Determination of methyl tert-butyl ether (MTBE) in Chinese fuels by gas chromatography/mass spectrometry and gas chromatography/flame ionization detector

A method was developed to determine the concentration of methyl tert-butyl ether(MTBE) in gasoline,diesel and heating oil by gas chromatography(GC) with mass spectrometry(GC-MS) or flame ionization detection(FID). The diluted gasoline was directly injected into the GC, and the complete separation of MTBE from co-eluting hydrocarbons was not required. GC/MS or GC/FID method can be used to analyze MTBE in different concentration range and have good consistency.     

污染地块有机污染物的顶空/气相色谱-质谱法测定和评价

本文通过优化土壤样品顶空前处理方法和仪器条件,采用顶空/气相色谱-质谱法测定某废弃农药厂土壤样品中53种有机污染物。根据测定值,参照《土壤环境质量建设用地土壤污染风险管控标准(试行)》(GB 36600—2018),重点对土壤样品中苯、氯苯、甲苯等25种有机物进行了单项污染指数法评价。评价结果表明,如果某废弃农药厂地块要用作第一类用地,需要对土壤中氯仿、1,2-二氯乙烷、苯、三氯乙烯和甲苯5种有机污染物做风险管控;如果用作第二类用地,需要对土壤中氯仿和甲苯2种有机污染物做风险管控。     

大气中羰基化合物GC/MS分析方法

介绍了一种灵敏度高、可靠并且能同时检测大气中20种羰基化合物(C1～C10)的分析方法.该方法是采用涂布PFPH(衍生剂)的Tenax TA作为固体吸附剂采集大气样品,然后再经过溶剂洗脱和气相色谱/质谱(GC/MS)分离检测的一项分析技术.校正曲线的可决系数(R2)、检测限(LOD)、平行样标准偏差(RSD,n=6)、回收率分别为0.995～1.00,0.15～1.04ng·m-3,7.3%～15.8%和92.7%～109.2%.该方法成功地应用到对大气中羰基化合物的定量检测.对羰基化合物浓度的日变化分析表明,上海大气中羰基化合物浓度变化与大气光化学反应的强弱有密切关系.     

Determination of selected semi-volatile organic compounds in water using automated online solid-phase extraction with large-volume injection/gas chromatography/mass spectrometry

A rapid, sensitive, and cost-effective analytical method was developed for the analysis of selected semi-volatile organic compounds in water. The method used an automated online solid-phase extraction technique coupled with programmed-temperature vaporization large-volume injection gas chromatography/mass spectrometry. The water samples were extracted by using a fully automated mobile rack system based on x-y-z robotic techniques using syringes and disposable 96-well extraction plates. The method was validated for the analysis of 30 semivolatile analytes in drinking water, groundwater, and surface water. For a sample volume of 10 mL, the linear calibrations ranged from 0.01 or 0.05 to 2.5 μg·L⁻¹, and the method detection limits were less than 0.1 μg·L⁻¹. For the reagent water samples fortified at 1.0 μg·L⁻¹ and 2.0 μg·L⁻¹, the obtained mean absolute recoveries were 70%–130% with relative standard deviations of less than 20% for most analytes. For the drinking water, groundwater, and surface water samples fortified at 1.0 μg·L⁻¹, the obtained mean absolute recoveries were 50%–130% with relative standard deviations of less than 20% for most analytes. The new method demonstrated three advantages: 1) no manipulation except the fortification of surrogate standards prior to extraction; 2) significant cost reduction associated with sample collection, shipping, storage, and preparation; and 3) reduced exposure to hazardous solvents and other chemicals. As a result, this new automated method can be used as an effective approach for screening and/or compliance monitoring of selected semi-volatile organic compounds in water.     

直接进水样气相色谱法测定水和工业排水中有机污染物

直接进水样,530μm毛细管柱分离,电子捕获检测器及氮磷检测器检测有机氯农药、有机磷农药、卤代轻、氯苯类、酚类、增塑剂、有机氮化合物、2,4－滴及氯氰菊酯等44咱有机物组份,在进样1～4μL时,大多数有机污染物的检测灵敏度可满足水中污染允许浓度的环境评价要求。530μｍ柱具有填充柱及毛细管柱各自的优点。由于水样不需处理,直接进样法保证了测定的精确度。方法简便快速,有着广阔的应用前景。     

