Analytical model for site-specific isotope fractionation in 13C during sorption: determination by isotopic 13C NMR spectrometry with vanillin as model compound

The aim of this study was to conceive a reactive transport model capable of providing quantitative site-specific enrichment factors for fractionation in ¹³C isotopic content during sorption. As test compound the model treats vanillin, for which the ¹³C isotopic content at natural abundance at each of the 8 carbon positions can be measured by quantitative ¹³C nuclear magnetic resonance spectrometry. This technique determines the isotope ratios with a resolution better than ±1‰ (0.1%) at each carbon position. Site-specific isotope fractionations were recorded in chromatography column experiments with silica RP-18 as stationary phase. The one dimensional reactive transport model accounted for the sorption/desorption behavior of 8 individual ¹³C-isotopomers and one ¹²C-isotopomer of vanillin and reproduced satisfactorily the bulk (average over the whole compound) fractionation observed during elution. After model calibration, the enrichment factors were fitted for each carbon site where a significant fractionation was recorded. To show the interest of such a transport model for environmental studies, the model, extended to three dimensions, was exploited to simulate reactive transport in an aquifer. These results show that significant ¹³C isotope fractionation is expected for 4 out of 8 ¹³C-isotopomers in vanillin, and illustrate that bulk isotope ratios measured by conventional compound specific isotope analysis and mass spectrometry would hardly document significant isotope fractionations in vanillin. It is concluded that modeling of site-specific isotope ratios in molecules is a priori feasible and may help to quantify unknown processes in the environment.     

青海湖沙柳河流域不同时期地表水与地下水的相互作用

氢氧稳定同位素技术是研究地表水和地下水相互作用的有效手段。依据青海湖沙柳河流域2018年消融期、多雨期和冰冻期所收集的降水、河水和地下水样品中对氢氧同位素组成(δD、δ18O)的测定结果,识别和量化不同时期高山草原带和高山草甸带地表水和地下水间的补给关系和比例,其目的旨在明确高寒内陆河流域地表水和地下水δD和δ18O受降水影响的时空差异。结果表明:青海湖沙柳河流域地表水和地下水δD和δ18O值受降水响应存在时空差异性,δD和δ18O值在消融期受降水影响最强,冰冻期最弱;在高山草甸带δD和δ18O值受降水的影响强于高山草原带。消融期的高山草甸带、高山草原带和冰冻期的高山草原带地表水补给地下水的比例分别为80.65%、93.36%和89.44%;多雨期的高山草甸带、高山草原带和冰冻期的高山草甸带地下水补给地表水的比例分别为44.50%、74.85%和88.58%。研究结果可为该流域水资源优化配置和管理提供科学依据。     

漓江地表水体有机碳来源

科学辨识河流有机碳来源是碳循环研究的关键.本文选取典型岩溶流域漓江流域为研究对象,通过同位素示踪法、相关分析法、端元混合模型,利用碳稳定同位素、C/N对其2016年7~9月有机碳来源进行研究.结果表明:(1)DIC浓度空间分布特征为:岩溶区岩溶区与非岩溶区的混合区非岩溶区;干流区DIC浓度从上游到下游递增,主要受控于流域碳酸盐岩的空间分布比例.(2)DOC是构成漓江水体TOC的主体,TOC来源以内源有机碳为主,内源碳浓度空间分布特征为:岩溶区混合区非岩溶区,可能与岩溶区水生植物丰茂、碳酸酐酶活性较强有关,TOC中内源碳的浓度介于1.02~5.14 mg·L~(-1),平均为2.54 mg·L~(-1);TOC中内源碳的比例空间分布差异不大,平均为73.07%.(3)POC浓度、POC中内源碳的浓度及POC中内源碳的比例空间分布差异不大,POC来源以外源碳为主,POC中内源有机碳浓度介于0.01~0.16 mg·L~(-1),平均为0.05mg·L~(-1),水生生物量对漓江流域POC贡献平均为17.31%.(4)DOC浓度及内源DOC浓度空间分布均为:岩溶区混合区非岩溶区,DOC主要来源于水生生物的初级生产力,DOC中内源碳的浓度介于0.97~5.10 mg·L~(-1),平均为2.48 mg·L~(-1);DOC中内源碳的比例空间分布差异不大,平均为79.51%.研究水生光合生物对流域有机碳的影响,可以为岩溶碳汇稳定性科学问题的解答提供基础.     

