四川鲜水河-安宁河断裂带温泉氢氧稳定同位素特征

温泉地下水同位素特征对确定断裂带地下水来源、循环过程和断裂带活动性至关重要.为了确定青藏高原东缘温泉的地下水同位素特征和流体来源,本研究采集了鲜水河-安宁河断裂带上温泉水、冷泉水、河流和积雪融水等样品,进行了氢氧稳定同位素和水化学组分测定,并进行了同位素特征的对比研究.分析结果表明,温泉水体δ18O变化范围为-19.0...     

小秦岭大湖矿区钼、金矿体地质、地球化学特征与差异性分析

本文针对小秦岭金矿田大湖钼金矿矿床地质、地球化学特征进行了系统的分析。矿区浅部为石英脉型金矿体,向深部延伸出现石英脉型钼矿体,F5断层是大湖矿区内金、钼矿主要的含矿构造,钼矿体与金矿体共生或独立存在。钼矿体顶板围岩主要发育钾长石化,而金矿体顶底板围岩则发育硅化、绢云母化、黄铁矿化,其中绢云母化和中细粒黄铁矿化与金矿体关系最为密切。含金石英脉流体包裹体气相组分以CO2、H2O为主,含有少量CH4、C2H2等还原性气体,液相组分主要为Na+、Ca2+、Cl-、F-等离子。钼矿体与金矿体的H、O同位素数据显示钼矿脉与金矿脉的成矿流体主要都是来自岩浆水,但是两种矿体的H、O同位素组成又表现出一定的差异。辉钼矿化石英脉与金矿体中钾长石化和黄铁矿化石英脉中的稀土组成具有明显的不同,辉钼矿化石英脉具有较高的的∑REE和轻重稀土分馏,指示金矿体与钼矿体成矿流体来源不同,金、钼可能形成于不同的成矿期。     

内蒙古西拉沐伦成矿带碾子沟钼矿床成矿流体地球化学特征

碾子沟钼矿床是内蒙古西拉沐伦钼多金属成矿带中石英脉型钼矿床的典型代表,矿体以石英大脉形式产于燕山期中粗粒黑云母二长花岗岩内,受断裂构造控制。流体包裹体研究发现包裹体均为气液两相,按照相比不同,可进一步分为WL型(5%～20%)和WV型(20%～50%)。Ⅰ阶段流体为低温(89.3～245.2℃)、中低盐度(2.07%～17.96%NaCleqv)流体;Ⅱ阶段流体具有中低温(134.4～458.8℃,峰值170℃～240℃)、中低盐度(0.53%～19.92%NaCleqv)特征;Ⅲ阶段流体为低温(134.9～202.4℃)、中低盐度(4.96%～14.97%NaCleqv)流体。流体成分均以H2O为主(96.1mol%),含少量挥发份CO2、N2、CH4、C2H6、Ar、H2S,阳离子以Na+为主,阴离子以SO42-、Cl-为主,属NaCl-H2O体系。各阶段成矿热液氢、氧同位素特征为:δ18OH2O介于-5.75‰～-1.90‰、δD介于-128.821‰～-109.234‰,说明成矿流体是岩浆热液与古大气降水混合而成。开放的断裂体系为流体混合创造了条件,流体的混合作用是造成碾子沟辉钼矿沉淀成矿的主要原因。这与斑岩型钼矿床的高盐度流体以及以沸腾为主的矿石沉淀机制具有显著区别。     

河道水体中氢氧稳定同位素组成的微分方程模型

介绍了前人提出并被广泛应用的瑞利分馏模型,指出了其优缺点。针对其不足,在作了一定的假定和简化的前提下,基于瑞利分馏原理和水力学基本定律分别推导了:①静止水体的氢氧稳定同位素组成随时间变化的微分方程模型,揭示了静止水体的同位素组成与时间、分馏系数和蒸发率之间的关系;②河道中运动水体的同位素组成随时间和空间变化的微分方程模型,导出了河道运动水体中稳定同位素组成与分馏系数、流速、流量、蒸发率之间的定量关系。最后通过数学推导论述了上述各模型之间的内在联系。上述模型的建立为定量计算和精确模拟运动水体中氢氧稳定同位素组成的变化提供了确定性的数学基础,也为更客观、更充分的解译水的稳定同位素数据提供了帮助。     