五氟苄基羟胺衍生与GC/MS联用分析大气中的单羰基化合物和多羰基化合物

利用涂布五氟苄基羟胺（PFBHA）的Tenax-TA作为固体吸附剂,采取主动采样的方式采集大气中羰基化合物,再经溶剂洗脱和氮吹浓缩后用气相色谱/质谱（GC/MS）分析,成功检测到14种单羰基化合物和2种二羰基化合物（乙二醛与甲基乙二醛）.研究表明：在吸附剂的装载量为50mg的前提下,当衍生剂的涂布量为260nmol,采集流速为50mL·min^-1时,采集效果最佳.羰基化合物的检测限、平行样的相对标准偏差和样品的加标回收率范围分别为0.54～3.83ng·m^-3、1.0%～14.2%、89.2%～113.8%.该方法在实际大气样品中合适的采样时间为0.5～8.0h.利用此法对上海市宝山区大气中羰基化合物进行了检测,成功检测到16种羰基化合物,且具有明显的日变化趋势.     

Protonated acetone ion chemical ionization time-of-flight mass spectrometry for real-time measurement of atmospheric ammonia

Ammonia (NH₃) is ubiquitous in the atmosphere, it can affect the formation of secondary aerosols and particulate matter, and cause soil eutrophication through sedimentation. Currently, the use of radioactive primary reagent ion source and the humidity interference on the sensitivity and stability are the two major issues faced by chemical ionization mass spectrometer (CIMS) in the analysis of atmospheric ammonia. In this work, a vacuum ultraviolet (VUV) Kr lamp was used to replace the radioactive source, and acetone was ionized under atmospheric pressure to obtain protonated acetone reagent ions to ionize ammonia. The ionization source is designed as a separated three-zone structure, and even 90 vol.% high-humidity samples can still be directly analyzed with a sensitivity of sub-ppbv. A signal normalization processing method was designed, and with this new method, the quantitative relative standard deviation (RSD) of the instrument was decreased from 17.5% to 9.1%, and the coefficient of determination was increased from 0.8340 to 0.9856. The humidity correction parameters of the instrument were calculated from different humidity, and the ammonia concentrations obtained under different humidity were converted to its concentration under zero humidity condition with these correction parameters. The analytical time for a single sample is only 60 sec, and the limit of detection (LOD) was 8.59 pptv (signal-to-noise ratio S/N = 3). The ambient measurement made in Qingdao, China, in January 2021 with this newly designed CIMS, showed that the concentration of ammonia ranged from 1 to 130 ppbv.     

Determination of hemoglobin adduct of a musk xylene metabolite in trout as biomarker of exposure by gas chromatography mass spectrometry

Introduction Nitromusksarewidelyusedassyntheticfragranceingredientsinformulationofsoaps,laundrydetergents,lotions,andbody careproducts,andsoon.Thecommercial anddomesticuseanddischargeofthesecompoundsfrommunicipalsewagesystemshaveledtotheirubiquitousoccurr…     

森林地区持久性有机污染物的沉降和释放

持久性有机污染物（POPs）是一类具有毒性、难降解性和生物富集性的污染物。由于具有半挥发性,POPs可以随大气进行长距离传输并富集到极地等寒冷的偏远地区。大气沉降和挥发是POPs全球传输的关键过程。森林是POPs的重要储库,其POPs的强吸收能力加速了POPs的沉降,使得森林成为POPs大气沉降研究的重要介质。本文综述了当前森林POPs沉降研究的主要成果,重点阐述了大气POPs向植被（树冠）沉降和植被POPs向林下土壤迁移沉降这两大关键过程的特征和机制,并简要总结了林下POPs的后沉降过程（循环及再释放）和机制。最后,提出森林POPs沉降研究应着眼于观测技术开发、微观机制解析、关键规律总结、释放特征观测和多污染物耦合等方向,进而拓展大气污染物干湿沉降研究范围、丰富大气污染物干湿沉降研究的理论和方法,力争为气候变化背景下污染防治提供科学依据和理论支撑。     

