基于有机物指纹图谱技术的长江南京段水中有机磷溯源研究

长江水环境污染物识别和溯源分析是保护长江水生态环境的前提。于2021年11月26—27日对长江南京段有机磷进行溯源调查,采用有机物指纹图谱识别技术对9个干流监测点位和7个临近入河排口监测点位之间以有机磷为代表的有机污染物的耦合关联性进行研究,筛查重点潜在污染水域及可能来源。研究结果表明,应用指纹图谱技术共识别出25类有机污染物,其中干流XC-02点位有机磷等有机污染物输入明显,主要受临近陆域污水处理厂、制药企业、石化企业及表面加工企业等的工业废水排放影响;干流XC-07点位有机磷离子峰强度升高,受上游传输与陆域入河排口XA-07点位共同影响。研究为河流有机污染物溯源提出了指纹图谱解析方法思路并得以应用,为水环境有机污染物管控提供技术支撑和决策依据。     

水质荧光指纹污染溯源技术在跨界断面污染监管中的应用

2020年11月,在我国北方X河流上某跨界断面发生的水质异常事件中,采用水质荧光指纹污染溯源技术开展水体污染溯源工作。使用在线式水污染预警溯源仪监测到水质异常,得到初步溯源结果。依据溯源信息及跨界断面上游产业分布情况,初步锁定重点排查对象。将人工排查和在线溯源相结合,发现水质异常的主要原因和排放源。该污染溯源过程用时仅21 h,且人工排查与在线溯源的结果吻合。结果表明,“在线溯源—人工排查”是一种快速、精准的新型污染监管模式,在解决跨界断面水体污染溯源难、责任划分不清的问题中可发挥重要作用。     

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。     

兴盐界河民主村断面水环境质量溯源调查分析

以民主村断面上游为研究对象，利用有机物非靶向筛查技术，结合现场快速筛查、实验室分析及现场实地勘查结果，判断重点监测区域污染情况，并使用卫星遥感、无人机及现场排查对民主村断面所在的兴盐界河开展全流域排查。结果表明，兴盐界河沿线排污口众多，民主村断面汇水区域及兴盐界河沿线广泛受到养殖业、生活源、种植业污染，河内源污染严重，加之水流不畅、汛期放大污染等自然因素，导致断面水质无法稳定达标，全年平均水质超Ⅲ类。     

天津市空气颗粒物中酞酸酯的分布特征

采用气相色谱-质谱仪(GC-MS)对天津市空气颗粒物中15种酞酸酯(PAEs)夏季和冬季的浓度进行了分析测定,研究了酞酸酯污染水平的季节变化,不同季节酞酸酯的功能区差异,15种酞酸酯在颗粒物中的分布特征,以及DBP和DEHP在夏冬两季中的污染特点,分析了产生上述结果的原因,基本说明了天津市空气颗粒物中酞酸酯的污染状况和特点。     

鞍山市空气颗粒物中酞酸酯的季节变化与功能区差异

采用气相色谱-质谱仪(GC-MS)对辽宁省鞍山市空气颗粒物中15种酞酸酯夏季和冬季的浓度进行了分析测定,研究了酞酸酯污染水平的季节变化,不同功能区酞酸酯浓度的差异,以及DBP和DEHP在夏冬两季中的污染特点,将鞍山市夏冬两季酞酸酯的浓度与国内外部分城市进行了比较,分析了产生上述结果的原因,基本说明了鞍山市空气颗粒物中酞酸酯的污染状况。     

CFCs生产企业废水及产品成分快速检测分析

采用车载GC-MS技术,建立了顶空-GC-MS方法对CFCs产品组分及排污废水中三氯一氟甲烷、二氯二氟甲烷、四氯化碳等成分进行监测分析,实现了快速鉴定企业是否违规生产CFCs相关产品,对于判定企业是否违规提供技术依据。同时,采用顶空-GC/ECD方法对废水中的四氯化碳进行定量分析,以排查企业是否超标排污。     

利用MALDI-TOF MS技术简便、快速检测水华蓝藻的方法研究

以水华蓝藻为研究对象,用基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)技术对其进行测定分析并获得了蛋白质指纹图谱。对铜绿微囊藻标准株(NIES-843)样品通过3种前处理方法得到的质谱图进行对比,确定了质谱分析的样品前处理方法,建立了利用MALDI-TOF MS技术简便、快速检测水华蓝藻的方法。对在水华中出现的4种不同蓝藻进行MALDI-TOF MS分析,结果表明各种蓝藻具有其特征性波谱,可据此对水华蓝藻进行区分和鉴定。该方法快速、简便、精确、可程序化,具有广泛的应用前景。     

