Isotope geochemistry (S,C, O,Sr, Pb) of the Chaudfontaine mineralization (Belgium)

Investigations on S, C, O, Sr, and Pb isotopes in ores, gangue, and country rocks of the Chaudfontaine ore deposit confirm that interbedded barite and white sparry calcites are cogenetic. They emphasize the marine origin of S and the nonmarine origin of the metals. They underline the important role played by the bacterial reduction at the site of deposition. Hypotheses concerning the source of the metals and the nature of the brines involved in their transportation are briefly discussed.     

The Paleozoic Ozbak-Kuh carbonate-hosted Pb-Zn deposit of East Central Iran: Isotope (C,O, S,Pb) geochemistry and ore genesis

Lead and zinc mineralization occurs in dolostones of the Middle Devonian Sibzar Formation at Ozbak-Kuh, which is located 150 km north of Tabas city in East Central Iran. The ore is composed of galena, sphalerite and calcite, with subordinate dolomite and bitumen. Wall-rock alterations include carbonate recrystallization and dolomitization. Microscopic studies reveal that the host rock is replaced by galena and sphalerite. The Pb–Zn mineralization is epigenetic and stratabound. The δ¹³C values of hydrothermal calcite samples fall in the narrow range between ?0.3‰ and 0.8‰. The δ¹⁸O values in calcite display a wider range, between ?14.5‰ and ?11.9‰. The δ¹³C and δ¹⁸O values overlap with the oxygen and carbon isotopic compositions of Paleozoic seawater, indicating the possible important participation of Paleozoic seawater in the ore-forming fluid. The δ¹⁸O signature corresponds to a spread in temperature of about 70 °C in the ore-bearing fluid. The δ¹³C values indicate that the organic materials within the host rocks did not contribute significantly in the hydrothermal fluid. The δ³⁴S values of galena and sphalerite samples occupy the ranges of 12.2‰–16.0‰ and 12.1–16.8‰, respectively. These values reveal that the seawater sulfate is the most probable source of sulfur. The reduced sulfur was most likely supplied through thermochemical sulfate reduction. The sulfur isotope ratios of co-precipitated sphalerite–galena pairs suggest that deposition of the sulfide minerals took place under chemical disequilibrium conditions. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios of the galena samples represent average values of 18.08, 15.66, and 38.50, respectively. These ratios indicate that galena Pb likely originated from an orogenic source in which supracrustal rocks with high ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb ratios are dominant. The average lead isotope model age portrays Cambrian age. This model age is not coeval with the host rocks, which are of middle Devonian age. It is probable that the pre-Middle Devonian model age shows the derivation of Pb from older sources either from host rocks of Cambrian age or from deposits previously formed in these rock units. The Pb isotopic composition of galena accords with the occurrence of an orogenic activity from Late Neoproterozoic to Lower Cambrian in Central Iran. The proposed genetic model considers the fact that mineralization formed in fractured and brecciated host rocks along shear zones and faults from metal-bearing connate waters that were discharged due to deformational dewatering of sediments.     

陕西陈家坝铜铅锌多金属矿床C、H、O、S、Sr同位素地球化学示踪

陈家坝铜铅锌多金属矿床为近年来在陕西勉(县)-略(阳)-宁(强)铜金镍矿化集中区新发现的铜铅锌多金属矿床。为了查明陈家坝矿床成矿物质来源,笔者开展了系统的C、H、O、S和Sr同位素地球化学研究。结果表明,陈家坝矿区的围岩的δ~(13)CPDB值范围-0.93‰～1.44‰,平均值为0.35‰,δ~(18)OV-SMOW值范围14.14‰～27.49‰,平均22.1‰,为沉积成因海相碳酸盐岩。脉石矿物白云石的δ~(13)CPDB范围在-0.53‰～-0.89‰,δ~(18)OV-SMOW值范围12.12‰～13.23‰,指示成矿流体中的CO_2主要来自岩浆水,少量CO_2来源于围岩海相碳酸盐岩的溶解作用。成矿流体中δD值范围-91‰～-72‰,δ~(18)OH矿流体以岩浆流体为主。成矿流体与围2岩的水-岩反应是导致该区铜铅锌2矿床中白云石和黄铜矿、闪锌矿和方铅矿矿物沉淀结晶的主要机制。矿石金属硫化物δ34S值范围4.88‰～8.90‰,平均值为7.37‰,介于岩浆硫与海水硫之间,且与矿集区内典型的徐家沟铜矿床矿石矿物δ34S变化区间重叠,表明硫主要来自于岩浆硫,部分硫来自海水硫酸盐。矿石中黄铁矿的初始锶同位素比值87Sr/86Sr比值为0.72,高于赋矿围岩锶同位素比值,接近大陆地壳的87Sr/86Sr比值(0.719),指示了成矿流体流经了雪花太坪组地层,并与其中具有高87Sr/86Sr比值的白云岩进行水岩反应及同位素交换。     