基于复合软电离源飞行时间质谱的小型化大气非甲烷烃在线快速监测系统的设计与应用

针对大气非甲烷烃(NMHCs)的时空分布监测需求,并弥补现有监测技术时间分辨率低、体积和功耗较大的不足,本研究自主研发出一套高性能、小型化的大气非甲烷烃在线快速测量系统.该方法基于串联吸附剂在特定温度下对目标物质的富集与解吸,采用单光子/化学复合软电离源飞行时间质谱(SPI/CI-TOFMS)作为分离和检测手段,实现对C_2～C_(10)挥发性有机物的快速分离和检测.通过对标准样品的测量表明:在SPI/CI模式下,C_2～C_(10)物种工作曲线(0～10×10~(-9))拟合优度R~20.99,大部分物种方法检出限为1×10~(-12)～80×10~(-12),仪器检出限为1×10~(-12)～35×10~(-12),RSD(n≥10)小于10%.将仪器初步应用于北京大学站点进行定点观测,测量结果与商业化仪器TH-300B离线分析结果吻合.本系统样品分析时间5～12 min可调,整机重量低于40 kg,整机尺寸小于50 cm×50 cm×80 cm,功率低于500 W,可满足大气非甲烷烃的快速监测需求,为提供高分辨率大气NMHCs时空分布数据提供技术支持.     

Addressing the environmental risk of persistent organic pollutants in China

The Stockholm Convention on persistent organic pollutants (POPs) was adopted in 2001. This year is the 10th anniversary of the adoption of the Convention. Until now, 22 chemicals or chemical categories have been listed as POPs in the Stockholm Convention. The POPs Research Center was established in Tsinghua University in the same year when the Convention was adopted. In the last ten years, much work has been done by Chinese researchers to understand the environmental risk of POPs in China. This article aims to review the recent research progress of our POPs Research Center and some other Chinese researchers’ studies in addressing the environmental risk of POPs, including the priority screening and inventory study of POPs, monitoring and modeling of POPs pollution and exposure, and environmental risk assessment and modeling of POPs. Although great advances in addressing the environmental risk of POPs have been made in recent years, we are still facing quite a few problems, such as data scarcity and uncertainty in environmental risk assessment of POPs. The study on the effect of POPs mixtures is in its infancy and currently POPs are usually assessed from legal perspective by risk assessment of single chemicals. These problems should be well addressed by further efforts. Further studies should also be taken in future to study environment risk of POPs by considering aspects of coupled dynamics between climate processes and POPs. Such sound scientific, riskbased information can support decision-making aiming to effectively minimize the risk level of POPs.     

持久性有机污染物(POPs)生物修复研究进展

持久性有机污染物(POPs)具有高毒性和低可降解性的特征,通过先进的生物修复技术来治理POPs污染正受到公众普遍的关注.而提高生物可利用性则可以突破原位生物修复的瓶颈;宏基因组技术可以获得大量的降解基因资源;利用生物工程手段,可以大幅度提高降解菌的能力这3个方面是目前POPs生物修复领域的研究热点.     

Determination of volatile organic compounds in river water by solid phase extraction and gas chromatography

A simple, rapid, and reproducible method is described employing solid-phase extraction (SPE) using dichloromethane followed by gas chromatography (GC) with flame ionization detection (FID) for determination of volatile organic compound(VOC) from the Buriganga River water of Bangladesh. The method was applied to detect the benzene, toluene, ethylbenzene, xylene and cumene(BTEXC) in the sample collected from the surface or 15cm depth of water. Two-hundred ml of n-hexane-pretreated and filtered water samples were applied directly to a C18 SPE column. BTEXC were extracted with dichloromethane and average concentrations were obtained as 0. 104 to 0.372 μg/ml. The highest concentration of benzene was found as 0.372 μg/ml with a relative standard deviation (RSD) of 6.2%, and cumene was not detected. Factors influencing SPE e.g., adsorbent types, sample load volume, eluting solvent, headspace and temperatures, were investigated. A cartridge containing a C18 adsorbent and using dichloromethane gave better performance for extraction of BTEXC from water. Average recoveries exceedina 90% could be achieved for cumene at 4℃ with a 2.7% RSD.     

