便携式GC-MS仪快速测定水中硝基苯及其在应急监测中的应用

采用便携式GC-MS仪快速测定水中硝基苯,通过优化水中离子强度和顶空加热时间,使方法在0μg/L^300μg/L范围内线性良好,方法检出限为2.5μg/L。标准溶液6次测定结果的RSD为7.8%~10.9%,实际水样的加标回收率为80.7%~103%。同步测定试验表明,硝基苯与7种苯系物分离良好。与国标方法对比,该方法单个样品测定时间由2 h缩短为15 min。将该方法用于应急监测工作中,及时有效的数据可为污水处理及事故调查提供分析和研判依据。     

模式识别在火灾调查中的汽油分类问题的应用研究

在火灾调查中,检测汽油成分并对其进行正确分类尤为重要.运用GC-MS对90#和93#两种普通汽油的共50个样本进行检测,所得的GC-MS原始数据通过PCA方法进行处理,以提取有用信息,避免冗余变量进入后续计算.在此基础上应用KNN方法对这两种汽油助燃剂进行分类.结果表明, KNN方法对这两种汽油的分类准确率达到100%,且当初始数据未经标准化预处理时也能达到同样准确的分类效果.研究表明:将模式识别方法正确地运用到助燃剂鉴定和分类工作中有助于火灾调查.     

便携式气相色谱-质谱仪在应急监测中的应用

通过一次有机污染物应急监测实例,结合HAPSITE便携式GC-MS的使用情况,介绍了该仪器在应急监测与处置工作中的特点,并根据使用结果,总结了便携式GC-MS能够迅速确定污染范围,有效确定污染物种类以及快速确定污染状况和污染程度等性能特点,为相关单位对便携式GC-MS的实际应用提供了指导。     

Plant steroid hormones produced under Ni stress are involved in the regulation of metal uptake and oxidative stress in Brassica juncea L

Brassinosteroids (BRs) are involved in the amelioration of various biotic and abiotic stresses. With an aim to explore the role of BRs under heavy metal stress, plants of Brassica juncea L. were grown in pots. The plants were subjected to various concentrations of Nickel metal (0.0, 0.2, 0.4 and 0.6 mM) and harvested on 60th day in order to observe the expression of these hormones. The isolated BRs from the leaves of Brassica plants characterized by GC-MS include 24-Epibrassinolide (24-EBL), Castasterone, Dolicholide and Typhasterole. The effect of isolated 24-EBL was studied on Ni metal uptake and antioxidative defense system in 60 d old plants of Brassica. It was observed that 24-EBL significantly increased the activities of stress ameliorating enzymes and lowered the metal uptake in plants. This is the first report in B. juncea L. plants showing the expression of BRs under metal treatments and effect of the isolated 24-EBL on metal uptake and in oxidative stress management.     

Decay profile and metabolic pathways of quinalphos in water, soil and plants

The widespread occurrence of pesticide residues in different agricultural and food commodities has raised concern among the environmentalists and food chemists. In order to keep a proper track of these materials, studies on their decay profiles in the various segments of ecosystem under varying environmental conditions are needed. In view of this, the metabolites of quinalphos in water and soil under controlled conditions and in plants, namely tomato and radish in field conditions have been analysed and possible pathways suggested. In order to follow the decay of the pesticide, an HPLC procedure has been developed. Studies conducted in water at different temperatures, pH and organic content reveal that the persistence of the pesticide decreases with the increase in all the three variables. In the three different types of soils studied, the effect of pH is more or less apparent on a similar line. On an average a faster decay is observed in the case of plants than in water and soil. The decay profiles in all these cases follow first order kinetics. The metabolites were identified by GC-MS. The investigations reflect that degradation occurs through hydrolysis, S-oxidation, dealkylation and thiono-thiol rearrangement. The pathways seem to be complex and different metabolites were observed with the change in the matrix. Quinalphos oxon, O-ethyl-O-quinoxalin-2-yl phosphoric acid, 2-hydroxy quinoxaline and quinoxaline-2-thiol were observed in all the matrices. Results further indicate that the metabolites, 2-hydroxy quinoxaline and oxon, which are more toxic than parent compound, persist for a longer time.     

饮用水中典型致嗅物质吹扫捕集-气相色谱质谱检测方法及优化

采用吹扫捕集/气相色谱-质谱（GC-MS）法对饮用水中致嗅物质2-甲基异茨醇（2-MIB）和土臭素（GSM）进行测定。通过调整吹扫温度、吹扫时间、吹扫时捕集阱的温度、六通阀温度和传输管线温度,分析吹扫捕集条件对吹扫捕集效率的影响,并确定最佳吹扫捕集条件。2-MIB和GSM的方法检出限（MDL）分别为0.729 ng·L-1和1.037 ng·L-1,方法定量限（MQL）分别为2.187 ng·L-1和3.112 ng·L-1,平均加标回收率分别在92%~108%和88%~104%范围内,相对标准偏差分别小于6.5%和9.0%.在20~300 ng·L-1的范围内,各异嗅化合物浓度与响应值的线性关系均良好,相关系数均大于0.999。该方法具有操作简便、检出限低,相关性良好、灵敏度高、重复性好等优点。     

