Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.     

Occurrence and evolution of the Xiaotangshan hot spring in Beijing, China

Thermal groundwater occurs in bedrock aquifers consisting of the dolomite of the Wumishan Group of the Jixianin System and the Cambrian carbonate in the Xiaotangshan geothermal field near the northern margin of the North China Plain, China. The hot water in the geothermal field of basin-type discharges partly in the form of the Xiaotangshan hot spring under natural conditions. The hot water has TDS of less than 600 mg/L and is of Na·Ca-HCO₃ type. The geothermal water receives recharge from precipitation in the mountain area with elevation of about 500 m above sea level to the north of the spring. Thermal groundwater flows slowly south and southeast through a deep circulation with a residence time of 224 years estimated with the Ra–Rn method. The Xiaotangshan hot spring dried up in the middle of the 1980s owing to the increasing withdrawal of the hot water in the geothermal field in the past decades. The water level of the geothermal system still falls continually at an annual average rate of about 2 m, although water temperature changes very little, indicating that the recharge of such a geothermal system of basin-type is limited. Over-exploitation has a dramatic impact on the geothermal system, and reduction in exploitation and reinjection are required for the sustainable usage of the hot water.     

冀北万全寺银金矿床地质地球化学特征

万全寺银金矿床位于张宣幔枝构造东侧的侏罗纪断陷盆地中,成矿时限晚于133.33Ma～101.82 Ma.通过硫、铅、氢、氧、碳及稀有气体同位素研究认为,成矿物质应源自地球深部,在中生代冀西北幔枝构造演化过程中集中成矿.成矿热液以岩浆水为主并加入了部分天水.     

邹平王家庄铜矿床成矿地球化学及成因探讨

王家庄铜矿床的矿化脉石英中流体包裹体均一温度介于116 ~ 566 ℃之间,均值为 289 ℃;盐度介于7.2%～63.2% NaCleq,均值为21.1% NaCleq。流体的气相成分主要为H2O和CO2。在均一温度为240 ~ 440 ℃区间内,出现了富气相的两相水溶液包裹体、富液相的两相水溶液包裹体和含子晶的三相水溶液包裹体共存现象,以及加温后富气相包裹体均一到气相和同期富液相包裹体均一到液相的特征,表明成矿流体曾发生过沸腾作用;其中第一次发生于360 ~ 400 ℃,主要形成高温、高盐度含子晶的三相水溶液包裹体和高温、中盐度富液相的两相水溶液包裹体及高温、低盐度富气相的两相水溶液包裹体;第二次发生于240 ~ 320 ℃,主要形成高—中温、高盐度的含子晶的三相水溶液包裹体和高—中温、中盐度富液相的两相水溶液包裹体及高—中温、低盐度富气相的两相水溶液包裹体;之后主要形成富液相的两相水溶液包裹体,具有中低温和中盐度的特征。矿化脉石英中的δ18OH2O介于-1.14‰ ~ 1.79‰之间,均值为0.94‰;δD介于-63.70‰ ~ -56.50‰之间,均值为-59.8‰;说明王家庄铜矿床的成矿流体主要来源于岩浆,后期混入大气降水。矿石矿物的δ34S变化于-8.80‰ ~ -2.80‰之间,均值为-6.33‰。矿石矿物的n(206Pb)/n(204Pb)介于18.1684 ~ 18.3637之间,均值为18.2892;n(207Pb)/n(204Pb)介于155546 ~ 156342之间,均值为155777;n(208Pb)/n(204Pb)介于38.1286 ~ 38.4840之间,均值为38.2780。说明矿石具有贫重硫和富放射性成因铅的特征,硫、铅主要来源于深部,后期可能受到地壳物质或大气降水的混染。     

华南前寒武系基底变质杂岩和中-新生代地幔岩的稀有气体同位素组成及其大地构造意义

对华南前寒武系变质岩浆杂岩稀有气体He、Ne、Ar和Xe的系统研究表明:扬子克拉通基底为含高³He的下地壳"原始岩石层",(³He/⁴He)×10^-6比值为2.8～4.6;而华夏板块基底变质岩浆杂岩则是在缺乏³He、低(³He/⁴He)×10^-8比值(3.15～17.7)的构造环境下形成的大陆中-上地壳变质岩浆杂岩层,反映出两者基底性质迥然不同。华南中-新生代爆破岩筒He同位素组成相反,相对稳定的扬子克拉通(³He/⁴He)×10^-8比值仅0.18～4.22,而郯庐-四会-吴川断裂以东,中-新生代活动地块(太平洋构造域)(³He/⁴He)×10^-8比值高达3.7～20.5。He同位素表明郯庐-四会-吴川断裂带为切割深至地幔的边界深大断裂,是扬子克拉通与华夏板块间的边界且控制了燕山期火山-侵入岩浆向西扩展。Ar同位素组成表明华南大陆中-新生代地幔形成接近"均一"的地幔组份。¹³⁶Xe/¹³⁰Xe-¹²⁹Xe/¹³⁰Xe相关组份表明它们具有地幔柱岩石同位素组成特征。     

