鱼中氯化二苯并二噁(PCDD)和氯化二苯并呋喃(PCDF)的分析

本工作建立了鱼中从四氯到八氯的二苯并二(口恶)(口英)和二苯并呋喃的分析方法。鱼样品经消化后以己烷提取,提取液经两套层析柱净化后,用反相HPLC进一步净化并分为两个级份。采用GC/SIM-MS测定各PCDD和PCDF。     

Maltooligosaccharides in the northwestern Adriatic Sea

The aim of this study was to monitor for the first time the oligosaccharide pattern in the northwestern Adriatic Sea. Oligosaccharides are components of the low-molecular-weight fraction of dissolved organic matter (DOM). They perform an important ecological function in the microbial loop prompting substrates for bacterial degradation. In particular, our investigation focused on maltooligosaccharides (glucose α 1–4 linked). The analyses were carried out using a dialysis-charcoal column sorption pre-concentration method, followed by liquid chromatography-tandem mass spectrometry analyses with a triple quadrupole mass spectrometer operating in multiple reaction monitoring mode. During the study period, the concentration of maltooligosaccharides with a low degree of polymerisation (ranging from maltose to maltotetraose) was higher than other maltooligosaccharides (maltopentaose and maltoeptaose) and all together they reached their highest concentration in June. This concentration was temporally shifted from a long period of diatom bloom (from January to April). Furthermore, the annual maltooligosaccharide trend was monitored together with several chemical, physical and biological parameters to investigate their potential role on the maltooligosaccharide accumulation. Our results suggested that the maltooligosaccharide accumulation could be related to the water column stratification.     

超声波辅助萃取—气质联用色谱法测定活性污泥中的多溴联苯醚

建立了活性污泥中多溴联苯醚(PBDEs)的分析方法。活性污泥经超声波辅助萃取,用酸性硅胶、铜粉及复合硅胶柱纯化后,采用气质联用色谱(GC/MS)对7种PBDEs单体进行测定,内标法定量。结果表明,该方法具有很好的精密性和准确性,方法检测限为17～121 pg/g,加标回收率为84.5%～109.0%,相对标准偏差(RSD)为0.5%～2.8%,回收率指示物3,3’,4,4’-四溴联苯醚(BDE-77)的回收率平均值为89.2%,RSD为0.8%,能够满足活性污泥中PBDEs的测定要求。采用所建立的方法对杭州和台州的活性污泥样品进行了测定,结果显示,台州样品中PBDEs含量高于杭州样品,但两者都低于相关文献所报道的北美及欧洲国家活性污泥中PBDEs的含量。     

Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water

This study focused on the input of hydrophilic biocides into the aquatic environment and on the efficiency of their removal in conventional wastewater treatment by a mass flux analysis. A fully automated method consisting of on-line solid phase extraction coupled to LC-ESI-MS/MS was developed and validated for the simultaneous trace determination of different biocidal compounds (1,2-benzisothiazoline-3-one (BIT), 3-Iodo-2-propynylbutyl-carbamate (IPBC), irgarol 1051 and 2-N-octyl-4-isothiazolinone (octhilinone, OIT), carbendazim, diazinon, diuron, isoproturon, mecoprop, terbutryn and terbutylazine) and pharmaceuticals (diclofenac and sulfamethoxazole) in wastewater and surface water. In the tertiary effluent, the highest average concentrations were determined for mecoprop (1010 ng/L) which was at comparable levels as the pharmaceuticals diclofenac (690 ng/L) and sulfamethoxazole (140 ng/L) but 1-2 orders of magnitude higher than the other biocidal compounds. Average eliminations for all compounds were usually below 50%. During rain events, increased residual amounts of biocidal contaminants are discharged to receiving surface waters.     

吹扫捕集-GC/MS法测定南宁市竹排冲黑臭河道水体嗅味物质

利用吹扫捕集-GC/MS法对引起南宁市竹排冲河道水体黑臭的嗅味物质进行检测分析。结果表明,导致竹排冲水体黑臭的嗅味物质主要为苯系物、硫类化合物和氯苯类化合物,其中甲硫醚(相对含量1.70%)、二甲基二硫醚(相对含量3.19%)、甲基丙基二硫醚(相对含量6.11%)等挥发性有机物为竹排冲水体中的主要致嗅物质,是竹排冲水体嗅味产生的主要原因。     

Levels of dechlorane plus and polybrominated diphenylethers in human milk in two Canadian cities

