罐采样与气相色谱/质谱结合在VOCs监测中的应用

气态挥发性有机物(VOCs)引起的污染严重威胁人们的健康,因而对其监测技术的研究也越来越多。其中罐采样与气相色谱/质谱联用的检测技术在VOCs气态污染物测定中的应用逐步受到关注。对罐采样技术进行了综述,重点介绍了罐采样与气相色谱/质谱联用技术在环境空气、室内空气、废气中VOCs检测的应用。     

基于单颗粒质谱技术的石家庄冬春季气溶胶成分特征及混合状态研究

利用位于石家庄市大气梯度监测站(20 m)的单颗粒气溶胶质谱仪分析了冬、春季大气环境中气溶胶的化学组成及混合状态,并采用ART-2a分类法对气溶胶分类。结果表明,石家庄市大气中主要存在8类颗粒物,即元素碳(EC)、有机碳(OC,相对分子质量小于150)、高分子有机碳(HOC,相对分子质量大于150)、混合碳(元素-有机碳混合,ECOC)、重金属、左旋葡聚糖碎片(LEV)、矿物质和富钾颗粒。8类颗粒中绝大部分包含SO_4~-、NO_2~-和NO_3~-等二次离子组分,表明采集到的颗粒物大都经历了不同的老化,或与二次组分进行了不同程度的混合。冬季气溶胶的主要成分是OC(数浓度36.1%),谱图含有C2H+3、C_2H_3O~+、C_5H_3~+、C_6H_5~+等离子,主要来自化石燃料、生物质等燃烧产生的一次排放颗粒,以及由挥发性有机物光化学氧化而成的二次有机颗粒;春季气溶胶的主要成分是EC(数浓度43.6%)和矿物质(数浓度15.4%)。EC中含有一系列单质碳峰,来自化石燃料或木材等生物质不完全燃烧的一次排放;矿物质颗粒中含有Mg~+、Al~+、Ca~+、Fe~+及SiO_3~-,主要来自扬尘。发生灰霾时,冬季OC和ECOC颗粒占比增大,EC颗粒占比减小;春季矿物质和ECOC颗粒占比变大,OC颗粒占比变小。随着灰霾天气发生,冬、春季碳气溶胶与二次无机气溶胶颗粒的混合加剧,而NH_4~+与碳气溶胶的混合加剧最为明显。冬季气溶胶的数浓度与气象因素的相关性高于春季,而低风速、高湿度和低气压易导致灰霾出现。石家庄市春季和冬季气溶胶污染应分别从机动车尾气、扬尘及燃煤、制药企业加以管控。     

钻孔间距对水力压裂促抽煤层瓦斯的影响

针对定量确定合理钻孔间距困难问题,基于损伤力学和多场耦合理论,建立了水力压裂和瓦斯抽采的煤层流固耦合模型,包括和水运移场、应力场以及孔隙度、渗透率演化方程,并采用Comsol联合Matlab求解,研究了不同钻孔间距时压裂和抽采过程中煤层弹模、损伤值、渗透率、瓦斯压力、抽采量和压裂贯通时间的变化规律。结果表明:耦合模型可较准确地模拟煤层水力压裂和瓦斯抽采过程;压裂贯通时间与钻孔间距呈指数增长关系;在马堡煤矿,当钻孔间距为4~8 m时,压裂损伤区在抽采孔贯通,渗透率呈“n”型曲线,瓦斯抽采后,瓦斯压力迅速下降,抽采有效区随间距的增加而增大;当钻孔间距为9~12 m时,压裂损伤区未贯通,煤层渗透率呈“m”型曲线,抽采有效区随间距的增加而减小,与间距4~8 m相比,瓦斯抽采量较小。     

南宁市一次污染过程大气颗粒物理化特性及来源

利用颗粒物粒径谱仪和单颗粒气溶胶质谱仪等,对南宁市2016年12月5~11日大气污染过程进行实时监测,分析颗粒物粒径分布特征、化学组分及其污染来源.结果表明,观测期间南宁市20 nm~10μm颗粒物数浓度粒径主要集中在23~395 nm之间,主峰值出现在100 nm左右.期间有3次新粒子生成现象,下午14:00~18:00有30 nm左右新粒子开始生成,晚20:00~次日06:00碰并长大到40~110 nm左右,3次新粒子生成过程受机动车尾气一次排放的污染影响.对污染期间细颗粒物化学成分在线溯源分析发现,污染期间有大量的二次反应颗粒物生成,判定颗粒物来源主要有生物质燃烧源、扬尘源和燃煤源,其中,远距离传输对生物质燃烧源有贡献.     