大气污染物指纹系统构建及在污染溯源中的应用

基于污染物检测特征信息结合区域产业结构、企业布局等信息构建了大气污染物指纹系统,通过污染物检测特征信息构建的第一级指纹数据库实现了对大气特征污染物的识别和污染物应急处置措施的推送;通过污染源行业及其排放的特征污染物信息构建的第二级指纹数据库实现了产排污行业的溯源;通过企业及其产排污信息,结合气象条件构建的第三级指纹数据库实现了对产排污企业的溯源。基于大气污染物指纹数据库的污染溯源技术为突发环境污染事故中污染物质的识别和污染源的追踪提供了新途径。实际应用验证表明,大气污染物指纹系统污染溯源响应快速、识别精准,实现了大气污染物从监测、溯源到应急处置的全过程无缝衔接。     

浅谈基层监测站"十二五"能力建设方向

依据环境监测能力建设标准,提出了"十二五"期间基层监测站能力建设的目标和要求,指出实现"三个说得清",应以科研工作为先导,以污染防治为核心,以信息化建设为载体,强化对环境质量综合分析和环境风险源筛分排查,充分发挥基层监测站的作用,更好地为环境管理提供准确有效技术支持的建设思路.     

The role of GC-MS and LC-MS in the discovery of drinking water disinfection by-products

Gas chromatography-mass spectrometry (GC-MS) has played a pivotal role in the discovery of disinfection by-products (DBPs) in drinking water. DBPs are formed when disinfectants, such as chlorine, ozone, chlorine dioxide or chloramine, react with natural organic matter in the water. The first DBP known--chloroform--was identified by Rook in 1974 using GC-MS. Soon thereafter, chloroform and other trihalomethanes were found to be ubiquitous in chlorinated drinking water. In 1976, the National Cancer Institute published results linking chloroform to cancer in laboratory animals, and an important public health issue was born. Mass spectrometry and, specifically, GC-MS became the key tool used for measuring these DBPs in water and for discovering other DBPs that were formed. Over the last 25 years, hundreds of DBPs have been identified, mostly through the use of GC-MS, which has spawned additional health effects studies and regulations. Early on, GC with low resolution electron ionization (EI)-MS was used, together with confirmation with chemical standards, for identification work. Later, researchers utilized chemical ionization (CI)-MS to provide molecular weight information and high resolution El-MS to aid in the determination of empirical formulae for the molecular ions and fragments. More recently, liquid chromatography-mass spectrometry (LC-MS) with either electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) has been used to try to uncover highly polar DBPs that most experts believe have been missed by earlier GC-MS studies. Despite 25 years of research in the identification of new DBPs, new ones are being discovered every year, even for chlorine which has been the most extensively studied.     

Performance of semipermeable membrane devices for sampling of organic contaminants in groundwater

Lipid-filled semipermeable membrane devices (SPMDs) are receiving increasing attention as passive, in situ samplers for the assessment of environmental pollutant exposure. Although SPMDs have been successfully used in a variety of field studies in surface waters, only a few studies have addressed their characteristics as groundwater samplers. In this study, the performance of the SPMDs for monitoring organic contaminants in groundwater was evaluated in a pilot field application in an area severely contaminated by chemical waste, especially by chlorinated hydrocarbons. The spatial distribution of hydrophobic groundwater contaminants was assessed using a combination of passive sampling with SPMDs and non-target semiquantitative GC-MS analysis. More than 100 contaminants were identified and semiquantitatively determined in SPMD samples. Along the 6 field sites under investigation, a large concentration gradient was observed, which confirms a very limited mobility of hydrophobic substances in dissolved form in the aquifer. The in situ extraction potential of the SPMD is limited by groundwater flow, when the exchange volume of well water during an exposure is lower than the SPMD clearance volume for the analytes. This study demonstrates that SPMDs present a useful tool for sampling and analyzing of groundwater polluted with complex mixtures of hydrophobic chemicals and provides guidance for further development of passive sampling technology for groundwater.     

工业城市有机化工异味应急监测快速溯源

结合淄博化工园区有机化工异味的应急监测,研究了工业城市有机化工异味的快速溯源。针对多种异味混杂,现场利用便携式GC-MS对空气中引起异味的有机化合物进行定性和定量,结合三点比较式臭袋法测定厂界臭气浓度值,根据风向,对照企业污染物名单快速溯源,并根据测定结果和厂界臭气浓度限值对排污企业进行行政处理。     

水纹预警溯源技术在地表水水质监测的应用

针对地表水对污染预警和溯源技术的迫切需求,在南方某水体开展水质指纹预警溯源技术的应用研究。结果表明,该水体的水纹在激发波长230 mm、发射波长340 nm和激发波长280 nm、发射波长320 nm处有2个代表性荧光峰。2个峰的荧光强度与氨氮呈线性正相关。枯水期的荧光强度较高。清华大学已将水纹溯源技术仪器化。在长期在线监测过程中,污染预警溯源仪检测到水情异常并快速确定了污染类型,为环境监管提供了有力的技术支撑。     

