厦门港和筼筜湖沉积物中多溴联苯醚类防火剂(PBDEs)的色谱-质谱联机同位素稀释法测定

利用^13C标记的多溴联苯醚标准作内标对厦门沿岸海域和筼筜湖沉积物进行色谱-质谱联机测定并采用同位索稀释法进行数据收集和计算,分别测定PBDE3、15、28、47、60、85、99、100、138、153、154和183共12个同类化合物,其回收率范围为75．8—100．5％,最低检测限0．02ng／g（d）,沉积物中总PBDE最高值为厦门第一码头2．06ng／g（d）,最低是厦门大学海水浴场为0．10ng／g（d）。     

白洋淀表层沉积物中的多卤代芳烃及其潜在风险

采用GC-MS/MS技术对45个白洋淀表层沉积物(0~5 cm)样品中的三类(多溴联苯、多溴联苯醚和多氯联苯)多卤代芳烃(PHAHs)进行分析。实验发现多氯联苯(PCBs)是优势污染物(20.57 ng.g-1.dw),PCB28,52,66,138,156和170是被检出的主要同族体;多溴联苯(PBBs)和多溴联苯醚(PBDEs)在沉积物中的检出浓度相对较低(0.47 ng.g-1.dw和1.78 ng.g-1.dw),PBDE28和PBDE47是最具支配地位的PBDE同族体,分别占PBDEs总量的16%和21%。实验结果与国内外最近的文献报道值相比较,显示这三类PHAHs在沉积物中的浓度处于低污染水平,引起的潜在风险也相对较低。     

室内空气中总挥发性有机物(TVOC)分析方法的研究

针对室内挥发性有机物测定方法的不完善,提出了利用热脱附-气相色谱质谱联用测定空气中挥发性有机物的测试方法,测定空气中挥发性有机物的线性范围为0ng～800ng,最低检出限可达0.05μg/m3(采样体积10L计),相对标准偏差4%～10%。该方法灵敏度高、操作简便、重现性好、准确可靠,适合室内空气中挥发性有机物的测定。     

土壤和沉积物中汞含量测定及应用

土壤和沉积物是汞的生物地球化学循环中重要的"汇"和"源"。采用RA-915M测汞仪固体模块的直接进样法,建立土壤和沉积物中汞含量的一种快速测试分析方法。该方法无需对固体样品进行消解、定容等前处理操作,具有快速、准确、分析成本低等特点。探讨该方法的检出限、精密度和加标回收率,结果显示方法检出限为0.132 ng/g,相对标准偏差小于5%(n=5),加标回收率为92.8%～106%。为进一步检验方法的可靠性,对土壤和沉积物样品分别使用RA-915M测汞仪固体模块、液体模块和原子荧光光度计测试。结果显示,固体直接进样法操作简便、可信度高,更适合测定土壤和沉积物中汞的含量。利用该方法对洞庭湖沉积物和北京农田土壤汞含量进行研究,研究结果与前人研究相符,表明该方法准确、高效,值得推广利用。     

ICP-MS测定土壤和水系沉积物中的微量银

样品经三酸(HF+HNO3+H2SO4)完全分解后采用ICP-MS测定银时,锆会产生强烈干扰。为消除这种干扰,提高结果准确度,建立离线干扰校正方法。通过测试4件水系沉积物及9件土壤国家标准物质,选择最适测定条件:溶液酸度为1.0%,内标为10 ng/m L Rh、In,采用94Zn消除锆对107Ag干扰。实测结果表明该方法检出限为5.8 ng/g,精密度为5.80%,测试值与推荐值吻合,误差在标准物质允许范围内。该方法具有简便、快捷、准确的优点,还能实现多元素同时测定。     

添加大豆寡糖沉积物对海底微生物燃料电池电化学性能的影响

通过向海底沉积物中添加不同浓度的大豆寡糖(SBOS),探究其对海底沉积物微生物燃料电池(MSMFCs)的影响。结果表明,阳极表面附近微生物数量与SBOS浓度有关,添加2 g SBOS组的微生物数量最多(9.310×10~(11)cfu/m~2),添加6 g SBOS组的微生物数量最少(7.680×10~8cfu/m~2);SBOS浓度影响阳极电化学性能,添加2 g SBOS组阳极的电容性、抗极化能力最好,添加6 g SBOS组的最差;高浓度SBOS有利于提高MSMFCs的实际输出电压,添加6 g SBOS组的平均输出电压高出空白组45 m V,高出其它实验组15~20 m V;空白组有机质消耗率最高,为66.15%,添加6g SBOS组的消耗率最低,为50.63%;SBOS以改变微生物数量的方式影响MSMFCs电化学、产电性能和有机质消耗率。     