新甘交界红柳河地区二叠纪玄武岩年代学、地球化学及构造意义

新甘交界红柳河地区二叠系剖面中发育有块状和枕状玄武岩,激光ArAr定年确定的玄武岩形成时间在280～300Ma之间;玄武岩SiO_2含量为44.71%～49.27%,Mg~#为42.4～52.4,(~(87)Sr/~(86)Sr)_i为0.703834～0.706819,(~(143)Nd/~(144)Nd)_i为0.518861～0.5121220,ε_(Nd)(t)为-3.01～3.67。玄武岩微量元素、稀土元素和Sr-Nd同位素均显示出与OIB性质相似的特征。其弱富集的不相容元素和轻稀土元素,显示出源区富集的特点。而Zr/Nb(14.63)和Th/U(2.83)则指示岩浆中可能有少量循环原始地幔和亏损地幔物质的加入。综合对比北山南部柳园地区二叠纪玄武岩源区特征,提出红柳河地区早二叠世OIB型玄武岩主要来源于北山地区晚古生代裂谷带下伏已被不同程度改造的富集地幔。     

杭州泗岭铝质A型花岗岩的发现及其构造意义

初步研究表明,以往被认为是典型的S型花岗岩或改造-重熔型花岗岩的泗岭岩体应为铝质A型花岗岩。该岩体高硅、碱、钾而明显贫钙、镁;高(K2O Na2O)/CaO值(平均16.79)和AKI指数(平均0.92);FeO*/MgO比值大(平均13.95),高于M型、S型和I型花岗岩,而与世界A型花岗岩平均值(13.4)相近;岩石为弱碱性、准铝-弱过铝质,富含稀土元素、HFSE元素,高Rb、F和Nb,反映其具A型花岗岩的成分特征。泗岭岩体氧同位素δ18O为 8‰～ 9‰,反映岩浆主要起源于下地壳。该岩体侵位于拉张的构造环境,是晚白垩世早期一次重要的构造-岩浆热事件,同时也反映了区域性孝丰—三门湾大断裂与学川—湖州大断裂在晚白垩世早期处于拉伸阶段。     

北大别白垩纪镁铁－超镁铁岩的铂族元素地球化学研究

采用镍锍火试金法结合ICP-MS分析了12个北大别白垩纪镁铁-超镁铁岩样品的Ir,Ru,Rh,Pt和Pd的含量,结果显示铂族元素（PGE）的含量较低,原始地幔标准化后的PGE分布模式呈正斜率型,PPGE相对原始地幔略微亏损,而IPGE强烈亏损,Pd/Ir值远高于相应的地幔比值。这些镁铁-超镁铁岩中PGE的强烈分异是地幔低程度的部分熔融过程中,PPGE主要受硫化物控制,而Ir则存在于非硫化物相如尖晶石,可能还有合金之中造成的。同时,铂族元素的分布特征表明这些镁铁-超镁铁岩是岩浆结晶分异的产物。     

西秦岭熊山沟岩体地球化学及构造环境分析

在区域地质调查及综合研究的基础上,对位于西秦岭天水东南部地区的原百花岩体进行了详细的岩石学、岩石地球化学、岩体接触关系、同位素年龄研究,从中解体出熊山沟岩体,并初步了解了该岩体的岩浆活动规律。熊山沟岩体早期岩石类型为斜长花岗岩,岩石化学成分K2O含量较低,K2O∕Na2O比值为0.33～0.42;晚期岩石类型为二长花岗岩,岩石相对富集K2O,K2O∕Na2O比值为1.01～1.43,岩石属拉斑-钙碱性系列;微量元素富集Th、Hf、Nb、Zr等元素;稀土元素以富集轻稀土,无铕负异常或铕负异常不明显为主要特征;氧同位素值较低（δ^18O为＋3.32‰）,岩石具Ⅰ型花岗岩的特征,岩浆来源于下地壳物质,形成于大陆弧构造环境。     

四川木洛稀土矿床碳酸岩地球化学

木洛稀土矿床成因上与碳酸岩-碱性杂岩密切相关。碳酸岩主要由方解石组成,CaO/（CaO＋MgO＋FeO＋Fe2O3＋MnO）比值在95.7%～99.6%,为方解石碳酸岩。碳酸岩相对富集大离子亲石元素Ba、Sr、LREE,亏损高场强元素Nb、Ta、Ti、Zr、P,高Zr/Hf和La/Nb值,低Sm/Nd和Rb/Sr值,暗示岩石来自富集地幔EMI。地质、地球化学研究表明,木洛碳酸岩是在峨眉山地幔柱地幔遗存物经喜马拉雅造山运动再次活化的产物,但碳酸岩熔浆在上侵过程中受到地壳物质混染。碳酸岩-碱性岩熔浆带来大量稀土元素,并在喜马拉雅造山期造山运动派生的局部引张部位成矿。