湘西花垣铅锌矿田成矿物质来源的C、O、H、S、Pb、Sr同位素制约

花垣地区铅锌矿床有望成为中国最大的铅锌矿床,也是铅锌矿资源储量超过千万吨的世界级超大型矿床之一。文章通过碳、氧、氢、硫、铅和锶同位素地球化学特征研究,探讨了成矿流体和成矿金属来源。测试结果显示,花垣地区铅锌矿床主成矿期方解石样品的δ~(13) CPDB值范围为-2.71‰~1.21‰,δ~(18) OSMOW值范围为16.09‰~22.48‰,该地区铅锌矿床成矿流体中的碳主要来源于海相碳酸盐岩的溶解作用。花垣矿区的围岩的δ~(13) CPDB值范围为0.29‰~1.05‰,δ~(18) OSMOW值范围为21.33‰~23.89‰,为沉积成因海相碳酸盐岩。矿石中硫化物的δ~(34) S变化于24.93‰~34.66‰之间,重晶石δ~(34) S为32.78‰~34.22‰,表明还原硫主要来自地层中海相硫酸盐的还原。矿石硫化物的铅同位素组成均一,~(206)Pb/~(204)Pb、~(207)Pb/~(204)Pb和~(208)Pb/~(204)Pb分别为17.999~18.919、15.554~15.798和38.088~38.576,铅模式年龄为437~534Ma,成矿金属可能主要来源于奥陶系—寒武系。方解石和闪锌矿样品中流体的δD_(SMOW)变化于-91.1‰~-15‰之间,δ~(18) Ofluid变化范围为-4.1‰~8.75‰,矿床成矿流体的主要来源是建造水和大气降水。成矿流体与围岩的水-岩反应是导致该区铅锌矿床中方解石和闪锌矿矿物沉淀结晶的主要机制。成矿流体~(87)Sr/~(86)Sr为0.70906~0.71022,高于赋矿围岩寒武系清虚洞组灰岩锶同位素比值0.70886~0.70921,表明成矿流体流经了清虚洞组下伏地层,并与其中具有高锶同位素比值的碎屑岩、页岩和泥岩等进行了水岩反应及同位素交换。     

滇东北矿集区茂租铅锌矿床地球化学特征

茂租铅锌矿床位于扬子地台西南缘,是滇东北矿集区内的一个大型矿床,矿体主要呈似层状产于震旦系灯影组白云岩中;矿石矿物以闪锌矿为主,次为方铅矿;脉石矿物主要为白云石、方解石和萤石。本文对该矿床中与铅锌矿密切共生的团块状白云石、方解石和萤石以及围岩灯影组白云岩的REE地球化学特征和C、O、Sr同位素进行了对比研究。结果表明:团块状白云石和方解石的稀土配分模式、C同位素和Sr同位素比值与围岩灯影组白云岩比较接近,表明形成团块状白云石和方解石的成矿流体主要来源于围岩灯影组白云岩的溶解;但这两种矿物的稀土总量ΣREE高于灯影组白云岩,说明成矿流体除了主要由围岩提供REE外,还有部分其他富含REE流体的加入。萤石则具有LREE亏损和分配曲线相对平缓的稀土配分模式特征,表明萤石形成于成矿的晚阶段,有更多的外部流体的加入。团块状白云石、方解石和萤石表现出明显的Eu正异常,且团块状白云石和方解石的O同位素低于灯影组白云岩,反映了存在较高温度的流体活动,这3种脉石矿物是由高温热液流体形成的。灯影组白云岩和3种脉石矿物都具有明显的Ce负异常,说明成矿流体可能主要来源于地层循环水,继承了围岩的Ce负异常特征。方解石和萤石的Sr同位素比值高于围岩震旦系灯影组白云岩和峨眉山玄武岩,但小于基底岩石昆阳群和会理群,说明成矿流体主要由赋矿围岩等沉积地层中的循环流体与流经了基底岩石的深部流体混合形成。     

