The source of sulfur in sulfide deposits in the Siberian Platform traps (from isotope data)

The source of sulfur in giant Norilsk-type sulfide deposits is discussed. A review of the state of the problem and a critical analysis of existing hypotheses are made. The distribution of δ³⁴S in sulfides of ore occurrences and small and large deposits and in normal sedimentary, metamorphogenic, and hypogene sulfates is considered. A large number of new δ³⁴S data for sulfides and sulfates in various deposits, volcanic and terrigenous rocks, coals, graphites, and metasomatites are presented. The main attention is focused on the objects of the Norilsk and Kureika ore districts. The δ³⁴S value varies from -14 to + 22.5‰ in sulfides of rocks and ores and from 15.3 to 33‰ in anhydrites. In sulfide-sulfate intergrowths and assemblages, δ³⁴S is within 4.2-14.6‰ in sulfides and within 15.3-21.3‰ in anhydrites. The most isotopically heavy sulfur was found in pyrrhotite veins in basalts (δ³⁴S = 21.6‰), in sulfate veins cutting dolomites (δ³⁴S = 33‰), and in subsidence caldera sulfates in basalts (δ³⁴S = 23.2-25.2‰). Sulfide ores of the Tsentral’naya Shilki intrusion have a heavy sulfur isotope composition (δ³⁴S = + 17.7‰ (n = 15)). Thermobarogeochemical studies of anhydrites have revealed inclusions of different types with homogenization temperatures ranging from 685 °C to 80 °C. Metamorphogenic and hypogene anhydrites are associated with a carbonaceous substance, and hypogene anhydrites have inclusions of chloride-containing salt melts. We assume that sulfur in the trap sulfide deposits was introduced with sulfates of sedimentary rocks (δ³⁴S = 22-24‰). No assimilation of sulfates by basaltic melt took place. The sedimentary anhydrites were “steamed” by hydrocarbons, which led to sulfate reduction and δ³⁴S fractionation. As a result, isotopically light sulfur accumulated in sulfides and hydrogen sulfide, isotopically heavy sulfur was removed by aqueous calcium sulfate solution, and “residual” metamorphogenic anhydrite acquired a lighter sulfur isotope composition as compared with the sedimentary one. The wide variations in δ³⁴S in sulfides and sulfates are due to changes in the physicochemical parameters of the ore-forming system (first of all, temperature and P_ch4) during the sulfate reduction. The regional hydrocarbon resources were sufficient for large-scale ore formation.     

The oldest (~ 1.9 Ga) metadolerites of the southern Siberian craton: age,petrogenesis, and tectonic setting

Geological, geochronological, and isotope-geochemical studies of the metadolerites of the Angaul complex, widespread in the Urik-Iya graben of the southern Siberian craton, were carried out. The metadolerites forming separate conformal bodies (sills) among the metasandstones of the Ingash Formation were studied in detail. U-Pb zircon (SHRIMP) dating of metadolerites yielded an age of 1913 ± 24 Ma, and U-Pb baddeleyite (ID-TIMS) dating of these rocks yielded an age of 1914.0 ± 1.7 Ma. Thus, the date of 1914 ± 2 Ma can be taken as the most precise age estimate for the studied rocks. The metadolerites of the Angaul complex correspond in chemical composition to the normal-alkaline tholeiitic basalts. Metadolerites are differentiated rocks with mg# of 36 to 58. They show fractionated REE patterns: (La/Yb)_n = 1.2-3.5. All metadolerites, independently of their mg# value, have low contents of Nb (1.6-10.2 ppm) and show well-pronounced negative Nb-Ta anomalies in multielement patterns (Nb/Nb* = 0.19-0.54). The metadolerites are characterized by positive ε_Nd(T) values ranging from 0.4 to 5.2, which correlate well with their SiO₂ content and mg# value. The isotope-geochemical parameters of the metadolerites of the Angaul complex indicate that fractional crystallization, along with the assimilation of the host rocks (AFC), might have been the main process during the formation of the most differentiated metadolerites. The geochemical characteristics of metadolerites with the maximum mg# values of 57-58 and ε_Nd(T) = 5.2 suggest that the parental mantle source of the metadolerites resulted from mixing of predominant depleted mantle material with the subcontinental-lithosphere material. Intrusion of the dolerites of the Angaul complex, as well as the deposition of the sedimentary strata of the Ingash Group, took place at the Paleoproterozoic stage of intracontinental extension caused by the collapse of the orogen resulted from the collision of the Biryusa block with the Tunguska superterrane in the southern Siberian craton.     

