太湖大气气溶胶中硫稳定同位素组成分析

用 MAT-253同位素质谱仪对太湖大气气溶胶中的硫稳定同位素组成特征进行了分析.结果显示,太湖大气气溶胶中δ34S 数值变化范围为4.46‰~9.87‰,表明该地区大气气溶胶的主要硫源与当地燃煤排放直接相关.Δ33S 绝对值普遍大于0.1‰,说明太湖大气气溶胶中存在显著的硫稳定同位素非质量分馏效应;基于正Δ33S 和负Δ36S 的关联,揭示太湖气溶胶中硫稳定同位素的分馏异常主要与平流层 SO2发生的光化学反应有关,该科学问题迫切需要做进一步系统深入的研究.     

广州地区酸雨硫源的硫同位素示踪研究

为研究酸雨硫源，本文对广州地区大气降水、大气SO2和气溶酸、工业用煤和重油及其燃烧产物样品进行了硫同位素组成测定。对煤和重浊在燃饶过程中的硫同位素分馏效应进行了试验研究，发现重油在燃烧过程中有明显的类似于煤的硫同位素分馏效应，其燃烧产物SO2气体富集轻硫同位素，而固体颗粒物则富集重硫同位素。依据同位素质量平衡，定量计算了四种硫源(人为成因硫、天然生物硫、海雾硫和远距离传输硫），对广州地区酸雨的贡献。上述结果，对研究全球环境地球化学有重要意义，其硫同位素组成为识别和跟踪污染硫源的循环提供了“内标”。     

山东新泰太古代层状硫化物中的硫同位素非质量分馏效应

物理、化学和生物作用引起的热力学和巩俐学同位素分馏均为与质量有关的分馏。非质量同位素分馏效应应是由一些特殊的气相光化学反应引起的，它可以解释一些元素浓度，甚至单个同位素比值无法揭示的特殊的作用过程。笔者首次在山东新泰地区新太古代层状硫化物中观测到了明显的硫同位素非质量分馏效应。δ33S、δ34S呈线性排列，且与硫同位素质量分馏线平行，33S小于0。     

我国酸沉降地区硫源的硫同位素组成研究

我国同世界大部分地区的酸雨类型一致,均为典型的硫酸型酸雨,因此硫同位素组成是示踪酸雨来源的重要手段。在前人研究的基础上,对酸雨硫同位素组成研究的思路和实验方法进行综述,重点介绍燃煤过程中硫同位素的分馏效应和大气SO2、气溶胶、大气降水、苔藓和小麦等植物中的硫同位素组成等,对环境地球化学的研究具有重要意义。     

新疆吐-哈地区硝酸盐矿床的氧同位素非质量效应

随着分析测试技术的提高以及同位素分馏理论的进步,氧同位素非质量分馏的应用范围已经从太空拓展到地球,逐渐发展成为研究行星和地球早期演化、地球表面各圈层相互作用的重要途径和手段.硝酸盐和硫酸盐是地球上少数几个具有明显氧同位素非质量分馏效应的矿物.本文测定了新疆吐-哈地区硝酸盐矿床中硝酸盐和硫酸盐矿物的氧同位素组成,结果显示,硝酸盐的氧同位素存在明显的非质量分馏效应,△17O高达14‰,δ18O高达40‰.为该超大型硝酸盐矿床的大气沉积成因提供了可靠依据.     

稳定同位素地球化学及其在矿床研究中的应用

第四讲 硫同位素地球化学(续) (五)硫同位素分镏的动力学效应 前面讲的是硫同位素分馏的热力学效应,它叙述了在达到平衡条件下,各物相间硫同位素的分馏及物理化学环境(温度、氧逸度、酸碱度等等)对硫同位素分馏的影响,本节将讨论在运动过程中,同位素的物理化学性质差异所引起的同位素分馏效应——动力学效应。     

