北方某城市饮用水中多环芳烃的来源及其在水处理过程中的行为研究

采用固相萃取(SPE)样品富集前处理技术和气相色谱/质联联用(GC/MS)分析方法,对北方某工业城市给水系统中的多环芳烃类化合物的含量水平进行了研究.结果表明,该城市多环芳烃污染水平较高,但总浓度均未超过城市供水水质标准(CJ/T206-2005)中限值(2μg/L).近郊水库由于受到燃料燃烧产生的多环芳烃的污染,成为该市饮用水中多环芳烃污染的主要来源.传统的混凝-砂滤工艺对多环芳烃有较好的去除效果,总去除率可达55.9%.     

人工湿地处理系统中多环芳烃的行为

采用Oasis HLB柱固相萃取的前处理技术,以气相色谱质谱联用仪(GC/MS)的分析方法,对我国北方永定河上游黑土洼人工湿地中多环芳烃污染的特征以及分布规律进行了研究.结果表明,该湿地系统以低环数多环芳烃污染为主,其中浓度最高的是菲和蒽,未检出高环数(5环、6环)多环芳烃.通过比较进水和出水的浓度,湿地系统总体上不能有效去除进水中的多环芳烃.但是比较不同工艺单元进出水浓度,复氧、植物根系及微生物等均影响到多环芳烃的去除效果,去除率在28%～65%之间.     

有机微污染物在污水处理过程中的变化研究

多环芳烃等有毒有机微污染物对污水处理综合指标BOD、COD和TOC等的贡献极小,但危害却很大.采用固相萃取的前处理方法和GC/MS、GC/μECD的分析方法,针对北京市某污水处理厂的总泵进水、二沉出水以及混凝沉淀出水中有机氯农药、多环芳烃和酚类的浓度进行分析.研究结果表明,在不同处理工艺段中,有机氯农药、多环芳烃和酚类的质量浓度分别为nd～10、nd～835、nd～3 248 μg/L.所有检出化合物均未超出中国污水与地表水相应标准限值,其中多环芳烃和酚残留水平较高,应为重点监测对象.这些污染物多数能够在二级处理过程中得到有效去除,但混凝沉淀并没有显著地进一步去除效果.     

人工湿地处理系统中多环芳烃的行为

采用Oasis HLB柱固相萃取的前处理技术,以气相色谱质谱联用仪（GC/MS）的分析方法,对我国北方永定河上游黑土洼人工湿地中多环芳烃污染的特征以及分布规律进行了研究.结果表明,该湿地系统以低环数多环芳烃污染为主,其中浓度最高的是菲和蒽,未检出高环数（5环、6环）多环芳烃.通过比较进水和出水的浓度,湿地系统总体上不能有效去除进水中的多环芳烃.但是比较不同工艺单元进出水浓度,复氧、植物根系及微生物等均影响到多环芳烃的去除效果,去除率在28%～65%之间.     

长跑环境中颗粒物载带多环芳烃的污染特征

2005年7月至8月监测了南开大学校内及其东、西、南三校门外长跑路段处的大气总悬浮颗粒物(TSP)中16种优控多环芳烃的污染状况。GC/MS分析结果表明,晚间长跑时段中校内外多环芳烃总量为(128.74±23.50)、(417.40±204.55)ng/m3,校外约为校内的3.24倍,PAHs含量特征显示交通污染源影响显著;多环芳烃浓度与车流量呈正相关性,且怠速车辆增多也使其浓度增大;校内上午的多环芳烃总量约为晚间1.32倍,这主要受交通污染源和风速、湿度等气象条件的共同影响。     

多环芳烃的一览子分子轨道计算和多环芳烃的致癌性能

大气中的多环芳烃极其多种多样,经GC/MS鉴定者已达200种以上。作者的“双区理论”及定量公式提出以后,已有可能运用分子轨道参数,对多环芳烃及其行生物进行理论子筛选。然而多环芳烃的数量理论上极其众多,而目前的分子轨道计算,包括简单分子轨道计算,本质上仍然是逐个进行的。群和图的方法虽能简化计算,但也难于从根本上解决计算问题。发挥算机优势,应用计算数学方     

