气相色谱法测定地下水中有机氯农药和多氯联苯

建立了地下水中常见有机氯农药和多氯联苯的气相色谱分析方法。有机氯农药检出限均小于2.21ng/L,多氯联苯中PCB1检出限为5.20ng/L,其他目标组分检出限在1.30ng/L以下。两大类待测组分回收率均可以达到63.5%～110.2%,各组分精密度(RSD,n=5)在2.2%～17.3%。除异狄氏剂外,有机氯农药基体加标回收率为87.34%～133.76%。方法稳定性和重现性较好,样品前处理操作简便,适用于实验室分析或进一步改进。     

太平洋鳕鱼脑中硫苷脂的分离纯化和分析

以太平洋鳕鱼为原料,从鳕鱼脑中分离硫苷脂,确立了提取及纯化的条件,并对硫苷脂的纯度和分子种进行分析。首先,采用氯仿/甲醇(2∶1,v/v)提取总脂。然后,依次采用氯仿/甲醇/水(7∶3∶0.3,v/v/v)洗脱硅胶柱层析,含0.2mol/L乙酸铵的氯仿/甲醇/水(30∶60∶8,v/v/v)洗脱DEAE Sephadex-A25离子交换柱层析,40%甲醇脱盐和100%甲醇洗脱反相C8柱层析,获得硫苷脂纯品。最后,利用500YMC Diol液相色谱柱(3.0mm×250mm,5μm)分离,以正己烷/异丙醇(70∶30,v/v),异丙醇/水/甲酸/氨水(100∶13∶1∶0.14,v/v/v/v)为流动相梯度洗脱,采用负电喷雾电离(ESI)和母离子扫描模式,用液相色谱-串联质谱(LC-MS/MS)法分析了鳕鱼脑硫苷脂的纯度和分子种组成,并比较了其与哺乳动物脑中硫苷脂分子种组成的异同。结果表明,本实验制得的鳕鱼脑硫苷脂纯度为90.74%,与哺乳动物类似,鳕鱼脑硫苷脂的长链碱基以鞘氨醇为主,主要分子种为d18∶1-C24∶1,但脂肪酸的羟基化程度略低,且含少量独特的分子种,如d18∶1-22∶1和d18∶2-25∶2。     

Measurement of trace nitrate concentrations in seawater by ion chromatography with valve switching

An ion chromatographic method with a valve switching facility was developed to determine trace nitrate concentrations in seawater using two pumps, two different suppressors, and two columns. A carbohydrate membrane desalter was used to reduce the high concentrations of sodium salts in samples. In this method, trace nitrate was eluted from the concentrator column to the analytical columns, while the matrix flowed to waste. Neither chemical pre-treatment nor sample dilution was required. In the optimized separation conditions, the method showed good linearity （R〉0,99） in the 0.05 and 50 mg/L concentration range, and satisfactory repeatability （RSD〈5%, n=6）. The limit of detection for nitrate was 0.02 mg/L. Results showed that the valve switching system was suitable and practical for the determination of trace nitrate in seawater.     

Marine hydrocarbon source rocks of the Upper Permian Longtan Formation and their contribution to gas accumulation in the northeastern Sichuan Basin,southwest China

Identification of the main hydrocarbon source rocks of the large Puguang gas field (northeastern Sichuan Basin, southwest China) has been the subject of much discussion in recent years. A key aspect has been the lack of a comprehensive understanding of the development of hydrocarbon source rocks of the Upper Permian Longtan Formation, which had been thought to contain mainly coal seams and thick carbonate layers. In this paper, based on geological data from more than ten wells and outcrops and their related mineralogy and geochemistry, we investigated the depositional environment and main factors controlling organic matter enrichment in the Longtan Formation. We propose a model which combines information on the geological environment and biological changes over time. In the model, organic matter from prolific phytoplankton blooms was deposited in quiescent platform interior sags with rising sea-levels. During the Longtan period, the area from Bazhong to Dazhou was a platform interior sag with relatively deep water and a closed environment, which was controlled by multiple factors including syngenetic fault settling, isolation of submarine uplifts and rising sea-levels leading to water column stratification. Although the bottom water was anoxic, the phytoplankton were able to bloom in the well-lit upper euphotic zone thus giving rise to a set of sapropelic black shales and marlstones containing mostly algal organic matter with minor terrestrial contributions. As a consequence, these rocks have a high hydrocarbon generation potentials and can be classified as high-quality source rocks. The area from Bazhong to Dazhou is a center of hydrocarbon generation, being the main source of reservoired paleo-oils and presently discovered as pyrobitumen in the Puguang gas field. The identification of these source rocks is very important to guide future petroleum exploration in the northeastern Sichuan Basin.     

Gas hydrate identified in sand-rich inferred sedimentary section using downhole logging and seismic data in Shenhu area,South China Sea

Downhole wireline log (DWL) data was acquired from eight drill sites during China's first gas hydrate drilling expedition (GMGS-1) in 2007. Initial analyses of the acquired well log data suggested that there were no significant gas hydrate occurrences at Site SH4. However, the re-examination of the DWL data from Site SH4 indicated that there are two intervals of high resistivity, which could be indicative of gas hydrate. One interval of high resistivity at depth of 171–175 m below seafloor (mbsf) is associated with a high compressional- wave (P-wave) velocities and low gamma ray log values, which suggests the presence of gas hydrate in a potentially sand-rich (low clay content) sedimentary section. The second high resistivity interval at depth of 175–180 mbsf is associated with low P-wave velocities and low gamma values, which suggests the presence of free gas in a potentially sand-rich (low clay content) sedimentary section. Because the occurrence of free gas is much shallower than the expected from the regional depth of the bottom simulating reflector (BSR), the free gas could be from the dissociation of gas hydrate during drilling or there may be a local anomaly in the depth to the base of the gas hydrate stability zone. In order to determine whether the low P-wave velocity with high resistivity is caused by in-situ free gas or dissociated free gas from the gas hydrate, the surface seismic data were also used in this analysis. The log analysis incorporating the surface seismic data through the construction of synthetic seismograms using various models indicated the presence of free gas directly in contact with an overlying gas hydrate-bearing section. The occurrence of the anomalous base of gas hydrate stability at Site SH4 could be caused by a local heat flow conditions. This paper documents the first observation of gas hydrate in what is believed to be a sand-rich sediment in Shenhu area of the South China Sea.     