大气颗粒汞同位素的分析方法与应用

<正>研究表明,大气汞同位素不仅具有质量分馏(MDF,δ202Hg),还具有偶数(200Hg)和奇数(199 or 201Hg)汞的非质量分馏(MIF,Δ199Hg)。汞同位素可为大气颗粒汞及其载体颗粒提供源解析信息。然而,分离和浓缩颗粒中的微量汞并准确分析其同位素比值是一个技术挑战。本研究通过优化热解-吸收法,富集纯化石英纤维膜负载颗粒汞,建立了颗粒汞的高精度同位素分析方法,并利用该方法对北京市区PM2.5中的汞同位素进行了初步研究。     

稳定同位素记录与环境、生命演化中的重大事件

自从地球诞生以来经历了许多重大事件：早期生命的出现、大气氧化事件（Atmospheric oxygenation）、雪球地球及多次生物绝灭与复苏事件。稳定同位素记录在古环境和生命演化研究中具有重要意义,在记录环境变化和生命演化的重大事件中发挥着重大作用：碳同位素的分馏记录了最早生命的开始,硫同位素的非质量相关分馏（Independent mass fractionation of sulphur isotopes）记录了大气中氧含量的重大变化,而在显生宙的几次重大生物灭绝事件中,均有碳同位素的负向漂移。     

硫化物中硫同位素分馏理论计算研究进展

硫化物是重要的矿物类,通常是一个或多个金属元素与硫结合而形成硫化物.硫化物作为大多数金属的主要来源具有重大的经济利用价值,硫化物中硫同位素分馏的研究一直是同位素地球化学研究的热点.研究不同金属硫化物之间的硫同位素分馏效应,对于利用硫同位素对成矿作用过程和成矿物质来源开展地球化学示踪,具有非常重要的意义.本文结合笔者近期的工作概述了硫化物中硫同位素分馏的理论计算研究,认为虽然半经验半理论的增量方法在同位素分馏计算中存在一定的局限性,但在没有其他实用的理论计算方法时,改进的增量方法可以作为硫化物中硫同位素分馏计算的一种理论估算方法.     

汞同位素地球化学概述

汞同位素是一个新兴的地球化学示踪手段。过去十多年来,随着质谱技术的飞跃发展,汞同位素地球化学研究取得了引人注目的进展,主要体现在如下两个方面。(1)实验及理论地球化学研究表明,汞生物地球化学循环的一系列过程都能导致显著的汞同位素质量分馏。此外,汞还是自然界少数存在同位素非质量分馏的金属元素之一。汞同位素非质量分馏对识别某些特殊地球化学过程(如光还原作用、挥发作用等)具有重要指示意义。(2)自然样品的汞同位素测试表明,自然界汞同位素组成(δ202 Hg和Δ199 Hg)变化可达10‰。目前,汞同位素地球化学已被应用于汞污染源示踪、汞生物地球化学过程判别等领域,并有望在不久的将来在汞的大气化学、生物地球化学等领域得到更为广泛的应用。     

Archean Mass-independent Fractionation of Sulfur Isotope:New Evidence of Bedded Sulfide Deposits in the Yanlingguan-Shihezhuang area of Xintai, Shandong Province

Multiple sulfur isotope ratios （^34S/^33S/^32S） of Archean bedded sulfides deposits were measured in the Yanlingguan Formation of the Taishan Group in Xintai, Shandong Province, East of China; 633S = -0.7%o to 3.8‰,δ^34S = 0.1‰-8.8‰, △^33S = -2.3‰ to -0.7‰. The sulfur isotope compositions show obvious mass-independent fractionation （MIF） signatures. The presence of MIF of sulfur isotope in Archean sulfides indicates that the sulfur was from products of photochemical reactions of volcanic SO2 induced by solar UV radiation, implying that the ozone shield was not formed in atmosphere at that time, and the oxygen level was less than 10-5 PAL （the present atmosphere level）. The sulfate produced by photolysis of SO2 with negative △^33S precipitated near the volcanic activity center; and the product of element S with positive △^33S precipitated far away from the volcanic activity center. The lower △^33S values of sulfide （-2.30‰ to --0.25‰） show that Shihezhuang was near the volcanic center, and sulfur was mostly from sulfate produced by photolysis. The higher △^33S values （-0.5‰ to -‰） indicate that Yanlingguan was far away from the volcanic center and that some of sulfur were from sulfate, another from element S produced by photolysis. The data points of sulfur isotope from Yanlingguan are in a line parallel to MFL （mass dependent fractionation line） on the plot of δ^34S--δ^33S, showing that the volcanic sulfur species went through the atmospheric cycle into the ocean, and then mass dependent fractionation occurred during deposition of sulfide. The data points of sulfur isotope from Shihezhuang represent a mix of different sulfur source.     

