土壤中有机污染物的气相色谱-四极杆飞行时间质谱非靶标筛查

本文基于气相色谱-四极杆飞行时间质谱(GC-QTOF/MS)对宜昌某化学工业园区内的土壤进行潜在有机污染物的非靶标筛查.根据已有高分辨数据库和保留时间信息,采用精确质量数提取筛查流程识别出样品中96种污染物,主要以多环芳烃及其代谢产物、氯苯类和农药为主.进一步通过未知物分析软件解卷积功能和质谱NIST数据库的匹配,发现了如二氯苯胺、9-芴酮、3-甲基二苯并噻吩等更多的污染物.该方法能够快速筛查和识别出样品中潜在有机污染物,为当地污染物的风险管控提供借鉴意义.     

太原市环境空气中TSP和PM_(10)来源解析

2001年到2002年,在太原市5个采样点分别采集了环境空气中的总悬浮颗粒物(TSP)和可吸入颗粒物(PM10)。用化学质量平衡模型和二重源解析技术解析了TSP和PM10的来源,结果表明,各主要源类对TSP的分担率依次为燃煤尘28%、扬尘24%、建筑水泥尘14%、硫酸盐10%、机动车尾气尘10%、土壤风沙尘5%、钢铁尘4%、硝酸盐4%、其它1%;对PM10的分担率依次为扬尘30%、燃煤尘18%、机动车尾气尘15%、硫酸盐11%、土壤风沙尘9%、建筑水泥尘7%、硝酸盐4%、其它1%。     

Organic pollutants in snow of urban and rural Russia and Finland

To check the effect of possible deposition of organic contaminants in northern regions of the Earth due to atmospheric transport snow samples were collected in early March in 6 places in Russia and 4 in Finland including arctic territories. GC‐MS was used as an analytical tool to identify and quantify individual organic compounds belonging to the various classes. As a result more than 250 compounds were detected. The possible presence of more than 100 other priority pollutants from the US EPA list was also screened.     

Influences of coal mining water irrigation on the maize losses in the Xingdong Mine area, China

In 2008, a maize underproduction disaster occurred in the Xianyu village after irrigation using the coal mining water from the Xingdong Mine, China. This disaster resulted in about 40 hectare maize underproduction and 20 hectare total loss of the maize yields. In order to study the reason, a total of 25 soil, water and plant samples were taken from the study area. These samples were analysed by inductively coupled plasma mass spectrometry and ion chromatography. The results indicate that the contents of both water-soluble fluorine and total fluorine are very high and resulting of maize underproduction and total loss of production. The possible pollution sources of fluorine in the study area could be from the coal mine water used for irrigation and glass chemical factory near the study area.     

Monitoring of waste deposit derived groundwater contamination with organic tracers

Specific anthropogenic substances derived from seepage and leakage water from a waste deposit landfill were analysed in groundwater and drainage effluents using gas chromatography-mass spectrometry (GC/MS). Here, we demonstrate the application of an organic marker approach to study lateral and vertical distribution of contamination as well as the long-term emission behaviour. Source-specific and environmentally-stable pesticides, plasticisers and pharmaceuticals, such as N,N-diethyl toluamide, N-butyl benzene sulfonamide, clofibric acid, mecoprop and bisphenol A, were quantitatively analysed. A distinct lateral expansion was detected. Although temporal variations were high, no significant trend was observed.     

