伟晶岩绿柱石矿物学及其通道水氢同位素研究进展

自然界绿柱石存在三个类质同象系列,即“八面体”绿柱石（ｃ／ａ＝０．９９１￣０．９９６）,“正常”绿柱石和“四面体”绿柱石。绿柱石矿物精细结构研究表明,二价离子置换八面体中Ａｌ,Ｌｉ置换四面体中Ｂｅ,而碱离子被绿柱石通道所容纳,用于补偿低价阳离子置换Ａｌ八面体和Ｂｅ四面体引起的电价不足。伟晶岩绿柱石通常含有〉１．６ｗｔ％的通道水,而包裹体中流体仅为０．１５ｗｔ％左右。室温下绿柱石通道中存在１型和Ⅱ     

海洋天然气水合物氢氧同位素分馏初探

天然气水合物的形成会造成氢、氧同位素的分馏.在实验室合成研究中,利用天然海水 [(含 0.03%十二烷基硫酸钠 (SDS)]与甲烷气体反应,通过对水合物生成前后溶液中的 Cl-的质量浓度和氢、氧同位素组成的测定,研究了天然气水合物生成过程中氢、氧同位素的分馏情况.实验证明氢、氧的重同位素易于富集在水合物中,其在天然海水-甲烷体系中的分馏系数分别为 1.018～ 1.036和 1.003 4～ 1.006 3,这一分馏系数稍大于前人在纯水和 NaCl溶液中所测得的分馏系数.     

Fluid Inclusions and Hydrogen,Oxygen, Sulfur Isotopes of Nuri Cu‐W‐Mo Deposit in the Southern Gangdese,Tibet

The Nuri Cu‐W‐Mo deposit is located in the southern subzone of the Cenozoic Gangdese Cu‐Mo metallogenic belt. The intrusive rocks exposed in the Nuri ore district consist of quartz diorite, granodiorite, monzogranite, granite porphyry, quartz diorite porphyrite and granodiorite porphyry, all of which intrude in the Cretaceous strata of the Bima Group. Owing to the intense metasomatism and hydrothermal alteration, carbonate rocks of the Bima Group form stratiform skarn and hornfels. The mineralization at the Nuri deposit is dominated by skarn, quartz vein and porphyry type. Ore minerals are chalcopyrite, pyrite, molybdenite, scheelite, bornite and tetrahedrite, etc. The oxidized orebodies contain malachite and covellite on the surface. The mineralization of the Nuri deposit is divided into skarn stage, retrograde stage, oxide stage, quartz‐polymetallic sulfide stage and quartz‐carbonate stage. Detailed petrographic observation on the fluid inclusions in garnet, scheelite and quartz from the different stages shows that there are four types of primary fluid inclusions: two‐phase aqueous inclusions, daughter mineral‐bearing multiphase inclusions, CO₂‐rich inclusions and single‐phase inclusions. The homogenization temperature of the fluid inclusions are 280°C–386°C (skarn stage), 200°C–340°C (oxide stage), 140°C–375°C (quartz‐polymetallic sulfide stage) and 160°C–280°C (quartz‐carbonate stage), showing a temperature decreasing trend from the skarn stage to the quartz‐carbonate stage. The salinity of the corresponding stages are 2.9%–49.7 wt% (NaCl) equiv., 2.1%–7.2 wt% (NaCl) equiv._, 2.6%–55.8 wt% (NaCl) equiv. and 1.2%–15.3 wt% (NaCl) equiv., respectively. The analyses of CO₂‐rich inclusions suggest that the ore‐forming pressures are 22.1 M Pa–50.4 M Pa, corresponding to the depth of 0.9 km–2.2 km. The Laser Raman spectrum of the inclusions shows the fluid compositions are dominated in H₂O, with some CO₂ and very little CH₄, N₂, etc. δD values of garnet are between ?114.4‰ and ?108.7‰ and δ¹⁸O_H2O between 5.9‰ and 6.7‰; δD of scheelite range from ?103.2‰ to ?101.29‰ and δ¹⁸O_H2O values between 2.17‰ and 4.09‰; δD of quartz between ?110.2‰ and ?92.5‰ and δ¹⁸O_H2O between ?3.5‰ and 4.3‰. The results indicate that the fluid came from a deep magmatic hydrothermal system, and the proportion of meteoric water increased during the migration of original fluid. The δ³⁴S values of sulfides, concentrated in a rage between ?0.32‰ to 2.5‰, show that the sulfur has a homogeneous source with characteristics of magmatic sulfur. The characters of fluid inclusions, combined with hydrogen‐oxygen and sulfur isotopes data, show that the ore‐forming fluids of the Nuri deposit formed by a relatively high temperature, high salinity fluid originated from magma, which mixed with low temperature, low salinity meteoric water during the evolution. The fluid flow through wall carbonate rocks resulted in the formation of layered skarn and generated CO₂ or other gases. During the reaction, the ore‐forming fluid boiled and produced fractures when the pressure exceeded the overburden pressure. Themeteoric water mixed with the ore‐forming fluid along the fractures. The boiling changed the pressure and temperature, oxygen fugacity, physical and chemical conditions of the whole mineralization system. The escape of CO₂ from the fluid by boiling resulted in scheelite precipitation. The fluid mixing and boiling reduced the solubility of metal sulfides and led the precipitation of chalcopyrite, molybdenite, pyrite and other sulfide.     

