岩浆去气作用碳硫同位素效应

根据开放体系条件下的瑞利分馏原理,并考虑岩浆中可能溶解的合碳和含硫组分,从理论上定量模式了岩浆去气作用对火成岩碳、硫同位素组成的影响。结果表明,岩浆CO₂去气作用能够导致岩石中碳酸盐显着亏损¹³C,其δ¹³C值能够从原始-5‰变化到-20‰(PDB);岩浆CH₄去气作用则导致岩石中碳酸盐相对富集¹³C,其δ¹³C值能够从原始-5‰变化到+4‰。岩浆SO₂去气作用可以导致岩石中硫化物显着亏损³⁴S,其δ³⁴S值能够从0‰变化到-8‰(CDT);岩浆H₂S去气作用则导致岩石中的硫化物相对富集4S,其δ³⁴S值能够从0‰变化到+6‰。因此,除源岩原始同位素不均一性和地壳物质混染能引起火成岩的碳、硫同位素组成发生较大变化外,岩浆去气作用也是重要原因之一。     

甘肃厂坝-李家沟超大型铅锌矿床成矿金属来源——来自闪锌矿原位S-Pb和Zn同位素证据

甘肃厂坝-李家沟铅锌矿床位于西秦岭多金属成矿带内的西成矿集区,为矿集区内重要的超大型铅锌矿床。矿体赋存在中泥盆统安家岔组的白云石化大理岩及石英片岩中,其成因认识一直存在争议,主要分歧集中在是同生还是后生。文章对不同成矿阶段的闪锌矿,采用多接收电感耦合等离子体质谱(MC-ICP-MS)测定Zn同位素组成、采用激光剥蚀-多接收电感耦合等离子体质谱(LA-MC-ICP-MS)原位微区分析技术测定S、Pb同位素组成,示踪成矿物质来源,并分析矿物沉淀机制,为深入理解矿床成因提供新的精细证据。研究结果显示,Ⅰ、Ⅱ、Ⅲ三个成矿阶段闪锌矿的δ⁶⁶Zn分别为0.08‰~0.29‰,平均0.20‰;0.19‰~0.37‰,平均0.30‰;0.36‰~0.37‰,平均0.37‰。其中,Ⅰ阶段的闪锌矿δ³⁴S_Ⅰ值为20.9‰~26.1‰,平均24.4‰;Ⅱ阶段的闪锌矿δ³⁴S_Ⅱ值为12.2‰~21.9‰,平均19.1‰;Ⅲ阶段的闪锌矿δ³⁴S_Ⅲ值为18.2‰~24.7‰,平均21.5‰。3个阶段的矿石矿物Pb同位素组成变化不大,²⁰⁶Pb/²⁰⁴Pb为17.922~18.013,²⁰⁷Pb/²⁰⁴Pb为15.567~15.647,²⁰⁸Pb/²⁰⁴Pb为37.990~38.266。δ⁶⁶Zn同位素值显示,成矿金属早期来源于围岩海相碳酸盐岩,由于混合了岩浆热液或者是瑞利分馏作用,在成矿作用中后期δ⁶⁶Zn同位素逐渐上升。δ³⁴S同位素值显示,早期硫源主要为地层中的硫酸盐,中后期的δ³⁴S同位素值降低,可能是成矿流体中岩浆热液中的S^2-成分逐渐增多导致,闪锌矿为硫酸盐通过TSR反应沉淀成矿。Pb同位素指示成矿物质来源于上地壳,并混入了部分古老的变质基底的成分。笔者研究发现,厂坝-李家沟铅锌矿的成矿机制为不同来源的流体混合,随着pH值、成矿流体的温度发生变化而沉淀成矿。     

