厦门港和筼筜湖沉积物中多溴联苯醚类防火剂(PBDEs)的色谱一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素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)。     

测定氨苄西林钠方法研究

目的建立测定氨苄西林钠新方法。方法在氢氧化钠介质中，高碘酸钾氧化鲁米诺产生化学发光，氨苄西林钠显著增强该体系的发光，据此建立了一种简单、快速测定氨苄西林钠的流动注射化学发光新方法。结果在优化的试验条件下，线性范围为0．01～10μg／ml，检出限（36）为3．0ng／ml，对1μg／ml氨苄西林钠进行了11次平行测定，其相对标准偏差为1．4％。结论将本法用于粉针剂中氨苄西林钠的测定，结果令人满意。     

呋苄西林钠含量与有关物质的高效液相色谱法测定研究

目的建立呋苄西林钠含量与有关物质的I-IPLC分析方法。方法采用ODS柱,以磷酸盐缓冲液（0．05mol／L磷酸二氢钾溶液,用磷酸调节pH值至3．5）：乙腈（75：25）为流动相A;以磷酸盐缓冲液：乙腈（20：80）为流动相B,含量测定以流动相A进行等度洗脱,有关物质测定采用线性梯度洗脱,流速为1．0ml／min,检测波长为254nm。结果呋苄西林在0．0964～19．29μg的范围内,进样量与峰面积的线性关系良好（r=0．9999）,最低检测限为1．2ng。结论本方法可用于呋苄西林钠的有关物质及含量测定,方法专属性强,重现性好,操作简便。     

呋苄西林钠有效成份检测

目的建立呋苄西林钠含量与有关物质的HPLC分析方法。方法采用ODS柱,以磷酸靛缓冲液（0．05mol／L磷酸二氢钾溶液,用磷酸调节pH值至3．5）：乙腈（75：25）为流动相A;以磷酸盐缓冲液：乙腈（20：80）为流动相B,含量测定以流动相A进行等度洗脱,有关物质测定采用线性梯度洗脱,流速为1．0rnl／min,检测波长为254nm。结果呋苄西林在0．0964～19．29μg的范围内,进样量与峰面积的线性关系良好（r=0．9999）,最低检测限为1．2ng。结论本方法可用于呋苄西林钠的有关物质及含量测定,方法专属性强,重现性好,操作简便。     

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。     

水产品中麻痹性贝类毒素（PSP）检测探析

目的：使用美国ABRAXIS麻痹性贝类毒素试剂盒对40个北海海域的文蛤样品进行PSP检测。方法：使用酶联免疫试剂盒对文蛤麻痹性贝类毒素进行检测，检测限为0．02ng／g，灵敏度为为0．015ng／go通过建立PSP纯溶液的标准曲线测定，待测水产品的PSP浓度。结果：建立标准曲线后，最终测得水产品样品PSP的平均含量为1．7ng／g结论：应用EusA法检测麻痹性贝类毒素，具有简便、快捷、成本低廉等特点，适用于快速检测的样品。可以应用于水产品质量的快速检测以及对贝类进行质量监控。麻痹性贝类毒素（PSP）指存在于贝类体内，摄食后可以产生麻痹作用的一种海洋生物毒性物质。PSP的化学结构主要是石房蛤毒索（Saxitoxin），是目前世界上一类分布最广、食物中毒频率最高、危害度最大的毒素。     

头孢吡肟中N-甲基吡咯烷杂质含量的气相色谱法测定分析

目的用气相色谱法测定盐酸头孢吡肟中N-甲基吡咯烷杂质含量。方法采用毛细管气相色谱法,氢火焰离子化检测器（FID）,弹性石英毛细管柱HP-1（60m×0．53mm,5μm）;柱温100℃;气化室温度250℃;检测器温度250℃;载气为氮气;进样量1μ1;分流比为10：1。结果N-甲基吡咯烷浓度在1．1213～134．56μg／ml时线性关系良好,线性方程：A吡咯烷／A内标=0．01561C-0．00854,相关系数r=0．99998;RSD（％）=0．00486。加样回收率101．73％;检测限0．6ng。结论本法简便、准确、适用性广,便于在生产过程中进行监控。     

固相小柱萃取法测定多目标生态地球化学评价土壤样品中有机氯农药含量

本文介绍了超声提取，固相小柱净化，气相色谱法测定土壤中六六六和DDT含量的方法，用正交法优化了萃取条件。方法检出限为O．045～01320ng／g，线性范围1.0-500ng／g，相关系数大于0.99，精密度为4．7～13．0％，加标回收率83～103％。     

AP系列新型环氧增韧剂问世

烟台奥利福化工有限公司已生产出氢化双酚A型环氧树脂AL-3040，经进一步改性又生产出固体氢化双酚A型环氧树脂（HBPA）。HBPA是一种高耐候性环氧树脂，AL-3040外观为淡黄色透明液体，色相（Gardner）≤2，环氧值0.41～0．44eq／100g，黏度（25℃）2500～1500mPa·s，可水解氯≤0．01eq／100g，无机氯≤0.001eq／100g，挥发分≤0．5％，其质量与日本同类产品ST．3000指标相当；     

盐酸左旋沙丁胺醇的有效成份测定

目的测定盐酸左旋沙丁胺醇缓释胶囊的有关物质。方法采用反相高效液相色谱法（RPHPLC法），色谱柱为KromasilC18柱（250mm×4．6mm，5um），以甲醇磷酸盐缓冲液（取磷酸二氢钠9．77g，加水溶解并稀释至1000mL，用磷酸调节pH值至3．10-0．05）（体积比20：80）为流动相，检测波长为224m，流速1．0mL．min-1。结果各杂质峰分离良好，左旋沙丁胺醇的最低检测限为14ng。结论本法可用于盐酸左旋沙丁胺醇缓释胶囊中有关物质的检测。     

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.