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.     

内蒙古兴和县曹四夭超大型斑岩钼铅锌金成矿系统年代学及其地质意义

曹四夭斑岩钼矿床位于内蒙古兴和县,是华北克拉通北缘最大的钼矿床。该矿床中部发育斑岩型钼矿体,外围和上部产出热液脉型铅锌金矿体。文章选取1件与斑岩钼矿化共生的绢云母样品进行了40Ar-39Ar定年,获得40Ar-39Ar坪年龄为(144.4±1.2)Ma,相应的39Ar/36Ar-40Ar/39Ar等时线年龄为(146.4±2.2)Ma(MSWD=0.31),将等时线年龄认作绢云母的Ar封闭年龄,表明曹四夭斑岩钼矿化发生在约146 Ma前。选取14件脉型铅锌矿石中的闪锌矿、黄铁矿和磁黄铁矿样品开展了Rb-Sr定年,获得4件闪锌矿的Rb-Sr等时线年龄为(145.1±3.0)Ma(MSWD=0.63);5件黄铁矿的Rb-Sr等时线年龄为(145.2±1.3)Ma(MSWD=0.53);4件闪锌矿、5件黄铁矿和1件磁黄铁矿的Rb-Sr等时线年龄为(145.3±1.0)Ma(MSWD=0.43)。硫化物Rb-Sr定年结果表明曹四夭矿床脉型铅锌矿化形成于约145 Ma前。本次绢云母40Ar-39Ar和硫化物Rb-Sr定年结果表明,曹四夭矿床斑岩型钼矿化和脉型铅锌金矿化为同期产物,两者均形成于晚侏罗世末期,属于同一个斑岩成矿系统。曹四夭矿床硫化物的w(Rb)和w(Sr)分别为0.1867×10~(-6)~1.305×10~(-6)和0.3175×10~(-6)~6.935×10~(-6),Sr同位素初始比值(87Sr/86Sr)i介于0.709 919~0.711 951之间,平均值0.710 952,结合前人获得的辉钼矿Re含量,认为曹四夭矿床的成矿物质主要来源于地壳。     

金川铜镍硫化物矿床中铂族矿物的主要类型和产出特征:热液蚀变过程中铂族元素的富集机理

金川铜镍硫化物矿床是我国最主要的铂族元素(PGE)资源产地,其矿石受热液蚀变作用影响明显,并产出多种铂族矿物(PGM)。岩浆演化和热液蚀变过程中PGE的迁移富集机制和PGM的成因,一直是研究PGE地球化学行为非常关注的问题。本文对金川铜镍硫化物矿床中PGM的研究发现,其主要类型包括含PGE的硫砷化物(硫砷铱矿)和砷化物(砷铂矿),Pd的铋化物、碲化物和硒化物,以及少量其他铂族矿物。其中,硫砷铱矿可包裹于各种贱金属硫化物(镍黄铁矿、磁黄铁矿和黄铜矿)中,表明硫砷铱矿可能结晶于早期的含As硫化物熔体,随后被包裹于硫化物熔体冷凝分异产生的单硫化物固溶体(MSS)和中间硫化物固溶体(ISS)中。硫化物熔体中的As可能主要通过地壳混染作用加入幔源岩浆。大量铋钯矿(PdBi)呈微细乳滴状包裹于黄铜矿中,为晚期ISS冷凝形成黄铜矿过程中出溶的产物。少量铋钯矿(PdBi_2)呈不规则状充填于矿物裂隙,与次生磁铁矿脉紧密共生,并随矿石的蚀变程度增加,铋钯矿的化学成分由PdBi逐渐向PdBi_2转变,表明这部分铋钯矿为后期热液蚀变产物。铋碲钯矿和钯的硒化物则主要产出于镍黄铁矿裂隙且与次生磁铁矿紧密共生,指示明显的热液成因。钯的硒化物的出现表明,岩浆期后酸性、高盐度、高氧逸度的富Cl~-流体对金川铜镍硫化物矿床中Pd的迁移和富集起到了关键控制作用。     