川东南地区石牛栏组碳、氧、锶同位素特征及其地质意义

前人对川东南地区石牛栏组地层已进行了大量的研究工作,但有关同位素地球化学方面的研究尚未见报道。本区石牛栏组沉积成因碳酸盐岩的碳同位素值与前人的研究结果一致,而氧同位素值则有所偏低;白云岩δ^13C值低,δ^18O值高,反映受成岩环境的影响较明显;裂缝中方解石的碳、氧同位素组成分布于两个不同的区间,说明不同期次裂缝充填物形成时的流体性质发生了明显的变化;沉积成因碳酸盐岩具异常低的锶同位素值,与前人研究结果有明显的差异,推测是受贫87Sr同位素的成岩流体的影响;晚期裂缝充填物锶同位素比值较高,也表明它们受到了地表淡水的影响。     

Calculation of Stable Isotope (O,C, Ca) Fractionation Factors for Apatite

The isotope fractionation β-factors have been determined for hydroxyapatite, fluorapatite, and carbon–apatite upon ¹⁸O/¹⁶O, ¹³C/¹²C, and ⁴⁴Ca/⁴⁰Ca substitutions depending on the temperature. Calculations were performed based on density functional theory (DFT). The results are expressed in terms of cubic polynomials against x = 10⁶/T(K)² and can be utilized as geothermometers if combined with β-factors of the coexisting phases. The new values of β-factors completely supersede the conventional semi-empirical (estimated by the method of increments) calibrations of isotopic equilibria involving apatite.

     

Petrology, geochemistry and genesis of rift-related carbonatites of Ambadungar, India

Summary The Ambadungar (Amba Dongar) alkaline carbonatite complex is emplaced in the Deccan traps igneous province. A wide range of carbonatites and alkaline rocks are exposed around Ambadungar. The alkaline rocks have been classified as tinguaite, phonolite and/or phononephelinite, melanephelinite, and syenite and/or nepheline syenite whereas carbonatites vary from calcio-carbonatites to ferro- and silicocarbonatites. The enrichment in large-ion lithophile elements (LILE), P, and rare-earth elements (REE) in carbonatites is considered to result from fractionation of a mantle derived magmatic liquid, i.e. nephelinitic magma, by liquid immiscibility which also produced melanephelinite and/or phononephelinite with high field strength elements (HFSE) such as Ca, Mg, Fe, and Mn in the alkaline silicate liquid fraction. The La:Lu ratios of the carbonatites are typical of igneous rocks and vary between 590 and 1945, similar to many known magmatic carbonatites. The ¹³C concentration varies between –2 and –8 whereas ¹⁸O-values vary between 7.7 and 26.8. The ¹³C concentration is typical of primary igneous carbonatites but ¹⁸O enrichment is thought to be the result of post-magmatic processes such as interaction with meteoric water and re-equilibration with hydrous fluids at low temperatures.

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Petrologie, Geochemie und Genese der riftgebundenen Karbonatite von Ambadungar, Indien

Zusammenfassung Der Ambadungar (Amba Dongar) Alkalikarbonatit-Komplex liegt in der magmatischen Deccan Provinz. Er umfaßt eine Vielzahl von karbonatitischen und alkalischen Gesteinen, die in der Umgebung von Ambadungar aufgeschlossen sind. Die Alkaligesteine sind als Tinguaite, Phonolite und/oder Phononephelinite, Melanephelinite, Syenite und/oder Nephelinsyenite zu klassifizieren, die Karbonatite als Calcio-, bis Ferro- and Silicokarbonatite. Die Anreicherung an LIL-Elementen und Seltenen Erden in den Karbonatiten werden als das Ergebnis der Fraktionierung von Mantelschmelzen, i.e. eines nephelinitisches Magmas, infolge von Nichtmischbarkeit interpretiert. Melanephelinite und/oder Phononephelinite and hohe Gehalte an HFS-Elementen (Ca, Mg, Fe and Mn) in der alkalisch-silikatischen Schmelzfraktion sind ebenfalls das Ergebnis dieser Prozesse. Die La/Lu-Verhältnisse sind typisch für magmatische Karbonatite and variieren zwischen 590 and 1945. Die ¹³C Konzentrationen variieren zwischen -2 and -8 %o, die ¹⁸O Werte zwischen 7.7 and 26.8 %0. Während die ¹³C Konzentration typisch für primär magmatische Karbonatite ist, ist die ¹⁸O-Anreicherung mit postmagmatischen Prozessen, wie etwa die Interaktion mit meteorischen Wässern and die Reequilibration mit niedrig temperierten wäßrigen Fluiden, erklärbar.