Multiple Sulfur Isotope Determination by SIMS: Evaluation of Reference Sulfides for Δ33S with Observations and a Case Study on the Determination of Δ36S

High spatial resolution multiple sulfur isotope studies undertaken by multi‐collector secondary ion mass spectrometry (SIMS) commonly use well‐characterised sulfide reference materials that do not (or are assumed not to) exhibit mass‐independent fractionation in ³³S and ³⁶S, taking advantage of the three‐isotope plot to evaluate the extent of such fractionation in unknown targets. As a result, few studies to date have used a mass independently fractionated reference sulfide to demonstrate accuracy of measurement and/or data reduction procedures. This article evaluates two mass independently fractionated sulfides, a pyrite from the 3.7 Ga Isua greenstone belt and a pyrrhotite from a 2.7 Ga gold deposit in Minas Gerais, Brazil, which may be used to provide additional confidence in the obtained multiple sulfur isotope data. Additionally, the article presents a method for measuring quadruple sulfur isotopes by SIMS at a comparable spatial and volume resolution to that typically employed for triple sulfur isotopes. This method has been applied to the Isua pyrite as well as to a sample of 2.5 Ga pyrite from the Campbellrand, Transvaal, South Africa, previously investigated using SIMS for triple sulfur isotopes, illustrating its potential for quadruple sulfur investigations.     

New high-precision measurements of the isotopic composition of atmospheric argon

Earth’s atmosphere is used as a standard reference gas for mass spectrometric determinations of argon (Ar) isotopes used principally in geochronology. There are three published independent determinations of the Ar isotope composition of modern atmosphere that differ subtly. We have made new high-precision measurements of Ar isotope ratios of five different sources of air using a high-sensitivity multi-collector noble gas mass spectrometer in order to distinguish between them. The isotope ratios, corrected only for backgrounds, reside on a inverse square-root mass law fractionation line that passes through the air value proposed by Lee et al. [Lee J. Y., Marti K., Severinghaus J. P., Kawamura K., Yoo H. S., Lee J. B. and Kim J. S. (2006) A redetermination of the isotopic abundances of atmospheric Ar. Geochim. Cosmochim. Acta70, 4507-4512]. They are distinct from both the other proposed compositions and provide the first independent confirmation of the atmospheric Ar isotope composition. We suggest that the revised values should now be in routine employment.     

海洋环境Fe同位素地球化学研究进展

Fe是海洋“生物泵”中限制浮游生物生长和控制海洋初级生产力的主要因素之一,也可间接影响大气中CO2含量,反馈于全球的气候变化。近年来基于多接收电感耦合等离子体质谱仪(MC ICP MS)分析方法的改进及测试精度的提高,应用Fe同位素组成、变化及其分馏机制,为研究海水中Fe的主要来源以及示踪海洋环境中Fe的循环过程等,提供了一个有效地球化学指标,也对示踪地球不同演化阶段的海洋沉积环境变化具有指示意义。较为详细地介绍了海洋环境中不同储库的Fe同位素组成,洋中脊热液流体—玄武岩、海水—大洋玄武岩等水—岩反应影响Fe同位素分馏效应的主要因素及地球不同演化阶段古海洋沉积环境中的Fe同位素变化。认为海洋环境下Fe同位素可以产生较为明显的分馏作用,轻铁同位素具有更易活动、易迁移的特征,并进一步提出不同相态、不同矿物间Fe同位素分馏系数的确定等相关问题仍是今后Fe同位素研究的主要方向。     