北京市某废弃焦化厂不同车间土壤中多环芳烃（PAHs）的分布特征及风险评价

以北京市某废弃焦化厂为研究对象,系统采集了6个车间0～4m深的26个土壤样本,利用GC/MS检测了U.S.EPA优控的16种多环芳烃(PAHs)的含量,分析了PAHs在焦化厂不同车间表层土壤的污染状况和深层土壤中的垂直分布特征并对土壤污染风险进行了评估.结果表明,1)该废弃焦化厂不同车间表层土壤(0～20cm)总PAHs(∑PAHs)的残留量介于672.8～144814.3ng·g-1之间;污染程度排序为:回收车间>老粗苯车间>焦油车间>炼焦车间>水处理车间>制气车间.2)该厂未受扰动的土壤样品显示PAHs主要聚集在表层土壤,并随着土壤深度的增加而迅速减少;其他样点由于土壤扰动,∑PAHs含量最大值出现在第三层土壤(80～180cm);该厂4m深底层土壤仍有高浓度PAHs,∑PAHs含量最高值出现在炼焦车间,达12953.1ng·g-1.3)焦化厂土壤PAHs污染主要集中在3环和4环的PAHs单体上,分别占到污染总量的51.3%和31.7%.4)根据Maliszewska-Kordybach的PAHs总量标准及加拿大土壤PAHs单体治理标准,该厂回收、老粗苯、焦油和炼焦车间表层和深层土壤PAHs含量均达到重污染水平,并对其周围土地带来较大风险,需要治理.     

Study on accumulation ability of two lichen species Hypogymnia physodes and Usnea hirta at iron-steel factory site, Turkey

The use of biological responses to contaminant exposure by lichen species has become a useful tool in environmental quality evaluation and risk assesment. Lichen Hypogymnia physodes and Usnea hirta samples were collected in 2006 from 10 sites around iron-steel factory in Karabük, Turkey. H. physodes and U. hirta samples from Yenice forest were used as a control. The aim of present study was to evaluate the bioaccumulation ability and to determine the environmental impact of an iron-steel factory in Karabük. Seven elements (Zn, Cu, Mn, Fe, Pb, Ni, Cr and Cd) were analysed by atomic absorption spectrometry (AAS). The analytical results were compared statistically by using SPSS. As expected, the study area (Yenice forest, Karabük) chosen as control site (site no 11) showed significantly lower impact in comparison to other site (site no 1-10). Compared with the two lichen species, H. physodes showed highest metal accumulating capacity while U. hirta showed lowest. These criteria attested the best suitability for H. physodes, followed by U. hirta.     

短链氯化石蜡及其环境污染现状与毒性效应研究

短链氯化石蜡是碳链长度为10至13个碳原子的正构烷烃经氯化衍生而成的复杂混合物.作为《关于持久性有机污染物的斯德哥尔摩公约》增列持久性有机污染物(persistent organic pollutants,POPs)中的一类化合物,2008年10月在瑞士日内瓦召开的联合国环境规划署POPs审查委员会的第     

Distribution of aromatic amines,phenols, chlorobenzenes,and naphthalenes in the surface sediment of the Dianchi Lake,China

• The total organic pollutant concentrations in sediment were 27.4-1620 ng/g. • The phenol concentrations were relatively high in the sediment of the Dianchi Lake. • Average total concentrations decreased as follows: Caohai>Waihai>Haigeng Dam. • 1,4-dichlorobenzene, 3- or 4-methylphenol, 1,2,4-trichlorobenzene might be risks. Organic pollutants are widespread environmental pollutants with high toxicity, persistence, and bioaccumulation. Our aim was to investigate the distribution of aromatic amines, phenols, chlorobenzenes, and naphthalenes in the surface sediment of the Dianchi Lake, China. Nineteen surface sediment samples were collected from the Dianchi Lake, and 40 types of organic pollutants were analyzed via gas chromatography–mass spectrometry. The total organic pollutant concentrations in the surface sediment of the Dianchi Lake varied from 27.4 to 1.62 × 10³ ng/g. The concentrations of phenols were much higher than those in other water bodies but still within a controllable range, whereas the concentrations of the other organic pollutant classes were similar or even lower. The detection ratio of 3- or 4-methylphenol was the highest (100.00%) among the pollutants. The average total organic pollutant concentrations decreased in the following order: Caohai (540 ng/g)>the middle of Waihai (488 ng/g)>the edge of Waihai (351 ng/g)>Haigeng Dam (90.4 ng/g). Pearson analysis showed a strong correlation among 1-methylnaphthalene, 2-methylnaphthalene, 1,3-dinitronaphthalene, and 1,4-dinitronaphthalene (p<0.01). Caohai, the north lakeshore of Waihai and the south of Waihai showed higher risk because of high concentration; meanwhile, 1,4-dichlorobenzene, 3- or 4-methylphenol and 1,2,4-trichlorobenzene were more likely to cause risks.     