灯盏花素葡萄糖注射液包装安瓿瓶中元素迁移性方法研究

以湿法消解对低硼硅玻璃安瓿瓶包装的灯盏花素葡萄糖注射液进行消解,建立ICP-AES及ICP-MS测定其中Al、Ca、K、Na等14种元素的方法,并从检出限、定量限、重复性等方面进行验证。结果表明:该方法检出限为0.009 ng/m L(Ni)~0.03μg/m L(Al);定量限为0.03 ng/m L(Ni)~0.09μg/m L(Al)。平均加标回收率介于95.6%~101.4%之间。     

顶空-固相微萃取-气相色谱-电感耦合等离子体质谱法联用测定大气颗粒物中的无机汞和甲基汞

大气中的汞有不同的存在形态,对环境的影响程度不同,目前对大气颗粒中汞的测定研究及其形态分析尚非常薄弱。该文尝试将顶空-固相微萃取与气相色谱-电感耦合等离子体质谱法联用测定大气颗粒物中的无机汞和甲基汞。该方法对甲基汞和无机汞的检出限分别为2 ng/L(0.02 ng)和0.5 ng/L(0.005 ng),测定下限分别为8 ng/L(0.08 ng)和2 ng/L(0.02 ng)。可实现大气颗粒物中无机汞的准确测定,也可以用于甲基汞污染情况下污染源废气或污染区大气颗粒物中甲基汞的监测。     

高效液相色谱法测定注射用盐酸瑞芬太尼有关物质

建立高效液相色谱法测定注射用盐酸瑞芬太尼的有关物质,色谱柱采用Kromasil氰基柱,流动相为0.03mol/L磷酸二氢钾缓冲液(pH 3.0)-甲醇-乙腈(80∶16∶4),检测波长225nm。盐酸瑞芬太尼在0.5046~1009.2μg/mL范围内与杂质峰面积显示有良好的线性关系(r=0.9999),最低检出限为0.001μg。该法简便、准确,专属性强,可用于注射用盐酸瑞分太尼有关物质测定。     

高效液相色谱法测定扑热息痛药代动力学参数

采用反相高效液相色谱法测定扑热息痛在健康人体内的药代动力学参数。Zorbax ODS色谱柱,流动相为甲醇一水一冰醋酸(20:75:5),茶碱为内标,检测波长245nm,线性范围0.5～25μg/mL,r=0.9987,回收率101.58%,日内、日间测定 RSD 均小于10%,血浆中扑热息痛最低检测浓度小于0.1μg/mL。     

Determination of polybrominated diphenyl ethers and polychlorinated biphenyls in human adipose tissue by large-volume injection-narrow-bore capillary gas chromatography/electron impact low-resolution mass spectrometry

A new analytical method has been developed for the quantification of polybrominated diphenyl ethers (PBDEs) in human adipose tissue samples. After Soxhlet extraction and a cleanup procedure using two successive solid-phase extraction cartridges containing acid silica and acid silica: neutral silica:deactivated basic alumina (from top to bottom), detection can been achieved by narrow-bore (0.10-mm i.d.) capillary gas chromatography/electron impact low-resolution mass spectrometry using a large-volume injection technique. Using narrow-bore capillaries, it is possible to analyze complex mixtures in a short time (up to 10 min), saving 50% or more of the analysis time of conventional columns while maintaining a similar resolution power. The method allows the determination of five major PBDE congeners (BDE 28, 47, 99, 100, and 153) at concentrations below 1 ng/g lipid weight. Detection limits in the selected ion mode varied between 0.05 and 0.30 ng/g lipid weight, depending on the degree of bromination. The sensitivity of this method can compete with low-resolution mass spectrometry with electron capture ionization, while a much better selectivity is obtained. Levels of PBDEs in 20 Belgian human adipose tissue samples ranged between 2.18 and 11.70 ng/g lipid weight and were similar to previously reported values from Europe.     

色谱-质谱联机测定厦门港和员当湖表层沉积物中的石油烃和多环芳香烃的含量

2002年4月厦门港沿岸设九个站,员当湖设两个站采集表层积物,用有机溶剂萃取,硅胶柱色层分离,气相色谱-质谱联机带SIM数据采集系统对样品的石油烃类(M/Z=55),多环芳香烃类(15个典型的多环芳香烃,9个甲基化多环芳香烃作外标)进行分析,结果显示员当湖石油烃和多环芳香浓度分别高达1397微克/克(干)和1376.5纳克/克(干)。厦门港沉积物石油烃和多环芳香浓度范围为:石油烃133.3～943.3微克/克(干)多环芳香烃97.6～308.5纳克/克(干)。厦门港船只活动,厦门港四周工业废水、车辆燃油滴漏是石油烃污染的主要来源。厦门工业用煤、用油、生活用煤及船只、车辆燃料泄漏是沉积物多环芳香烃的主要来源,其工业排废、生活废水排放,市区雨水冲刷和大气灰尘沉降是多环芳香烃进入海湾的主要途径。     