金厂峪金矿床成矿流体地球化学性质对金沉淀的制约

本文对河北金厂峪金矿床蚀变围岩和石英脉组分进行的对比分析,得知蚀变围岩中Al₂O₃、P₂O₅、MnO₂含量变化较小,石英脉中SiO₂、FeO、CaO、MgO、Sr、Ba、Sc、Zn、Ga、Ta、Au、Ag、Y、Pb、REE分布模式等相对于蚀变岩有明显不同。矿石中硫化物δ³⁴S值接近0‰ ,矿石围岩胪δ³⁴S为-5.0‰ ~ +3.2‰,矿石铅的²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb明显高于岩石铅。矿石中铁白云石δ¹³C值变化于-2.3‰ ~ -8.4‰ ,与初生碳δ¹³C值(-5‰ ~ -8‰ )接近,石英包亵体δ¹³C值变化于-3.55‰ ~ -8.44‰ 。脉体内的石英与碳酸盐岩,以及金属矿物都是相同成矿流体的产物,成矿流体具有深源特征。大气水及形成裂隙引起的减压作用是深源流体性质改变和组分沉淀的主要因素。     

西秦岭新生代高钾质玄武岩流体组成及其地幔动力学意义

西秦岭新生代高钾质玄武岩是认识大陆碰撞俯冲体制下地幔流体组成及深部动力学的岩石探针。本文采用分步加热质谱法测定了西秦岭高钾质玄武岩中斑晶及基质的流体化学组成和碳同位素组成,结果表明流体组分在200~400℃、400~800℃和800~1200℃阶段性释出,以H₂O为主,其次为CO₂和SO₂,并含有相对较高的He含量。从橄榄石斑晶到斜长石斑晶和基质H₂O和CO₂逐步升高。橄榄石斑晶流体挥发份主要释气峰温度(900~1200℃)明显高于中国东部地幔捕虏体及其它地区超镁铁质岩体中的橄榄石,流体组份以SO₂和CO₂等氧化性组份为主,其CO₂的δ¹³C值(-26.21‰~-20.85‰,平均-23.32‰)和CH₄的δ¹³C值(-42.35‰~-38.17‰,平均-40.03‰)低于基质的δ¹³C_CO2值(-16.43‰~-11.67‰,平均-13.22‰)和δ¹³C_CH4值(-44.22‰~-34.03‰,平均-39.70‰)。基质中CO₂和CH₄碳同位素组成具有机质热裂解特征。原始岩浆的流体挥发份主要为SO₂、N₂和CO₂,可能起源于较深的混杂地幔源区、演化于高f_O2的环境。流体挥发份化学和同位素组成表明高钾质玄武岩浆挥发份中存在地幔和地壳来源组分,幔源岩浆上升演化过程中可能加入了大量的H₂O和CO₂等,可能存在碳酸岩岩浆的混合或岩浆穿透区域碳酸盐地层的混染;其中的再循环壳源组分可能为古特提斯洋闭合俯冲或其后华北克拉通与扬子克拉通碰撞相关的再循环壳源沉积物脱出的流体组分。     