Flame retardant dechlorane plus (DP) and several polybrominated diphenylether (PBDE) congeners have been measured in 87 human milk samples collected in two Canadian cities: Kingston and Sherbrooke. The levels of PBDEs in human milk (mean (median), ng g^− 1 lipid weight = 10 (5.9), 4.1 (2.8), 3.0 (1.6), 5.12 (1.6), and 15 (ND) for BDE-47, BDE-99, BDE-100, BDE-153, and BDE-209, respectively) were comparable to those reported in Europe, U.S.A. and China. The levels of DP, with a mean value of 0.98 ng g^− 1 and a median value of 0.60 ng g^− 1 (lipid weight), were two to ten times lower than those of concurrently measured major PBDEs including BDE-209. While there is little difference in the levels of measured contaminants in milk samples collected from the two cities, the contaminants levels in human milk show, indicated by Principal Components Analysis, that DP, deca-BDE, and penta-BDE come from three distinct sources. The mean and median isomer ratio values of DP in milk were 0.67 and 0.69, respectively, very similar to that of DP commercial products.     

Validation of a GC-MS/MS method for simultaneous determination of 86 persistent organic pollutants in marine sediments by pressurized liquid extraction followed by stir bar sorptive extraction

A multiresidue method for the analysis of 86 persistent pollutants in marine sediments at ultra-trace level has been developed and validated using pressurized liquid extraction (PLE) and stir-bar sorptive extraction (SBSE) coupled with thermal desorption and gas chromatography-triple quadrupole mass spectrometry (TD-GC-MS/MS QqQ). The compounds analyzed belong to various families such as polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenylethers, organophosphorus and organochlorine pesticides and other pesticides such as urons, and triazines. The analytes have very different polarities and log K_ow values, which is an important parameter in the optimization of a SBSE method. Due to PLE high efficiency and throughput rates, along with the proven ability for multiresidue analysis and excellent sensitivity of SBSE, we present an efficient method. The limits of quantification obtained ranged from 0.014 to 1.0 ng g⁻¹, with detection limits below pg g⁻¹ levels. In order to validate the proposed methodology, quality parameters such as recovery, linearity and reproducibility were studied. Recoveries ranged from 63% to 119%, reproducibility (in terms of Relative Standard Deviation for ten determinations) was lower than 35% in all cases, and determination coefficients higher than 0.990 for all analytes. The main factors that affect PLE, SBSE and GC-MS/MS procedures were optimized. The method was applied to the analysis of nine marine sediments obtained from the nine main submarine wastewater discharge points (emissaries) presents along the coast of Tenerife Island (Canary Islands, Spain).     

Temporal trend (1988-2008) of hexabromocyclododecane enantiomers in herring gull eggs from the German coastal region

Levels of α-, β-, and γ-hexabromocyclododecane (HBCD) were determined in pooled eggs from herring gulls (Larus argentatus) sampled on three bird sanctuaries near the German North Sea coast between 1988 and 2008 (Mellum and Trischen) and the German Baltic Sea coast between 1998 and 2008 (Heuwiese) and archived by the German Environmental Specimen Bank. Pressurized fluid extraction, gel permeation chromatography, and LC-MS/MS using ¹³C₁₂-labelled isotope standards and a chiral column were applied. α-HBCD was the dominating diastereomer and ranged between 3.7 and 107 ng g⁻¹ lw while β- and γ-HBCD were throughout close to LOQ. The highest α-HBCD concentration was found in eggs from Mellum sampled in the year 2000. Interestingly, HBCD in eggs from the three islands displayed similar time courses with levels increasing to a peak contamination around 2000 and decreasing levels ever since. Chiral signatures of α-HBCD in eggs differed among the islands but indicated a preferential enrichment of the first eluting enantiomer (−)-α-HBCD.     

加速溶剂萃取-GC/MS法研究济南市环境空气颗粒物中的多环芳烃

以济南市为研究区域,利用TH-150C型智能中流量总悬浮颗粒物采样器采集了7个点位环境空气颗粒物样品,采用加速溶剂萃取、旋转蒸发、硅胶柱层析、氮吹仪氮吹后用GC/MS测定的实验研究方法,获得了济南市7个点位环境空气颗粒物中16种PAHs的质量浓度和ΣPAHs值.结果表明,7个点位环境空气颗粒物中ΣPAHs的含量在103...     

气相色谱-质谱法测定水中挥发性有机物的测量不确定度评定

根据测量不确定度评定与表示理论,采用气相色谱一质谱法测定水中挥发性有机物。以氯乙烯为例,通过计算和评定,得出当氯乙烯的测量结果为4．99μg／L时,取包含因子k=2（约95％置信概率）,扩展不确定度U=0．96μg／L。该不确定度评定方法在实际工作中具有较强的实用价值。