常顶瓦斯油吸附法脱除微量氯的实验研究

炼油厂将常压塔顶油和减一线油作为重整原料,但由于氯含量过高(30×10-6)无法利用,传统方法是将其中的有机氯转化为无机氯化氢后脱除,但其对加氢催化剂有毒害,采用常顶瓦斯油吸附法可直接脱除微量氯。     

Paleo-oil reservoir pyrolysis and gas release in the Yangtze Block imply an alternative mechanism for the Late Permian Crisis

The causes of the global mass extinction that occurred around the Permian–Triassic boundary have been widely studied through the geological record and in various locations. The results show that volcanic activity was a key factor in initiating the crisis during the Late Permian. Compared to other thermal events triggered by volcanic activity, pyrolysis of petroleum in Pre-Permian reservoirs has rarely been suggested as a significant source of the greenhouse gases that caused the mass extinction. In this study, geochemical analysis is carried out of a huge paleo-oil reservoir in the Yangtze Block (YB), South China. The detection of mineral inclusions and pyrobitumens is evidence of rapid pyrolysis of accumulated oil in the Ediacaran reservoir. New evidence from hydrothermal minerals and the presence of domain mesophase in the pyrobitumen suggest that the pyrolysis process occurred abruptly and that greenhouse gases were rapidly released through venting pipes. The dating of such a complex geological event in this old and deeply buried reservoir is inevitably difficult and potentially unreliable. However, cross-validation of the multiple evidence sources, including hydrothermal minerals and domain mesophase, indicates that the rapid oil pyrolysis must have been driven by a major thermal event. Reconstruction of burial and thermal histories suggests that the thermal event was most likely to have been triggered by the Emeishan Large Igneous Province (ELIP), which was in a period of significant volcanic activity during the Late Permian. Massive volumes of gases, including methane, carbon dioxide, and possibly hydrogen sulfide, were released, causing a significant increase in greenhouse gases that may have contributed to global warming and the resulting mass extinction during the Late Permian Crisis (LPC).     

常见稀有气体采样容器研究进展及意义

稀有气体是地学研究的重要手段之一,在研究成矿流体来源、壳幔相互作用过程中具有重要的研究意义,其组成及同位素比值是研究天体和地质体来源、成岩机理及各种地质和物理化学过程的关键,可作为地球化学示踪剂。如何有效地在大气圈、水圈和岩石圈进行稀有气体同位素样品的提取,是气体同位素研究急需解决的基础科学问题,所以气体采样容器和取样技术显得尤为重要。本文在文献调研的基础上,对常见的采样容器的优缺点进行对比,并总结了不同采样容器对稀有气体取样的优劣性。常见的气体采集容器包括不锈钢瓶、铜管、玻璃瓶、气体采样袋、注射器等,而稀有气体的采集容器常为不锈钢瓶和铜管等;通过对比表明不锈钢瓶具有耐高温、耐高压、抗强腐蚀、不易燃、不易爆等特点和优越性,在气体样品采集和运输过程中稳定性最好,实验效果也最好;铜管采样效果和密封性好,但操作较为复杂;玻璃采样容器效果次之;石英玻璃瓶虽然操作简便,但是运输保存不便;气体采样袋和注射器的采集和运输储存效果较差。因此建议稀有气体样品采集使用不锈钢瓶和铜管以及钠钙材质的玻璃瓶,不建议将石英材质玻璃容器以及注射器和气袋作为稀有气体的采样工具。该工作可为气体地球化学的研究提供新的参考。     

戊基磷酸二戊酯萃取色层分离-电感耦合等离子体质谱法测定铀产品中9种杂质元素

铀产品中杂质元素的含量测定在核法证学溯源分析或燃料元件厂质量检验中具有重要应用价值,保证测量的准确度主要在于控制流程空白、提高杂质元素的回收率。本文建立了戊基磷酸二戊酯(UTEVA)树脂快速分离铀与杂质元素、电感耦合等离子体质谱法(ICP-MS)测定杂质元素含量的系统流程。结果表明,UTEVA树脂对铀的吸附能力强,铀样品取样量为16.43 mg时,全流程对铀的去污因子大于3×105,9种杂质元素(锰钼镍铜铬铝钛钒镉)的回收率为95.1%~105.1%,国家标准物质GBW04205中杂质元素的分析结果与参考值在不确定度(k=2)范围内一致。本工作建立的分离流程对铀的去污效果好,特别适用于样品量少的情况下铀中杂质元素的分析,为核法证分析最终的归因溯源或燃料质量检验提供了技术支持。     

http://www.sciencedirect.com/science/article/pii/S1674987114000668

Microbial diversity in the hydrate-containing (sites SH3B and SH7B) and-free (sites SH1B, SH5B, SH5C) sediments collected from the Shenhu area of the South China Sea (SCS) was investigated using 16S rR...