Role of peat organic matter on isotopic composition of most abundant benthic organisms in intertidal habitats of SW Iceland

The transfer of peat organic matter (OM) from tidal pools of upper littoral to downstream rocky shores and its potential incorporation into marine biota were investigated using the stable isotope approach. Samplings were carried out in September 2004 in two SW Icelandic sites (Osar and Hvassahraun), where we selected (1) areas with shores where grass gently declined towards rocks and, on reaching the sea line, formed small tidal peat pools and (2) areas where grass and rocky shores were not contiguous, rather the grass lower limits were several hundreds of meters back from the shore. In both grass and no grass areas, in the intertidal zone, all benthic organisms and all potential OM sources were sampled. Dominant macroalgae were Ascophyllum nodosum ([Linnaeus] Le Jolis) and Fucus vesiculosus Linnaeus. In grass sites, organisms partially reflected the isotopic composition of peat OM, while in no grass sites, peat represented only a negligible amount of available OM, or its signal was totally absent from the environment. Intertidal organisms could rely on peat both directly by suspension feeding, grazing or scavenging and indirectly by predation (crabs) on low level consumers (barnacles).     

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.     

氮氧同位素示踪南昌秋冬季降水中NO3-来源及其贡献

为确定南昌市秋冬季降水中硝酸盐来源及贡献,于2016年9月1日至2017年2月28日对南昌地区雨水进行采集,分析了其化学组成及NO₃^-同位素组成并利用贝叶斯混合模型对NO₃^-四种潜在来源贡献进行计算.结果显示NO₃^-浓度范围为7.3~99.5μmol/L,平均值为36.1μmol/L;δ¹⁵N-NO₃^-变化范围为-6.0‰~+8.3‰,平均值为-0.8‰,两者均呈现冬季高秋季低的变化趋势.NO₃^-浓度季节性变化可能是受到降雨量等因素的影响,而δ¹⁵N-NO₃^-变化可能是冬季降水中机动车尾气排放偏高和秋季降水中煤燃烧来源偏高双重因素作用的结果.同位素及贝叶斯混合模型源解析结果表明,南昌市降水中NO₃^-主要来源于生物质燃烧（32.5%）、机动车尾气排放（30.8%）和煤燃烧（23.1%）,三者贡献超过86%;而机动车尾气排放和生物质燃烧释放均超过30%,这可能与近年来机动车快速增加和秋冬季野外生物质大量燃烧有关.煤燃烧虽然也是重要来源,但相对生物质燃烧和机动车尾气排放较小,这可能与近年我国减排措施有关.     

滇南蒙自地区降水稳定同位素特征及其水汽来源

大气降水中δD、δ~(18)O值具有规律性变化特征,与诸多气象要素及水汽来源之间存在密切联系.根据2009年1月至2011年12月对滇南蒙自地区大气降水的连续性采样,结合欧洲中期数值预报中心(ECMWF)以及美国国家环境预报中心/美国国家大气研究中心(NCEP/NCAR)的再分析资料,并利用HYSPLIT_4.8后向轨迹追踪模型,分析了天气尺度下蒙自地区大气降水中δD、δ~(18)O的变化特征,探究了降水稳定同位素与温度、降水量、风速及水汽来源之间的关系.结果表明,蒙自地区降水中δD、δ~(18)O值表现出明显的季节变化,即干季偏高,湿季偏低;降水中δ~(18)O与温度、降水量之间存在显著负相关,但与不同气压层(300、500、700、800 h Pa)风速之间呈现出显著正相关,表明风速也是影响降水中δ~(18)O变化的一个重要因素;随着降雨等级的增加,其大气水线的斜率与截距也增大,说明降水稳定同位素存在一定程度的云底二次蒸发效应;水汽输送轨迹显示,干季降水的水汽主要来自于西风带输送及局地再蒸发水汽,而湿季降水的水汽主要来源于远源海洋水汽的输送,并且在受台风影响期间,降水中δD、δ~(18)O值更加偏负.     

联合PMF模型与稳定同位素的地下水污染溯源

基于传统水质监测与污染排放的污染源识别方法,存在监测频率与识别结果模糊等限制,难以实现污染源及迁移转化的准确量化.联合多元统计分析与稳定同位素技术,以成都平原典型混合用地区地下水污染为研究对象,提出利用正定矩阵因子分析（PMF）模型识别污染主控因子,减小环境因素对污染源判别的干扰,并基于水化学分析与土地利用构建贝叶斯稳定同位素混合模型,进一步量化不同污染源对地下水典型污染物硝酸盐氮（NO₃^-）的贡献率.结果表明,研究区地下水NO₃^-、NO₂^-、NH₄⁺、Mn、Fe、SO₄^2-和Cl^-均存在不同程度超标,且具有空间异质性.地下水中"三氮"主要以NO₃^-为主,NO₃^-浓度在菜地的地下水中普遍偏高（平均值为9.29 mg·L^-1）,其次是在养殖场（平均值为7.66 mg·L^-1）和耕地（平均值为7.09 mg·L^-1）,在工业区最低（平均值为2.20 mg·L^-1）.研究区地下水水质受原生地质作用、农业活动、水文地球化学演化、生活污染和工业污染的复合影响,且农业活动是研究区地下水NO₃^-增长的主要原因.研究区内农业区地下水NO₃^-的主要来源贡献为化肥（32%）和土壤氮（25%）;工业区地下水NO₃^-的主要来源贡献为污水排放（28%）和大气降雨（27%）.通过多元统计与稳定同位素技术的有机结合,有效识别了地下水污染来源及其贡献率,可为地下水污染源头防控提供科学依据.     