A century-long trend of metal pollution in the Sheyang River,on the coast of Jiangsu (China), reconstructed from sedimentary record

In order to reveal the historical context of metal element accumulation under the economic boom during the last decades in eastern China, concentrations of nine metal elements, radionuclides (²¹⁰Pb), Pb isotope ratios (²⁰⁷Pb/²⁰⁶Pb) and sedimentary characteristics were investigated in two sediment cores collected from the Sheyang River. The sediments have recorded the heavy metal deposition and thus allow establishing a connection between the temporal evolution of the heavy metal pollution and historical changes in industrial and urban discharges. Enrichment factors (EFs) were calculated to estimate the level of contamination in these sediments. A significant anthropogenic enrichment of Cu, Ni, Pb, Cr and Zn was highlighted, which were identified from anthropogenic discharges from cities and industrial sources, according to a cluster analysis. According to the annual variation in GDP growth rate, industrial growth rate, ratio of ²⁰⁷Pb/²⁰⁶Pb and EFs, it was obvious that sedimentary accumulation of metals has a close relationship with anthropogenic activities. In the pre-industrial period, natural inputs prevailed with lower EF and constant ²⁰⁷Pb/²⁰⁶Pb ratios around 0.82. However, during 1980–1995, the rapid industrial development caused a gradual increase in EFs and ²⁰⁷Pb/²⁰⁶Pb (>0.83). Our results disinterred the evolution of anthropogenic metal inputs in the last century into the Sheyang River.     

Using biochemical and isotopic tracers to characterise organic matter sources and their incorporation into estuarine food webs (Rufiji delta,Tanzania)

Fatty acid biomarkers and stable isotope signatures were used to identify the sources of particulate and sedimentary organic matter and its input into the food web through the dominant consumer within the mangrove-dominated Rufiji estuary, Tanzania. Specific fatty acids were used to identify the preferred basal sources of dominant fauna (i.e. filter feeder bivalves, snails, crabs, shrimps, and three fish species), and their presence in the water and sediment samples in the estuary. Both fatty acid and stable isotope results revealed that food web in the Rufiji estuary depended on a variety of carbon sources (mangroves, allochthonous terrestrial inputs, macroalgae, and phytoplankton), contributing to a different degree into the diets of primary consumers and members of near-shore fish, but none of them were obligatory for the survival of these species. The δ¹⁵N values of major primary producers and consumers/predators revealed a trend for δ¹⁵N enrichment with increasing trophic level. The ratio of docosahexaenoic acid to eicosapentaenoic acid (DHA:EPA) decreased from pelagic to benthic feeding fish. This indicated that fish with different feeding modes derived their fatty acids from different primary sources of nutrition, and suggested that the DHA:EPA ratio may be a useful indicator of feeding mode.     

杭州市静稳天气指数构建及应用研究

采用杭州市近7年的气象与环保监测资料,综合考虑2 m相对湿度、10 m水平风速、日均海平面气压、24 h变压、24 h变温、低层逆温等气象因子,通过历史样本统计划分阈值范围再权重求和的方法,构建了静稳天气指数（SWI）.经过实况回算检验,分析所建指数与污染天气的对应关系,并应用到重污染天气成因分析、空气质量预报和污染减排评估等方面.结果表明：①SWI可以综合反映大气静稳程度,与PM_2.5浓度有较好对应关系,SWI越大越容易出现污染天气,SWI大值最易出现在冬季,其次为秋季和春季,夏季主要污染物往往是臭氧,不易发生中度以上的污染天气.②SWI可用于判断杭州秋冬季重度及以上污染天气的成因,平均而言SWI<6.7时不易出现重度及以上污染;若SWI<6.7时仍出现重污染天气,可判断主导风向上游的外来污染物输入是引起重污染的主要原因,根据前期SWI的相对大小可判断有无叠加前期本地污染物积累;若SWI持续大于6.7且出现重度及以上污染天气,可判断由大气静稳而产生的本地污染物堆积是主要成因.③依据预报数据计算的SWI对空气质量分级预报有较好的参考价值,在短期和中期预报时效内均有表现力.④将SWI应用到G20会议期间污染减排效果评估中发现,在气象条件静稳程度相当时,减排措施有效降低了污染程度.     