序批式生物反应器—芬顿氧化工艺处理焦化反渗透浓水的研究

研究了序批式生物反应器(SBR)—芬顿氧化工艺对焦化反渗透浓水(以下简称浓水)的TN和COD去除率,采用全二维气相色谱—飞行时间质谱(GC×GC—TOF/MS)解析了处理过程中有机物的组成变化。结果表明:(1)SBR稳定运行225d,浓水经过SBR处理后出水TN平均质量浓度为10mg/L,去除率为79.2%,达到了《炼焦化学工业污染物排放标准》(GB 16171—2012)的排放限值(20mg/L);(2)当pH=4.0,Fe2+质量浓度为200mg/L,芬顿氧化出水COD平均质量浓度可降至60mg/L左右,SBR—芬顿氧化工艺对COD的去除率可达44.4%,也达到了GB 16171—2012的排放限值(80mg/L);(3)目标筛查共检出8种多环芳烃,浓水进水、SBR出水和芬顿氧化出水的多环芳烃总质量浓度分别为1.950、1.390、0.917μg/L,组合工艺对多环芳烃的去除率达到50%以上;(4)GC×GC—TOF/MS非目标筛查在浓水进水、SBR出水和芬顿氧化出水中分别检出237、125、53种化合物。     

超声波萃取-GC/MS法测定橡胶轮胎中的多环芳烃

建立了超声波萃取-气相色谱/质谱(GC/MS)联用测定轮胎制品中多环芳(PAHs)的分析方法.优化了超声波萃取条件,采用MS的选择离子检测方式对PAHs进行定性定量分析.结果表明,16种PAHs的平均加标回收率为75.4%～88.0%,相对标准偏差(n=5)为0.66%～11.90%,方法检出限在1.0～4.0 ng/mL.     

三维荧光联合气相色谱/质谱快速溢油鉴别技术研究

通过一个具体溢油事例的研究,提出了通过三维荧光联合气相色谱/质谱(GC/MS)进行海面溢油鉴别的方法。采用三维荧光指纹信息(谱图形状、荧光特征峰位置、荧光特征峰强度)对14个可疑溢油源样品进行筛选,排除了13个可疑溢油源样品后,再利用GC/MS方法对溢油样品以及剩余可疑溢油源样品中难降解的生物标志化合物(饱和链烷烃、萜烷、甾烷、多环芳烃)进行分析,计算相应的诊断比值并采用"重复性限"方法进行溢油样品和可疑溢油源样品的鉴别分析。结果表明,溢油样品与其中的一个可疑溢油源样品一致,为同一来源;采用三维荧光联合GC/MS进行海面溢油鉴别,既可保证鉴别的准确性,又可大幅度减少检测工作量,缩短鉴定周期。     

应用活性炭再生含多环芳烃植物油的可行性及性能评价

为利用植物油去除污染土壤中的多环芳烃,研究了应用活性炭F400吸附柱再生含多环芳烃植物油的可行性,对含高浓度多环芳烃的植物油进行二级再生处理,优化了过程参数,比较了原植物油和经活性炭再生的植物油去除土壤中多环芳烃能力的差别.结果表明,活性炭吸附法可以实现含多环芳烃植物油的再生,证明了修复策略的可行性.二级处理可以进一步吸附植物油中的多环芳烃,且高分子量多环芳烃几乎完全被去除.再生植物油和原植物油去除土壤中多环芳烃的能力没有明显差别.     

Determination of tris(4-chlorophenyl)methanol and tris(4-chlorophenyl)methane in fish, marine mammals and sediment

Tris(4-chlorophenyl)methanol (TCP) and tris(4-chlorophenyl)methane (TCPMe) were determined in aquatic organisms and sediment by a method based on Soxhlet extraction, gel permeation chromatography, fractionation over silica and gas chromatography/mass spectrometry (GC/MS) analysis. TCPMe was identified as the 4-substituted isomer after synthesis of this compound. TCP could be determined by GC/MS with negative chemical ionistation (GC/NCI-MS) with a detection limit of 0.02 g kg(-1) and a recovery of 90%. TCP concentrations in marine mammals from the North Sea and Dutch Wadden Sea ranged from 0.2 to 2 mg kg(-1), and those in marine and freshwater fish samples from 0.005 to 0.4 mg kg(-1) on a lipid wt basis. TCP concentrations in two Rhine delta sediment samples were 1.2 and 3.0 microg kg(-1) dry wt, respectively. TCPMe concentrations, determined by GC/MS with electron impact (GC/EI-MS), were 10-50% of the TCP concentration in all samples analysed.     