湖南黄沙坪W-Mo-Bi-Pb-Zn多金属矿床硫铅同位素地球化学研究

湖南黄沙坪W-Mo-Bi-Pb-Zn多金属矿床规模大、矿种多、范围小、分带明显,是南岭有色金属成矿带的代表性矿床之一。成矿地质体为碱长花岗斑岩,与下石炭统灰岩接触带发生大规模矽卡岩化,形成大型钨、钼、铋、萤石以及铁的共生矿床。围绕矽卡岩向外,分布铜锌、铅锌、铅锌银的分带,对应的矿化组合分别为粗粒磁黄铁矿-闪锌矿-黄铜矿、中粗粒磁黄铁矿-闪锌矿-方铅矿、胶状黄铁矿-闪锌矿-方铅矿。围绕花岗斑岩,硫化物矿物的δ³⁴S值呈带状分布,其δ³⁴S总体变化为2.3‰~17.5‰,花岗斑岩中浸染状辉钼矿δ³⁴S为17.1‰,矽卡岩中硫化物δ³⁴S>15‰,矽卡岩附近及外侧的铅锌矿体10‰<δ³⁴S<15‰,外围的铅锌银矿体δ³⁴S<10‰。下石炭统中代表沉积特点的细粒浸染状黄铁矿δ³⁴S为-3.1‰~-22.6‰。铅同位素²⁰⁶Pb/²⁰⁴Pb为18.525~18.603,²⁰⁷Pb/²⁰⁴Pb为15.706~15.792,²⁰⁸Pb/²⁰⁴Pb为38.889~39.178。综合研究表明,黄沙坪矿床成矿物质硫和铅主要来自花岗斑岩。经硫同位素热力学平衡计算,引起δ³⁴S值围绕花岗斑岩体分带的主要原因是随温度下降以及物理化学条件变化导致的热力学分馏作用,其次是沉积岩围岩中低δ³⁴S值硫的加入。对南岭地区花岗岩、古生代地层等的δ³⁴S值对比研究发现,引起花岗斑岩岩浆高δ³⁴S值的主要原因是深部富含硫化物(δ³⁴S值高)地层对富含挥发份(Li-F)的碱长花岗岩岩浆的混染作用,其次是成矿作用过程中地层与岩浆的相互作用(包括同化混染)。围绕黄沙坪矿床,湘南地区矽卡岩型钨多金属矿存在一个较高的δ³⁴S值分布区。宝山矽卡岩型Cu-Mo-Pb-Zn矿床矿石硫化物δ³⁴S为-1‰~3.6‰,²⁰⁶Pb/²⁰⁴Pb为18.602~18.672,²⁰⁷Pb/²⁰⁴Pb为15.693~15.780,²⁰⁸Pb/²⁰⁴Pb为38.901~39.186。因此,宝山矿床与黄沙坪矿床的物质来源和成矿机制不同,宝山矿床硫、铅同位素组成集中,分布范围不同于黄沙坪,成矿物质来自岩浆岩。黄沙坪、宝山矿床代表了南岭地区燕山早期存在两类不同性质的岩浆活动与成矿组合。     

渔塘坝富硒硅质岩成因及沉积环境探讨：硅、氧、碳和硫同位素证据

鄂西渔塘坝含碳硅质岩段(P³₁m)为硒矿床的主要赋硒层位,其硅、氧同位素组成δ³⁰Si变化范围为0.5‰~1.8‰（平均1.25‰）;δ¹⁸O为22.7‰~27.1‰ （平均25.3‰）;硅质岩中黄铁矿 δ³⁴S的值变化范围为-27.7‰~-5.65‰,幅度大于20‰;硅质岩层位中方解石样品的δ¹³C值范围为4.19‰~0.52‰。综合研究表明,渔塘坝硅质岩在成因上主要表现为热水沉积特征,成岩温度为45℃,形成于半封闭的浅海至滨浅海（滞留的盆地）缺氧沉积环境。     

氧同位素在岩石成因研究的新进展

通过氧同位素分析可以对岩石的成因进行认识,使之成为岩石学研究的一个强有力工具。根据花岗岩的氧同位素高低可以判断其来源于变沉积岩还是变火成岩;对于一个复式岩体,如果不同期次岩石的氧同位素组成存在明显变化,可以有效地判断该岩浆在演化过程中存在不同来源物质的混染,因为岩浆从镁铁质成分向长英质成分的化学分异过程,不会引起明显的氧同位素分馏,分馏值一般不超过0.3‰。氧同位素分析手段从常规BrF₅法,到激光探针BrF₅法,再到离子探针分析法,对岩石矿物样品从全熔分析到微区分析的发展,显示了它们的发展历程和各自的优势及应用范围。本文介绍了氧同位素的不同分析方法,以花岗岩(流纹岩)和变质岩的研究为例阐述了氧同位素分析技术的发展。苏州花岗岩利用全岩和造岩矿物常规氧同位素分析方法得出其为低δ¹⁸O和正常δ¹⁸O岩浆成因的不同认识,近年通过锆石激光氧同位素分析技术,获得岩浆锆石的δ¹⁸O平均为4.92‰,证实其来源于壳源的低δ¹⁸O岩浆。类似地,利用全岩和造岩矿物常规氧同位素分析方法得出的观点难以解释美国黄石高原低δ¹⁸O流纹岩中矿物颗粒间和颗粒内部的氧同位素变化,该氧同位素变化只能通过离子探针矿物微区原位分析得出。在变质岩研究方面,通过激光探针氧同位素分析,人们普遍认为苏鲁造山带变质岩极负的δ¹⁸O值是在新元古代原岩形成时获得的,但是最新的离子探针锆石原位氧同位素分析表明苏鲁造山带变质岩极负的δ¹⁸O主要是在三叠纪超高压变质作用过程中获得的。今后单颗粒矿物尺度上的氧同位素组成分布规律将是氧同位素研究的发展方向。     

