稳定同位素在石油天然气地质中的应用与进展

分析总结了稳定同位素资料在判识天然气成因类型、确定干酪根母质来源、进行油 /气 /源对比、追索油气二次运移路线、探讨有机质的热演化规律、分析油气的次生变化以及油气混层开采中所起的重要作用 ,并介绍了稳定同位素应用于理论研究和生产实践的最新进展。     

Stable chlorine intramolecular kinetic isotope effects from the abiotic dehydrochlorination of DDT

INTENTION, GOAL, SCOPE, BACKGROUND: Identifying different sources and following reaction pathways of chlorinated organic contaminants in the environment can be challenging, especially when only their concentrations are available. Compound-specific stable chlorine measurements of some contaminants have recently been shown to provide additional information and an increased understanding of their biogeochemistry. These studies, however, have been generally limited to volatile molecules. OBJECTIVE: Here, the stable chlorine isotope ratios of the semi-volatile pesticide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) were investigated. Specifically, the intramolecular stable chlorine isotopic compositions of DDT and the kinetic isotope effect (KIE) for the abiotic dehydrochlorination of DDT to 2,2-bis(p-chlorophenyl)-1,1-dichloroethene (DDE) were determined. METHODS: Selective chemical oxidation of DDT to dichlorobenzophenone (DCBP) and analysis of each compound was used to calculate the stable chlorine isotope ratios of the alkyl and aromatic chlorines in DDT. To determine the KIE for dehydrochlorination, DDT was reacted in a basic solution to yield DDE at 52 degrees C, 60 degrees C, and 72 degrees C for 3, 5, and 5 days, respectively. RESULTS AND DISCUSSION: Significant intramolecular stable chlorine isotopic differences were observed in one sample of DDT where the alkyl and aromatic delta 37Cl values were -5.76 +/- 0.45 and -2.21 +/- 0.24%@1000, respectively. Dehydrochlorination of DDT to DDE in basic solutions at 52, 60, and 70 degrees C resulted in a substantial intramolecular KIE where the alkyl chlorines of DDE shifted by approximately 3%@1000 relative to the alkyl chlorines in DDT. However, no temperature dependence was observed. The KIE, calculated by an iterative program, was 1.009. CONCLUSIONS: Intramolecular differences in the stable chlorine isotope ratios were observed in DDT and this is the first such finding. Dehydrochlorination of DDT yields a measurable and distinct intramolecular stable chlorine KIE. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate the existence of significant intramolecular differences in chlorinated organic compounds. Many other chlorinated semi-volatile and volatile organic contaminants are synthesized from multiple sources of chlorine, and we recommend that similar studies be performed on many such molecules in order to attain a clear understanding of their intramolecular chlorine isotopic differences. The existence of a measurable KIE for the dehydrochlorination of DDT to DDE shows the potential strength of using isotopic measurements to investigate the biogeochemistry of these important compounds. For example, the isotopically depleted aqueous chloride produced by dehydrochlorination of DDT to DDE may be a useful tracer of these reactions in freshwater environments.     

石羊河流域降水稳定同位素变化的区域差异

为了了解干旱内陆河流域降水稳定同位素变化过程及其影响因素,基于石羊河流域荒漠区、绿洲区和山区8个站点2013年7月至2014年7月,497个降水样品氢氧稳定同位素数据及相应气象数据,研究了石羊河流域降水稳定同位素的时空变化、环境效应以及降水水汽来源.结果显示：石羊河流域局地大气水线斜率和截距表现出夏低冬高的变化趋势;降水稳定同位素表现出夏高冬低的变化趋势,从荒漠区、绿洲区到山区,稳定同位素值随海拔升高而降低,海拔效应为-0.22‰/100m,这是温度效应的另一种体现;流域降水稳定同位素表现出显著的温度效应,温度效应为0.43‰/℃,在天气尺度下受季风水汽和降水淋洗过程的影响表现出降水量效应;流域降水来源主要受西风水汽控制,夏季也会会受到季风水汽影响,冬季也受到极地气团影响.     

2017年最大降水对再生水受水河道径流组成的影响

再生水受水河道水文条件作为河流水生环境及生化反应重要控制因子,会受到丰水季降水汇入的影响.以潮白河典型受水河道——顺义段为例,通过丰水期前（2017-06-11）、降水中（2017-07-06）、降水后（2017-07-08、2017-07-09）河水中氢氧同位素特征和氯离子浓度的变化,识别地表径流组成对2017年最大日降水量（重现期3.3a）的响应,揭示河流汇水过程径流组成的时空差异及原因.结果表明,在降水初期,降水中氢氧同位素主要受雨量效应影响,后期微小变幅主要受水汽来源差异影响,整个河段接受降水的同位素值相近.降水后3 d内坡地汇流尚未停止,在各断面占比各异;坡地汇流占比沿程增加（2%~85.6%）,再生水占比沿程减少（90%~67%）,再生水通过优先通道到达下游断面.降水后3 d内SY01~SY05断面水量由坡地汇流、再生水、原位水组成,有明显的河网汇水过程,SY06~SY07断面水量由坡地汇流及原位水组成.     

