by sonication. Purification of extracts was carried out by solid-phase extraction with C(18) and PAHs were eluted with acetonitrile. PAHs were determined by isotope dilution gas chromatography with electron impact mass spectrometric detection in the selected ion-monitoring mode (GC-MS-SIM), using deuterated PAHs as internal standards. The limits of detection ranged from 0.03 ng/g for acenaphthylene to 0.45 ng/g for benzo[b]naphtho[2,1-d]thyophene. After optimization, the method was validated with a certified reference sludge. The proposed analytical method was applied to determine PAH levels in sewage sludge samples collected from 19 water treatment plants located in the province of Madrid (Spain). In most of the examined samples, phenanthrene was the main compound with a mean concentration of 1062 ng/g. PAHs were detected in all of the samples, with total concentrations between 390 and 6390 ng/g dry weight for the 27 PAHs analyzed and from 310 to 5120 ng/g dry weight for the sum of the 10 PAHs considered in the draft European Union directive.  相似文献   

7.
A method based on matrix solid-phase dispersion (MSPD) has been developed for the determination of 16 organochlorine pesticides (OCs) in sludge from municipal sewage plants. Samples of lyophilized sludge were blended with alumina, placed in small columns and OCs extracted with dichloromethane assisted by sonication. Purification of the extracts was accomplished by solid-phase extraction on C18 columns and OCs were eluted with acetonitrile. Analyses were performed by gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode (GC–MS-SIM) using deuterated OCs as internal standards. The limits of detection were between 0.03 ng/g for 4,4′-DDE and 0.7 ng/g for endrin aldehyde.

Levels of OCs were determined in sewage sludge collected from 19 water treatment plants located in the province of Madrid (Spain). In all of the analyzed samples, aldrin was the compound most often found with a mean concentration of 76 ng/g. Endosulfan-I, -BHC, 4,4′-DDE and 4,4′-DDT were also present at high concentrations, with average values ranging from 32.3 to 74.3 ng/g. OCs were detected in all of the samples, with a total concentration ranging from 52 to 528 ng/g dry weight.  相似文献   


8.
Concentrations of polybrominated diphenyl ethers (PBDEs) in Baltic Sea herring Clupea harengus membras L. collected from Estonian coastal waters are reported. In the period 2006–2008 the total PBDE concentrations (ΣPBDE, sum of 15 congeners) in Baltic herring varied between 0.57 and 4.08 ng g−1 fresh weight. Highest ΣPBDE concentrations were in a 2007 sample from the mouth of the Gulf of Finland and in a 2007 sample from the Gulf of Riga. The former contained a high concentration of BDE 209 (16.3 ng g−1) and in the latter this congener was the second most abundant. It is not clear whether the BDE 209 concentration in the Gulf of Finland sample is not an artefact and this value was not included in the above range. The PBDE concentrations increased with the age of herring are similar to those reported in [1] in fish collected in the Bothnian Sea in 2002 and did not increase between 2002 and 2008. The majority of concentrations in herring from the Estonian coastal zone was <1.0 ng g−1 fresh weight. The PBDE congener profiles varied regionally as well as with age of the fish. The main congeners were mostly the BDEs 47, 99, and 100. Some of the variations probably caused by measurement artefacts.  相似文献   

9.
Analysis of 11 polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A bis 2,3-dibromopropylether (TBBPA-bis), tetrachlorobisphenol A (TCBPA), tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) was optimized by ultrahigh pressure liquid chromatography/tandem mass spectrometry (UPLC–MS/MS) operating in negative ion (NI) mode. Electrospray ionization (ESI), atmospheric pressure photoionization (APPI) and atmospheric pressure chemical ionization (APCI) sources were tested and for PBDEs APCI gave higher sensitivity than APPI while for TBBPA-bis APCI and APPI showed similar performance. ESI was the best option for TCBPA, TBBPA and HBCDs. Detection limits were between 20 and 59 fg for the compounds analyzed by ESI, 0.10 and 0.72 pg for PBDEs and 6 pg for TBBPA-bis. The matrix effect of sewage sludge extract was also tested showing negligible ion suppression for APCI and an increase of the background level of all investigated pollutants leading to a worsening of the limits of quantification by a factor between 1.2 and 3.3. The UPLC-APCI/MS/MS method for PBDEs, after pressurized liquid extraction (PLE), was validated by comparison with the concentration values from the NIST 1944 standard reference material. The advantages of the methods include low detection limits, PBDE congeners specificity using selected multiple reaction monitoring (MRM) transitions, and the absence of thermal degradation of higher PBDE congeners, especially BDE-209. The methods were applied for the determination of the above reported flame retardants in sewage sludge in order to get more information about the degradation on PBDEs (in particular BDE-209) during municipal wastewater treatments.  相似文献   