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with 11 figures     

云南会泽铅锌矿田成矿物质来源：Pb、S、C、H、O、Sr同位素制约

云南会泽铅锌矿田是我国著名的超大型特富铅锌矿田之一,由相距3公里的矿山厂和麒麟厂两个独立的矿床组成,Zn Pb 金属量超过五百万吨,矿石品位在25%至35%之间。为确定矿床成矿流体和成矿金属来源,本文系统研究了矿床的 Pb、S、C、O、H 和 Sr 同位素组成特征。矿石硫化物的铅同位素组成均一,~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb 和~(208)Pb/~(104)Pb 的变化范围分别为18.251～18.530,15.663～15.855和38.487～39.433,与围岩碳酸盐岩中浸染状黄铁矿一致,与碳酸盐地层相近,在~(208)Pb/~(204)Pb-~(206)Pb/~(204)Pb 图上显示明显的线性关系,表明铅同位素组成相近的碳酸盐围岩地层提供了成矿物质。矿石硫化物的δ~(34)S 变化范围为10.9‰～17.4‰,多数集中于13‰～17‰,表明还原硫主要来自地层中海相硫酸盐的还原,还原方式为热化学还原,下伏页岩、碎屑岩和泥质岩中的有机质在硫酸盐还原过程中发挥了重要作用。三种不同产状的脉石矿物方解石的碳氧同位素组成均一且没有明显差别,δ~(13)C 变化范围为-2.1‰～-3.5‰,δ~(18)O 为16.8‰～18.6‰。脉石矿物方解石中流体包裹体水的δD_(FI)为-50‰～-60‰,取温度为200℃计算包裹体水的δ~(18)O_(H_2O)值为7.0‰～8.8‰。碳、氧和氢、氧同位素研究结果表明,成矿流体为来自下部上升的变质流体,由于下伏页岩、碎屑岩和泥质岩中有机质的参与,成矿流体具有低的δ~(13)C和δD_(FI)值,在上升过程中与围岩发生了同位素交换。矿石中黄铁矿、闪锌矿和方解石的初始锶同位素组成(~(87)Sr/~(86)Sr)_i值的变化范围为0.714～0.717,赋矿围岩中未蚀变白云岩的初始锶同位素组成(~(87)Sr/~(86)Sr)_i值为0.7083～0.7093,明显低于蚀变白云岩(0.7106),表明成矿流体具有高的(~(87)Sr/~(86)Sr)_i比值。相对围岩碳酸盐岩而言,下伏地层中的页岩、碎屑岩和泥质岩往往具有高得多的~(87)Sr/~(86)Sr,因此,流经或者起源于这些地层的流体具有高的锶同位素比值。     

广东大降坪硫(铅锌)矿床岩浆热液叠加作用——来自闪锌矿Rb-Sr年龄及硫同位素的证据

广东大降坪硫(铅锌)矿床位于与岩浆作用有关的大绀山多金属矿田的中部,主矿体为赋存在震旦纪变质岩中的层状、透镜状黄铁矿矿体,最近在两个不同产状的黄铁矿矿体下部又新发现了脉状及层状铅锌矿体。文章通过对铅锌矿体的年龄及硫同位素研究,探讨其与主矿体的成因关系,获得了脉状铅锌矿体中闪锌矿的Rb-Sr等时线年龄为(88.5±3.9)Ma,即晚白垩世,与上部黄铁矿矿体的年龄(约630 Ma)相差较大,而与整个大绀山多金属矿田的成矿作用时限一致。三种不同产状的矿体硫同位素组成差异明显:层状黄铁矿矿体富集硫的轻同位素(δ34S=-10.90‰~-25.55‰),且与围岩的硫同位素范围一致,说明硫来自生物的细菌还原硫;透镜状黄铁矿矿体δ34S组成范围较宽(-9.38‰~22.69‰),具多源性硫的特征;铅锌矿体的δ34S在-7.1‰~6.4‰之间变化,硫可能来自深源岩浆,并受围岩成分混染。多方面的证据表明,大降坪黄铁矿矿体下部的铅锌矿体形成于晚白垩世的岩浆热液成矿作用,透镜状黄铁矿矿体受到岩浆热液的叠加。     