N2O产生机制的同位素方法研究进展

N₂O是一种重要的温室气体,是由多种微生物的硝化与反硝化作用产生,但是它产生的生物地球化学机制还不十分清楚。本文结合N₂O产生的微生物过程,阐述了国内外利用同位素标记法、N₂O的δ¹⁵N和δ¹⁸O双同位素法、N₂O的δ¹⁵N^α（¹⁴N¹⁵N¹⁶O）和δ¹⁵N^β（¹⁵N¹⁴N¹⁶O）、SP值同位素异构体法以及多种同位素法相结合研究N₂O的产生机制及微生物过程,比较了这些方法的优缺点,尤其重点阐述了近些年来兴起的N₂O同位素异构体计算各过程贡献比例及其判别源与汇的理论及其应用。¹⁵N同位素富集因子法和SP值法也分别应用于产生N₂O的微生物群落结构、数量和活性变化的研究,以从根本上达到控制N₂O排放量的目的。同时指出同位素方法研究N₂O产生机制的困难和不足。     

CHARACTERIZING GROUND WATER FLOW IN THE MUNICIPAL WELL FIELDS OF CEDAR RAPIDS,IOWA, WITH SELECTED ENVIRONMENTAL TRACERS1

ABSTRACT: Cedar Rapids obtains its municipal water supply from a shallow alluvial aquifer along the Cedar River in east-central Iowa. Water samples were collected and analyzed for selected isotopes and chlorofluorocarbons to characterize the ground-water flow system near the municipal well fields. Analyses of deuterium and oxygen-18 indicate that water in the alluvial aquifer and in the underlying carbonate bedrock aquifer was recharged from precipitation during modern climatic conditions. Analyses of tritium indicate modern, post-1952, water in the alluvial aquifer and older, pre-1952, water in the bedrock aquifer. Mixing of the modern and older waters occurs in areas where (1) the confining layer between the two aquifers is discontinuous, (2) the bedrock aquifer is fractured, or (3) pumping of supply wells induces the flow of water between aquifers. Analyses of chlorofluorocarbons were used to determine the date of recharge of water samples. Water in the bedrock aquifer likely was recharged prior to the 1950s. Water in the alluvial aquifer likely was recharged from the 1960s to 1990s. Biodegradation or sorption probably affected some of the ground water analyzed for chlorofluorocarbons. These processes reduce the concentrations of CFCs, which results in older than actual calculated dates of recharge.     

Evolutionarily stable strategies of age-dependent sexual advertisement

In various models of sexual selection mediated by the viability indicator (“good genes”) mechanism, a sexually selected trait will truly reflect male quality if its expression is costly for the male. However, in long-lived species, the expression of a trait often increases with age while the genotype of the male remains unchanged. This fact may obscure the indicator mechanism. Hitherto, game theory models of honesty in sexual advertisement have not taken life-history effects into account, whereas life-history models of reproductive effort have only seldom considered the dependence of mating success on the actions of other individuals. Here, the two approaches are combined, and I examine whether honesty is maintained if males can divide their advertisement effort over their lifetime. The model shows that an increase in the expression of the sexually selected trait over several years is an evolutionarily stable strategy (ESS) under a wide range of situations, so that a correlated preference for old age can emerge through a viability indicator mechanism. Honesty in the strict sense is not preserved: an optimally behaving low-quality male will in some cases advertise more than a high-quality male of equal age, to the extent that the strongest advertisement found in the population can be associated with a low-quality male. Due to life-history trade-offs, however, honesty in an average sense holds true over the lifetime of individuals: “cheater” age classes will remain small enough, that a female will obtain a higher expected mate quality if she trusts in the trait as an indicator of viability. Received: 25 June 1996 / Accepted after revision: 15 April 1997     

Isotopic and hydrogeochemical evaluation of groundwater at Qusier-Safaga area,eastern desert,Egypt

The groundwater resources of the El-Qusier-Safaga area on the Red Sea coastal zone have still to be utilised fully for social and economic development. In the present study, an inventory of recharge sources and quality of groundwater in different water bearing formations is made to assist in management of these vital resources. From a hydrochemical point of view, the origin of salinity in the five investigated aquifers are mainly dissolution of terrestrial minerals, leaching of soilsvia floods or ion exchanges processes. Stable isotope data clarify the interaction between different aquifers and indicate that the source of recharge is mainly meteoric water originating from palaeowater of the Pleistocene pluvial period, and from local precipitation as well as some marine water. Evaluation of the groundwater quality for domestic, irrigation and industrial purposes is discussed.     

地幔流体的稳定同位素地球化学综述

总结了 2 0年来国内外学者对地幔流体研究的成果和认识。主要包括地幔流体的性质和组成 ;地幔流体中同位素的含量、组成和赋存形式 ;同位素分馏和地幔脱气等作用对地幔组分的影响等。在不同地区和不同构造环境条件的地幔流体中 ,各种组分含量和同位素组成变化可以很大 ,从一个侧面指示地幔组分的不均一性 ,反映了不同地幔物质的形成历程不同或来自不同的地幔源区。此外 ,还讨论了目前存在的几个疑点     

A carbon-13 method for evaluating degradation of starch-based polymers

A new method for evaluating biodegradability of starch-based and certain other polymer blends uses the pre- and postexposure stable carbon isotope composition of material coupled with weight loss data to determine which components have degraded. The naturally occurring stable isotope of carbon.¹³C, is enriched in corn starch (¹³C, approx. –11) compared to petroleum-derived synthetic polymers (¹³C, approx. –32). Results on starch-synthetic polymer blends indicate that the ¹³C signatures of these blends are near-linear mixtures of their component ¹³C. Values of a ¹³C for starch-synthetic polymer blends exposed to biologically active laboratory soil and artificial seawater conditions are depleted in¹³C compared to unexposed samples, suggesting loss of the starch component. Combined with weight loss data for the exposed samples, the ¹³C values are statistically consistent with models requiring loss of the soluble component glycerin, followed by loss of starch, then petrochemical polymer, or simultaneous loss of starch and petrochemical polymer. Replicate ¹³C analyses of starch-synthetic polymer blends increase the statistical power of this relatively inexpensive, accessible technique to discriminate between degrading components.