Isotope stratigraphy and U-Pb dating of detrital zircons from the Vendian-Cambrian deposits of the North Muya block

U-Pb dating of detrital zircons from the sandstones of the Mamakan Formation has been made. Geochemical and isotope parameters of the carbonate deposits of the Yanguda Formation in the Vendian-Cambrian cover of the North Muya continental block have been estimated. It has been established that only the Neoproterozoic (630-915 Ma) rocks of the North Muya block were the provenances of terrigenous material. In the least altered carbonate rocks of the Yanguda Formation, the ⁸⁷Sr/⁸⁶Sr ratio is within 0.70814-0.70879 and δ¹³C varies from -0.4 to + 1.9‰. Comparison of the evaluated isotope parameters with those of carbonate rocks of typical Vendian-Cambrian sections shows that the carbonate deposits of the Yanguda Formation accumulated in the Early Cambrian, about 520 Ma. Sedimentation of the Mamakan and Yanguda Formations took place in the local sedimentary basin in the Vendian-Early Cambrian, in the absence of tectonic activity within the North Muya block. Detrital material that formed during the destruction of the rocks of the Siberian Platform basement and cover was not supplied into the basin.     

Episodic crustal growth in the Tanzania Craton: evidence from Nd isotope compositions

The analysis of available Nd isotope data from the Tanzania Craton places important constraints on the crust-mantle separation ages, and events marking juvenile crustal addition and crustal recycling. Nd model ages date the oldest crust extraction to 3.16 Ga in the Tanzania Craton, although a rock record of such antiquity is yet to be found there. The most significant period of juvenile crustal addition as well as crustal recycling is 2.7–2.6 Ga. The Nd isotopes of mafic samples show that chemical heterogeneity existed in the mantle beneath the Tanzania Craton, with some samples originating from significantly depleted mantle, and most samples originating from the mixture of primitive mantle and depleted mantle. The Nd isotope section reveals significant differences in Nd isotopes between the north craton and central craton; compared to the north craton, the central craton yields a Nd model age that is approximately 100 Ma older, and its ε_Nd(t) values are more negative, indicating that the two parts of the craton have different mantle source regions. Different types of granitoids are distributed in the Tanzania Craton, such as high-K and low-Al granite, calc-alkaline granite, peraluminous granite and transitional types of tonalite-trondhjemite-granodiorites (TTGs). Most of the granitoids formed later than the mafic rocks in syn-collision and post-collision events.     

四川盆地东部垫江凹陷三叠系嘉陵江组岩盐氯同位素特征与成钾指标研究

垫江凹陷位于四川盆地东部,是四川盆地三叠纪时期重要的成盐凹陷之一,但当时古卤水是否达到钾盐沉积阶段,是否具备形成海相钾盐的良好条件,一直存在争议。本文通过对垫江凹陷长平3井、高探1井和ZK001井嘉陵江组岩盐样品进行化学成分分析,以及对长平3井典型岩盐样品进行氯同位素分析来判断古卤水沉积阶段和成钾条件。结果发现垫江凹陷三叠系嘉陵江组岩盐δ37 Cl值均为负值,均小于-0.32‰,最低达到-1.18‰,绝大部分岩盐样品溴氯系数大于0.31,有很大一部分样品溴氯系数超过0.45,进一步表明垫江凹陷在嘉陵江期古卤水浓缩已达到钾石盐析出阶段,与岩盐包裹体成分分析结果一致。综合气候-物源-构造因素,认为垫江凹陷三叠纪嘉陵江期气候条件炎热,物质来源丰富,存在次级凹陷,古构造条件优越,具备良好的成钾潜力。     

Meteoric diagenesis and dedolomite fabrics in precursor primary dolomicrite in a mixed carbonate–evaporite system