塔里木盆地玉尓吐斯组高频层序沉积充填演化特征及控烃作用

结合9个野外剖面和17口井,对塔里木盆地玉尔吐斯组沉积演化及其对烃源岩的制约作用进行了系统研究和分析。在精细对比后发现,塔里木盆地下寒武统玉尔吐斯组可分为2个三级层序(SQ1、SQ2)、5个四级层序(sq1—sq5),其中三级层序SQ1可分为3个四级层序,SQ2可分为2个四级层序。SQ1发生在寒武纪初期,海进速度较慢,影响范围相对局限,而SQ2的海进则相对迅速,影响范围较大。四级层序sq1发生在第一次海侵初期,水体浅,主要沉积紫红色白云岩、灰黑色砂屑白云岩,起填平补齐的作用;sq2、sq4发生在海侵—海退的转换时期,是两套深水的沉积,岩性以黑色泥岩、硅质泥岩和硅质岩为主,局部发育泥岩与条带状白云岩互层;sq3、sq5是海退过程中的浅水沉积,主要发育灰色白云岩和藻白云岩,局部有泥质夹层。利用Mn、Fe、Ti、Rb、K、Sr、Ba、Cu、U、V、Mo等元素及其比值进行沉积环境分析表明,sq2时期,水体深度大、盐度低、气候温暖湿润,有利于生物发育,并且其硫化缺氧的环境极其有利于有机质的保存;sq4时期,水体深度较大,盐度相对较小,气候相对温暖湿润,较为适合生物生存,并且其硫化缺氧夹次氧化的环境,较为适合有机质保存。高频海平面变化与沉积环境演化影响着玉尔吐斯组的烃源岩分布与品质,sq2时沉积的烃源岩品质优于sq4,但是其分布范围小于sq4。     

长江中下游成矿带铜陵矿集区层控硫化物矿床成因研究进展

安徽铜陵矿集区是长江中下游成矿带内重要的多金属成矿区,该矿集区具有大规模的成矿作用和多种类型的复杂成矿系统演化,找矿潜力大,研究程度较高.区内广泛发育一系列层状硫化物矿床,其成因问题一直是中国矿床学界争议的焦点之一.文章从成矿年代学、成矿流体来源以及成矿物质来源等方面,对近半个世纪以来国内外学者对该矿集区内层控硫化物矿...     

海底热液硫化物矿体内部流体混合过程的数值模拟:以大西洋TAG热液活动区为例

大型海底热液硫化物矿体的形成机制是涉及多种控制因素的复杂地质过程,其中热液流体同海水的混合扮演着重要角色。大洋钻探计划(ODP)资料表明在大西洋TAG区热液硫化物矿体内部,热液流体同经过改造的海水之间发生着广泛的混合作用,这个过程在很大程度上控制着海底热液硫化物矿体的内部结构和化学组成。以TAG热液硫化物矿体为例,利用数值模拟方法模拟了热液流体与经过不同程度改造的海水的混合过程,试图探讨海水与热液流体混合在热液硫化物矿体形成中的作用。模拟计算结果表明:(1)来自矿体深部的热液流体与经围岩加热的下渗海水的混合是造成TAG热液活动区硬石膏大量沉淀的重要原因;(2)在热液流体与海水的混合过程中,混合流体的化学性质和矿物沉淀情况在330~310℃上下发生了较大变化,330~310℃是一个特殊的温度区域;(3)利用数值计算结果探讨了TAG热液活动区不同区块(TAG-1,TAG-2和TAG-5等)的流体混合作用和热液活动过程。     

Dimethylsulfide production in Sargasso Sea eddies

Lagrangian time series of dimethylsulfide (DMS) concentrations from a cyclonic and an anticyclonic eddy in the Sargasso Sea were used in conjunction with measured DMS loss rates and a model of vertical mixing to estimate gross DMS production in the upper 60 m during summer 2004. Loss terms included biological consumption, photolysis, and ventilation to the atmosphere. The time- and depth (0–60 m)-averaged gross DMS production was estimated to be 0.73±0.09 nM d⁻¹ in the cyclonic eddy and 0.90±0.15 nM d⁻¹ in the anticyclonic eddy, with respective DMS replacement times of 5±1 and 6±1 d. The higher estimated rate of gross production and lower measured loss rate constants in the anticyclonic eddy were equally responsible for this eddy's 50% higher DMS inventory (0–60 m). When normalized to chlorophyll and total dimethylsulfoniopropionate (DMSP), estimated gross production in the anticyclonic eddy was about twice that in the cyclonic eddy, consistent with the greater fraction of phytoplankton that were DMSP producers in the anticyclonic eddy. Higher rates of gross production were estimated below the mixed layer, contributing to the subsurface DMS maximum found in both eddies. In both eddies, gas exchange, microbial consumption, and photolysis were roughly equal DMS loss terms in the surface mixed layer (0.2–0.4 nM d⁻¹). Vertical mixing was a substantial source of DMS to the surface mixed layer in both eddies (0.2–0.3 nM d⁻¹) owing to the relatively high DMS concentrations below the mixed layer. Estimated net biological DMS production rates (gross production minus microbial consumption) in the mixed layer were substantially lower (by almost a factor of 3) than those estimated in a previous study of the Sargasso Sea, which may explain the relatively low mixed-layer DMS concentrations found here during July 2004 (3 nM) compared to previous summers (4–6 nM).     

