硫酸盐矿物中制备质谱分析样方法的研究

硫酸盐类矿物特别是大洋水中的硫酸盐矿物的硫同位素分布及演化是硫同位素地质学研究的重要内容之一,海水硫酸盐参与海相沉积物中的氧化还原作用是海相沉积物中的硫化物以及矿床硫的主要来源,这也是研究层控矿床的重要依据之一。基于硫酸盐硫同位素的研究在地质上的重要性,国内外对硫酸盐制备SO_2的研究也很重视,在分析方法上趋于简便、高效率、准确性好。目前多数实验室从硫酸盐矿物中制备硫同位素分析样品(SO_2)的方法主要有两种:即     

陆相咸化湖泊沉积硫酸盐岩硫同位素组成及其地质意义

现代海洋中的硫酸盐矿物和海水硫酸盐本身常有相似的硫同位素组成,因而可根据现代蒸发岩的硫酸盐同位素来判断古环境。据李任伟［１］引用Ｈｏｌｓｅｒ和Ｋａｐｌａｎ及格里年科的资料报道,海相蒸发岩及其所反映的古海洋硫酸盐的硫同位素组成只在较狭窄的范围内变化,现...     

三叠纪海的硫同位素

前言自Ault和Kulp(1959)发表第一批海相硫酸盐岩的硫同位素分析数据以来,海相硫酸盐岩(石膏、硬石膏)的硫同位素研究工作已进行了二十余年。     

华南震旦、寒武系海相沉积成因重晶石的硫同位素组成及其在地质学上的意义

华南震旦、寒武系海相沉积成因重晶石的硫同位素组成,其δS~(34)值为 35— 47‰。究其原因,沉积环境对沉积物的稳定同位素组成的影响是最重要的。这一发现对各时代海相硫酸盐的同位素演化的研究,提供了新的资料。     

贵州天柱大河边重晶石矿床硫同位素研究

对贵州天柱大河边重晶石矿床硫同位素组成进行了系统研究,该矿床重晶石的硫同位素组成为36.7‰-41．6‰,具有比同期海水硫酸盐高得多的硫同位素组成特征,且在834S分布直方图上呈塔式,表明形成该矿床的硫来源单一,主要来自于海水中硫酸盐并经历了较强的生物细菌分馏作用,且矿床形成环境为半封闭一封闭的台地泻湖环境。     

扬子地台灯影组碳酸盐岩中的硫和碳同位素记录

扬子地区灯影组的海相碳酸盐岩地层不仅记录了当时海水的碳同位素变化，也保存了海水的硫同位素记录，能够通过测定所提取的微量硫酸盐的硫同位素组成来获得。灯影组碳酸盐岩中微量硫酸盐的δ^34S值大部分在 20.0‰～ 38．7‰之间变化，碳酸盐岩的δ^13C值变化在 0．5‰～ 5．0‰之间。除灯影组顶、底界线处外，δ^34S和δ^13C值总体上变化幅度较小，大体上呈逐渐降低的变化趋势。灯影组碳酸盐岩中连续的硫、碳同位素记录分别反映了同期海水中溶解硫酸盐和碳酸盐的硫、碳同位素的变化特征。灯影组微量硫酸盐和碳酸盐岩的同位素特征，意味着灯影期海洋中具有高的生物产率和有机碳埋藏速率；除了顶底界线处，具有相对稳定的古气候条件和古海洋环境。灯影期海水的δ^34S值和δ^13C值同时呈逐渐降低的变化趋势，可能是由海洋深部水体逐渐氧化所致。     

由BaSO4直接热分解制备用于同位素分析的SO2

硫同位素地质研究工作中,经常遇到的研究对象是硫酸盐矿物。如何把这些硫酸盐矿物转化为适于质谱测定硫同位素组成的SO₂气体,是我国硫同位素地质研究中急待建立的实验手段之一。 经典的方法中,可溶于水的硫酸盐,通常是先把它沉淀为BaSO₄,然后通过一系列的化学反应转化为SO₂。 七十年代初期,B.D.Holt等人提出直接加热分解BaSO₄制备SO₂的方法。     