远程火箭弹高弹道飞行温度环境分析

目的在不采用防热涂层的前提下,为满足远程火箭弹高弹道飞行的防热需求,提出增加壳体厚度的设计思路。方法通过弹道耦合的气动加热计算,分析不同材料、不同厚度壳体的弹头壁面在飞行过程中的温度变化情况。结果壳体厚度达到20 mm以上时,铝、钢、铜三种材料壳体的外壁面温度均低于150℃,而相同厚度的壳体,钢壳的降温能力最强。结论增加壳体厚度可以有效降低弹头壳体壁面温度。     

四川妇女血清中多溴联苯醚的浓度水平与组成特征

用气相色谱-质谱的选择离子法测定四川省妇女血清中多溴联苯醚的质量浓度,并对其组成特征及主要来源进行了研究.在被测的11种多溴联苯醚当中,BDE-209是主要成分,质量浓度从0.12～2.38μg.L-1,中值为0.63μg.L-1,占多溴联苯醚总量的质量分数为63.57%～90.34%,其次是BDE-66、-99和-100,其它多溴联苯醚几乎没有检出,表明污染主要来自十溴联苯醚,其次是四溴和五溴联苯醚.实验结果与其它国家的数据相比,表明多溴联苯醚对普通妇女的污染在四川还处于一个较低的水平.     

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.     

LC-MS/MS determination of pesticide residues in fruits and vegetables

The aim of the research is to evaluate pesticide residue contamination of fresh and frozen fruits and vegetables, agricultural raw material, purchased from Polish farmers for production of frozen fruits and vegetables, and the estimation of the multiresidue method effectiveness expressed as the proportion of pesticides detected in food samples to the total number of pesticides analyzed by multiresidue methods. A total of 144 samples (of black currants, red currants, raspberries, cherries, strawberries, blackberries, cauliflowers and broccoli) were analyzed using LC-MS/MS method for the determination of 60 pesticides. QuEChERS extraction, matrix-matched calibration and dynamic multiple reaction monitoring method were used. Residues of 15 compounds, mainly fungicides and insecticides, were detected in 46 samples. The percentage of samples with residues above the maximum residue levels (MRL) was 15%, whereas samples with residues below MRL were 17%. A total of 13 samples contained more than one pesticide residue. Pesticide residues were detected most often in samples of black currants (50%), broccoli (36.4%), raspberries (29%) and red currants (21.8%). The most frequently detected pesticides were carbendazim and acetamiprid. The proportion of pesticides detected during our study to the total number of analyzed pesticides amounted to 25%. It was compared to literature findings. For three fourth of multiresidue methods, the proportion was below 50% for methods developed for the analysis of less than 100 pesticides, and below 30% for methods developed for the analysis of more than 100 pesticides. It appears that a lot of efforts and means is lost on pesticides never or rarely detected in examined samples. The workload and cost effectiveness of the development and application of multiresidue methods along with the range of pesticides covered by the method should be carefully and thoroughly considered anytime when a new method or workflow is developed. Including non-targeted screenings in pesticide residue control seems to be an alternative worth considering.     

天津市城市扬尘及土壤尘单颗粒质谱特征

为探究城市扬尘及不同类型的土壤尘单颗粒质谱特征,使用SPAMS（单颗粒气溶胶质谱仪）对天津城市扬尘及不同类型土壤尘（菜地、果园、林地、农田）进行分析.结果表明:天津城市扬尘粒径在0.5~1.0 μm之间的占比较高;4种土壤尘在不同粒径段的分布略有差异,整体而言小粒径段（0.2~1.0 μm）占比低于大粒径段（1.0~2.0 μm）,说明土壤尘更易分布在大粒径段.在小粒径段,天津城市扬尘颗粒含有更多的碳组分及硫酸盐,大粒径段含有较多的金属、氯、硝酸盐、磷酸盐及硅酸盐组分.与城市扬尘相比,土壤尘中23Na+、46NO₂-峰强显著降低,39K+、35Cl-、42CNO-峰强增高,通过其峰强比值分布可将城市扬尘与土壤尘明显区分.与城市扬尘相比,土壤尘中含碳颗粒显著减少,同时出现钾类颗粒.城市扬尘作为一种混合源,含碳颗粒可能受多种排放源（机动车、燃煤等）影响,而土壤尘中钾类颗粒可能与农作物施肥有关.两种源类含27Al+、26CN-、35Cl-、42CNO-、46NO₂-、76SiO₃-、79PO₃-的颗粒占比均高于50%,其中40Ca+、46NO₂-和62NO₃-颗粒在天津城市扬尘中占比更高,76SiO₃-颗粒在土壤尘中占比更高,表明天津城市扬尘中更多的颗粒含有钙和硝酸盐组分,土壤尘中含硅酸盐颗粒较多.与机动车尾气、生物质燃烧等排放的颗粒物相比,天津城市扬尘及土壤尘中含97HSO₄-颗粒占比较低,表明天津城市扬尘及土壤尘颗粒中含有更少的硫酸盐,可作为将天津城市扬尘、土壤尘与其他源类区分的指标.