The effect of gas-phase chemistry on aqueous-phase sulfur dioxide oxidation rates

The rates and mechanisms of both gas and liquid phase reactions for the oxidation of sulfur dioxide play an important role in the production of atmospheric acids and aerosol particles. Rhodeet al. (1981) concluded that sulfate production rates were highly non-linear functions of sulfur dioxide emission rates. Their modelling study used an HO _x termination mechanism for the HO—SO₂ reaction in the gas-phase. Stockwell and Calvert (1983) determined that one of the products of the overall reaction of HO with sulfur dioxide was an HO₂ radical. The National Research Council (1983) using a version of the Rhodeet al. (1981) model modified to include HO₂ production from the HO—SO₂ reaction concluded that sulfate production becomes much more linear with respect to reductions in sulfur dioxide emissions. However, the cause of this increased linearity was not explained by the National Research Council report. It is demonstrated that the increased linearity is due to the coupling of gas-phases and aqueous phase chemistry. The gas-phase sulfur dioxide oxidation mechanism has a very significant effect on hydrogen perodide production rates.     

水位波动下的呼伦湖上覆水体与沉积物间隙水之间溶质的运移特征

为了探求内蒙古呼伦湖上覆水体和沉积物间隙水之间溶质运移机制,对呼伦湖的1个沉积物柱芯的间隙水、3个湖泊水体以及湖周边7个地下水体中的氯离子(Cl~-),氢、氧稳定同位素(δD和δ~(18)O)分别进行分析测试,并利用其示踪性对沉积物中溶质运移特征进行研究.结果显示,δD、δ~(18)O和Cl~-浓度在不同水体中的分布具有相似的分布规律,整体上从底部沉积物到上部湖水浓度分布呈现逐渐递减的抛物线趋势,在间隙水中最大值位于所取沉积物柱芯的最深处,Cl~-浓度为306 mg/L,δD和δ~(18)O分别为-58‰和-5.9‰;最小值位于沉积物柱芯上层,并与上覆水体中的值相似,Cl~-浓度为159 mg/L,δD和δ~(18)O分别为-66‰和-7.3‰.为了明确沉积物柱芯中间隙水的高浓度Cl~-和偏正δD、δ~(18)O的来源,比较不同水体的δ~(18)O-δD关系点分布,表明含有偏正值的δD、δ~(18)O和高浓度Cl~-的间隙水与上覆湖水关系密切,可能是由于低水位时期湖水与间隙水相互发生扩散作用而产生的结果.一维对流扩散迁移模型证实扩散作用是控制着沉积物间隙水中溶质浓度在垂向上分布的主要机制,同时湖水水位的变化会影响沉积物间隙水与上覆水体的扩散过程,特别是在水位上升期,富集在沉积物中的溶质可能成为湖水的重要物质来源,影响上覆水体的水质.因此,对于封闭湖泊水位的控制和管理不仅在维持湖泊水量方面有着直接的作用,同时在稳定湖泊水质条件上也有着重要的意义.     

西藏冈底斯中段雄村铜金矿床成矿流体特征与成因探讨

雄村铜金矿是在西藏冈底斯中段新发现的一个矿床,流体包裹体组成分析揭示该矿床成矿流体为富含CO2、N2和有机气体的Na _K _Ca2 _Cl-_SO2-4_HS-_CO2-3体系,Na/K、Na/Ca和Cl-/SO2-4摩尔比值分别为1.5～7.1、0.2～2.1和1.0～29.3。氢、氧同位素分析显示,成矿流体δ18O值范围为-4.7‰～ 2.2‰,δD值范围为-104‰～-82‰,表明成矿流体以大气水为主,但岩浆流体可能也对矿床的形成起了重要作用。硫化物硫同位素组成也显示硫主要来自深源岩浆,雄村矿床高盐度流体的形成可能与岩浆流体的低压不混溶密切相关。高盐度流体是雄村贱金属元素活化、迁移的重要介质;地下水中高的有机质还原SO2是诱发贱金属沉淀成矿的重要机制。有机质还原SO2也为Au的活化、迁移提供了介质和有利的还原环境。雄村矿床的形成与岩浆流体和循环地下水共同作用有关,浅部稳定的热体制和高的有机质还原SO2机制是形成雄村矿床特殊蚀变矿化样式的重要原因。     

Determination of Halogens (F, Cl, Br, I), Sulfur and Water in Seventeen Geological Reference Materials