Chemical and isotopic (C, O, Sr, Nd) characteristics of the Xiluvo carbonatite (central-western Mozambique)

Summary The Xiluvo complex of central Mozambique is made up of coarse- to fine-grained calciocarbonatites (sövites and alvikites), heavily altered lamprophyres and syenitic rocks that intruded the Precambrian basement ca. 120Ma ago. The carbonatites have fractionated rare earth element patterns (chondrite-normalized La/Yb=30–80) and markedly negative Rb, K, P, Zr and Ti anomalies in mantle-normalized incompatible element diagrams. The ¹⁸O (+7 to +8), ¹³C (–5), and the age-corrected ⁸⁷Sr/⁸⁶Sr (0.7032–0.7033) and ¹⁴³Nd/¹⁴⁴Nd (0.51263–0.51262) indicate an origin in the mantle. A few carbonatitic samples have higher ¹⁸O (+13), indicating interaction with high-¹⁸O crust or late-stage fluids. The chemical and isotopic compositions of the Xiluvo carbonatites and nearby carbonatites of similar age in Malawi indicate very similar sources, characterized by time-integrated depletion of Rb with respect to Sr and of Sm with respect to Nd. These characteristics point to a source similar in many respects to those of other East African carbonatites and to those of some ocean island basalts, with the additional influx of components possibly located in the African lithospheric mantle.     

Sr,Nd,Pb Isotope Geochemistry and Magma Evolution of the Potassic Volcanic Rocks,Wudalianchi,Northeast China

Wudalianchi volcanic rocks are the most typical Cenozoic potassic volcanic rocks in easten China.Compositional comparisons between whole rocks and glasses of various occurrences indicate that the magma tends to become rich in silica and alkalis as a result of crystal differentiation in the course of evolu-tion.They are unique in isotopic composition with more radiogenic Sr but less radiogenic Pb.^87Sr/^86Sr is higher and ^143Nd/^144Nd is lower than the undifferentiated global values.In comparison to continental pot-ash volcanic rocks,Pb isotopes are apparently lower.These various threads of evidence indicate that the rocks were derived from a primary enriched mantle which had not been subjected to reworking and shows no sign of incorporation of crustal material.The correlation between Pb and Sr suggests the regional heterogeneity in the upper mantle in terms of chemical composition.     

Sr, C, and O isotope geochemistry of Ordovician brachiopods: a major isotopic event around the Middle-Late Ordovician transition

Here we present Sr, C, and O isotope curves for Ordovician marine calcite based on analyses of 206 calcitic brachiopods from 10 localities worldwide. These are the first Ordovician-wide isotope curves that can be placed within the newly emerging global biostratigraphic framework. A total of 182 brachiopods were selected for C and O isotope analysis, and 122 were selected for Sr isotope analysis. Seawater ⁸⁷Sr/⁸⁶Sr decreased from 0.7090 to 0.7078 during the Ordovician, with a major, quite rapid fall around the Middle-Late Ordovician transition, most probably caused by a combination of low continental erosion rates and increased submarine hydrothermal exchange rates. Mean δ¹⁸O values increase from −10‰ to −3‰ through the Ordovician with an additional short-lived increase of 2 to 3‰ during the latest Ordovician due to glaciation. Although diagenetic alteration may have lowered δ¹⁸O in some samples, particularly those from the Lower Ordovician, maximum δ¹⁸O values, which are less likely to be altered, increase by more than 3‰ through the Ordovician in both our data and literature data. We consider that this long-term rise in calcite δ¹⁸O records the effect of decreasing tropical seawater temperatures across the Middle-Late Ordovician transition superimposed on seawater δ¹⁸O that was steadily increasing from ≤−3‰ standard mean ocean water (SMOW). By contrast, δ¹³C variation seems to have been relatively modest during most of the Ordovician with the exception of the globally documented, but short-lived, latest Ordovician δ¹³C excursion up to +7‰. Nevertheless, an underlying trend in mean δ¹³C can be discerned, changing from moderately negative values in the Early Ordovician to moderately positive values by the latest Ordovician. These new isotopic data confirm a major reorganization of ocean chemistry and the surface environment around 465 to 455 Ma. The juxtaposition of the greatest recorded swings in Phanerozoic seawater ⁸⁷Sr/⁸⁶Sr and δ¹⁸O at the same time as one of the largest marine transgressions in Phanerozoic Earth history suggests a causal link between tectonic and climatic change, and emphasizes an endogenic control on the O isotope budget during the Early Paleozoic. Better isotopic and biostratigraphic constraints are still required if we are to understand the true significance of these changes. We recommend that future work on Ordovician isotope stratigraphy focus on this outstanding Middle-Late Ordovician event.     

