An infrared spectroscopic study of lawsonite to 20 GPa

The infrared spectrum of CaAl₂Si₂O₇ · H₂O-lawsonite, has been characterized to pressures of 20 GPa at 300 K. Our results constrain the response to compression of the silicate tetrahedra, hydroxyl units, and water molecules in this material. The asymmetric and symmetric stretching and bending vibrations of the Si₂O₇ groups (at zero pressure frequencies between 600 and 1000 cm⁻¹) increase in frequency with pressure at rates between 3.6 and 5.9 cm⁻¹/GPa. All silicate modes appear to shift continuously with pressure to 20 GPa, although the lowest frequency stretching vibration becomes unresolvable above 18 GPa, and a splitting of the main bending vibration is observed near this pressure. The O-H stretches of the hydroxyl units exhibit a discontinuity in their mode shifts at ∼8–9 GPa, which we interpret to be produced by a pressure-induced change in hydrogen bonding. The stretching and bending vibrations of the water molecule are relatively unaffected by compression to 20 GPa, thus demonstrating that the structural cavities in which water molecules reside are relatively rigid. Significant changes in the amplitude of the O-H stretches of the hydroxyl and water units are observed at this pressure as well; nevertheless, our results demonstrate that the dominant structural units in lawsonite persist metastably at 300 K with only modest structural modifications well beyond the known stability field of this phase. Received: 10 July 1998 / Revised, accepted: 23 October 1998     

金刚石呈色机制的新观点

已知金刚石中能产生颜色的点缺陷(即色心)主要有氮、硼、空穴、填隙子以及各种形式的氮与空穴的复合体。随着各种现代微束与谱学分析技术以及量子化学计算的应用，对金刚石晶格中氮、硼以外的杂质—氢与过渡金属离子的赋存状态的研究，我们发现了新的致色点缺陷：成键氢，镍、钴离子，及其与氮的复合体，从而形成了氢致色与过渡金属离子致色的金刚石呈色机制的新观点。     

湖泊沉积有机质的地球化学记录与古气候古环境重建

与深海沉积与冰芯记录相比,湖泊沉积主要反映区域气候变迁史,可以揭示百年、甚至十年尺度的古气候事件,是高分辨率古环境、古气候重建的理想场所.传统的地质地球化学方法主要侧重于宏观物理 /化学特性描述和孢粉学的研究,近 10年来,沉积有机质分子碳、氢同位素地球化学技术的渗入,使研究工作从传统的宏观、微观层次向分子级水平发展,对诸如古生产率估算、C3/C4植被演替史、古二氧化碳分压及古温度计算等深层次问题解决提供了强有力支持.本文评述了湖泊沉积有机质分子与碳、氢同位素地球化学记录及其在区域古环境、古气候研究中的应用前景.     

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     

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.     

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。     

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.     

海南福基田幔源辉石结构OH与氢氧同位素

采用IR光谱和质谱技术分析了海南福基田幔源巨晶和包体中辉石的结构羟基红外光谱和氢氧同位素。测试的所有巨晶普通辉石和包体中透辉石及顽火辉石均含结构OH,对比印证了国内外同类矿物的红外光谱特征。结构水质量分数分别是:普通辉石87×10-6~389×10-6;透辉石127×10-6~273×10-6;顽火辉石69×10-6~207×10-6。包体中结构水质量分数为1 811×10-6~5 377×10-6,平均为3 133×10-6。包体中辉石的氢氧同位素特征如下:透辉石的δ(D)为-123.17‰,顽火辉石的δ(D)为-132.04‰;透辉石的δ(18O)为5.96‰,顽火辉石的δ(18O)为5.60‰。实验和对比表明,辉石是海南福基田上地幔重要的"水储库",包体未受地壳成分污染,继承和保持了上地幔"富水贫氘"的特征。上述结果为该地区上地幔研究提供了结构水和氢氧同位素的基础资料。     

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.     

猪毛菜在不同降水条件下的水分来源差异研究

通过测定大柴旦与都兰地区猪毛菜木质部水分及其不同潜在水源的稳定性氢氧同位素值,利用多源线性混合模型分析不同水分来源对猪毛菜的贡献率.研究结果表明:大柴旦地区大气降水线为y=7.565x+4.796(R²=0.908),都兰地区大气降水线为y=6.005x-7.856(R²=0.7391),说明两个地区都存在较强的蒸发作用.但是,都兰地区较大柴旦风速大,温度高,雨水蒸发速度快,造成雨水δ¹⁸O偏高,形成比大柴旦地区斜率更小的当地大气降水线.大柴旦和都兰地区的猪毛菜,在两个样地的用水策略上存在显著差异.在降水较少的大柴旦地区,猪毛菜以土壤水为主要水源.在降水较多的都兰地区,则以降水为主要水源.就其对土壤水的使用情况来看,大柴旦的猪毛菜多利用深层土壤水,而都兰地区的猪毛菜却对表层土壤水利用比例较大.两地猪毛菜在生长季的不同时期都存在对利用水源的转换现象.为适应不同地区降水量的变化,猪毛菜根据不同水源调节利用比例.降水格局的改变将导致猪毛菜的水分利用策略发生适应性的变化.