石碌钴-铜矿床流体包裹体和稳定同位素特征及成因

海南石碌钴-铜矿体赋存于石碌群第六层的下段,即介于铁矿体与石碌群第五层片岩之间的含钴-铜层位中,容矿岩石主要为白云岩、透辉石透闪石化白云岩。钴-铜矿床的形成经历了海底喷溢沉积期、石英-硫化物期(热液期)和表生期。海底喷溢沉积期石英包裹体均一温度变化于112~205℃,多集中在130~205℃;盐度w(NaCl_eq)为1.74%~6.59%;密度变化于0.88~0.95 g/cm³。温度范围与很多古代沉积喷流矿床及正在活动的海底热液成矿作用的温度相似,盐度低于曾报道的多数沉积喷流矿床的流体包裹体盐度值, 但与那些同为低密度成矿流体的喷流沉积矿床极为相近。海底喷溢沉积期形成的硬石膏δ³⁴S值为+21.4‰~+21.8‰,平均值为+21.6‰,强烈富集重硫,硬石膏δ³⁴S值代表着新元古代石碌群沉积时海水的δ³⁴S值。石英-硫化物期石英、白云石和方解石均一温度多集中在170~270℃;盐度w(NaCl_eq)为1%~7%;密度变化于0.88~0.95 g/cm³。成矿流体属于中温低盐度流体。石英-硫化物期成矿流体δD值为-63‰~-83‰,成矿流体δ¹⁸O_水值变化于1.3‰~6.8‰之间,指示成矿流体来源于岩浆,成矿后期有大气降水的加入。石英-硫化物期硫化物δ³⁴S值为+8.1‰~+21.2‰,硫源来源于石碌群中蒸发岩的溶解作用。石碌钴-铜矿床属中温热液充填交代矿床,与矿床周围花岗质岩浆活动有关。     

川滇黔二叠系铅锌成矿物质来源：C-H-O-S-Pb同位素制约——以云南太平子铅锌矿为例

【研究目的】川滇黔地区铅锌矿成因具有多样性,特别是与峨眉山玄武岩的关系存在较大的争议,本文从前人关注较少的二叠系碳酸盐岩中的铅锌矿入手,研究成矿物质来源。【研究方法】以云南寻甸县太平子铅锌矿为研究对象,运用S、Pb、C、H、O同位素实验数据及流体包裹体测温等方法,对成矿物质来源及成矿流体特征进行探讨。【研究结果】矿石铅同位素组成比较均一,分布集中,²⁰⁶Pb/²⁰⁴Pb、²⁰⁷Pb/²⁰⁴Pb、²⁰⁸Pb/²⁰⁴Pb的变化范围分别为18.543～18.584、15.646～15.694、38.799～38.958,属于正常普通铅,具壳源特征,主要来源于基底岩石,水岩反应可能使赋矿围岩贡献少量的成矿物质。矿石硫化物δ³⁴S变化范围为-13.6‰～-7.3‰,方铅矿的δ³⁴S高于闪锌矿,硫同位素分馏并未达到平衡,生物成因硫酸盐还原作用（BSR）是还原硫的主要来源。热液方解石δ¹³C_V-PDB范围为3.8‰～4.7‰,δ¹⁸O_V-SMOW范围为12.0‰～16.7‰,相较于滇东北其他重要的铅锌矿床,具有明显的低δD、高δ¹⁸O_fluid特点,成矿流体中的水主要来源于岩浆水和有机水的混合,具有中—高温、低盐度特征。【结论】太平子铅锌矿在成矿物质、流体、成矿温度等均与区域上其他典型铅锌矿有较明显差别,具有典型的岩浆-热液成因特点。     