Discovery of emerging organic pollutants in the atmosphere through an omics approach

● We review the framework of discovering emerging pollutants through an omics approach. ● High-resolution MS can digitalize atmospheric samples to full-component data. ● Chemical features and databases can help to translate untargeted data to compounds. ● Biological effect-directed untargeted analyses consider both existence and toxicity. Ambient air pollution, containing numerous known and hitherto unknown compounds, is a major risk factor for public health. The discovery of harmful components is the prerequisite for pollution control; however, this raises a great challenge on recognizing previously unknown species. Here we systematically review the analytical techniques on air pollution in the framework of an omics approach, with a brief introduction on sample preparation and analysis, and in more detail, compounds prioritization and identification. Through high-resolution mass spectrometry (HRMS, typically coupled with chromatography), the complicated environmental matrix can be digitalized into “full-component” data. A key step to discover emerging compounds is the prioritization of compounds from massive data. Chemical fingerprints, suspect lists and biological effects are the most vital untargeted strategies for comprehensively screening critical and hazardous substances. Afterward, compressed data of compounds can be identified at various confidence levels according to exact mass and the derived molecular formula, MS libraries, and authentic standards. Such an omics approach on full-component data provides a paradigm for discovering emerging air pollutants; nonetheless, new technological advancements of instruments and databases are warranted for further tracking the environmental behaviors, hence to evaluate the health risk of key pollutants.     

饮用水水源中半挥发性有机污染物监测方法的探讨

江苏省饮用水水源地水质中富含有机物质,这类化合物种类多、浓度高,在色谱分析中,容易与痕量半挥发性有机毒物形成共流物,干扰分析。根据四极杆质谱检测器和离子阱质谱检测器的工作原理,建立了54种半挥发性有机物的选择性离子监测和2级质谱法监测方法,确定了选择性离子监测方法所选的离子范围,2级质谱法监测所选的母离子、CID电压,对比了选择性离子监测和2级质谱法监测的检测限。在此基础上初步建立了将两种质谱监测相结合的方法,该方法在实际样品分析中简便准确,可有效减少前处理工作。     

Environmental pollutants and type 2 diabetes: a review of human studies

The incidence of diabetes has increased dramatically in recent decades and become one of the leading health problems worldwide. Lifestyle and dietary changes alone cannot account for the dramatic rise of diabetes, while an increasing number of publications have reported the possible relationships between exposure to environmental pollutants and risk of diabetes. In the present review, our objective was to summarize the human studies on environmental pollutants, which includes persistent organic pollutants, pesticides (not on the Stockholm Convention list), bisphenol A, and phthalates, and the risk of diabetes. Currently published results suggest a positive relationship between certain persistent organic pollutants (dichlorodiphenyldichloroethene, dichlorodiphenyltrichloroethane, hexachlorobenzene, and polychlorinated biphenyls) and bisphenol A exposure and risk of diabetes. For pyrethroids, organophosphates, carbamates, and phthalates, there are insufficient studies to reach conclusions and therefore more studies, especially prospective studies, are needed along with in vivo and in vitro studies to understand the underlying mechanisms.     

三氯酚暴露致稀有鮈鲫肝脏损伤的比较蛋白质组研究

为探讨2,4,6-三氯酚(2,4,6-TCP)暴露致鱼类肝脏损伤的毒性效应,以稀有鮈鲫(Gobiocypris rarus)为模式生物,TCP暴露浓度为1、10、100μg·L-1,进行流水暴露实验(28d),利用二维凝胶电泳方法(2-DE),结合质谱分析技术(MALDI-TOF-MS),对TCP致稀有鮈鲫肝脏损伤的蛋白表达谱进行了研究.结果显示,共发现35个差异蛋白点,其中11个蛋白被成功鉴定(C.I.>95%).对鉴定的蛋白根据GOTerms进行功能分类,发现它们主要参与脂类代谢与转运、氧化应激以及蛋白修复和氧化磷酸化等生物学过程。以上结果表明,TCP对稀有鮈鲫具有明显的肝脏毒性效应.     