云南会泽铅锌矿田硫同位素研究

为探讨会泽铅锌矿田成矿流体总硫同位素组成、成矿温度、硫源及还原硫的形成机制,在分析前人的硫同位素数据基础上对麒麟厂矿床上部原生矿体硫化物(黄铁矿、闪锌矿和方铅矿)及麒麟厂和矿山厂矿床外围新发现的硫酸盐矿物(重晶石)进行了硫同位素研究。结果显示,原生矿体中的硫化物的δ34S变化为8.0‰~17.68‰,成矿流体中硫同位素已达分馏平衡;矿床外围的硫酸盐δ34S变化为17.95‰~24.30‰。利用共生矿物对Pinckney法,估算获得成矿流体的δ34SΣS为14.44‰,与海相硫酸盐的δ34S相近;通过同位素地质温度计,估算获得成矿温度为134~388℃;包裹体测温发现,重晶石为热液成因,暗示成矿流体中的硫可能来自矿区及矿区外围各个地层的海相硫酸盐或是矿区发现的热液重晶石。硫酸盐的还原机制应为热化学还原作用(TSR)。     

现代沉积物中硫、碳含量及其与沉积环境的关系

为了确定全硫,全碳有机碳与沉积环境的关系,分析了267个现代沉积物样品中的这些元素,这些样品取自不同的沉积环境中,即:日本群岛附近的九个湖泊和六个海域。在还原条件下淡水沉积物中的全硫平均含量低于半咸水和海水沉积物中的全硫量。然而,在氧化的海湾沉积物与给养丰富的淡水湖泊沉积物之间,全硫含量不存在明显的差异。有机碳的含量,在湖泊沉积物中比在海相沉积物中高;而碳酸盐碳,在海相沉积物中却比湖泊沉积物中更为丰富。至于硫的化学状态,除深海沉积物(没有测定硫化物硫)外,50％以上的全硫以硫化物状态存在。在多数情况下,在较强氧化条件下形成的沉积物中,全硫和有机碳含量之间表现为一种密切的正相关关系。在现代沉积物中全硫、有机碳和硫酸盐硫似乎比古老沉积岩中更丰富,虽然全硫含量对确定沉积岩的堆积环境是很有用的,但是非碳酸盐碳与全硫的浓度比值为区分海相成因沉积岩与非海相沉积物提供了更好的标志。     

西藏南部中白垩世的锶、硫同位素组成及其古海洋地质意义

讨论了西藏南部中白垩世海相碳酸盐锶同位素组成和黑色页岩中黄铁矿硫同位素组成的主要特征及其古海洋地质意义。主要结论是:①该区中白垩世海相碳酸盐的锶同位素组成在0．7084～0．7090之间,大陆壳来源的锶占28%～30%,陆源物质输入的影响高于其它地区;火山熔岩中锶的同位素组成为0．7095,高于同期玄武岩的平均值,火山熔岩中大陆壳来源的锶约为65．2ｘ10-6,占总锶量的34%左右,火山熔岩形成过程中,同化了大量的壳源物质。②该区中白垩世黑色页岩中的黄铁矿的硫同位素组成为27‰～31．6‰,它来源于同期海水硫酸盐,且系中晚期成岩作用的产物,不同时间、不同沉积环境中形成的黄铁矿,其δ34S值差异明显,它们动态地反映成岩作用中环境的演化过程。     

城门山及武山铜矿床的硫同位素研究

地质概况江西城门山矿床和武山矿床是长江中下游铁铜成矿带大冶-九江成矿亚带东南部位的两个与斑岩有成因关系的铜矿床。在地质构造上,前者处于九江-瑞昌东西向拗陷带中的长山-城门湖背斜倾伏端的北翼,后者处在横立山-黄桥向斜东端的北翼。两矿区的地层分布相似,主要是志留系至三叠系地层。其中,泥盆系上统五通组砂岩及石炭系中统黄龙组灰岩与矿床关系密切。     

浙江长兴二叠系和三叠系界限地层的碳同位素

研究海相碳酸盐岩的碳和氧同位素已有三十多年,积累了数千个数据,其目的在于研究古海洋碳和氧同位素的演变。在此期间,一部分研究者认为,海相碳酸盐岩的δ¹³C值在0±2范围内变化,未表现出与地质时代相关的变化趋势(Clayton和Degens,1959;Degens和Epstein,1962;Keith和Weber,1964;Galimov,1965;Becker和Clayton,1972;Schidlowski等,1975)。但是,另一些学者,如Jeffery等(1955),Baertschi(1975),Compston(1960),Weber(1967),Garrels和Parry(1974)却认为,海相碳酸盐岩的δ¹³C值随地质时代而有规律地变化。     