盐场卤水成色原因分析及脱色方法研究

以天津汉沽盐场高镁卤水为研究对象,对其杂质形式、成色原因进行了系统分析。研究表明,卤水中的成色物质主要是大量的饱和脂类、羧酸类、醇醚类、胺类及不饱和的芳烃类、醛酮类、烯烃类等有机物质,经过氧化氢氧化-氢氧化锆吸附联合脱色工艺后,卤水色度及CODCr去除率分别可达99%和85%,镁离子的损失率可控制在1%以下,吸附剂氢氧化锆经脱附再生后可循环使用,大大降低了工艺运行成本。     

Hydrogen incorporation in orthopyroxene: interaction of different trivalent cations

The incorporation of hydrogen into ferrosilite, Fe-bearing enstatite and orthopyroxene containing different trivalent cations (Cr³⁺ and Al³⁺, Cr³⁺ and Fe³⁺) was investigated experimentally at 25 kbar. Hydrogen concentration was determined by FTIR-spectroscopy on oriented crystal sections and by secondary ion mass spectroscopy, whereas Mößbauer spectroscopy and optical spectroscopy were used to characterise the valence state of Fe in orthopyroxene. Results suggest that hydrogen incorporation in ferrosilite is achieved by a similar mechanism as in pure enstatite. In Cr-bearing samples, however, hydrogen incorporation is reduced by the presence of other trivalent cations by an increased tendency to form Tschermaks substitutions, e.g. Si _T ⁴⁺ + Mg _M1 ²⁺ ? Al _T ³⁺ + Cr _M1 ³⁺ . Thus, hydrogen solubility in natural orthopyroxenes from the Earth’s mantle, containing significant amounts of Cr³⁺, Al³⁺, and Fe³⁺, may be much more limited than expected from their trivalent cation content, as a large fraction of the trivalent cations does not participate in H-incorporating reactions as 2 Mg _M1 ²⁺ ? M _M1 ³⁺ + V_M1 + H _i ⁺ .     

Hydrogen bonding and vibrational properties of hydroxy groups in the crystal lattice of dioctahedral clay minerals by means of first principles calculations

The hydroxy groups of the crystal lattice of dioctahedral 2:1 phyllosilicates were investigated by means of quantum-mechanical calculation. The standard Kohn-Sham self-consistent density functional theory (DFT) method was applied using the generalized gradient approximation (GGA) with numerical atomic orbitals and double-zeta polarized functions as basis set. Isomorphous cation substitution of different cations in the octahedral and tetrahedral sheet was included along with several interlayer cations reproducing experimental crystal lattice parameters. The effect of these substitutions and the interlayer charge on the hydroxyl group properties was also studied. These structures represent different cation pairs among Al³⁺, Fe³⁺ and Mg²⁺ in the octahedral sheet of clays joined to OH groups. The geometrical disposition of the OH bond in the crystal lattice and the hydrogen bonds and other electrostatic interactions of this group were analyzed. The frequencies of different vibrational modes of the OH group [(OH), (OH) and (OH)] were calculated and compared with experimental data, finding a good agreement. These frequencies depend significantly on the nature of cations which are joined with, and the electrostatic interactions with, the interlayer cations. Besides, hydrogen-bonding interactions with tetrahedral oxygens are important for the vibrational properties of the OH groups; however, also the electrostatic interactions of these OH groups with the rest of tetrahedral oxygens within the tetrahedral cavity should be taken into account. The cation substitution effect on the vibration modes of the OH groups was analyzed reproducing the experimental behaviour.Dr. V. Botella passed away last February     