Bioanalytical characterisation of multiple endocrine- and dioxin-like activities in sediments from reference and impacted small rivers

A comprehensive evaluation of organic contamination was performed in sediments sampled in two reference and three impacted small streams where endocrine disruptive (ED) effects in fish have been evidenced. The approach combined quantitative chemical analyses of more than 50 ED chemicals (EDCs) and a battery of in vitro bioassays allowing the quantification of receptor-mediated activities, namely estrogen (ER), androgen (AR), dioxin (AhR) and pregnane X (PXR) receptors. At the most impacted sites, chemical analyses showed the presence of natural estrogens, organochlorine pesticides, parabens, polycyclic aromatic hydrocarbons (16 PAHs), bisphenol A and alkylphenols, while synthetic steroids, myco-estrogens and phyto-estrogens were not detected. Determination of toxic-equivalent amounts showed that 28-96% of estrogenic activities in bioassays (0.2-6.3 ng/g 17β-estradiol equivalents) were explained by 17β-estradiol and estrone. PAHs were major contributors (20-60%) to the total dioxin-like activities. Interestingly, high PXR and (anti)AR activities were detected; however, the targeted analysed compounds could not explain the measured biological activities. This study highlighted the presence of multiple organic EDCs in French river sediments subjected to mixed diffuse pollution, and argues for the need to further identify AR and PXR active compounds in the aquatic environment.     

固相萃取—气相色谱—质谱测定再生水中邻苯二甲酸酯类物质

探讨了一种再生水中邻苯二甲酸酯类物质的测定方法——固相萃取—气相色谱—质谱,检测了相关再生水标准中涉及的邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)两类物质。在质量浓度为20～1 000μg/L时,两类物质的回归方程的相关系数均大于0.999,检出限分别是0.060、0.002μg/L,DBP、DEHP的相对标准偏差分别为4.1%～7.4%、5.1%～6.1%。利用固相萃取技术进行预处理,平均加标回收率为96.6%、89.6%。检测了北京市4座再生水厂出水中DBP和DEHP含量,其中,DBP在1.74～5.59μg/L,低于《城市污水再生利用景观环境用水水质》(GB/T 18921—2002)规定的限值(不超过0.1mg/L),但高于《城市污水再生利用地下水回灌水质》(GB/T 19772—2005)规定的限值(不超过3μg/L);DEHP在0.42～4.93μg/L,满足GB/T 19772—2005要求(不超过8μg/L)。     

航空压力环境对锂离子电池热解气体爆炸极限影响*

针对航空锂离子电池热失控释放气体安全性研究不足的问题,采用气体拉曼光谱技术、气相色谱仪(Gas Chromatography,GC)和质谱(Mass Spectroscopy,MS)耦合来探究压力和荷电状态(State of Charge,SOC)对锂离子电池早期故障气体类型、气体动态演变及气体潜在危险性等特征的影响规律,同时综合考虑压力、电压和电池温度等多种因素分析锂离子电池热失控危害。研究结果表明:电池SOC越高且环境压力越低,电池越早触发热失控,爆炸极限越宽,其中30 kPa下100%SOC电池热解气体爆炸极限为8.01%~53.35%;SOC和环境压力越高,电池热失控越危险,释放的气体体积越多;CO,CO2,PF3,C2H4及电解液（C3H6O2、C3H6O3、C4H8O2）等气体可作为航空锂离子电池早期故障诊断特征。研究结果对保障锂离子电池在航空领域的安全运输及应用具有重要意义。     

The use of anthracene as a model compound in a comparative study of hydrous pyrolysis methods for industrial waste remediation

Polycyclic aromatic hydrocarbons are very stable compounds and tend to bioaccumulate in the environment due to their high degree of conjugation and aromaticity. Hydrous pyrolysis is explored as a technique for the treatment of industrial water containing PAH, using anthracene as a model compound. The reactivity of anthracene under a range of temperatures and durations are studied in this paper. Aliquots of 1.0-10.0 mg of anthracene in a range of 1.0-5.0 mL of H₂O are subjected to hydrous pyrolysis under varied conditions of temperature, reagents and duration. The conditions include oxidising systems comprising distilled water, hydrogen peroxide and Nafion-SiO₂ solid catalyst in water; and reducing systems of formic acid and formic acid/Nafion-SiO₂/Pd-C catalysts to assess a range of redox reaction conditions. Oxygen in air played a role in some of the reaction conditions. Pyrolysed products were identified and quantified by the use of Gas Chromatography-Mass Spectrometry (GC-MS). The major products were anthrone, anthraquinone, xanthone from oxidation; and multiple hydro-anthracene derivatives from reductive hydogenation. The nature of reaction conditions influenced the extent of anthracene degradation. The products formed are more reactive (less stable) as compared to anthracene the starting material and will therefore be less persistent in the environment.