10.
将超声辅助碱液分解杂质与溶剂萃取相结合,采用气相色谱-电子捕获检测(GC-ECD)建立了一种快速高效净化、萃取海洋沉积物中8种常见多溴联苯醚(PBDEs)的分析方法。样品在2.00 mol/L NaOH甲醇溶液中超声30 min,经正己烷萃取、单层硅胶净化、正己烷洗脱、旋蒸浓缩后定容至100 μL,采用GC-ECD分析。结果表明,PBDEs各单体的加标回收率为63.6%~110.3%,相对标准偏差(RSD)为1.7%~15.5%(n=5);十溴联苯醚(BDE-209)的检出限为0.097 ng/g,其他7种单体的检出限为0.002~0.011 ng/g(信噪比为3)。该方法的准确度和精密度较高,稳定性和回收率良好,可满足沉积物中PBDEs的分析要求。利用建立的方法测定了渤海表层沉积物中PBDEs的含量,8种PBDEs总含量在1.566~6.760 ng/g之间,其中BDE-209的含量为1.461~6.438 ng/g,总体呈现出由近岸向远岸递减的趋势,表明人为活动、表层冲刷和陆地河流的输入对渤海地区PBDEs的含量有重要影响。  相似文献   

11.
A simple and economical method for the determination of eight polybrominated diphenyl ethers (BDE‐28, 47, 99, 100,153,154,183, and 209) in water was developed. This method involves the use of ultrasound‐assisted dispersive liquid–liquid microextraction combined with GC‐MS in negative chemical ionization mode. Various parameters affecting the extraction efficiency, including the type and volume of extraction and dispersive solvents, salt concentration, extraction time, and ultrasonic time, were investigated. A volume of 1.0 mL of acetone (dispersive solvent) containing 10 μL tetrachloroethylene (extraction solvent) was injected into 5.0 mL of water samples and then emulsified by ultrasound for 2.0 min to produce the cloudy solution. Under the optimal condition, the enrichment factors for the eight PBDEs were varied from 845‐ to 1050‐folds. Good linearity was observed in the range of 1.0–200 ng L?1 for BDE‐28, 47, 99, and 100; 5.0–200 ng L?1 for BDE‐153, 154, and 183; and 5.0–500 ng L?1 for BDE‐209. The RSD values were in the range of 2.5–8.4% (n = 5) and the LODs ranged from 0.40 to 2.15 ng L?1 (S/N = 3). The developed method was applied for the determination of eight BPDEs in the river and lake water samples, and the mean recoveries at spiking levels of 5.0 and 50.0 ng L?1 were in the range of 70.6–105.1%.  相似文献   

12.
The analysis of brominated flame retardants, such as polybrominated diphenyl ethers (PBDEs), has received increased interest because of their toxicity and ubiquity. According to European Union Directive 2008/105/EC, the development of highly sensitive and selective methods capable of determining PBDEs at low concentration levels (<0.5 ng/L) is necessary. In this work, an SPE method was developed for the analysis of the six PBDEs (BDE‐28, BDE‐47, BDE‐99, BDE‐100, BDE‐153, BDE‐154) specified by the aforementioned directive in surface waters. The analyses were performed by GC coupled to magnetic sector high‐resolution MS. The conditions were also optimized to detect the target compounds in water samples at concentrations below the environmental quality standards established by European legislation. The validated method provided adequate linearity (determination coefficient, R2 ≥ 0.9960), recovery (101–120%, except for BDE‐47 at 5 ng/L, 127%), and precision values (RSD < 20%) at two fortification levels (0.2 and 5 ng/L). The method showed LODs and LOQs ranging from 0.02 to 0.05 and from 0.05 to 0.1 ng/L, respectively. The method was applied in surface water samples, allowing the determination of these compounds at the limits established by current legislation.  相似文献   