Constraining atmospheric oxygen and seawater sulfate concentrations during Paleoproterozoic glaciation: In situ sulfur three-isotope microanalysis of pyrite from the Turee Creek Group, Western Australia

Previous efforts to constrain the timing of Paleoproterozoic atmospheric oxygenation have documented the disappearance of large, mass-independent sulfur isotope fractionation and an increase in mass-dependent sulfur isotope fractionation associated with multiple glaciations. At least one of these glacial events is preserved in diamictites of the ∼2.4 Ga Meteorite Bore Member of the Kungarra Formation, Turee Creek Group, Western Australia. Outcrop exposures of this unit show the transition from the Boolgeeda Iron Formation of the upper Hamersley Group into clastic, glaciomarine sedimentary rocks of the Turee Creek Group. Here we report in situ multiple sulfur isotope and elemental abundance measurements of sedimentary pyrite at high spatial resolution, as well as the occurrence of detrital pyrite in the Meteorite Bore Member. The 15.3‰ range of Δ³³S in one sample containing detrital pyrite (−3.6‰ to 11.7‰) is larger than previously reported worldwide, and there is evidence for mass-independent sulfur isotope fractionation in authigenic pyrite throughout the section (Δ³³S from −0.8‰ to 1.0‰). The 90‰ range in δ³⁴S observed (−45.5‰ to 46.4‰) strongly suggests microbial sulfate reduction under non-sulfate limiting conditions, indicating significant oxidative weathering of sulfides on the continents. Multiple generations of pyrite are preserved, typically represented by primary cores with low δ³⁴S (<−20‰) overgrown by euhedral rims with higher δ³⁴S (4-7‰) and enrichments in As, Ni, and Co. The preservation of extremely sharp sulfur isotope gradients (30‰/<4 μm) implies limited sulfur diffusion and provides time and temperature constraints on the metamorphic history of the Meteorite Bore Member. Together, these results suggest that the Meteorite Bore Member was deposited during the final stages of the “Great Oxidation Event,” when pO₂ first became sufficiently high to permit pervasive oxidative weathering of continental sulfides, yet remained low enough to permit the production and preservation of mass-independent sulfur isotope fractionation.     

沉积地层中的黄铁矿形态及同位素特征初探——以华南埃迪卡拉纪深水相地层为例

地质历史时期新元古代大气氧含量普遍较低。在硫酸盐还原细菌作用下,作为海洋重要的氧化性离子,陆源硫酸根离子有效促进了深层海水的氧化进程。在此过程中,硫元素在硫酸根和黄铁矿之间发生显著同位素分馏,其分馏程度可反推当时古海洋的氧化还原状态。沉积地层中的黄铁矿普遍具有多种形态,不同形态黄铁矿的形成环境多有不同。如草莓状黄铁矿多形成于底层缺氧水体或沉积物的浅表面,而大颗粒单晶黄铁矿或脉状黄铁矿则多沉积于成岩早期的沉积物孔隙或形成于成岩后期的热液改造。与草莓状黄铁矿不同,大颗粒单晶或脉状黄铁矿的硫同位素组成并不能反映沉积时期的古海洋氧化还原条件。判定沉积地层中不同形态的黄铁矿及形成过程,是获得有效反映海洋沉积环境硫同位素组成特征的基本前提。简要总结了地质历史时期沉积地层中的黄铁矿类型及矿物形成过程,并以华南埃迪卡拉纪蓝田组岩芯样品为例,识别出各个样品中的黄铁矿形态组成特征,对比分析了全岩黄铁矿与样品中大颗粒黄铁矿硫同位素组成差异。研究结果表明:不同岩性样品中黄铁矿的形态种类及含量均存在差异。页岩样品保存有更好形态的自形晶以及草莓状黄铁矿;碳酸盐岩样品中具有较多自形晶以及他形晶黄铁矿,并且其中的少量草莓状黄铁矿遭受后期成岩作用而发生不同程度的晶体蚀变。样品中大颗粒黄铁矿的硫同位素值（δ34S_L-pyr）通常显著高于全岩黄铁矿的硫同位素值（δ34S_T-pyr）,最大差值可达48.5‰。在利用黄铁矿的硫同位素组成来反推当时古海洋环境时,需要区分不同形态黄铁矿,仔细剔除大颗粒黄铁矿,降低成岩期黄铁矿对样品中硫同位素组成的影响。更细致的微区黄铁矿硫同位素分析工作将依赖于SIMS分析测试手段进行。     