湄洲湾水体中持久性有机污染物的污染特征与风险评估

对湄洲湾海域表层水体中的持久性有机污染物(POPs)的特征进行了综合的调查分析.结果显示,湄洲湾水体中有机氯农药(OCPs)、多氯联苯(PCBs)、多环芳烃(PAHs)的浓度分别为:1.51~10.3ng/L[平均值(4.28±2.72)ng/L]、5.31~42.6ng/L[平均值(18.52±10.58)ng/L]、125~167ng/L[平均值(145±11.8)ng/L].与国内其他海域水体相比,湄洲湾的POPs污染均处于中等偏低的水平.湄洲湾海域水体中不同种类的POPs空间分布存在较大差异.HCHs分布表明该区域存在工业品HCHs和林丹的使用;滴滴涕(DDTs)则以工业早期残留为主并伴有新的污染输入;沿岸的化工企业排放的污水可能是该海域PCBs的主要来源;PAHs主要来源石油源,这与该海域密集的油码头与频繁的船运有关.依据目前的环境控制标准判定,湄洲湾海域水体中POPs仅PCBs的浓度有超出风险值限定,可能对生态环境造成危害,应采取相应的污染物控制与减排措施.     

气相色谱法测定环境空气中吡啶

建立了用气相色谱法测定环境空气中吡啶的方法。环境空气中吡啶活性炭吸附,二硫化碳解吸,DB-200毛细管柱分离,直接进样分析,氢火焰离子化检测器检测,时间定性,峰面积定量,吡啶回收率为91．5％～103．1％,当采样体积为20L,吡啶最低检出质量浓度分别为0．006mg/m 3。本方法前处理简便,分离度好,分析灵敏度高,满足环境分析要求。     

分散液液微萃取气相色谱质谱联用法测定海水中三氯苯

本文建立了分散液液微萃取结合气相色谱质谱联用法测定海水中三氯苯(TCBs)的方法。考察了萃取剂和分散剂的种类、体积、超声萃取时间、萃取温度等对模拟海水加标样品的萃取效率的影响,得到最佳萃取实验条件为:以丙酮为分散剂、氯苯为萃取剂,超声萃取时间为10 min,萃取温度为25℃。样品的加标回收率为97.8%~102.5%,相对标准偏差为2.8%~6.6%。1,3,5-,1,2,4-和1,2,3-TCB的方法检出限分别为1.5 g/L,0.5 g/L和2.0 g/L。该方法与顶空、液液萃取和固相萃取法相比具有检出限低、富集因子高、重现性好、操作简便、干扰小等优点。采用本方法对5个实际海水样品中的TCBs进行了定量检测,结果表明其中两种样品含有2~3种待测物,浓度范围为1.9~6.7 g/L。     

顶空气相色谱法测定海水中三氯乙醛

三氯乙醛是海水淡化杀生剂副产物,随浓海水排放入海,对海洋生物具有致畸性,建立海水中三氯乙醛检测方法,具有重要意义。本文采用顶空方法对海水样品中的三氯乙醛进行分离富集,建立了气相色谱-电子捕获检测器(μECD)的分析方法。讨论了顶空时间、顶空温度、水样盐度等实验条件对顶空富集效率的影响。方法在0.05~20.0 μg/L范围呈线性关系,相关系数0.9996,方法检出限(3S/N)为0.006 μg/L,相对标准偏差(RSD)0.51%~1.9%,加标回收率在96.1%~113.9%之间。     

氢化发生/低温捕集/气相色谱/原子吸收法测定天然水中的烷基锡化合物

建立了天然水中一甲基锡（MMT）、二甲基锡（DMT）、三甲基锡（TMT）、一丁基锡（MBT）、二丁基锡（DBT）、三丁基锡（TBT）等烷基锡化合物同时测定的方法,该方法是将烷基锡化合物衍生为相应氢化物,经液氮低温捕集、色谱分离后由电热石英炉原子吸收检测。对分离度和灵敏度的影响因素进行了优化。绝对检出限为0.81～2.30ngSnn,相当于分析0.4L水时2.0～5.8ngSn/L。各烷基锡6ngSn的相对标准偏差,一般不超过9.2％,采用新的措施可以延长色谱柱使用寿命,本文还给出了海河河口水样的测定结果。     

离子色谱法测定烟气中的氟和氯

采用试验对比研究的方法测试武汉某玻璃窑烟气中氟和氯的浓度,结果表明:采用EPA Method 26A方法进行采样,一次采样可获得气态氟、气态氯、卤化氢和卤素浓度等多个数据,相对误差小,具备节省时间和人力的优势。分析烟气吸收液优化的色谱条件:设定EG40淋洗液自动发生器KOH浓度为30 mmol/L;淋洗液流速为1.2 mL/min;进样量为25 μL。该方法相对标准偏差小于3.0%,精密度高,样品加标平均回收率为96.7%~104.3%,准确度良好,完全满足烟气样品吸收液氟离子和氯离子浓度的检测要求。