基于PLS1的哈尔滨市PM2.5与空气污染物相关性分析

以往对PM2.5的研究多集中在气象因子或单一空气污染物对PM2.5质量浓度变化的影响,未考虑多种空气污染物对PM2.5质量浓度的协同作用。通过哈尔滨市环保局发布的2014年1月份（共31 d）市区内主要空气污染物SO2、NO2、PM10、CO、O3、PM2.5的质量浓度数据,运用相关性分析、PLS1和通径分析方法,研究哈尔滨市区内主要空气污染物对PM2.5质量浓度变化的直接影响、通过其他空气污染物的间接影响及污染物之间的协同作用。结果表明,SO2、NO2、PM10、CO 与 PM2.5质量浓度显著性相关,O3与 PM2.5质量浓度相关性不显著,SO2、NO2、PM10、CO 之间存在严重的复相关性。依据相关性分析结果,建立了SO2、NO2、PM10、CO对PM2.5质量浓度的PSL1模型,模型的拟合优度r2为0.852,模型拟合良好。对所建立的模型进行通径分析,结果显示,SO2、NO2、PM10、CO对PM2.5质量浓度变化的直接作用分别为0.005、-0.142、-0.140、1.191,CO对PM2.5质量浓度变化的直接影响作用最大。SO2、NO2、PM10通过CO对PM2.5质量浓度变化的间接作用分别为0.706、1.011、1.118均大于它们对PM2.5质量浓度变化的直接作用。SO2、NO2、PM10、CO对PM2.5质量浓度变化的总决定系数为85.9%。CO是主要空气污染物中影响PM2.5质量浓度变化的主要因素,降低冬季煤炭供暖期CO的排放量,有利于提高空气环境质量,降低对人体的健康危害。     

Contaminants in water: non-target UHPLC/MS analysis

Contamination of water resources is one of the major problems to be faced for environment preservation and sustainability. The monitoring of target compounds based on mass spectrometry and selected reaction monitoring mode is often insufficient to definitely assess the quality of surface water. Also potentially harmful non-target pollutants simultaneously present must be taken into account. Liquid chromatography coupled with tandem mass spectrometry is suitable to obtain complete information on water composition. Hybrid mass spectrometers such as triple quadrupole/linear ion trap, hybrid quadrupole/time-of-flight and linear ion trap/orbitrap analyzers should be used. Here, we review ultra-high performance liquid chromatography coupled with mass spectrometry methods developed for post-target and non-target screening analysis of water emerging contaminants, such as pesticides and their degradation products, pharmaceuticals and drug side-reaction products, surfactants and illicit drugs. The major points are the following: (1) the possibility of performing retrospective analysis only by high-resolution mass analyzer; (2) the compatibility of mass analyzer with ultra-high performance liquid chromatography; (3) the use of deconvolution software to detect unknowns; and (4) the limited availability of library database.     

Bestimmung von Nitrodiphenylaminen und verwandten Verbindungen im Sickerwasser einer Rüstungsaltlast

Goal, Scope and Background

Nitrodiphenylamines can be found at abandoned military sites where the explosive 2,2′,4,4′,6,6′-hexanitrodiphenylamine (hexyl) or diphenylamine as a stabilizer of smokeless powder was handled. Aim of the present study is the development of HPLC methods for the analysis of contaminants which can be expected in particular under aerobic conditions at premises which are contaminated by nitrodiphenyl-amines and related compounds.

Methods

A list of 13 compounds which can be expected at these explosives factories was deduced from literature studies. HPLC methods were developed for the analytes. Water samples from the unsaturated zone of a former hexyl-producing factory were collected by suction cups and the material was analysed according to these procedures to demonstrate the practicability of the new methods and to verify the existence of the postulated compounds in the environment of the former nitration plant.