Dedolomitization is a common diagenetic process in shallow burial environments and is often associated with sulphates in mixed carbonate‐evaporite successions. In these settings, elevated Ca²⁺/Mg²⁺ ratios necessary for dedolomitization result from the dissolution of sulphate phases by the incursion of undersaturated groundwater. Reported dedolomite textures from other studies are varied, but the most prevalent is a rhombic texture interpreted to result from the partial to complete pseudomorphic replacement of secondary dolomite rhombs formed in the burial diagenetic realm. In this study of primary cryptocrystalline to finely crystalline dolomicrites in the Prairie Evaporite Formation of north‐eastern Alberta, dedolomitization has resulted in sutured to loosely packed mosaics of dedolomite that range from subhedral to distinctly euhedral (rhombic) crystal fabrics; however, no prior aggrading neomorphism producing dolomite rhombs is evident in the precursor dolomicrites. Non‐pseudomorphic dedolomitization of the dolomicrites results in textures that include rhombic dedolomite crystals with cloudy cores comprising remnant dolomicrite and clear rims. These textures are similar to those observed in the pseudomorphic dedolomitization of secondary dolomite rhombs. The Prairie Evaporite Formation of north‐eastern Alberta has experienced extensive karstification near the erosional margin of the sedimentary succession. Dedolomitization of dolomicrites occurs in marker beds within the Prairie Evaporite succession associated with evaporite karstification. Along with stratigraphic and petrographic considerations, stable isotope results support the interpretation of a shallow dedolomitization event influenced by meteoric waters derived from the basin margin. Negative δ ¹⁸O and low δ ¹³C values (averages of −13·6‰_VPDB and 0·5‰_VPDB, respectively) of the dedolomite, compared with those of the primary dolomicrite (averages of −6·0‰_VPDB and 1·2‰_VPDB, respectively), point to isotopically light diagenetic fluids. These results show that rhombic dedolomite textures can form through shallow, non‐pseudomorphic dedolomitization of dolomicrites by meteoric fluids in the presence of sulphates, with resulting textures that are similar to the pseudomorphic dedolomitization of secondary dolomite rhombs.     

Os水吸收液ICP-MS测量信号强度衰减原因研究

蒸馏法能从样品中有效分离出OsO_4,吸收液直接用于ICP-MS测定,是辉钼矿Re-Os定年的关键技术环节。但实验发现,长时间放置的吸收液中Os信号强度显著降低。根据OsO_4化学性质推测原因在于一是挥发使吸收液Os含量减少,二是还原使+8价Os变成低价态,气态比例降低,若雾化效率不变,进入质谱仪的Os减少,两者都会导致信号降低,但具体影响情况不明,需深入研究。本文利用辉钼矿标准物质制备不同放置时间、酸度和温度的吸收液,对比上述条件对ICP-MS信号强度的影响。实验时将残余吸收液与稀释剂、氧化剂封入Carius管加热蒸馏,测定Os含量。结果表明:吸收液放置时间越长,酸度越低,温度越高,信号降幅越大,幅度达到3.2%~68.6%。室温下放置相同时间,低酸度吸收液的Os保存率高于高酸度吸收液,但Os信号强度低于后者,证明了挥发和还原共同导致信号衰减,且还原是主导原因。本文提出,冷冻(-18℃)可抑制OsO_4挥发,提高酸度(约3.5 mol/L)可减弱OsO_4还原,两者结合抑制信号衰减,提高了蒸馏法的灵活性和适用性。     

滇西芦子园远程矽卡岩Pb-Zn-Fe(Cu)多金属矿床流体包裹体初探及矿床成因探讨

滇西镇康芦子园是"三江"成矿带保山地块内迄今发现的唯一超大型Pb-Zn-Fe(Cu)多金属矿床,是区内系列同类层控热液铅锌矿床的典型代表。矿体呈似层状、脉状及透镜状产于寒武系碳酸盐岩建造的矽卡岩和大理岩层间破碎带,矿石构造以条带状、浸染状和脉状-网脉状为主要特征;围岩蚀变复杂、分带明显,由下至上依次为石榴子石-透辉石-透闪石-阳起石化带→绿泥石-绿帘石-阳起石-蔷薇辉石化带→碳酸盐-大理岩化带。矿床成矿流体从早期到晚期经历了多个矿化阶段。本文选取了该矿床早矽卡岩阶段、晚矽卡岩阶段、石英硫化物阶段和石英碳酸盐阶段的多种脉石矿物及闪锌矿进行了系统的流体包裹体研究。结果显示,早矽卡岩阶段发育微溶CO_2富液相和纯液相水溶液包裹体,并含大量K~+、Na~+、Ca~(2+)、F~-和Cl~-和少量SO_4~(2-),气相成分主要为H_2O、CO_2及少量CH_4和N_2,包裹体均一温度为233.6~315.6℃,盐度为10.6%~17.6%NaCleqv;晚矽卡岩阶段发育含CO_2和子矿物三相包裹体,均一温度214.9~388.0℃,盐度5.9%~16.4%NaCleqv;石英硫化物阶段发育含CO_2的水溶液包裹体,气相成分为CH_4、H_2O和少量CO_2,均一温度150.0~285.0℃,盐度为2.5%~13.8%NaCleqv;石英碳酸盐阶段为单一成分的水溶液包裹体,均一温度为105.0~187.5℃,盐度为0.5%~12.3%NaCleqv。结合H-O同位素研究表明,成矿流体最初来源于具中高温、中高盐度、高K、Na,富CO_2、Cl、F等特征的深部岩浆热液,在石英硫化物阶段开始有大气降水混入,演化为中阶段中低温、低盐度、贫CO_2的热液流体,至成矿晚阶段转化为以大气降水占主导。该矿床成矿环境的改变、流体混合以及流体的沸腾作用可能是导致成矿物质富集沉淀的重要机制。综合矿床地质特征、成矿流体包裹体和HO同位素研究认为,该矿床为与陆陆碰撞造山和深部隐伏岩体有关的远程矽卡岩成矿系统。     

