吸附态轻烃气相色谱分析方法及其在天然气水合物测定中的应用

建立了毛细管柱气相色谱测定土壤中吸附态轻烃（酸解烃、顶空气轻烃）的方法,采用适于批量处理的酸解烃样品制备和通过振荡、加热达到解吸平衡的顶空气样品制备的前处理方法,在优化的仪器条件下,对天然气水合物区土壤中吸附态轻烃进行检测。顶空气轻烃的方法检出限为0．018×10^-6（以甲烷计算）,精密度为6．6％（甲烷）-16％（异丁烷）;酸解烃的方法检出限为0．016μL／kg（以甲烷计算）,精密度为2．2％（甲烷）～19％（正戊烷）。该方法应用于大批量实际样品分析中,效果良好。     

Molecular Fingerprints of Soil Organic Matter in a Typical Freshwater Wetland in Northeast China

Natural wetlands are known to store huge amounts of organic carbon in their soils. Despite the importance of this storage,uncertainties remain about the molecular characteristics of soil organic matter(SOM), a key factor governing the stability of soil organic carbon(SOC). In this study, the molecular fingerprints of SOM in a typical freshwater wetland in Northeast China were investigated using pyrolysis gas-chromatography/mass-spectrometry technology(Py-GC/MS). Results indicated that the SOC, total nitrogen(TN),and total sulfur contents of the cores varied between 16.88% and 45.83%, 0.93% and 2.82%, and 1.09% and 3.79%, respectively. The bulk δ^13C and δ^15N varied over a range of 9.85‰, between –26.85‰ and –17.00‰, and between –0.126‰ and 1.002‰, respectively. A total of 134 different pyrolytic products were identified, and they were grouped into alkyl(including n-alkanes(C:0) and n-alkenes(C:1),aliphatics(Al), aromatics(Ar), lignin(Lg), nitrogen-containing compounds(Nc), polycyclic aromatic hydrocarbons(PAHs), phenols(Phs), polysaccharides(Ps), and sulfur-containing compounds(Sc). On average, Phs moieties accounted for roughly 24.11% peak areas of the total pyrolysis products, followed by Lg(19.27%), alkyl(18.96%), other aliphatics(12.39%), Nc compounds(8.08%), Ps(6.49%), aromatics(6.32%), Sc(3.26%), and PAHs(1.12%). Soil organic matter from wetlands had more Phs and Lg and less Nc moieties in pyrolytic products than soil organic matters from forests, lake sediments, pastures, and farmland.δ^13 C distribution patterns implied more C3 plant-derived soil organic matter, but the vegetation was in succession to C4 plant from C3 plant. Significant negative correlations between Lg or Ps proportions and C3 plant proportions were observed. Multiple linear analyses implied that the Ar and Al components had negative effects on SOC. Alkyl and Ar could facilitate ratios between SOC and total nitrogen(C/N), while Al plays the opposite role. Al was positively related to the ratio of dissolved organic carbon(DOC) to SOC. In summary, SOM of wetlands might characterize by more Phs and lignin and less Nc moieties in pyrolytic products. The use of Pyrolysis gas-chromatography/mass-spectrometry(Py-GC/MS) technology provided detailed information on the molecular characteristics of SOM from a typical freshwater wetland.     

Determination of Acidolysis Hydrocarbons in Oil/Gas Geochemical Exploration Sample By Gas Chromatograph

正1 Introduction Although a mumerous of papers were reported for the chemcial or instrumental analysis of inorganic elements for the geocheical samples(Sun and Xie,2014;Sun et al.,2014;Rao et al.,2004).However,the analytical methods     

Measurements of Volatile Organic Compounds (VOC) During POPCORN 1994: Applying a New On-Line GC–MS-Technique