Historical alteration in the nitrogen concentration and N natural abundance of mosses in Germany: Indication for regionally varying changes in atmospheric nitrogen deposition within the last 140 years

Historical alterations of nitrogen deposition in the western part of Germany were investigated by comparing nitrogen concentrations and ¹⁵N natural abundance of historical and recent samples of the two pleurocarpous mosses Pleurozium schreberi and Scleropodium purum. Pooling of the data revealed only slight tissue N increases over the past 140 years which were significant nevertheless. At closer examination on the single site level historical increases of N concentrations were found particularly for some sites in regions where agricultural activities were considerably intensified during the second half of the 20th century. The comparison of δ¹⁵N values showed a strong depletion of ¹⁵N natural abundance in areas currently heavily influenced by livestock management. This indicates an increased impact of NH_y compounds. However, the almost unchanged δ¹⁵N values in some low mountain range areas with only moderate intensification of agriculture point to a more or less constant ratio of NH_y/NO_x input over time. Significant correlations of both tissue N concentrations and ¹⁵N natural abundance between the two species justify the assumption that they use the same nitrogen source, probably atmospheric deposition.     

Variations in stable hydrogen and oxygen isotopes in atmospheric water vapor in the marine boundary layer across a wide latitude range

The newly-developed cavity ring-down laser absorption spectroscopy analyzer with special calibration protocols has enabled the direct measurement of atmospheric vapor isotopes at high spatial and temporal resolution. This paper presents real-time hydrogen and oxygen stable isotope data for atmospheric water vapor above the sea surface, over a wide range of latitudes spanning from 38°N to 69°S. Our results showed relatively higher values of 8180 and 82H in the subtropical regions than those in the tropical and high latitude regions, and also a notable decreasing trend in the Antarctic coastal region. By combining the hydrogen and oxygen isotope data with meteoric water line and backward trajectory model analysis, we explored the kinetic fractionation caused by subsiding air masses and related saturated vapor pressure in the subtropics, and the evaporation-driven kinetic fractionation in the Antarctic region. Simultaneous observations of meteorological and marine variables were used to interpret the isotopic composition characteristics and influential factors, indicating that d-excess is negatively correlated with humidity across a wide range of latitudes and weather conditions worldwide. Coincident with previous studies, d-excess is also positively correlated with sea surface temperature and air temperature （Tair）, with greater sensitivity to Tair. Thus, atmospheric vapor isotopes measured with high accuracy and good spatial- temporal resolution could act as informative tracers for exploring the water cycle at different regional scales. Such monitoring efforts should be undertaken over a longer time period and in different regions of the world.     

稳定同位素识别水体硝酸盐污染来源的研究进展

水体硝酸盐污染已经成为一个世界性的水质问题。为了确保供水安全和有效治理水环境中硝酸盐污染,准确识别水体中硝酸盐的污染来源显得尤为重要。近年来,硝酸盐稳定氮(δ15 N)和氧(δ18 O)同位素示踪技术被广泛用于识别水环境中硝酸盐的污染来源。然而,水环境中硝酸盐污染来源的复杂性和同位素分馏的影响,致使该项技术的应用存在一定的局限性。概括了硝酸盐中的δ15 N和δ18 O的典型值域范围,阐述了多种同位素技术联合识别水体中硝酸盐污染来源的方法以及应用模型定量解析硝酸盐污染源贡献率,最后,对该领域未来的发展方向进行了阐述。     

北京市交通干道空气中CO2和δ13C变化及来源分析

采用离轴积分腔输出光谱技术分析了夏季和冬季北京市四环路空气中CO2浓度和δ13C值变化特征。结果表明,四环路上车流量大,夏季和冬季均超过15万辆/d,06:00-10:00和15:00-19:00车行缓慢,平均车速小于25 km/h,车道占有率超过60%。机动车排放出大量的CO2,导致四环路的空气中CO2浓度呈双峰曲线日变化和δ13C值呈双波谷曲线日变化。同位素定量区分结果显示,四环路空气中CO2主要来源于机动车尾气排放,夏季和冬季均在52%以上。逐步回归分析表明,平均车速和车道占有率是影响四环路上CO2浓度和δ13C值的主要因子。06:00-10:00和15:00-19:00来源于汽车尾气的CO2比例比整个白天来源于汽车尾气的CO2比例高出6个百分点以上,表明车行缓慢显著增加了CO2的排放。     

南京市大气沉降中重金属特征及对土壤环境的影响

为明确城市大气重金属沉降对土壤环境的影响,在对南京市6个典型城市功能区连续4a大气(干、湿)沉降中重金属(Cu、Zn、Pb、Cr、Ni)含量、通量、时空变异等方面研究的基础上,结合不同功能区表土重金属含量与土壤剖面206Pb/207Pb特征,分析其在城市土壤的累积特征.研究显示,Cu、Zn和Pb在大气沉降中强烈富集,其中又以Cu和Pb为潜在生态危害的关键元素.大气沉降导致除在相对未受城市人为活动影响的风景区外各功能区表土重金属均有明显富集,这种富集受大气沉降重金属含量和沉降量的共同影响.土壤累积模式预测钢铁工业区表土受大气重金属沉降影响的长期累积增量最大,以Zn和Pb最明显.钢铁工业区土壤剖面Pb含量和同位素特征显示表层20cm土体受大气沉降影响明显,206Pb/207Pb二元模型与预测模式对定量大气Pb沉降的土壤影响结果较一致,表明土壤中某些重金属的累积与大气沉降密切相关.