GC/MS在监测甲胺磷工业废水中的应用

就甲胺磷工业废水监测中甲胺磷及其干扰组分进行了色谱分离及质谱定性分析,并以火焰光度检定量,用甲胺磷工业原油作为标准,圆满完成了甲胺磷工业废水的监测任务。     

Application of a permethrin immunosorbent assay method to residential soil and dust samples

A low-cost, high throughput bioanalytical screening method was developed for monitoring cis/trans-permethrin in dust and soil samples. The method consisted of a simple sample preparation procedure [sonication with dichloromethane followed by a solvent exchange into methanol:water (1:1)] with bioanalytical detection using a magnetic particle enzyme-linked immunosorbent assay (ELISA). Quantitative recoveries (83–126 %) of cis/trans-permethrin were obtained for spiked soil and dust samples. The percent difference of duplicate ELISA analyses was within ± 20 % for standards and ± 35 % for samples. Similar sample preparation procedures were used for the conventional gas chromatography/mass spectrometry (GC/MS) analysis except that additional cleanup steps were required. Recoveries of cis/trans-permethrin ranged from 81 to 108 % for spiked soil and dust samples by GC/MS. The ELISA-derived permethrin concentrations were highly correlated with the GC/MS-derived sum of cis/trans-permethrin concentrations with a correlation coefficient (r) of 0.986. The ELISA method provided a rapid qualitative screen for cis/trans-permethrin in soil and dust while providing a higher sample throughput with a lower cost as compared to the GC/MS method. The ELISA can be applied as a complementary, low-cost screening tool to prioritize and rank samples prior to instrumental analysis for exposure studies.     

Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant

Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant were analyzed by GC/ECD and GC/MS. Wax and the rest of the needles were analyzed separately. As a rule the concentrations of -HCH (0.5–13.6 ng/g), γ-HCH (0.4–7.3 ng/g), HCB (0.2–3.4 ng/g), PCB congeners (0.2–67 ng/g), PCDDs and PCDFs were higher in the older needles. The ratio of the concentration in the wax to the concentration in the rest of the needles was higher in the younger needles. The concentrations of PCB congeners, TeCDDs and TeCDFs were higher in the needles collected in the area nearest to the plant. The samples, obviously, contained tri- and tetrachlorodibenzothiophenes but these were not determined quantitatively due to interfering peaks in GC/MS.     

Evaluating peats for their capacities to remove odorous compounds from liquid swine manure using headspace “solid‐phase microextraction”

Abstract

This paper reports on research designed to investigate the capacities of different highly characterized peats to remove odorous compounds from liquid swine manure (LSM). Peat types representing a wide range of properties were tested in order to establish which chemical and physical properties might be most indicative of their capacities to remediate odors produced by LSM. Eight percent slurries (of peat/LSM) were measured for odor changes after 24 hours using odor panel and GC/MS‐Solid‐phase microextraction (GC/MS‐SPME) analysis.

The GC/MS‐SPME and odor panel results indicated that, although all peats tested in this study were found to be effective at removing odor‐causing compounds found in LSM, some peats tended to work better than others. Overall, the peats that were the most effective at removing odor‐causing compounds tended to have lower bulk densities, ash contents, fulvic acids contents, and guaiacyl lignins contents,and higher water holding capacities, hydraulic conductivities, “total other lignins”; contents, hydrogen contents, carbon contents, and total cellulose contents.

GC/MS‐SPME analysis was found to be a reasonably inexpensive and efficient way of conducting this type of research. It allows one to identify a large number of the odor‐causing compounds found in LSM, and more importantly, to detect with some precision specific differences in the amounts of these compounds between peat types.     

Determination of dimethyl fumarate (DMFu) in silica gel pouches using gas chromatography coupled ion trap mass spectrometry

A simple method for the determination of dimethyl fumarate (DMFu) in silica gel pouches has been developed. The gas chromatographic behaviour of DMFu was investigated; the instrumental method, based on EI mass spectrometry coupled with an Ion Trap Detector operating whether in full scan mode or in MS/MS mode was also investigated. Several factors have been evaluated and optimized during the development process: solvent and temperature of extraction, type of stationary phase in capillary column. The analytical procedure consists of two steps as follows: (a) the sample preparation using 10 g of sample extracted with acetonitrile in an ultrasonic, heated bath and (b) the determination by gas chromatography-ion trap mass spectrometry. Mass spectrometry in conjunction with chromatographic separation is a very powerful combination for identification of an analyte in the extract in spite of selective detectors employed with GC, such as ECD, FPD and NPD, that offer only limited specificity. Blank samples show no interfering peaks in the areas of interest, so the specificity of the method was assured under the investigated GC/MS conditions. The method has been validated in terms of recovery, repeatability, linearity, detection limits and measurement uncertainty. The results obtained meet both the method validation criteria and requirements of the European/National legislation. The method was verified to be accurate with 97 % mean recoveries at 0.05 mg/kg and 1.00 mg/kg levels; the repeatability (expressed as RSD %) was found to be better than 15 %. Good linearity was found in the range between 0.05 μg/mL and 5.0 μg/mL and a value of R2 > 0.9998 was calculated. The procedure ensures high specificity and a good sensitivity with detection limit (ld) of 0.02 mg/kg and quantification limit (LOQ) of 0.05 mg/kg. This procedure has been successfully applied for the analysis of several hundred of real samples collected during a monitoring control plan started last year in our country. All samples exceeding the maximum allowed level of DMFu (0, 1 mg/kg) were confirmed by GC/MS/MS (ITD) for a higher degree of confidence in identification. The main advantages of this method include: rapidity, simplicity (few, simple steps), reliability, cheapness, no need for long and difficult clean-up and evaporation steps, high specificity by using GC/MS and GC/MS/MS, availability for routine monitoring.     