Microstructure and geochemistry studies on Messinian gypsum deposits from the Northern Coast of Egypt

Messinian gypsum deposits from Dir El-Baraqan area, Northern Coast of Egypt, were investigated by stable sulfur isotope method, X-ray diffraction, infrared spectroscopy, optical microscopy, and scanning electron microscopy to differentiate features formed under substantial microbial influences as indicator of paleoenvironments. Petrographically, gypsum deposits were classified into three types: biolaminated gypsum, disordered selenite, and swallow-tail selenitic crystals. Biolaminated gypsum is characterized by regular alternating dark and light laminae, which were formed due to the seasonal environmental changes in Dir El-Baraqan area. Stable sulfur isotope data show that the gypsum deposits are characterized by δ³⁴S values ranging from +18.1 to +28.1 ‰. In swallow-tail gypsum, the δ³⁴S values are characterized by a narrow range (from +20.0 to +20.2 ‰) which is considered as the primary phase. In biolaminated gypsum, the δ³⁴S values ranged from +22.8 to +28.1 ‰ which is considered as the secondary phase. However, the white laminae are characterized by δ³⁴S values ranging from +22.8 to +24.1 ‰, while dark laminae are characterized by δ³⁴S values ranging from +27.2 to +28.1 ‰. The high δ³⁴S values of dark laminae revealed the increasing activity of sulfate-reducing bacteria.     

Different isotopic evolutionary trends of δ34S and δ18O compositions of dissolved sulfate in an anaerobic deltaic aquifer system

Concentration and isotope ratios (δ³⁴S_SO4 and δ¹⁸O_SO4) of dissolved sulfate of groundwater were analyzed in a very large anaerobic aquifer system under the Lower Central Plain (LCP) (25,000 km²) in Thailand. Groundwater samples were collected in two different kinds of aquifers; type 1 with a saline water contribution and type 2 lateritic aquifers with no saline water contribution. Two different isotopic compositional trends were observed: in type 1 aquifers sulfate isotope ratios range from low values (+2.2‰ for δ³⁴S_SO4 and +8.0‰ for δ¹⁸O_SO4) to high values (+49.9‰ for δ³⁴S_SO4 and +17.9‰ for δ¹⁸O_SO4); in type 2 aquifers sulfate isotope ratios range from low values (−0.1‰ for δ³⁴S_SO4 and +12.2‰ for δ¹⁸O_SO4) to high δ¹⁸O_SO4 ratios (+18.4‰) but with low δ³⁴S_SO4 ratios (<+12.9‰). Isotopic comparison with possible source materials and theoretical geochemical models suggests that the sulfate isotope variation for type 1 aquifer groundwater can be explained by two main processes. One is the contribution of remnant seawater, which has experienced dissimilatory sulfate reduction in the marine clay, into recharge water of freshwater origin. This process accounts for the high salinity groundwater. The other process, explaining for the modest salinity groundwater, is the bacterial sulfate reduction of the mixture water between high salinity water and fresh groundwater. Isotopic variation of type 2 aquifer groundwater may also be explained by bacterial sulfate reduction, with slower reduction rate than that of the groundwater with saline water effect. The origin of groundwater sulfate with low δ³⁴S_SO4 but high δ¹⁸O_SO4 is recognized as an important topic to be examined in a future investigation.     

Geochemistry of Triassic Carbonates: Exploration Guide to Pb–Zn Mineralization in North Tunisia