青海玉树东莫扎抓铅锌矿床S、Pb、Sr-Nd同位素组成:对成矿物质来源的指示

青海玉树地区东莫扎抓铅锌矿床位于青藏高原金沙江缝合带和班公湖-怒江缝合带夹持的羌塘地体东北缘,是"三江"北段铜铅锌多金属成矿带铅锌矿床的典型代表。在野外地质观察基础上,本文对矿石矿物和重晶石进行了S同位素组成分析,对矿石矿物、脉石矿物和区域地层进行了Pb同位素组成分析,对脉石矿物进行了Sr-Nd同位素组成分析。结果表明,硫化物δ³⁴S值为-29‰~6‰,峰值为-8‰~-6‰,反映了总体富轻硫的特征,而重晶石δ³⁴S值为18.3‰~+22.8‰,来自于第三纪陆相盆地。宽的δ³⁴S变化可以解释为流体在盆地内活动期间与不同地层单元发生相互作用,从而继承了不同物质单元的S同位素特点,还原硫应主要来自于硫酸盐的细菌还原或者含硫有机质的热还原,反映硫来自沉积盆地。矿石矿物的²⁰⁶Pb/²⁰⁴Pb、²⁰⁷Pb/²⁰⁴Pb和²⁰⁸Pb/²⁰⁴Pb分别为18.387~18.703、15.391~15.768、38.372~38.809,而脉石矿物的²⁰⁶Pb/²⁰⁴Pb、²⁰⁷Pb/²⁰⁴Pb和²⁰⁸Pb/²⁰⁴Pb分别为18.423~18.612、15.491~15.701、38.497~38.612。矿石矿物和脉石矿物的Pb同位素组成介于区域上地壳Pb组成范围内,总体类似于MVT矿床,显示Pb等金属元素来源于上地壳岩石。脉石矿物的(⁸⁷Sr/⁸⁶Sr)_ⅰ、ε_Sr(t)、(¹⁴³Nd/¹⁴⁴Nd)_ⅰ和ε_Nd(t)分别为0.70855~0.70928、58.0~68.4、0.512273~0.512353、-6.2~-4.7。Sr-Nd同位素特征亦显示脉石矿物的物质来源于上地壳岩石。     

Carbon and oxygen isotopic compositions of Newania Dolomite Carbonatites, Rajasthan, India: implications for source of carbonatites

The Newania carbonatite complex of Rajasthan, India is one of the few dolomite carbonatites of the world, and oddly, does not contain alkaline silicate rocks thus providing a unique opportunity to study the origin and evolution of a primary carbonatite magma. In an attempt to characterize the mantle source, the source of carbon, and the magmatic and post-magmatic evolution of Newania carbonatites, we have carried out a detailed stable carbon and oxygen isotopic study of the complex. Our results reveal that, in spite of being located in a metamorphic terrain, these rocks remarkably have preserved their magmatic signatures in stable C and O isotopic compositions. The δ¹³C and δ¹⁸O variations in the complex are found to be results of fractional crystallization and low temperature post-magmatic alteration suggesting that like other carbonatites, dolomite carbonatites too fractionate isotopes of both elements in a similar fashion. The major difference is that the fractional crystallization of dolomite carbonatites fractionates oxygen isotopes to a larger extent. The modes of δ¹³C and δ¹⁸O variations in the complex, ?4.5?±?1‰ and 7?±?1‰, respectively, clearly indicate its mantle origin. Application of a multi-component Rayleigh isotopic fractionation model to the correlated δ¹³C versus δ¹⁸O variations in unaltered carbonatites suggests that these rocks have crystallized from a CO₂ + H₂O fluid rich magma, and that the primary magma comes from a mantle source that had isotopic compositions of δ¹³C ~ ?4.6‰ and δ¹⁸O ~ 6.3‰. Such a mantle source appears to be a common peridotite mantle (δ¹³C = ?5.0?±?1‰) whose carbon reservoir has insignificant contribution from recycled crustal carbon. Other Indian carbonatites, except for Amba Dongar and Sung Valley that are genetically linked to Reunion and Kerguelen plumes respectively, also appear to have been derived from similar mantle sources. Through this study we establish that dolomite carbonatites are generated from similar mantle source like other carbonatites, have comparable evolutionary history irrespective of their association with alkaline silicate rocks, and may remain resistant to metamorphism.     