Atmospheric concentrations of ca. 250 C6–C15 hydrocarb on and C4–C12 oxygenated volatile organic compounds (VOC) including alkanes, benzene and alkyl benzenes, monoterpenes and aldehydes were measured in August 1994 during the POPCORN campaign (POPCORN = Photo-Oxidant formation by Plant emitted Compounds and OH Radicals in North-Eastern Germany). About 80 substances together contributed 90% of the atmospheric carbon in this range of molecular weight. During this field campaign VOC-emissions from several crop and tree species and the ambient concentrations of CO, C2–C7 non-methane hydrocarbons (NMHC), C1 and C2 aldehydes, nitrogen oxides, ozone and hydroxyl-radicals (OH) were also measured. These data were used to interpret the VOC measurements presented here. The on-line GC–MS used for the VOC measurements combines adsorptive sampling with thermal desorption and GC–MS analysis in an automated system. Internal standards were used to quantify the measurements. Ozone was destroyed prior to the sample preconcentration through the gas phase reaction with NO. Aromatic compounds like benzene, toluene and xylenes were the most abundant compound class among the measured substances, -pinene and 3-carene, most probably originating from pineforests ca. 1 km away from the measuring site, were the most abundant monoterpenes. The highest mixing ratios of most compounds were measured in nights with strong inversion situations. The toluene mixing ratios then reached 630 pptv; -pinene mixing ratios went up to 430 pptv. The median of all toluene and -pinene measurements during the campaign was 125 pptv or 22 pptv, respectively. These values are on the lower end of ambient measurements reported for continental sites. In most samples also n-pentanal, n-hexananl, n-nonanal and n-undecanal were present. Median mixing ratios were 9, 16, 14 and 8 pptv, respectively. Emission studies indicate that these highly reactive compounds are most probably emitted from maize. It is shown by a simple first order approach that the potential for ozone formation during the POPCORN campaign was roughly equal for anthropogenic and biogenic VOC. From measured concentrations of ozone, OH-radicals, methane, CO, C2–C15 nonmethane hydrocarbons (NMHC) and C5–C11 aldehydes a photochemical production of ozone in the order of 3.5 ppb/h can be estimated. Apart from formaldehyde and acetaldehyde, which are at least partly products of VOC oxidation, the substance group with the largest contribution to the VOC turnover are the monoterpenes. They contribute ca. 30%. However, the mechanism of terpene oxidation is very complex and presently only partly understood. Thus the actual contribution of monoterpenes to ozone formation is very uncertain. Other measured compound classes such as light alkenes, alkanes, aromatics, and C5–C11 aldehydes contribute each between 10% and 15% to ozone formation. The measuring site was not influenced directly from strong biogenic or anthropogenic sources, and the results obtained during the POPCORN campaign can be regarded as a typical picture of a remote rural central European environment.     

气相色谱法测定地下水多环芳烃准确度的保证措施

针对环境中常见且对人体危害极大的USEPA优先控制污染物16种多环芳烃(PAHs)在地下水中的监测方法进行了研究,主要从影响方法准确度的空白溶剂的选择、标准样品测定、基质加标回收率方面进行了实验研究,利用数理统计的t 检验进行显著性检验,并对研究区水中的多环芳烃进行了测定。结果表明,该方法宜选用市售纯净水做空白溶剂,基质加标回收率在71 5%~99 7%范围内,标准样品测定的相对误差在1 0%~17 2%;经系统误差检验确定本方法不存在系统误差,可以达到测定地下水中多环芳烃的目的。实际样品的测定结果说明煤矸石中的多环芳烃随降水淋滤以及酸性矿坑排水进入地下水和地表水的可能性是存在的,其迁移转化机理需进一步深入研究。     

海洋沉积物中吸附态轻烃的气相色谱分析

改进了可用于少量样品的酸解烃脱气装置，建立了毛细管柱气相色谱测定海洋沉积物中吸附态轻烃(酸解烃、顶空间轻烃)的方法，并用于大批量实际样品分析，结果良好。讨论了分析柱的优化以及定量分析等问题。方法的检测限(释放气)为0．048～0．78μL／L，精密度(RSD，n=10)为0．52％～0．98％。