The Triassic carbonate rocks in Northern Tunisia (Nappes, Domes, Jurassic Mountains zones), consist of massive carbonates, clays and gypsum with authigenic minerals. These are associated with several Pb–Zn deposits and occurrences. At Jebel Ichkeul, Bechateur and Oum Edeboua, these Triassic carbonates exhibit enrichment in Pb (0.32 to 228 ppm), Zn (17 to 261 ppm), Cd (5 to 6 ppm) and Co (0.3 to 89.5 ppm), with respect to their average contents in crustal carbonates. The enrichment is more pronounced at Oum Edeboua (near the ore zone). Permeability is one of the most effective factors of dispersion of metallic trace elements, causing the development of geochemical halos. The genetic relationship of the Triassic carbonate rocks with the ore deposits was controlled by diapirism and tectonic movements, which favored mineralization along the Triassic‐cover contact as well as the remobilization of metals from the mineralized rocks. Analysis of metallic trace elements in Triassic rocks provides clues to the presence of possible mineral deposits. These could be effectively used for both geochemical interpretation and mineral exploration. Carbon and O‐isotope data (– 9.3‰ < δ¹³C < +3‰; +21.9 < δ¹⁸O < +31‰) suggest that the Triassic carbonates of all study areas have marine carbonates as their origin; some of them show significantly lower δ¹⁸O values indicating some exchange with hydrothermal fluids. Calcites associated with mineralization at Oum Edeboua have δ¹³C of –6.2‰ to –8.22‰ and δ¹⁸O of +24.88‰ to +25‰. The C‐isotope compositions of these calcites are ¹³C depleted, indicating an organic origin.     

罗河铁矿的硫同位素分馏机制和矿床形成的物理化学条件的研究

罗河铁矿(又称庐枞铁矿)是我国长江中下游火山岩地区大型铁矿床之一,是一种重要的矿床类型。十多年来,各研究单位和生产部门对该矿床进行了多方面、较系统的研究,取得可喜成果(张荣华等,1974;张荣华,1981;陈锦石等,1982)。然而,要进一步阐明这类矿床的成矿机理,还需要对该矿床的蚀变和成矿条件进行深入研究。本文着重讨论罗河铁矿的硫同位素分馏机制,并在此基础上结合地质和矿物包裹体的资料,近似定量地推算该矿床形成各阶段的物理化学条件范围及变化规律。     

Geochemical Characteristics of Deep—Seated Potassium—Rich Brine in the Middle Triassic Leikoupo Formation,Sichuan,China

Brine extremely rich in potassium, boron and bromine has been discovered from the Middle Triassic Leikoupo Formation at a depth of 4300 m in Sichuan Province. It contains ～50 g/L of K⁺, >92 g/L of Na⁺, >12 g/L of B₂O₃, >2.36 g/L of Br^? and ～0.030 g/L of I⁺. The solid precipitates during evaporation at 25°C include KB₅O₈·4H₂O, K₂B₄O₇·3H₂O, MgCl₂·6H₂O and KMgCl₃·6H₂O. The brine ranges from 2.2‰ to 2.8‰ (SMOW) in δ¹⁸O, ? 38‰ – ? 53‰ (SMOW) in δD, 15.6‰ in δ³⁴S, and 13.5‰–15.1‰ in δ¹¹B. These data, particularly the isotopic composition of boron, indicate that the brine has a composite derivation from marine and nonmarine brines and dissolved marine evaporites in the Triassic system.     

The origin of sulphur in gypsum and dissolved sulphate in the Central Namib Desert,Namibia