Semiautomated high-throughput extraction and cleanup method for the measurement of polybrominated diphenyl ethers and polybrominated and polychlorinated biphenyls in breast milk

A semiautomated extraction and cleanup method has been developed to measure eight polybrominated diphenyl ethers (PBDEs), 2,2',4,4',5,5'-hexabromobiphenyl (BB-153), and 2,2',4,4',5,5'-hexachlorobiphenyl (CB-153). The method employs solid-phase dispersion on diatomaceous earth in a solid-phase extraction cartridge followed by automated addition of internal standards ((13)C-labeled). Extraction is then performed using an automated modular solid-phase extraction system. The extraction procedure includes drying the sample on diatomaceous earth by pressurized nitrogen and eluting target analytes and lipids with dichloromethane. Lipid content is determined gravimetrically. Lipid determinations performed using this method are compared with other standard methods and with a certified reference material. A relative standard deviation of 7.9% was obtained for 130 determinations of the lipid content in a breast milk quality control sample. Final analytical determination of target analytes was performed by gas chromatography-isotope dilution high-resolution mass spectrometry. Relative standard deviations for the measurements of target analytes for which a labeled internal standard was available were below 10% for analytes at concentrations above 1 ng/g of lipid. Mean recoveries of the (13)C-labeled internal standards ranged from 60 to 89% for the eight PBDE congeners; 74 and 113% were recovered for BB-153 and CB-153, respectively.     

Quantitative analysis of 39 polybrominated diphenyl ethers by isotope dilution GC/low-resolution MS

A GC/low-resolution MS method for the quantitative isotope dilution analysis of 39 mono- to heptabrominated diphenyl ethers was developed. The effects of two different ionization sources, electron impact (EI) and electron capture negative ionization (ECNI), and the effects of their parameters on production of high-mass fragment ions [M - xH - yBr](-) specific to PBDEs were investigated. Electron energy, emission current, source temperature, ECNI system pressure, and choice of ECNI reagent gases were optimized. Previously unidentified enhancement of PBDE high-mass fragment ion [M - xH - yBr](-) abundance was achieved. Electron energy had the largest impact on PBDE high-mass fragment ion abundance for both the ECNI and EI sources. By monitoring high-mass fragment ions of PBDEs under optimized ECNI source conditions, quantitative isotope dilution analysis of 39 PBDEs was conducted using nine (13)C(12) labeled PBDEs on a low-resolution MS with low picogram to femtogram instrument detection limits.     

Determination of estrogens in sludge and sediments by liquid extraction and GC/MS/MS

Two methods have been developed that enable the determination of estrogens down to 2 ng/g in digested and activated sludge from domestic sewage treatment plants (STPs) and down to 0.2 ng/g in freshwater sediments. The method for sludge analysis consists of solvent extraction; a gel permeation chromatography (GPC) cleanup step, a 1 g silica gel column; and finally, detection by GC-ion trap MS/MS of the silylated estrogens with MSTFA. For sediments, the solvent extraction was successively followed by silica gel cleanup, solid phase enrichment (SPE), and a HPLC cleanup before derivatization and GC/MS/MS detection. Mean recoveries of the estrogens mainly exceeded 70% in sludge and 90% in sediments. In activated and digested sewage sludge, estrone and 17beta-estradiol were detected up to 37 ng/g and 49 ng/g, respectively, and 17alpha-ethinylestradiol up to 17 ng/g. The occurrence of estrogens in digested sludge indicates that estrogens can be persistent during sludge digestion. In river sediments, estrone and 17beta-estradiol were detected up to 2 ng/g (estrone), and the contraceptive 17alpha-ethinylestradiol was found with a maximum of 0.9 ng/g. Mestranol, a prodrug for 17alpha-ethinylestradiol, was not detected either in sludge or in sediments.     

Exposure of Hong Kong residents to PBDEs and their structural analogues through market fish consumption

High concentrations of polybrominated diphenyl ethers (PBDEs) and their structural analogues (such as methoxylated (MeO) and hydroxylated (OH) PBDEs) had been observed in environmental samples and human tissues. This study evaluated the occurrence, potential source and human exposure of these organobrominated compounds via market fish consumption in Hong Kong. The contamination of 22 PBDEs, 7 MeO-BDEs, 15 OH-BDEs and 3 bromophenols (BRPs) were analyzed in 20 fish species (279 samples). The estimated daily intakes of PBDEs, MeO-BDEs, OH-BDEs and BRPs via fish consumption ranged from 4.4 to 14, 0.50 to 4.3, 0.02 to 0.43 and 0 to 0.21 ng/kg day for Hong Kong residents, respectively, based on 50^th and 95^th centile concentrations. BDE-47 and 99 were found to be the major PBDE congeners while 2′-MeO-BDE-68, 6-MeO-BDE-47 and 3-MeO-BDE-47 were the dominant MeO-BDEs. Concentrations of OH-BDEs and BRPs were 10-100-fold less than those of PBDEs, with small frequencies of detection (max 36.7%). Dietary intake of PBDEs via fish consumption by Hong Kong residents was greater than many developed countries, such as the USA, UK, Japan and Spain. To our knowledge, this is the first report to estimate the dietary intake of MeO/OH-BDEs and BRPs via fish consumption. Our results indicated that the toxicity potential of these compounds should not be neglected.     