Postorogenic carbonatites at Eden Lake, Trans-Hudson Orogen (northern Manitoba, Canada): Geological setting, mineralogy and geochemistry

The Eden Lake pluton in the Trans-Hudson Orogen is the first known occurrence of carbonatites in Manitoba. The pluton is largely made up of modally and geochemically diverse syenitic rocks derived from postorogenic magma(s) of shoshonitic affinity. Their diversity can be accounted for by a combination of crystal fractionation and fluid release in the final evolutionary stage (crystallization of quartz alkali-feldspar syenite). At Eden Lake, carbonatites, represented predominantly by coarse-grained massive to foliated sövite, occur as branching veins and lenticular bodies up to 4 m in thickness showing crosscutting relations with respect to all of the syenitic units. The host rocks are intensely fenitized at the contact, and there is also abundant mineralogical and textural evidence for assimilation of silicate material by carbonatitic magma through wallrock reaction and xenolith fragmentation and digestion. The bulk of the carbonatites are composed of (in order of crystallization): Sr–REE-rich fluorapatite, aegirine–augite, and coarse calcite crystals surrounded by fine-grained calcite (on average,  90 vol.% of the rock). Noteworthy accessory constituents are celestine, bastnäsite-(Ce) (both as primary inclusions in calcite), Nb–Zr–rich titanite, low-Hf zircon, allanite-(Ce) and andradite. The calcite is chemically uniform (Sr-rich, Mg–Mn–Fe-poor and low in ¹³C), but shows clear evidence of ductile deformation and syndeformational cataclasis. Geochemically, the carbonatites are enriched in Sr, Ba, light rare-earth elements, Th and U, but depleted in high-field-strength elements (particularly, Ti, Nb and Ta). The stable-isotope composition of coarse- and fine-grained calcite from the carbonatites and interstitial calcite from syenites is remarkably uniform: ca. − 8.16 ± 0.27‰ δ¹³C (PDB) and + 8.04 ± 0.19‰ δ¹⁸O (SMOW). The available textural and geochemical evidence indicates that the Eden Lake carbonatites are not consanguineous with the associated syenites and may have been derived from a Nb–Ti-retentive and ¹³C-depleted source such as the subducted crustal material underlying the Eden Lake deformation corridor.     

扬子陆块北缘马元铅锌矿床成矿物质来源探讨: 来自C、O、H、S、Pb、Sr同位素地球化学的证据

呈层状、似层状产于震旦系灯影组角砾状白云岩层间构造带中的马元铅锌矿床是近年来在扬子陆块北缘铅锌找矿的新突破。文章通过碳、氧、氢、硫、铅和锶同位素地球化学特征研究,探讨了成矿流体和成矿金属来源。研究结果表明:矿石中热液脉石矿物的δ13CPDB为-4.24‰~0.93‰,δ18OSMOW为15.92‰~23.24‰,表明成矿流体中的CO2为震旦系碳酸盐岩的溶解成因。矿石中硫化物的δ34S变化于12.94‰~19.4‰之间;硫酸盐矿物的δ34S为32.2‰~33.48‰,表明还原硫主要来自地层中海相硫酸盐的还原。矿石硫化物的铅同位素组成均一,206Pb/204Pb、207Pb/204Pb和208Pb/204Pb分别为17.62~18.02、15.49~15.63和37.57~38.35,成矿金属可能主要来源于震旦系—志留系。脉石矿物石英流体包裹体的δDFI为-92‰和-113‰,如果取成矿温度200℃,根据δ18O石英值计算的相应流体包裹体的δ18O水为6.03‰~12.73‰,推测成矿流体可能起源于大气降水为主的盆地卤水,或为其他来源的流体与有机质反应形成。成矿流体87Sr/86Sr为0.70967~0.71146,高于赋矿围岩震旦系灯影组白云岩锶同位素比值(0.70890~0.70945),表明成矿流体流经了古生代地层(及基底),并与其中具有高锶同位素比值的碎屑岩、页岩和泥岩等进行了水岩反应及同位素交换。     