This study investigates the sulphur source of gypsum sulphate and dissolved groundwater sulphate in the Central Namib Desert, home to one of Africa's most extensive gypsum (CaSO₄·2H₂O) accumulations. It investigates previously suggested sulphate precursors such as bedrock sulphides and decompositional marine biogenic H₂S and studies the importance of other potential sources in order to determine the origin of gypsum and dissolved sulphate in the region. An attempt has been made to sample all possible sulphur sources, pathways and types of gypsum accumulations in the Central Namib Desert. We have subjected those samples to sulphur isotopic analyses and have compiled existing results. In addition, ionic ratios of Cl/SO₄ are used to determine the presence of non-sea-salt (NSS) sulphur in groundwater and to investigate processes affecting groundwater sulphate. In contrast to previous work, this study proposes that the sulphur cycle, and the formation of gypsum, in the Namib Desert appears to be dominated by the deposition of atmospheric sulphates of phytoplanktonic origin, part of the primary marine production of the Benguela upwelling cells. The aerosol sulphates are subjected to terrestrial storage within the gypsum deposits on the hyper-arid gravel plain and are traceable in groundwater including coastal sabkhas. The hypothesis of decompositional marine biogenic H₂S or bedrock sulphide sources, as considered previously for the Namib Desert, cannot account for the widespread accumulation of gypsum in the region. The study area in the Central Namib Desert, between the Kuiseb and Omaruru rivers, features extensive gypsum accumulations in a ca. 50–70 km wide band, parallel to the shore. They consist of surficial or shallow pedogenic gypsum crusts in the desert pavement, hydromorphic playa or sabkha gypsum, as thin isolated pockets on bedrock ridges and as discrete masses of gypsum selenite along some faults. The sulphur isotopic values (δ³⁴S ‰CDT) of these occurrences are between δ³⁴S +13.0 and +18.8‰, with lower values in proximity to sulphuric ore bodies (δ³⁴S +3.1 and +3.4‰). Damaran bedrock sulphides have a wide range from δ³⁴S −4.1 to +13.8‰ but seem to be significant sources on a local scale at the most. Dissolved sulphate at playas, sabkhas, springs, boreholes and ephemeral rivers have an overall range between δ³⁴S +9.8 and +20.8‰. However, they do not show a systematic geographical trend. The Kalahari waters have lower values, between δ³⁴S +5.9 and +12.3‰. Authigenic gypsum from submarine sediments in the upwelling zone of the Benguela Current between Oranjemund and Walvis Bay ranges between δ³⁴S −34.6 to −4.6‰. A single dry atmospheric deposition sample produced a value of δ³⁴S +15.9‰. These sulphur isotopic results, complemented by meteorological, hydrological and geological information, suggest that sulphate in the Namib Desert is mainly derived from NSS sulphur, in particular oxidation products of marine dimethyl sulphide CH₃SCH₃ (DMS). The hyper-arid conditions prevailing along the Namibian coast since Miocene times favour the overall preservation of the sulphate minerals. However, sporadic and relatively wetter periods have promoted gypsum formation: the segregation of sulphates from the more soluble halite, and the gradual seaward redistribution of sulphate. This study suggests that the extreme productivity of the Benguela Current contributes towards the sulphur budget in the adjacent Namib Desert.     

Cadmium and sulfur isotopic compositions of the Tianbaoshan Zn–Pb–Cd deposit,Sichuan Province,China

Although Zn–Pb deposits are one of the most important Cd reservoirs in the earth, few studies have focused on the Cd isotopic fractionation in Zn–Pb hydrothermal systems. This study investigates the causes and consequences of cadmium and sulfur isotope fractionation in a large hydrothermal system at the Tianbaoshan Zn–Pb–Cd deposit from the Sichuan–Yunnan–Guizhou (SYG) metallogenic province, SW China. Moderate variations in Cd and S isotope compositions have been measured in sphalerite cover a distance of about 78 m. Sphalerite has δ^114/110Cd values ranging from 0.01 to 0.57‰, and sulfides (sphalerite, galena and chalcopyrite) have δ³⁴S_CDT values ranging from 0.2 to 5.0‰. Although δ³⁴S_CDT and δ^114/110Cd values in sphalerites have no regular spatial variations, the δ³⁴S_CDT values in galena and calculated ore-forming fluid temperatures decreased from 2.1 to 0.2‰ and from about 290 to 130 °C, respectively, from the bottom to the top of the deposit. Heavy Cd isotopes are enriched in early precipitated sphalerite in contrast to previous studies. We suggest that Cd isotopic compositions in ore-forming fluids are heterogeneous, which result in heavy Cd isotope enrichment in early precipitated sphalerite. In comparison with other Zn–Pb deposits in the SYG area, the Tianbaoshan deposit has moderate Cd contents and small isotope fractionation, suggesting differences in origin to other Zn–Pb deposits in the SYG province.In the Tianbaoshan deposit, the calculated δ³⁴S∑_S-fluids value is 4.2‰, which is not only higher than the mantle-derived magmatic sulfur (0 ± 3‰), but also quite lower than those of Ediacaran marine sulfates (about 30 to 35‰). Thus, we suggest that reduced sulfur of ore-forming fluids in the deposit was mainly derived from the leaching of the basement, which contains large amount of volcanic or intrusive rocks. Based upon a combination of Cd and S isotopic systems, the Tianbaoshan deposit has different geochemical characteristics from typical Zn–Pb deposits (e.g., the Huize deposit) in SYG area, indicating the unique origin of this deposit.