Water-soluble organics in atmospheric particles: A critical review of the literature and application of thermodynamics to identify candidate compounds

Although organic compounds typically constitute a substantial fraction of the fine particulate matter (PM) in the atmosphere, their molecular composition remains poorly characterized. This is largely because atmospheric particles contain a myriad of diverse organic compounds, not all of which extract in a single solvent or elute through a gas chromatograph; therefore, a substantial portion typically remains unanalyzed. Most often the chemical analysis is performed on a fraction that extracts in organic solvents such as benzene, ether or hexane; consequently, information on the molecular composition of the water-soluble fraction is particularly sparse and incomplete.This paper investigates theoretically the characteristics of the water-soluble fraction by splicing together various strands of information from the literature. We identify specific compounds that are likely to contribute to the water-soluble fraction by juxtaposing observations regarding the extraction characteristics and the molecular composition of atmospheric particulate organics with compound-specific solubility and condensibility for a wide variety of organics. The results show that water-soluble organics, which constitute a substantial fraction of the total organic mass, include C2 to C7 multifunctional compounds (e.g., diacids, polyols, amino acids). The importance of diacids is already recognized; our results provide an impetus for new experiments to establish the atmospheric concentrations and sources of polyols, amino acids and other oxygenated multifunctional compounds.     

苯并噻吩系列化合物的成因模拟及其地球化学意义

在硫和β胡萝卜素反应产物中有丰富的苯并噻吩系列化合物,在硫与饱和链状化合物反应产物中既有噻吩系列化合物也有苯并噻吩系列化合物。所以推断苯并噻吩系列是硫作用于噻吩系列或含侧链的苯而形成的。噻吩系列和苯并噻吩系列的相对含量可以指示成熟度:在沉积条件相同的前提下,前者多后者少指示成熟度低,反之则指示成熟度高。     

Biofouling confounds the uptake of trace organic contaminants by semi-permeable membrane devices (SPMDs)

The outer layers of layflat, low density polyethylene plastic tubing (the principal component of semi-permeable membrane devices, SPMDs) were biofouled at a clean site in Hong Kong coastal waters for periods of 1–4 weeks. Following pre-fouling, triolein was added to the SPMDs and, along with control (unfouled) devices, they were exposed to a range of organochlorine pesticides (-HCH, aldrin, p,p^′-DDT) and PAHs (anthracene, fluoranthene and benzo(a)pyrene) under laboratory conditions. Results showed that the uptake of contaminants by SPMDs was severely reduced by as much as 50% under fouling conditions in comparison to unfouled controls. The ultimate utility of SPMDs as passive monitors is thus reduced, although alternative measures, such as the use of permeability reference compounds may compensate, and allow for realistic evaluations of dissolved environmental concentrations in aquatic environments. However, due to the complexities involved in such procedures––especially as they need to be conducted on a case-by-case basis––the utility of SPMDs appears to be limited for estimates of bioavailability unless necessary calibrations are undertaken within each environment that the sampler is used.     

The Atmospheric Oxidation of the HS Radical: Reaction with NO2

The atmospheric reaction between HS and NO₂ was theoretically investigated at 298 K and 1 atm of pressure. Our results show that the first reaction step will lead to the formation of HSNO₂ or HSONO, spontaneously and exothermically. HSONO easily decomposes into HSO + NO. On the other hand, HSNO₂ can hardly dissociate in the reactants, and its isomerization to other adducts is much hindered. Production of HNO + SO and SNO + OH was found to be unfavorable. Thus, the main products would be HSO + NO and HSNO₂, and new investigations focusing on the atmospheric fate of HSNO₂ are suggested. A general discussion of the fate of HS under atmospheric conditions is presented. Recent investigations indicate that NO₂, O₂ and N₂O should be the most important oxidants of HS, while the O₃ influence will not be significant.     