Physicochemical model for the generation of the isotopic composition of the carbonate travertine produced by the Tokhana spring,mount Elbrus area,northern Caucasus

The isotopic composition of calcite from travertine deposits of the Tokhana-Verkhnii hot spring in the Elbrus area shows broad variations in δ¹³C and δ¹⁸O (from +3.8 to +16.3‰ and from +24.6 to +28.1‰, respectively). The δ¹³C and δ¹⁸O values increase toward the sole of the travertine dome. The isotopically heaviest carbonates (δ¹³C of up to +16.3‰) were found near the bottom of the dome and composed ancient travertine, which are now not washed by mineral water. The scatter of the δ¹³C values of the fresh sample is slightly narrower: from +3.8 to +10‰. Calculations indicate that all carbonates of the Tokhana dome were not in equilibrium with spontaneous carbon dioxide released by the spring (\(\delta ^{13} C_{CO_2 } \) = ?8‰). To explain the generation of isotopically heavy travertine, a physicochemical model was developed for precipitation of Ca carbonates during the gradual degassing of the mineral water. The character of variations in the calculated δ¹³C values (from +5.5 to +13‰) is in good agreement with the tendency in the variations of the δ¹³C in the carbonate samples. The calculated and measured pH values are also consistent. Our results demonstrate that the isotopic composition of large travertine masses can be heterogeneous, and this should be taken into account during paleoclimatic and paleohydrogeological reconstruction.     

Sulfur Isotope Fractionation in Magmatic Systems：Models of Rayleigh Distillation and Selective Flux

The effect of Rayleigh distillation by outgassing of SO2 and H2S on the isotopic composition of sulfur remaining in silicate melts is quantitatively modelled.A threshold mole fraction of sulfur in sulfide component of the melts is reckoned to be of critical importance in shifting the δ^34S of the melts mith respect to the original magmas.The partial equilibrium fractionation in a magmatic system is evaluated by assuming that a non-equilibrium flux of sulfur occurs between magmatic volatiles and the melts,while an equilibrium fractionation is approached between sulfate and sulfide within the melts.The results show that under high fo2 conditions,the sulfate/sulfide ratio in a melt entds to increase,and the δ^34S value of sulfur in a solidified rock might then be shifted in the positive direction.This may either be due to Rayleigh outgassing in case the mole fraction of sulfide is less than the threshold,or due to a unidirectional increase in δ^34S value of the sulfate with decreaing temperature,Conversely,at low fo2,the sulfate/sulfide ratio tends to decrease and the δ^34S value of total sulfur could be driven in the negative direction,either because of the Rayleigh outgassing in case the mole fraction of sulfide is greater than the threshold,or because of a unidirectional decrease inδ^34S value of the sulfide.To establish isotopic equilibrium between sulfate and sulfide,the HM,QFM or WM buffers in the magmatic system are suggested to provide the redox couple that could simultaneously reduce the sulfate and oxidize the sulfide.CaO present in the silicatte Melts is also called upon to participate in the chemical equilibrium between sulfate and sulfide,Consequently,the δ^34S value of an igneous rock could considerably deviate from that of its original magma due to the influence of oxygen fugacity and temperature at the time of magma solidification.     