Distribution and ecotoxicological significance of polycyclic aromatic hydrocarbons in sediments from Iko River estuary mangrove ecosystem

The distribution of polycyclic aromatic hydrocarbons (PAHs) in epipelic and benthic sediments from Iko River estuary mangrove ecosystem has been investigated. Total PAHs ranged from 6.10 to 35.27 mg/kg dry weight. Quantitative difference between the total PAHs in epipelic and benthic sediments showed that the benthic sediment known for higher capability to serve as sink for chemical pollutants accumulated less PAHs. This implies that PAHs in the epipelic sediment may plausibly be from industrial sources via runoff and/or of biogenic origin. A strong pyrolytic source fingerprint has been detected with slight influence of petrogenic sources. Total organic carbon normalized PAHs (sum of 16 PAHs, 59.7 to 372.4 mg/kg OC) were under (except for ES3 and BS3) the threshold effects concentrations (TEC, 290 mg/kg OC). Total PAHs in Iko River estuary sediments were in the range between ERL and ERM.     

Quantification of bacterial lipopolysaccharides (endotoxin) by GC-MS determination of 3-hydroxy fatty acids

A GC-MS method for the quantification of bacterial lipopolysaccharides (LPS, endotoxin) is presented. After hydrolytic cleavage of 3-hydroxy fatty acids (3-OH FAs) from the lipid A region of LPS, derivatisation of both the hydroxyl and the carboxyl group was performed in one step with a mixture of methyl-bis(trifluoracetamide)(MBTFA) and N-methyl-N-(tert-butyldimethylsilyl)trifluoracetamide (MTBSTFA). Using GC-MS in the EI mode with selected ion monitoring (SIM) for analysis, baseline separation of 3-OH FAs (and of possibly interfering 2-OH FAs) was achieved. The sensitivity of the method (LOD 7-50 pg/injection for the different 3-OH FAs investigated) allows for the efficient quantification of LPS in occupational and environmental samples. Degradation of 3-OH FAs as well as of their derivatives during sample preparation and GC-MS separation as a possible source of errors in analytical methods based on 3-OH FA determination is reported for the first time. Thermal elimination of water from the underivatised 3-OH FAs and of trifluoroacetic acid from the derivatives was identified as the cause of degradation. The resulting alpha,beta-unsaturated compounds showing the same mass spectra as the 3-OH FA derivatives were detected as more or less prominent satellite peaks. By using alkaline instead of acidic hydrolysis and cool on-column instead of split/splitless injection, elimination was reduced to an acceptable level.     

《突发性污染事故中常见危险品档案库》研制

研制建立了《突发性污染事故中常见危险品档案库》,从 1档案库的内容—— 1 3 0 0余种化学危险品六个方面的信息和环境保护相关信息 ,2档案库的计算机实现技术两大方面进行了研究和开发 ,并制成了《突发性污染事故中常见危险品档案库》光盘。该档案库是对化学危险品引起的突发性污染事故进行快速处理的技术信息支持库 ,是为环境管理、环境监测、环境监察、环境卫生、化学危险品管理等行业的管理和技术人员提供的实用工具软件     

Optimizing a GC-MS method for screening of Stachybotrys mycotoxins in indoor environments

Presence of Stachybotrys chartarum in indoor environments has been linked to building-associated disease, however, the causative agents are unknown. Verrucarol (VER) and trichodermol (TRID) are hydrolysis products of some major S. chartarum mycotoxins, i.e. macrocyclic trichothecenes and trichodermin. We optimized gas chromatography-mass spectrometry (GC-MS) methods for detecting VER and TRID in S. chartarum-contaminated indoor environmental samples. Heptafluorobutyryl derivatives of both VER and TRID exhibited little MS fragmentation and gave much higher detection sensitivity (sub-picogram injected onto the GC column), both in GC-MS and GC-MSMS, than trimethylsilyl derivatives. Optimal detection sensitivity and specificity was achieved by combining chemical ionization and negative ion (NICI) detection with MSMS. With this method, VER and TRID were detected in building materials colonized by S. chartarum and TRID was demonstrated in dust settled in the breathing zone in a house where an inner wall was colonized. In summary, we have shown that NICI-GC-MSMS can be used to demonstrate mycotoxins in house dust in S. chartarum-contaminated dwellings.     

环境水系统中氯氟烃替代品降解产物TFA的测定

三氟乙酸为氯氟烃替代品的降解产物,对植物和土壤微生物群落的生长有一定抑制作用.建立测定TFA质量浓度的实验方法,将样品中的三氟乙酸与甲醇在硫酸溶液中衍生化为三氟乙酸甲酯(MTFA),利用三氟乙酸甲酯的易挥发性,以顶空进样进行富集浓缩.使用质谱定性手段确定出峰时间,再通过电子捕捉检测器ECD对实际样品进行分析.仪器检测限为30μg/L,方法检出限约为30ng/L,加标回收率60%～90%.