A method for determining pyrene in mucus using synchronous fluorimetry with multiple standard additions

A new method was proposed to determine pyrene in mucus, which combined the synchronous fluorimetry with the multiple standard addition method (SFMSA). The method was used to determine pyrene in mucus directly without pretreatment. The method detection limit (MDL) for pyrene in mucus was measured as 0.47 ng/ml with a relative standard deviation of 12.7% (n = 7). The standard addition graph was linear in the range 0.05-50.00 ng/ml (r(2) = 0.9989). SFMSA was validated using a GC/MS method as a reference method, and nice agreement was found. The pyrene in mucus can be directly monitored by SFMSA without solvent extraction of samples. This indicates that SFMSA is more timesaving, less laborious and cheaper than the GC/MS method with solvent extraction. SFMSA has lower MDL and higher average recovery than the GC/MS method.     

Relevance study of bare and coated zero valent iron nanoparticles for lindane degradation from its by-product monitorization

Zero-valent iron nanoparticles (NZVI) as well as polymer–stabilized nanoparticles were synthesized and used for lindane (γ-hexachlorocyclohexane) degradation in aqueous solution. To study the effectiveness of the different coated nanoparticles, simple and rapid analytical methods have been developed to measure and to detect lindane and its by-products. For the monitorization of lindane degradation solid-phase extraction (SPE) was used, while volatile by-products formation measurement was carried out by headspace-solid phase microextraction (HS–SPME) followed by GC/MS. The SPE–GC/MS method provides low detection limits (0.2 μg L⁻¹), high recovery (above 95%) and it is a valuable tool for kinetic studies of the degradation process for each polymer used, while HS–SPME–GC/MS has proved to be an effective tool for the extraction and evaluation of volatile degradation by-products.     

Enantiomer fractions of chiral organochlorine pesticides and polychlorinated biphenyls in standard and certified reference materials

Enantiomeric ratios (ERs) and enantiomeric fractions (EFs) of a number of chiral organochlorine pesticides and PCB atropisomers were measured by chiral gas chromatography/mass spectrometry (GC/MS) in five standard (SRM) and certified (CRM) reference materials: SRM 1588a (organics in cod liver oil), SRM 1945 (organics in whale blubber), Marine Mammal Quality Assurance Exercise Control Material IV (NIST IV, organics in whale blubber), CRM trout, and CRM EC-5 (sediment). Target analytes were cis- and trans-chlordane, heptachlor exo-epoxide, oxychlordane, U82, MC5, MC6, MC7, o,p^′-DDT, and PCB congeners 91, 95, 136, 149, 174, 176, and 183. Measured ERs and EFs are in close agreement with the few literature values reported for some of these analytes in SRMs and CRMs. Chiral PCB ERs and EFs measured by one-dimensional chiral GC/MS were similar to values measured using multidimensional chiral GC/MS. Non-racemic chiral compositions are in agreement with known uptake and biotransformation in the respective environmental matrices. These values should aid in the quality assurance/quality control methodologies for chiral environmental chemistry using standardized reference materials.     

Comparison of dioxin and furan TEQ determination in contaminated soil using chemical,micro-EROD,and immunoassay analysis

High resolution mass spectrometry gas chromatography (GC/MS) is the standard method for dioxin and furan analysis in environmental matrices. Considered as very accurate, this method is however time consuming and expensive. Methods based on biological interactions have the necessary sensitivity but began only recently to be investigated in the context of environmental applications. We have compared dioxin and furan toxicity levels (expressed as toxic equivalent quantities (TEQs)) in soil samples by three analytical approaches: the micro-ethoxyresorufin-o-deethylase (EROD) bioassay (a receptor-based method), an immunoassay (antibody-based method) and GC/MS analysis (used as a reference) using a shortened extraction-purification method. Both biological methods were sensitive to interferences from compounds co-extracted from samples. Most samples were underestimated by the immunoassay and, at a greater extent, overestimated by the EROD bioassay. The average accuracy of TEQ estimation (86 +/- 45% of values established by GC/MS) and the absence of false-negatives showed by the immunoassay suggest the usefulness of this method for semi-quantitative, preliminary characterization of potentially contaminated sites.