Unique Origin of Skarn at the Ohori Base Metal Deposit,Yamagata Prefecture,NE Japan: C,O and S Isotopic Study

The Ohori ore deposit is one of the Cu–Pb–Zn deposits in the Green Tuff region, NE Japan, and consists of skarn‐type (Kaninomata) and vein‐type (Nakanomata) orebodies. The former has a unique origin because its original calcareous rocks were made by hydrothermal precipitation during Miocene submarine volcanism. Carbon and oxygen isotope ratios of skarn calcite and sulfur isotope ratios of sulfides were measured in and around the deposit. Carbon and oxygen isotope ratios of the skarn calcite are δ¹³C = ?15.51 to ?5.1‰, δ¹⁸O = +3.6 to +22.5‰. δ¹³C values are slightly lower than those of the Cretaceous skarn deposits in Japan. These isotope ratios of the Kaninomata skarn show that the original calcareous rocks resemble the present submarine hydrothermal carbonates at the CLAM Site, Okinawa Trough, than Cenozoic limestones, even though some isotopic shifts had occurred during later skarnization. δ³⁴S ratios of the sulfide minerals from the Kaninomata and Nakanomata orebodies are mostly in a narrow range of +4.0 to +7.0‰ and they resemble each other, suggesting the same sulfur origin for the both deposits. The magnetite‐series Tertiary Kaninomatasawa granite is distributed just beneath the skarn layer and has δ³⁴S ratios of +7.5 to 8.1‰. The heavy sulfur isotope ratio of the skarn sulfides may have been affected by the Kaninomatasawa granite.     

Sulfide mineralogy and sulfur isotope geochemistry of layered sills in the Deer Lake Complex,Minnesota

The Deer Lake Complex, located in north-central Minnesota, consists of a series of layered peridotite-pyroxenite-gabbro sills. Sulfide minerals occur as fine disseminations throughout pyroxenite and gabbro units, and occur more sporadically in peridotite and basal chilled margin units. Sulfide volume percentage rarely exceeds 0.5. A distinct zonation in sulfide mineralogy and sulfur isotopic composition characterizes the sills. Cobaltian pentlandite is the dominant sulfide mineral in peridotite (pd) units, with Ni-enrichment most likely linked to the serpentinization process. δ³⁴Spd values are variable, ranging from ?3.5 to +2.8‰. Sulfide assemblages in pyroxenite (px) and lower gabbro units consist of chalcopyrite, pyrrhotite, and minor pentlandite. δ³⁴S_px values range from ?1 to +1 ‰. Pyrite is the principal sulfide mineral in upper gabbro (μg) units. Its origin may be related to increased f0₂ conditions of the remaining melt and to reaction between a S-bearing volatile phase and mafic silicates. δ³⁴S_ug values range from 1 to 3.5 ‰. Sulfur isotopic values of chilled margin (2–9 ‰) and peridotite units, together with the erratic spatial distribution of sulfide minerals in these zones, suggests that the parent magma was not initially saturated with sulfur, and that local sulfide concentrations are the result of incorporation of sulfur derived from metasedimentary country rocks. Sulfide saturation was more uniformly reached during pyroxenite formation, with contained sulfur being of magmatic origin. Enrichment in ³⁴S of pyrite from upper gabbro may be explained by buildup of isotopically heavy sulfur following a Rayleigh process, coupled with possible involvement of a SO₂-rich fluid phase during hydrothermal alteration.     

Carbon isotope heterogeneity in metamorphic diamond from the Kokchetav UHP dolomite marble,northern Kazakhstan