GEOCARBSULF: A combined model for Phanerozoic atmospheric O2 and CO2

A model for the combined long-term cycles of carbon and sulfur has been constructed which combines all the factors modifying weathering and degassing of the GEOCARB III model [Berner R.A., Kothavala Z., 2001. GEOCARB III: a revised model of atmospheric CO₂ over Phanerozoic time. Am. J. Sci. 301, 182-204] for CO₂ with rapid recycling and oxygen dependent carbon and sulfur isotope fractionation of an isotope mass balance model for O₂ [Berner R.A., 2001. Modeling atmospheric O₂ over Phanerozoic time. Geochim. Cosmochim. Acta65, 685-694]. New isotopic data for both carbon and sulfur are used and new feedbacks are created by combining the models. Sensitivity analysis is done by determining (1) the effect on weathering rates of using rapid recycling (rapid recycling treats carbon and sulfur weathering in terms of young rapidly weathering rocks and older more slowly weathering rocks); (2) the effect on O₂ of using different initial starting conditions; (3) the effect on O₂ of using different data for carbon isotope fractionation during photosynthesis and alternative values of oceanic δ¹³C for the past 200 million years; (4) the effect on sulfur isotope fractionation and on O₂ of varying the size of O₂ feedback during sedimentary pyrite formation; (5) the effect on O₂ of varying the dependence of organic matter and pyrite weathering on tectonic uplift plus erosion, and the degree of exposure of coastal lands by sea level change; (6) the effect on CO₂ of adding the variability of volcanic rock weathering over time [Berner, R.A., 2006. Inclusion of the weathering of volcanic rocks in the GEOCARBSULF model. Am. J. Sci.306 (in press)]. Results show a similar trend of atmospheric CO₂ over the Phanerozoic to the results of GEOCARB III, but with some differences during the early Paleozoic and, for variable volcanic rock weathering, lower CO₂ values during the Mesozoic. Atmospheric oxygen shows a major broad late Paleozoic peak with a maximum value of about 30% O₂ in the Permian, a secondary less-broad peak centered near the Silurian/Devonian boundary, variation between 15% and 20% O₂ during the Cambrian and Ordovician, a very sharp drop from 30% to 15% O₂ at the Permo-Triassic boundary, and a more-or less continuous rise in O₂ from the late Triassic to the present.     

基于共生金属硫化物硫同位素分馏程度约束热液活动温度：以川中下寒武统龙王庙组为例

硫循环及硫同位素(δ³⁴S)分馏研究对地表圈层的成岩作用具有重要意义,其中多种金属硫化物中硫同位素的分馏程度可以约束成矿热流体温度,进而作为地温计证据约束热液活动。四川盆地龙王庙组储集层内的热液改造影响着该储集层的非均质性,本研究着重讨论目的层中与热液成因白云石所伴生的黄铁矿(FeS₂)-黄铜矿(CuFeS₂)成矿现象：基于详尽的岩石学证据,应用纳米二次离子探针(NanoSIMS)对金属硫化物内部硫同位素分布进行测定,并基于热力学驱动下的硫化物间平衡分馏程度计算其成矿温度,进而约束层段内热液活动过程。研究发现：(1)微区硫同位素分布显示黄铁矿(FeS₂)与黄铜矿(CuFeS₂)沉淀过程中不仅存在热力学分馏,还存在动力学分馏现象,其中动力学分馏程度可以达到40.1‰,应用NanoSIMS微区测定手段可以有效剔除动力学分馏数据影响,获取热力学平衡分馏数据;(2)黄铁矿(FeS₂)与黄铜矿(CuFeS₂)成矿过程或利用不同的硫源,其中黄铁矿...