Fluorine, chlorine, bromine, iodine and sulfur were determined in seventeen geological reference materials after extraction by pyrohydrolysis. Fluorine, Cl and S (as sulfate ions) were determined in the extraction solution by ion chromatography with detection limits of around 0.2 mg l⁻¹. Bromine and I were measured by ICP-MS with detection limits of 1 μg l⁻¹ for Br and 0.1 μg l⁻¹ for I. For rock samples, using normal extraction conditions (500 mg of sample and 100 ml of final solution) detection limits were 40 mg kg⁻¹ for F and Cl, 15 mg kg⁻¹ for S, 0.2 mg kg⁻¹ for Br and 0.02 mg kg⁻¹ for I. These detection limits may be improved by increasing the amount of sample and hence the concentration of the final solution. Water was also determined using an extraction technique based on H₂O degassing, reduction on zinc at 1000 °C and H₂ manometry. Our results for fluorine, chlorine, sulfur and water are in good agreement with literature data. Very few reference materials have recommended values for bromine and especially for iodine. Among the analysed samples, three are new reference materials: BHVO-2, BCR-2 and AGV-2.     

青海湖地区生物中正构烷烃及其氢同位素组成与影响因素

青海湖是我国最大的内陆咸水湖泊。本文应用GC-MS和GC-TC-IRMS同位素分析技术,对青海湖水生生物和周围地区陆生生物中正构烷烃及其氢同位素进行了分析,研究了生物中正构烷烃及其同位素组成。结果显示了不同生物中正构烷烃碳数分布范围在C1 5~C33之间,呈单峰型分布;主峰碳数是水生生物(除海韭菜外)相对较低,主要为C23和C25,陆生木本植物次之,为C27;陆生草本植物较高,为C27和C29;CPI值分布在4.0~29.7之间;ACL值为26.0~29.6,分布与植物类型有关。青海湖水生生物中正构烷烃氢同位素组成分布在-209.8‰~-85.6‰之间,平均值为-169.2‰~-121.2‰;陆生植物的正构烷烃δD值为-196.7‰~-84.3‰之间,平均值为-173.0‰~-108.6‰。青海湖不同水生生物和不同陆生生物之间的正构烷烃氢同位素组成差别显著。研究发现,湖泊的含盐量对水生植物的正构烷烃氢同位素具有显著影响,环境湿度和降水量明显影响了陆生植物的正构烷烃氢同位素组成;植物的正构烷烃平均氢同位素组成随着其ACL值增加,具有变轻的趋势;不同种类植物的正构烷烃合成期间具有不同的氢同位素分馏效应,与陆生植物相比较,水生植物的正构烷烃相对于环境水更富集轻氢同位素,并且随着ACL值增加,环境水和正构烷烃之间的氢同位素分馏增大。     

塔里木盆地东部地区天然气地球化学特征及成因探讨(之二)

天然气的组分和碳、氢同位素组成特征研究表明塔里木盆地已发现的天然气均为热解气。通过气源对比可知,该盆地东部地区的天然气主要有两种类型 :1)是来自震旦纪到下古生界海相腐泥型母质的油型气,其甲烷、乙烷、丙烷δ13C值,分别为-44.5‰～-33.8‰、- 42‰～-2 8.1‰和-35.4‰～-2 8.4‰,其甲烷的氢同位素组成大于- 2 0 0‰;2 )是产自中生代陆相腐殖型源岩的煤型气,其甲烷、乙烷、丙烷的δ13C值分别为-40.5‰～-33.1‰、- 2 9.7‰～-2 1.3‰和-2 6.3‰～-2 0.3‰,其甲烷的氢同位素组成小于-2 0 0‰。将天然气的地化特征与地质背景相结合判断可知,在塔北隆起地区一些天然气藏是由成熟 (高成熟 )阶段的油型气与过成熟阶段的油型气混合形成,另一些天然气藏是由成熟阶段的油型气和成熟阶段的煤型气混合形成.     

辽宁朝阳小塔子沟-东五家子金矿田地球化学特征

在朝阳小塔子沟-东五家子金矿田范围内,北地金矿、小塔子沟金矿和东五家子金矿,因距离岩体的远近不同,形成了不同的特征.石英流体包裹体研究表明,位于岩体内接触带的北地金矿为中温、中-深成热液矿床,位于岩体外接触带的小塔子沟金矿为中温、中成热液矿床,远离岩体的东五家子金矿为中-低温、浅成热液矿床.氢、氧同位素研究表明,北地金矿和小塔子沟金矿的成矿流体主要为岩浆水,东五家子金矿的成矿流体为岩浆水和大气降水混合成因.微量元素研究表明,北地金矿矿石以Mo、Bi等元素相对富集为特征,小塔子沟金矿矿石以Cu、Zn等元素相对富集为特征,东五家子金矿矿石以Pb、Ag等元素相对富集为特征.矿床离岩体越远,金矿物中Au/Ag比值越小.