富营养化浅水湖泊稳态转换理论与生态恢复探讨

从清水稳态与浊水稳态转换的过程、稳态阈值、稳态恢复力等方面介绍了浅水湖泊的稳态转换理论,总结了浊水稳态与清水稳态恢复力的影响因素,以及清水稳态与浊水稳态相互转换的驱动力,分析了富营养化引起的植物群落演替和稳态转换的过程.根据稳态转换理论和太湖五里湖的生态恢复实践,提出以改善生境条件为稳态转换驱动力进行生态恢复,并阐述了降低营养盐浓度、提高水体透明度、清除某些鱼类、改善基底、调节水位、软围隔消浪等生境改善措施.      

安徽铜陵鸡冠石银(金)矿床地质地球化学特征

鸡冠石银 (金 )矿床是铜陵地区一个具中型规模的银 (金 )矿床 ,在整个长江中、下游地区都有其代表性。矿床分四个主要成矿阶段 :夕卡岩阶段、氧化物 -硫化物阶段、石英 -硫化物阶段和石英多金属硫化物-碳酸盐阶段。对矿床的微量元素分析结果表明 ,独立的银、金矿物和含Au、Ag低的硫化物、含Ag硫盐矿物 ,主要形成于热液成矿期中晚阶段 ;矿床的轻、重稀土元素总浓度比值与辉石二长闪长岩相近 ,反映出二者的同源特征 ;稳定同位素和流体包裹体成分分析结果 ,反映出该矿床以岩浆热液为主的成因标志 ;成矿热液以岩浆水为主 ,但在成矿晚期有大气降水和地层成分加入 ;成矿流体为NaCl-KCl -H2 O体系 ;矿床成因属夕卡岩 -中低温热液充填 -交代型矿床     

The emergence of stable isotopes in environmental and forensic geochemistry studies: a review

In the past decade, environmental forensics has emerged as a discipline directed toward determining parties liable for causing spills of contaminants into the environment. Such investigations, while geared toward determining the guilty parties in order to recover costs of the cleanup and remediation, require various questions to be addressed. These include determination of the nature of the product; Where did it come from?; Extent of weathering, if any; How long has it been there?; and Is it degrading naturally? Traditionally, these studies have been addressed through utilization of techniques such as gas chromatography (GC) and gas chromatography–mass spectrometry (GCMS). However, in recent years, stable isotopes, primarily determined through the use of combined gas chromatography–isotope ratio mass spectrometry (GCIRMS), have emerged as an equally important tool in environmental forensics. For relatively low molecular, volatile compounds such as MTBE, BTEX, or chlorinated solvents, the isotopes, primarily carbon and hydrogen, have been used extensively for evaluating the onset of natural attenuation. For larger molecules such as PCBs or PAHs, in which the effects of biodegradation on the isotope composition of these molecules is minimal, the isotopic fingerprints of the individual compounds can be used for correlation purposes. In this paper, a brief introduction to isotope geochemistry will be given, followed by a review of applications of stable isotopes to a variety of environmental problems. While the review may not necessarily be exhaustive, it will provide a comprehensive overview of areas where isotopes have been used and potential applications for the future. Most of the review is concerned with carbon and hydrogen isotopes, although a brief overview of the emerging area of chlorine isotopes will also be discussed.     

降水稳定同位素的iAWBM模拟及其与GNIP实测值的比较

利用iAWBM的模拟数据,分析了全球降水中平均δ~(18)O、δ~(18)O季节差、降水量效应和温度效应的空间分布以及全球大气水线(MWL),模拟结果与GNIP监测数据进行了比较.结果表明,iAWBM的模拟很好地再现了全球降水中稳定同位素的纬度效应、大陆效应和高度效应;模拟的δ~(18)O季节差的空间分布与实际分布基本对应,在北半球低纬度地区,δ~(18)O的季节差主要表现为负值,而在高纬度大陆地区主要表现为正值;模拟的δ~(18)O的降水量效应主要出现在中低纬度的海洋和季风区,温度效应主要出现在中高纬度的内陆地区,这与实测结果吻合;模拟的全球MWL为δ~2H=7.93δ~(18)O+10.19,该方程的斜率和截距均与实测结果相近.