13.
Decabromodiphenyl ether (BDE209) is poorly absorbed by mammals, and little information is available on the toxicokinetics of BDE209 and its metabolites in fish. In the present study, rainbow trout (Oncorhynchus mykiss) were administered to 100 ng/g and 500 ng/g body wet weight of BDE209 via a single intraperitoneal injection and parent BDE209 and its metabolites were sequentially monitored for 28 days. The results showed that toxicokinetic profiles of BDE209 could be described by the one-compartment model. In the higher dose group (500 ng/g wet weight), the calculated half-life (t 1/2) and elimination rate (k e) were 17.7 d and 0.039/d in the liver, and 100.3 d and 0.007/d in the muscle, respectively. Three major methoxylated brominated diphenyl ethers (MeO-BDEs) were detected with 2,2′,4,4′-tetrabromo-5-methoxydiphenyl ether (5-MeO-BDE47) being detected in all tissue samples. There was no significant temporal change of 5-MeO-BDE47 concentration in the muscle, whereas an exponential increase was observed in the liver. Therefore, the metabolism rate of BDE209 depended on the administered dose. BDE209 was hardly accumulated in the muscle of rainbow trout, while the liver was a primary metabolic organ. MeO-BDEs were formed via metabolism of BDE209, which probably played a significant role in fish toxicology as a potential indicator.  相似文献   

14.
气相色谱-负化学源质谱快速测定母乳中的多溴联苯醚   总被引:1,自引:0,他引:1  
建立了母乳中8种多溴联苯醚(PBDEs:BDE28,BDE47,BDE99,BDE100,BDE153,BDE154,BDE183,BDE209)的气相色谱-负化学源质谱测定方法(GC-NCI/MS)。样品经索氏提取、酸化硅胶除脂、硅胶氧化铝色谱柱净化后,在7 m长的毛细管气相色谱柱上快速分离,NCI/MS以选择离子监测模式测定目标化合物。其中,三溴~七溴联苯醚采用内标法定量,十溴联苯醚(BDE209)采用同位素稀释法定量。8种PBDEs的检出限为1.74~6.35 pg/g(以脂肪计)。加标回收试验的回收率为61.5%~108%,相对标准偏差为2.06%~10.1%(n=6)。并采用母乳参考物质进一步证实了该方法的准确可靠。该方法提高了BDE209的分析灵敏度,而且分析成本相对较低,分析时间短,适于推广。  相似文献   

15.
建立了一种同时测定沉积物中不同赋存形态的多溴联苯醚(PBDEs)和四溴双酚A(TBBPA)的分析方法.样品由等体积的丙酮和正己烷混合溶剂抽提得到自由态目标物,再通过碱性水解反应释放束缚态目标化合物.通过调节酸度(pH值)实现PBDEs和TBBPA的分离和提取.PBDEs由复合硅胶柱净化,运用气相色谱-质谱(负离子化学源)-分时段选择离子监测技术测定;TBBPA经重氮甲烷衍生化反应后由酸性硅胶柱预纯化,运用气相色谱-质谱(电子轰击源)-分时段选择离子监测技术测定.8种低溴联苯醚(BDE28,-47,-66,-100,-99,-154,-153,-183),十溴联苯醚(BDE209)和TBBPA的检出限分别为0.6~12.5 pg/g,172 pg/g,4 2 pg/g.方法具有良好的准确度和精确度,回收率均在74%~106%之间,RSD≤10%.对东江沉积物样品的分析表明,本方法能够实现不同形态的PBDEs 和TBBPA的有效检测.  相似文献   

16.
Shi Z  Wang Y  Feng J  Huang P  Wu Y 《色谱》2011,29(6):543-548
建立了凝胶渗透色谱(GPC)结合气相色谱-负化学源质谱(GC-NCI/MS)检测鱼肉及鱼油中8种多溴联苯醚(PBDEs)同系物及2种得克隆阻燃剂(DP)的分析方法。试样中加入内标物BDE-77和13C12-BDE-209后进行索氏提取,提取液经自动GPC系统除脂,多层硅胶层析柱净化后,在15 m长的毛细管气相色谱柱上分离,NCI/MS以选择离子监测方式检测目标化合物。以鱼肉样品为基质,当PBDEs的加标水平为0.2 ng/g和2 ng/g、BDE-209和DP的加标水平相应提高10倍时,其平均加标回收率为71.1%~121.4%,相对标准偏差为2.96%~13.31%(n=5);以信噪比(S/N)为3计算方法的检出限(LOD)为2.2~39.8 ng/kg。用该方法检测市售鱼肉及鱼油样品,其中多溴联苯醚总含量为2.18~15.93 ng/g,以BDE-209、BDE-47为主,两种DP均未检出。该方法准确、灵敏度高,能够满足富含脂质的动物性样品中痕量DP和PBDEs残留的分析要求。  相似文献   