C, O, S and Sr isotope studies on the genesis of Fe-carbonate and barite mineralizations in the Attepe iron district (Adana, Southern Turkey)

The Attepe district consists of Precambrian, Lower–Middle Cambrian, Upper Cambrian–Lower Ordovician and Mesozoic formations. It contains several iron deposits and occurrences. Three types of iron-mineralizations can be distinguished in the area; (i) Sedimentary Fe-sulfide in Precambrian bituminous metapelitic rocks, and Fe-oxides in Precambrian metasandstones (SISO), (ii) vein-type Fe-carbonate and oxides composed of mainly siderite, ankerite and hematite including barite in Lower–Middle Cambrian metacarbonates of the Çaltepe Formation (HICO), (iii) karstic Fe-oxides and hydroxides essentially in the Lower–Middle Cambrian metacarbonates and the unweathered Fe-carbonates (KIO). The latter type is more widespread and located at the upper parts of the most important mineable iron deposits like Attepe deposit.

Oxygen-, carbon-, sulfur- and strontium-isotope studies have been performed on siderites and barites in the vein-type ores, and on calcites in the recrystallized Çaltepe Limestones to investigate the sources and formation mechanism of primary ore-forming constituents. The δ¹³C values of siderites and calcites in limestones of the Çaltepe Formation range from −10.10‰ to −8.20‰, and from −0.8‰ to 2.30‰. Both carbonate minerals show δ¹⁸O values between 17.50–18.30‰ and 16.20–23.00‰, respectively. The δ¹³C and δ¹⁸O isotopic variations do not indicate any direct or linear relations between siderites and limestones. However, it is possible that the carbon and oxygen isotopic compositions of carbonate minerals could be changed to some extent, when limestones were subjected to hydrothermal processes or thermal alterations during metamorphism.

The isotopic values of barites display 32.40–38.30‰ for δ³⁴S and 12.20–14.70‰ for δ¹⁸O. The strontium isotope ratios (0.717169–0.718601) of barites and the sulfur isotope compositions of barites and pyrites suggest that there are no direct linkages of ore-forming compounds neither with a magmatic source nor with sedimentary pyrite formations in the Precambrian bituminous shales of the Attepe formation.

According to the field observations and the stable isotope data, siderites and ankerites should be formed by interaction between iron-rich hydrothermal fluids and Çaltepe limestones, whereas isotope ratios of barites indicate that they were formed by mixing of sulfur-rich meteoric waters and deeply circulated hydrothermal solutions.     

闽中丁家山铅锌矿床同位素地球化学及其地质意义

通过铅、硫、铷、锶同位素地球化学特征的系统分析,对闽中丁家山铅锌矿床的成矿物质来源、成矿时代及矿床成因进行了深入研究。围岩全岩及矿石内方铅矿的Pb同位素变化范围较宽,方铅矿的²⁰⁶Pb/²⁰⁴Pb比值在18.182~18.605之间, ²⁰⁷Pb/²⁰⁴Pb比值在15.010~15.932之间,²⁰⁸Pb/²⁰⁴Pb比值在38.331~39.666之间,具有明显的壳-幔混合来源特征,可能由龙北溪组地层和燕山期重熔型花岗岩共同提供。黄铁矿、磁黄铁矿、闪锌矿、方铅矿的δ³⁴S组成为-1.7‰~5.6‰,平均值为2.7‰,具有向正值偏移的塔式分布特征;系统δ³⁴S初始值为3.97‰,深源硫特征明显,说明硫由燕山期重熔型花岗岩提供。成矿期的石英铷-锶等时线年龄为(146.15±3.95) Ma,成矿时间属燕山早期第三阶段。以上结果进一步证实,丁家山铅锌矿床为马面山群龙北溪组上段经区域变质的富钙质沉积岩与燕山期重熔型花岗岩发生接触交代作用,形成的矽卡岩型矿床。     

Multi-proxy approach (H/H, O/O, C/C and Sr/Sr) for the evolution of carbonate-rich groundwater in basalt dominated aquifer of Axum area, northern Ethiopia