We analysed isotopic compositions of metamorphic microdiamond secondary ion mass spectrometry. Typical microdiamonds in this dolomite marble show star-shaped morphologies (S-type) consisting of single-crystal cores and polycrystalline rims. Four S-type microdiamonds and two R-type microdiamonds (single crystals with rugged surfaces) were analysed using a 5 μm diameter ion beam. S-type microdiamonds have heterogeneous carbon isotopic compositions even in a single grain. Analysis of a typical S-type microdiamond (no. xx01-1-13) revealed clear difference in δ¹³C between core and rim. The rim shows lighter isotopic compositions ranging from??17.2‰ to??26.9‰, whereas the core is much heavier, with δ¹³C ranging from??9.3‰ to??13.0‰. The δ¹³C values of R-type microdiamonds fall into narrow ranges from??8.3‰ to??14.9‰ for no. xx01-1-10 and from??8.3‰ to??15.3‰ for no. xx01-1-16. These δ¹³C values are similar to those of the S-type microdiamond cores. The R-type probably formed at the same stage as the core of the S-type, whereas rim growth at a second stage did not occur or occurred very weakly in R-type microdiamonds. These carbon isotopic data support the two-stage growth of microdiamonds in the Kokchetav ultrahigh-pressure host rock. To explain the second stage growth of S-type microdiamonds, we postulate a simple fluid infiltration of light carbon from neighbouring gneisses into the dolomite marble.     

Ore Genesis of the Kalatongke Cu–Ni Sulfide Deposits, Western China: Constraints from Volatile Chemical and Carbon Isotopic Compositions

The Kalatongke Cu–Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt (CAOB). The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200–400°C, 400–900°C and 900–1200°C. The released volatiles from silicate mineral separates at 400–900°C and 900–1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O (av. ~92 mol%) with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values (from ?20.86‰ to ?12.85‰) of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantle-derived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200–400°C are dominated by H2O with minor CO2, N2+CO and SO2, with δ13CCO2 values (?25.66‰ to ?22.98‰) within the crustal ranges, and are considered to be related to secondary tectonic– hydrothermal activities.     

The effect of Rayleigh degassing of magma on sulphur isotope composition: a quantitative evaluation

The effect of Rayleigh distillation by outgassing of SO₂ and H₂O on the isotopic composition of sulphur remaining in silicate melts is quantitatively modelled. A threshold mole fraction of sulphur in the sulphide component of the melts is reckoned as being critically important in shifting the δ³⁴S value of degassed melts with respect to the original magmas. During the outgassing, melts above the threshold are depleted in ³⁴S, whereas melts below the threshold are enriched in ³⁴S. In particular, the outgassing of SO₂ above the sulphide threshold can produce large negative δ³⁴S values in the degassed melts, whereas the outgassing of H₂S below the threshold will strongly drive the δ³⁴S value of the melts in the positive direction. The correlation between δ³⁴S value and sulphur content of total sulphur in the solidified rocks is indicative of the Rayleigh-type degassing.     

Carbon isotopic composition of diamonds from the Archangelsk diamond province

The first data are reported on the carbon isotopic composition of diamond crystals from the Grib pipe kimberlite deposit of the Archangelsk diamond province (ADP). The δ¹³C value of the crystals ranges from ?2.79 to ?9.61‰. The isotopic composition of carbon was determined in three zoned crystals (δ¹³C of ?5.8 ?6.96 ‰, ?5.64/ ?5.85 ‰, and ?5.94/ ?5.69 ‰), two “diamond in diamond” samples (diamond inclusion with δ¹³C of ?4.05 and ?6.34 ‰ in host diamond crystals with δ¹³C of ?8.05 and ?7.54 ‰, respectively), and two samples of coated diamonds (cores with δ¹³C of ?6.98 and ?6.78‰ and coats with δ¹³C of ?7.51 and ?8.01 ‰, respectively). δ¹³C values were obtained for individual diamond crystals from bort-type aggregates (δ¹³C of ?4.24/ ?4.05 ‰, ?6.58/ ?7.48 ‰, and ?5.48/ ?6.08 ‰). Correlations were examined between the carbon isotopic composition of diamonds and their crystal morphology; the color; the concentration of nitrogen, hydrogen, and platelet defects; and mineral inclusions content. It was supposed that the observed δ¹³C variations in the crystals are most likely related to the fractionation of carbon isotopes rather than to the heterogeneity of carbon sources involved in diamond formation. The isotopic characteristics of diamonds from the Grib pipe were compared with those of previously investigated diamonds from the Lomonosov deposit. It was found that diamonds from these relatively closely spaced kimberlite fields are different; this also indicates the existence of spatially localized peculiarities of isotope fractionation in processes accompanying diamond formation.