傅立叶变换红外光谱联用技术在化石燃料分析中的应用

对傅立叶变换红外光谱联用技术在化石燃料分析中的应用进行了较全面的总结评述,重点介绍了气相色谱／红外光谱联机、高压液相色谱／红外光谱联机、薄层色谱／红外光谱联机、超临界流体色谱／红外光谱联机、裂解色谱／红外光谱联机、热重分析／红外光谱联机、气相色谱／红外光谱／质谱三机联用技术等在化石燃料的结构组分分析、成因机理研究及其勘探等诸方面的重要应用,尤其是在芳香族化合物和几何异构体的分离鉴定方面发挥出的突出功效。引用文献５９篇。     

对流层平流层气溶胶粒子的形态和化学组成

分析研究了１９９３年和１９９４年的８月、９月在香河地区上空采集的单个气溶胶粒子的形态及化学元素和化合物的组成。结果表明：１９９３年,在对流层大气中的气溶胶颗粒经常出现不规则形的粒子,可能是土壤粒子;而在平流层大气中的颗粒以具有“卫星”结构的硫酸粒子为主;硫酸铵粒子则经常出现在对流层的中、下部。香河地区上空颗粒物的化学元素组成比较复杂,单一化学元素组成的粒子较少,粒子主要含有Ｓｉ,Ｆｅ,Ａｌ和Ｓ等元素。气溶胶的化合物有硫酸盐、硅酸盐、硝酸盐和磷酸盐等     

基于傅里叶变换质谱的烃源岩成熟度评价方法及地质意义

<正>伴随非常规油气资源的勘探开发,油气资源开采的广度和深度进一步扩大,一定程度上缓解了我国油气供需矛盾、保障了我国能源安全,同时有力推动了能源结构战略转型。但同时也对能源地质研究工作提出了新的挑战。有机质成熟度是油气评价的重要参数之一,不同成熟阶段的有机质会对应产出不同成因、不同性质、不同质量的油气,如何准确评价沉积有机质成熟度是当前油气资源勘探开发工作的关键问题之一。前人在科研实践工作中从光学、化学、谱学等角度提出了适用条件各异的成熟度评价方法,在部分地质环境中获得了良好的应用效果,但已有的成熟度指标多受测定方法原理的制约导致其适用性不同程度受限(肖贤明等,2020),制约了油气资源的高质量勘探开发。     

气相色谱-质谱法同时测定河流沉积物中多环芳烃和有机氯农药

建立了用加速溶剂萃取,气相色谱-质谱法同时测定河流沉积物中16种多环芳烃和19种有机氯农药的分析方法,优化了萃取溶剂、萃取温度和时间、凝胶渗透色谱收集时间、固相萃取洗脱溶剂和洗脱体积等条件。16种多环芳烃的方法检出限在0.15~0.59 ng/g,加标回收率为82%~102%,相对标准偏差(RSD,n=5)为1.1%~4.5%。19种有机氯农药的方法检出限在0.14~2.23 ng/g,加标回收率为71%~108%,相对标准偏差(RSD,n=5)为1.0%~4.5%。实际样品的测定结果表明,该方法分离效果较好,能够满足沉积物样品中多环芳烃和有机氯农药的分析要求。     

样品前处理过程中多环芳烃的稳定碳同位素分馏

利用多环芳烃标准样品连续和穿插进样相结合的方式,检验了气相色谱-燃烧-同位素比质谱仪(GC-C-IRMS)测定多环芳烃单体碳同位素比值(δ13C)的稳定性和准确性,观察了测定过程中色谱柱的分离效果。结果表明,出峰面积和分离程度是影响化合物δ13C平行性的主要原因。通过多次实验,分析了样品前处理过程中多环芳烃各个化合物稳定碳同位素的分馏情况,包括凝胶渗透色谱(GPC)和硅胶柱等净化过程,以及旋转蒸发和氮气吹扫等浓缩过程。实验表明,各前处理过程中样品内多环芳烃的稳定碳同位素分馏均不明显,其中硅胶柱净化过程相比GPC过程对样品中多环芳烃的δ13C影响较大,但总体上仍未超过未处理标样δ13C值的2倍标准偏差范围。旋转蒸发和氮吹过程对样品中多环芳烃的δ13C影响程度相当,都位于未处理标样δ13C值1倍标准偏差以内的水平。     

吹扫捕集-气相色谱/质谱法测定地下水中的挥发性有机物

利用吹扫捕集-气相色谱/质谱联用技术,建立了适用于地下水中氯代烃、苯系物、氯代苯类等25种挥发性有机污染物的分析方法。采用选择离子监测与全扫描交替方式进行质谱定性,内标法定量,方法检出限为0.10～0.20μg/L,样品加标的平均回收率在83.9%～104.5%,相对标准偏差(RSD,n=7)在3.23%～10.1%。方法检出限低,精密度好,分析快速,适用于大批量地下水中挥发性有机物的分析。