Hydrogen diffusion in Dora Maira pyrope

Kinetics of hydrogen extraction were investigated by FTIR spectroscopy on a Dora Maira pyrope single crystal. Annealing experiments were performed at ambient pressure, between 1073 and 1323 K, and under two different redox conditions (pO₂=0.21 atm and pO₂ 10^–16 atm). During hydrogen extraction the two principal OH absorption bands behave independently. The OHa triplet, centred on 3651 cm^–1, decreases at least five times faster than the OHb band at 3602 cm^–1. This suggests the presence of two distinct H defects, each with its own kinetics, which are slightly dependent on oxygen partial pressure:Both kinetics are slower than previous data (Wang et al. 1996), but activation energies are similar. At the same time as the OHa bands decrease, an exchange of hydrogen from OHa to OHb occurs. The extent of this transfer can be modelled by assuming it is directly proportional to the fraction of OHa band which has been removed, independent of temperature. This suggests that OHb defects could be produced by partial dehydrogenation of OHa defects. Activation energies and values of diffusion coefficients are very close to those found by Kohlstedt and Mackwell (1998) for the diffusion of metal vacancies in olivine. Thus it is very likely that cation vacancies control the kinetics of dehydrogenation reactions in pyrope.     

大柴旦温泉沟泉的地球化学成因

大柴旦温泉沟泉水作为柴达木盆地出露的典型富矿水体,对于揭示柴达木盆地成盐、成矿至关重要。为了研究泉水的地球化学成因,开展了热泉水、冷泉水和八里沟河流水体的元素和氢氧同位素地球化学研究及其对比分析,并结合区域地质构造特征对其水体的来源、水文过程形成了较为细化的新认识:温泉沟的泉水来源于冰雪融水,而与雨水关系不大;八里沟水体相对富集B、Li,且具有类似于泉水的地球化学特征,推断其成因与断裂带密切相关。对于岩浆水与泉水的关系,需要进一步开展研究。     

Origin and distribution of hydrogen sulfide in the Yuanba gas field,Sichuan Basin,Southwest China

The Yuanba gas field in the Permian Changxing Formation (P₂c), which exhibits wide variations in its hydrogen sulfide (H₂S) concentration (1.20–12.16%), is a typical sour gas field in the northern Sichuan Basin. The sulfur-rich reservoir's solid bitumen (atomic S/C ratios are 0.032–0.142), and late calcite cement δ¹³C values, which are smaller than the δ¹³C values of the host dolostone, indicate that the H₂S originated from thermal sulfate reduction (TSR) and oil was involved in TSR. The gas souring index (GSI) of P₂c's gases is generally lower than 0.1. The ethane δ¹³C values increase as the GSI increases, although no obvious increase was observed in the methane δ¹³C values. The calcite cements' δ¹³C values (−15.36 to +4.56‰) in dolostone are heavier than the typical reported values, which implies that only limited heavy hydrocarbon gases were involved in TSR. No anhydrites developed in P₂c's reservoirs, and dissolved sulfate anions (SO₄²⁻) were mainly enriched during dolomitization. Insufficient dissolved SO₄²⁻ most likely caused the lower H₂S concentrations in the Permian to Triassic reservoirs in the northeastern Sichuan Basin compared to the Permian Khuff Formation in Saudi Arabia and the Jurassic Smackover Formation in Mississippi. Except for the SO₄²⁻ in residual water in paleo-oil zones, SO₄²⁻ from bottom water may also be involved in TSR; therefore, oil reservoirs with bottom water have more SO₄²⁻ and can produce more H₂S than pure oil reservoirs. This phenomenon may be the main cause of the great difference in the H₂S concentrations between reservoirs, while gravitational differentiation during late uplift most likely creates differences in H₂S concentrations in a single reservoir. Carbon dioxide (CO₂), which has a relatively heavy δ¹³C value (−3.9 to −0.3‰), may be the combined result of TSR, the balance between CO₂ and inorganic fluid systems, and carbonate decomposition.