Polybrominated diphenyl ethers (PBDEs) in indoor and outdoor window organic films in Izmir, Turkey

Polybrominated diphenyl ether (PBDE) concentrations of outdoor and indoor organic films on window glasses were measured at different locations (offices, laboratories, and homes in urban, suburban, rural, and industrial sites) in Izmir, Turkey. ∑(7)PBDE concentrations were dominated by technical penta and deca-BDE mixture components. Average total outdoor PBDE (∑(7)PBDE) concentrations for suburban, urban, and industrial sites were 43.5, 45.5, and 206 ng m(-2), respectively. This spatial gradient (industrial>urban>suburban concentrations) was similar to one observed for ambient air concentrations recently in Izmir, Turkey. The highest concentrations measured in the industrial area were attributed to the significant PBDE emissions from several steel plants located in the area. Air-organic film partitioning modeling results have suggested that organic films can be used in conjunction with the dynamic uptake model to approximate the gas-phase ambient air concentrations. Modeling results have also indicated that congeners in the gas-phase with very large octanol-air partition coefficients (i.e., BDE-154, -153, and -209) will require several months to approach equilibrium with the surface films. This finding may have important implications for gas-particle and gas-film partitioning, transport, and photolytic degradation of atmospheric PBDEs.     

Elevated concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans and polybrominated diphenyl ethers in hair from workers at an electronic waste recycling facility in eastern China

Hair samples collected from e-waste recycling workers (n=23 males, n=4 females) were analyzed to assess occupational exposures to polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) at a large e-waste recycling facility in Taizhou, eastern China. Hair samples from a reference population composed of residents of Shanghai (n=11) were analyzed for comparison. The mean concentration of ∑PBDEs (range, 22.8-1020 ng/g dw; mean, 157 ng/g dw) found in hair samples from e-waste recycling workers was approximately 3 times higher than the mean determined for the reference samples. The congener profiles of PBDEs in hair from e-waste recycling workers were dominated by BDE 209, whereas the profiles in the reference-population samples showed comparable levels of BDE 47 and BDE 209. Total PCDD/F concentrations in hair from e-waste workers (range, 126-5820 pg/g dw; mean, 1670 pg/g dw) were approximately 18-fold greater than the concentrations measured in hair from the reference population. Concentrations of PCDFs were greater than concentrations of PCDDs, in all of the hair samples analyzed (samples from e-waste and non-e-waste sites). Tetrachlorodibenzofurans (TCDFs) were the major homologues in hair samples. Overall, e-waste recycling workers had elevated concentrations of both PBDEs and PCDD/Fs, indicating that they are exposed to high levels of multiple persistent organic pollutants.     

Determination of priority polybrominated diphenyl ethers by isotope dilution gas chromatography(electron ionization)MS using 81Br-labeled standards

A mixture of (81)Br-labeled polybrominated diphenyl ethers (PBDEs), previously synthesized in our laboratory, was separated by liquid chromatography for the individual isolation of different (81)Br-labeled PBDEs containing from 3 to 6 bromine atoms. The different fractions were collected, and a mixed labeled standard was then prepared adequate for the determination of priority PBDEs (congeners 28, 47, 99, 100, 153, and 154) in environmental samples. The spike mixture was then characterized using gas chromatography(electron ionization)MS (GC(EI)MS) both in isotope composition and concentration in combination with multiple least-squares. Contamination from natural abundance BDEs 153 and 154 was detected in the spike mixture, and a new isotope dilution equation was developed to take into account the natural abundance contribution from the spike. The spike mixture was shown to be stable during at least 4 months, and no isotope exchange between natural abundance and labeled PBDEs was detected during this period of time. Finally, the (81)Br-labeled PBDEs standard was used for the determination of congeners 28 (+33), 47, 49, 99, 100, 153, and 154 in a standard reference material (Lake Michigan fish tissue SRM 1947) using three different sample to spike ratios. No methodological calibration needed to be prepared, as no isotopic effects were detected using this labeling mode. Concentrations found were in agreement with the certified concentrations (recoveries between 89% and 116%), and reproducibility was always below 7% RSD. Kragten procedure was used to calculate expanded uncertainties. Very low limits of detection were obtained for all compounds (between 0.02 and 0.9 ng·g(-1)) using the procedure developed here.