藏南喜马拉雅造山带造山型马扎拉Au-Sb矿床和沙拉岗Sb矿床流体包裹体He-Ar同位素组成:对成矿流体来源的制约

马扎拉Au-Sb矿床和沙拉岗Sb矿床是藏南金锑成矿带中典型的造山型矿床。马扎拉Au-Sb矿床中矿体以含金辉锑矿石英脉的形式产于下中侏罗统陆热组地层中,主要组成矿物有自然金、辉锑矿、石英和碳酸盐矿物;沙拉岗Sb矿床中矿体主要以辉锑矿石英脉的形式产于下白垩统多久组地层和辉长岩体中,主要组成矿物为辉锑矿、辰砂、锑华、石英和少量碳酸盐矿物。在两个矿床的矿脉石英和辉锑矿中均发现有三类原生和假次生包裹体:水溶液包裹体、CO2-水溶液包裹体和有机包裹体。流体包裹体显微测温结果显示:马扎拉Au-Sb矿床的成矿温度为160～280℃,沙拉岗Sb矿床的成矿温度为140～240℃。He-Ar同位素分析显示马扎拉Au-Sb矿辉锑矿石英脉矿石中辉锑矿和石英以及赋矿地层中沉积层状硫化物中黄铁矿的流体包裹体均具有低的3He/4He比值,分别为0. 01382～0. 05642Ra和0. 03353～0. 08744Ra,40Ar/36Ar比值具有比较大的变化范围,分别为346. 8～4770. 1和349. 4～2689. 1;沙拉岗Sb矿床中辉锑矿样品的3He/4He比值为0. 02385～0. 11488Ra,40Ar/36Ar比值变化小,为300. 6～537. 5。与藏南Au-Sb成矿带中造山型Au矿床成矿流体中含一定量的幔源挥发份相对比,马扎拉AuSb矿床和沙拉岗Sb矿床成矿流体中均无幔源流体的参与,马扎拉Au-Sb矿床成矿流体为壳源变质流体与改造型饱和大气水形成的混合流体;沙拉岗Sb矿床成矿流体以改造型饱和大气水为主,并有壳源变质流体的加入。     

南秦岭小茅岭复式岩体地球化学特征及其构造意义

南秦岭北缘小茅岭复式岩体主要由宋家屋场基性辉绿(辉长)岩,迷魂阵、磨沟峡和叶家湾中性-偏酸性闪长岩组成,形成于新元古代早期870~840 Ma。岩石地球化学研究显示,宋家屋场基性岩属亚碱性系列岩石,富集轻稀土元素及大离子亲石元素,Nb、Ta、Ti、P等具有弱的负异常,Zr、Hf等高场强元素的含量较高,Zr/Y、Ta/Yb比值较高,Zr/Nb比值较低,与岛弧玄武岩的地球化学特征相似,在构造环境判别图解中投于火山弧岩石区域,一些元素的富集特征可能来源于受俯冲块体流体交代的岩石圈地幔。迷魂阵、磨沟峡及叶家湾闪长岩体均属准铝质亚碱性系列岩石,具有岛弧火成岩的地球化学特征。Sr-Nd-Hf同位素地球化学分析显示,宋家屋场岩体主要来自亏损地幔源区,磨沟峡和叶家湾岩体主要为新生基性下地壳的部分熔融,而迷魂阵岩体主要为古老地壳物质的部分熔融。上述特征表明小茅岭复式岩体各组成部分可能形成于870~840 Ma俯冲相关的岛弧构造背景,俯冲块体脱水形成的流体交代上覆地幔楔,这种地幔部分熔融形成了宋家屋场角闪辉绿(辉长)岩,由于基性岩浆的加热,诱发新生基性下地壳及原古老地壳物质部分熔融,岩浆上升、侵位,形成磨沟峡、叶家湾及迷魂阵岩体。结合陡岭地区~850–780 Ma变质作用及岩浆事件相关报导,在南秦岭北缘小茅岭—陡岭隆起带上,新元古代早期存在一期构造-岩浆-变质事件,该事件的区域大地构造属性则有待进一步研究。