塔里木克拉通东北缘二叠纪镁铁质岩浆氧化物与硫化物成矿条件对比

塔里木克拉通东北缘坡北、磁海等地二叠纪幔源岩浆活动形成了镍钴硫化物矿床和铁钴氧化物矿床,两者赋矿镁铁-超镁铁岩体的年龄相近(290～260 Ma),主、微量元素和Sr-Nd-Hf同位素组成相似,分配系数接近的微量元素比值分布于相同趋势线,揭示两者岩浆源区相同,可能为俯冲板片流体交代的亏损地幔或软流圈地幔。两类矿床镁铁-超镁铁质岩中Co与Ni含量正相关,Co主要富集在基性程度高的岩石中;块状硫化物与磁铁矿矿石中Co与Ni相关性差,Co和Ni具有不同的富集机制,Co热液富集作用明显。北山镁铁-超镁铁杂岩体是地幔柱相关软流圈上涌,诱发俯冲板片交代的亏损岩石圈地幔发生部分熔融,形成的高镁母岩浆演化过程中经历壳源混染、硫化物饱和富集镍钴形成铜镍钴硫化物矿床,富铁母岩浆氧逸度高、富水,岩浆分离结晶磁铁矿、叠加热液作用富集钴,形成铁钴氧化物矿床。     

超慢速扩张环境下超镁铁质岩系统的热液硫化物成矿机理以及启示

西南印度洋63.5°E热液区是在超慢速扩张洋脊发现的首个超镁铁质岩热液系统。对取自该区的热液硫化物样品进行了系统的矿物学和地球化学分析,矿物学分析结果表明:该热液区硫化物为富Fe型高温硫化物,且经历了较深程度的氧化蚀变,大量中间态的Fe氧化物充填在硫化物矿物间的孔隙及内部解理中;这些硫化物相以白铁矿为主,其次是等轴古巴矿和少量铜蓝,缺乏黄铁矿、闪锌矿。据推断,该区的热液成矿作用分为4个阶段:低温白铁矿阶段→高温等轴古巴矿阶段→自形白铁矿阶段→后期海底风化阶段（少量铜蓝以及大量的Fe的羟氧化物）。与之相对应,地球化学分析结果表明这些硫化物的Fe含量较高（31.57%~44.59%）,Cu含量次之（0.16%~7.24%）,而Zn含量普遍较低（0.01%~0.11%）;微量元素较为富集Co（328×10-6~2 400×10-6）和Mn（48.5×10-6~1 730×10-6）。该区硫化物中较高含量的Fe、Co与超镁铁质岩热液系统相似,明显高于镁铁质岩热液系统。独特的热液硫化物矿物学特征和元素组成可能与该区普遍出露的地幔岩、橄榄岩蛇纹石化作用以及拆离断层的广泛发育的环境有关。     

胡安·德富卡洋脊因代沃段热液黑烟囱体成矿物质来源:硫同位素的限制

选取胡安·德富卡洋脊(Juan de Fuca Ridge,JDFR)因代沃(Endeavour)段的17个热液黑烟囱体样品对其中的硫同位素进行分析测定,讨论了因代沃段热液活动区内黑烟囱体成矿的物质来源、将硫同位素数据与已发表的热液流体及硫化物数据耦合,并结合前人的成果得到如下认识:(1)因代沃段硫化物的硫同位素组成与其他无沉积物覆盖的洋脊硫化物硫同位素组成相似,然而其相比于南胡安·德富卡洋脊(South Juan de Fuca Ridge,SJFR)硫化物亏损重同位素;(2)结合前人研究成果,如果SJFR硫化物的硫全部来自基底玄武岩的淋洗与海水中的硫酸盐,那么因代沃段硫化物的硫可能有1%~3%来自沉积物的贡献,故提出因代沃段成矿系统中的硫来源主要来自基底玄武岩,同时伴随有少量海水硫酸盐来源及沉积物来源的硫加入;(3)将硫同位素数据与已发表的热液流体及硫化物数据进行耦合发现热液流体中的沉积物信号与硫化物中的硫可能来自不同的源,并提出沉积物端元可能位于下渗区。