Isotopic and chemical composition of groundwater from wells and springs, and surface water from the basalt-dominated Axum area (northern Ethiopia) provides evidence for the origin of water and dissolved species. Shallow (depth < 40 m) and deep groundwater are distinguished by both chemical and isotopic composition. Deep groundwater is significantly enriched in dissolved inorganic carbon up to 40 mmol l⁻¹ and in concentrations of Ca²⁺, Mg²⁺, Na⁺ and Si(OH)₄ compared to the shallow type.The δ²H and δ¹⁸O values of all solutions clearly indicate meteoric origin. Shifts from the local meteoric water line are attributed to evaporation of surface and spring water, and to strong water–rock interaction. The δ¹³C_DIC values of shallow groundwater between −12 and −7‰ (VPDB) display the uptake of CO₂ from local soil horizons, whereas δ¹³C_DIC of deep groundwater ranges from −5 to +1‰. Considering open system conditions with respect to gaseous CO₂, δ¹³C_DIC = +1‰ of the deep groundwater with highest PCO₂ = 10^−0.9 atm yields δ¹³C_CO2(gas) ≈ −5‰, which is close to the stable carbon isotopic composition of magmatic CO₂. Accordingly, stable carbon isotope ratios within the above range are referred to individual proportions of CO₂ from soil and magmatic origin. The uptake of magmatic CO₂ results in elevated cations and Si(OH)₄ concentrations. Weathering of local basalts is documented by ⁸⁷Sr/⁸⁶Sr ratios of the groundwater from 0.7038 to 0.7059. Highest values indicate Sr release from the basement rocks. Besides weathering of silicates, neoformation of solids has to be considered, which results in the formation of, e.g., kaolinite and montmorillonite. In several solutions supersaturation with respect to calcite is reached by outgassing of CO₂ from the solution leading to secondary calcite formation.     

The Gumeshevo skarn-porphyry copper deposits in the Central Urals,Russia: Evolution of the ore-magmatic system as deduced from isotope geochemistry (Sr,Nd, C,O, H)

The Early Devonian Gumeshevo deposit is one of the largest ore objects pertaining to the dioritic model of the porphyry copper system paragenetically related to the low-K quartz diorite island-arc complex. The (⁸⁷Sr/⁸⁶Sr)_t and (ɛ_Nd)_t of quartz diorite calculated for t = 390 Ma are 0.7038–0.7045 and 5.0–5.1, respectively, testifying to a large contribution of the mantle component to the composition of this rock. The contents of typomorphic trace elements (ppm) are as follows: 30–48 REE sum, 5–10 Rb, 9–15 Y, and 1–2 Nb. The REE pattern is devoid of Eu anomaly. Endoskarn of low-temperature and highly oxidized amphibole-epidote-garnet facies is surrounded by the outer epidosite zone. Widespread retrograde metasomatism is expressed in replacement of exoskarn and marble with silicate (chlorite, talc, tremolite)-magnetite-quartz-carbonate mineral assemblage. The ⁸⁷Sr/⁸⁶Sr ratios of epidote in endoskarn and carbonate in retrograde metasomatic rocks (0.7054–0.7058 and 0.7053–0.7065, respectively) are intermediate between the Sr isotope ratios of quartz dioritic rocks and marble (⁸⁷Sr/⁸⁶Sr = 0.70784 ± 2). Isotopic parameters of the fluid equilibrated with silicates of skarn and retrograde metasomatic rocks replacing exoskarn at 400°C are δ¹⁸O = +7.4 to +8.5‰ and δD = −49 to −61‰ (relative to SMOW). The δ¹³C and δ¹⁸O of carbonates in retrograde metasomatic rocks after marble are −5.3 to +0.6 (relative to PDB) and +13.0 to +20.2% (relative to SMOW), respectively. Sulfidation completes metasomatism, nonuniformly superimposed on all metasomatic rocks and marbles with formation of orebodies, including massive sulfide ore. The δ³⁴S of sulfides is 0 to 2‰ (relative to CDT);⁸⁷Sr/⁸⁶Sr of calcite from the late calcite-pyrite assemblage replacing marble is 0.704134 ± 6. The δ¹³C and ⁸⁷Sr/⁸⁶Sr of postore veined carbonates correlate positively (r = 0.98; n = 6). The regression line extends to the marble field. Its opposite end corresponds to magmatic (in terms of Bowman, 1998b) calcite with minimal δ¹³C, δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr values (−6.9 ‰, +6.7‰, and 0.70378 ± 4, respectively). The aforementioned isotopic data show that magmatic fluid was supplied during all stages of mineral formation and interacted with marble and other rocks, changing its Sr, C, and O isotopic compositions. This confirms the earlier established redistribution of major elements and REE in the process of metasomatism. A contribution of meteoric and metamorphic water is often established in quartz from postore veins.