Results and Conclusion

The new HPLC methods are suitable for the exploration of sites contaminated by nitrodiphenylamines. Beside some hexyl its intermediates 1-chloro-2,4-dinitrobenzene, 2,4-dinitrodiphenylamine und 2,2′,4,4′-tetranitrodiphenylamine were identified in the leachate water.

Recommendation and Perspective

It is advisable to include at least these 4 compounds in the examination of former hexyl-producing plants. Several unknown peaks were observed in the HPLC-chromatogram. It is recommendable to perform further investigations of the unidentified compounds to compile a final list of analytes for military sites polluted by nitrodiphenylamines.     

毛细管气相色谱-负离子化学电离源质谱法测定空气颗粒物中的硝基多环芳烃

本文用毛细管气相色谱-负离于化学电离源质谱法（GC-NICIMS）测定了空气颗粒物中的硝基多环芳烃（NO_2-PAH）、通过与标准物的保留时间和质谱图的比较,确定空气颗粒物中含有四种NO_2-PAH,它们是2-硝基芴,9-硝基蒽,1-硝基芘和2-硝基萤蒽,用同一样品进行了毛细管气相色谱正离子电子轰击源质谱分析（GC-EIPIMS）,并与GC-NICIMS进行了比较,结果表明,GC-NICIMS对于NO_2PAH的测定具有较高的选择性和灵敏度,用内标法定量使GC-NICIMS测定结果的精密度得到改善。     

电感耦合等离子体质谱法在土壤环境监测中的应用及进展

电感耦合等离子体质谱（ICP-MS）作为高灵敏度的分析仪器,已被许多国家应用于环境监测中.本文综述了近年来电感耦合等离子体质谱在土壤样品分析测试中的应用,重点比较了土壤样品前处理中不同的消解体系和消解方式,介绍了激光熔蚀法、氢化物发生法和碰撞反应池技术等土壤环境监测中的新方法,以及ICP-MS在土壤环境监测中用于稀土元...     

A comparative study of three different methods for the sequential extraction of heavy metals in soil

Three different methods for the sequential extraction of heavy metals from soil (viz those of Tessier et al. (A. Tessier, P.G. Campbell and N. Bisson (1979). Anal. Chem., 51, 844.), Sposito et al. (G. Sposito, L.J. Lund and A.C. Chang (1989). Soil. Sci. Soc. Am. J., 46, 260.) and Mann and Ritchie (S.S. Mann and G.S.P. Ritchie (1993). Aust. J. Soil Res., 31, 255.)) were examined in terms of the distribution of Cu, Zn and Pb in the soil phases and the bioavailability of these elements in soil. To this end, several samples of soils polluted with metals from a copper mine were fractionated by using the three studied methods and analyzed by atomic absorption spectrometry. The results revealed differences in extraction efficiency among the methods due to the extractant used, or its concentration, and to the soil/solution ratio. The three methods were found to provide accurate heavy metal background contents. However, the method of Tessier et al. is to be preferred for quantifying increased levels of heavy metals on account of its high extraction power.     

离子色谱在砷化物形态分析中的应用

砷的分析方法最初有光度法、原子吸收光谱法和极谱法等，但这些方法仅能用于总砷，不能用于砷的形态分析．因而又发展了电感耦合等离子体质谱法(ICP-MS)、离子色谱法(IC)、气相色谱法、气相色谱-原子吸收光谱联用、液相色谱-质谱联用、离子色谱-电感耦合等离子体质谱、离子色谱-原子吸收／发射光谱联用技术等．由于砷化物在水中多以离子形式存在，采用离子色谱法能同时分析不同形态的砷离子．同时，采用电感耦合等离子体质谱及原子吸收光谱测定砷化物具有较高的灵敏度，因此，离子色谱及离子色谱与电感耦合等离子体质谱、原子吸收／发射光谱的联用技术在砷化物的形态分析中得到了较多的应用^[1-8]。