17.
This paper reports the applicability of low-pressure gas chromatography-mass spectrometry operated in electron-capture negative ionization mode (LP-GC-ECNI-MS) for the analysis of decabrominated diphenyl ether (BDE-209). Particular attention was paid to find optimal injector and oven conditions for minimal thermal degradation of BDE-209. The analytical characteristics were compared for LP-GC columns (10 m x 0.53 mm) with different film thicknesses (d(f) 0.15 microm versus 0.25microm) and for a conventional GC column (15 m x 0.25 mm, 0.10 microm d(f)). Short residence times (6.5 and 9.8 min) of BDE-209 were found for the LP-GC systems with 0.15 and 0.25microm d(f), respectively, resulting in a low elution temperature and minimal degradation. Additionally, baseline separation of 22 polybrominated diphenyl ether (PBDE) congeners (major components of PBDE technical mixtures) was possible in less than 12 min using the LP-GC-ECNI-MS system with 0.15microm d(f). The optimized method was applied for the determination of PBDEs in Belgian indoor dust samples. The obtained concentrations of BDE-209 (range 8-292 ng/g dry weight) were in the same range or lower than concentrations in dust from other European countries.  相似文献   

18.
建立了凝胶渗透色谱(GPC)结合气相色谱-负化学源质谱(GC-NCI/MS)检测鱼肉及鱼油中8种多溴联苯醚(PBDEs)同系物及2种得克隆阻燃剂(DP)的分析方法。试样中加入内标物BDE-77和13C12-BDE-209后进行索氏提取,提取液经自动GPC系统除脂,多层硅胶层析柱净化后,在15 m长的毛细管气相色谱柱上分离,NCI/MS以选择离子监测方式检测目标化合物。以鱼肉样品为基质,当PBDEs的加标水平为0.2 ng/g和2 ng/g、BDE-209和DP的加标水平相应提高10倍时,其平均加标回收率为71.1%~121.4%,相对标准偏差为2.96%~13.31%(n=5);以信噪比(S/N)为3计算方法的检出限(LOD)为2.2~39.8 ng/kg。用该方法检测市售鱼肉及鱼油样品,其中多溴联苯醚总含量为2.18~15.93 ng/g,以BDE-209、BDE-47为主,两种DP均未检出。该方法准确、灵敏度高,能够满足富含脂质的动物性样品中痕量DP和PBDEs残留的分析要求。  相似文献   

19.
A rapid and reliable analytical method based on pressurised solvent extraction (PSE) and GC-NCI-MS was developed for the determination of 41 different PBDEs in soil. All PBDEs, including mono- to hepta-BDEs (sum of 39 congeners), one nona-BDE and deca-BDE, were efficiently extracted from soil samples using the extraction technology of PSE. The extract was then cleaned up on a florisil column. Satisfactory separation of 41 PBDE congeners was obtained on a 15-m DB-5MS capillary column, saving the use of another 30-m column specific for the separation of mono- to hepta-BDEs. PBDEs were identified and quantified by GC-MS in negative chemical ionisation (NCI) mode, and further confirmed in semi electron impact (SEI) mode when the ion source was also NCI. The method detection limits ranged from 0.01 to 0.03?ng?g?1?dw for mono- to hepta-BDEs, 1.43?ng?g?1?dw for the nona-BDE and 0.20?ng?g?1?dw for deca-BDE. The applicability of the method was tested in soil samples collected from an e-waste recycling site at Guiyu. Twenty-one PBDEs (mono- to deca-) were detected, and eighteen congeners were quantified. The concentration range of PBDEs was 0.78–436?ng?g?1?dw. BDE-47, BDE-99, BDE-153, BDE-183, BDE-206 and BDE-209 were the dominant congeners, and BDE-209 accounted for 62% of the total PBDEs. The congener profiles of PBDEs in soil samples were similar to those in three commercial PBDE products (Penta-, Octa- and Deca-BDE), and Deca-BDE product was the most important contributor.  相似文献   

20.
This study evaluated the removal of multiple pollutants,i.e.,polybrominated diphenyl ethers(PBDEs),novel halogenated flame retardants(HFRs),sulfonamide antibiotics(SAs),and heavy metals(HMs),by a fullscale reversed A2/O process in a sewage treatment plant(STP) in Guangzhou,China.The reversed A2/O process demonstrated high removal efficiencies(REs) for total PBDEs(60.5% ± 4.3%),novel HFRs(98.4% ±2.8%) and HMs(70.1% ±1.2%),and a relatively low RE for SAs(25.0% ± 2.3%).BDE 209...  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号