MAT 253气体同位素质谱仪测定微量氢同位素组成进样方法初探

幔源流体活动区天然气中微量H2是研究幔源H2同位素组成的最佳样品,但受目前测试技术的限制,能准确测试同位素组成的H2浓度下限仍然有待继续降低。前人研究表明,当H2浓度低于1.5%时,测试结果的误差较大,可信度较低,这可能与载气进样时在进样针孔附近发生了随机分馏有关。为了避免这种随机分馏,文章提出了一种利用压差进样的方法,即利用饱和NaC l溶液增加样品瓶内的压力实现进样。实验结果表明,利用这种进样方法,不同浓度条件下,H2同位素组成测试值的极差与标准偏差都随H2浓度的增加而减小,统计得到的绝对误差与仪器的误差范围相当。因此,该进样方法可以有效避免微量H2在进样过程中发生的随机分馏,提高测试结果的精度和可信度。同时表明可以对现有设备进行合理改造,挖掘仪器的测试潜能。     

氢氧同位素习性及其在四川盆地卤水成因分类的研究

依据氢、氧同位素地质学方法及其分布规律性，可将四川盆地广泛分布的卤水划分出四种类型：大气水渗入淋滤型、海相沉积型、海相沉积与大气降水叠加型、海相沉积与岩浆水叠加型卤水。用氢、氧同位素法研究水成因，分类明确，标志明显，有确定的成因涵义，应用效果良好，可弥补水文、地球化学法的不足。     

Mineral-chemistry and stable-isotope constraints on the magmatism, hydrothermal alteration, and related PGE–(base-metal sulphide) mineralisation of the Mesoarchaean Baula-Nuasahi Complex, India

The Baula-Nuasahi Complex, on the southern flank of the Singhbhum Archaean nucleus in north-eastern India, exposes a series of Mesoarchaean igneous suites. These are (1) a gabbro–anorthosite unit, which is petrographically homogeneous, although mineral-chemistry data hint at a subtle eastward differentiation; (2) a peridotite unit (with three chromitite layers) together with (3) a pyroxenite unit which display cumulate textures, modal layering, and (for the peridotite unit) differentiation trends in both mineralogy and mineral chemistry; and (4) the Bangur gabbro (~3.1 Ga), which defines an oblong intrusion, crosscutting the older igneous suites in the southern part of the complex, with a curvilinear NW-trending apophysis, 2 km long and up to 40 m wide. Magmatic breccia comprising ultramafic and chromitite wall-rock clasts in a gabbro matrix is exposed at the contact of the main Bangur gabbro body and also forms the entire Bangur gabbro apophysis. Concentrations of platinum-group minerals (PGMs) are found where the breccia contains abundant chromitite clasts, and two types of platinum-group-element (PGE) mineralisation are recognised. Type 1 (Pt 1.1–14.2, Pd 0.1–2.1 ppm, with an average Pt/Pd=8–9) is a contact-type mineralisation which occurs in the breccia at the contact between the Bangur intrusion and its ultramafic host. The PGMs—Pt alloys (isoferroplatinum) and sulphides (braggite, malanite)—are enclosed by pyroxene and plagioclase, reflecting a magmatic origin. Significant wall-rock assimilation by the magma (giving rise to the Bangur gabbro) is indicated by changes in pyroxene composition and by the presence of relicts of chromite (from the host) now altered to secondary ferritchromite in the contact zone. Type 2 PGE mineralisation (Pt 0.3–1.6, Pd 1.8–6.0 ppm, with Pt/Pd~0.5–3.0) is restricted to the breccia apophysis of the Bangur gabbro where it occurs in the breccia matrix, associated with an intense hydrothermal alteration which does not exist in the contact zone. PGMs (PGE arsenides, tellurides, bismuthides and antimonides) and, where present, base-metal sulphides (BMSs) form intergrowths with hydrous silicates, reflecting a hydrothermal origin. Oxygen isotope geothermometry documents the main stages of hydrothermal alteration within a decreasing temperature range between 700–1,000 and 500–600 °C, and oxygen, hydrogen and sulphur isotopes show that the hydrothermal fluids were derived from the magma rather than an external source. Pervasive hydrothermal alteration in the breccia apophysis likely represents upward channelling of late-magmatic fluids along a narrow, near-vertical, subplanar conduit which led away from the main magma chamber. We suggest that Type 2 mineralisation was produced by late-magmatic hydrothermal remobilisation and reconcentration of Type 1 PGE mineralisation, and that the composition of the hydrothermal fluids controlled whether BMSs were enriched along with the PGMs.Editorial handling: P. Lightfoot     

四川大渡河金矿田成矿流体来源的氦氩硫氢氧同位素示踪

四川大渡河金矿田位于扬子地台西缘金成矿带北段,受大渡河剪切带控制。本文以该矿田黄金坪、白金台子、黑金台子金矿为例,根据对黄铁矿流体包裹体氦氩同位素、黄铁矿硫同位素以及与黄铁矿共生的石英流体包裹体的氢氧同位素组成测定,讨论了大渡河金矿田成矿流体的来源。结果显示,该金矿田黄铁矿流体包裹体中的~3He/~4He变化较小,为0.16～0.86Ra,而~(40)Ar/~(36)Ar的变化较大,为298～3288;而黄铁矿δ~(34)S同位素变化范围较窄,一般为0.7‰～4.2‰,集中于2.5‰～3‰,显示硫地幔来源的特点;石英流体包裹体的氢、氧同位素分别为-2.6‰～ 3.64‰和-39.13‰～-108.23‰,说明成矿流体为岩浆水和大气降水的混合流体。本文认为大渡河金矿田成矿流体是地幔流体与地壳流体的混合作用的结果,而以地壳流体占主导地位。其中,地幔流体为与下伏隐伏岩体有关的岩浆水,而地壳流体端元则是含有一定放射成因Ar的大气降水,并且温度小于200℃。     

Hydrogen isotopic compositions, distributions and source signals of individual n-alkanes for some typical crude oils in Lunnan Oilfield, Tarim Basin, NW China

Petroleum mainly comprises carbon and hydrogen elements. The stable carbon isotopic analysis for whole oil was undertaken as early as the 1930s. After decades, the stable carbon isotopic analytical methods have been developed from analysis for whole oil and oil fractions (e.g., saturated, aromatic and polar frac-tions) into compound-specific isotopic analysis with the emergence of the newly developed GC-C-IRMS analytical technique. Especially, by using com-pound-specific isotopic analytical…     

Geological and Geochemical Characteristics of the Zhulazhaga Gold Deposit in Inner Mongolia, China

Located in Alxa Zuoqi (Left Banner) of Inner Mongolia, China, the Zhulazhaga gold deposit is the first largescale gold deposit that was found in the middle-upper Proterozoic strata along the north margin of the North China craton in recent years. It was discovered by the No. l Geophysical and Geochemical Exploration Party of Inner Mongolia as a result of prospecting a geochemical anomaly. By now, over 50 tonnes of gold has been defined, with an average Au grade of 4 g/t. The ore bodies occur in the first lithological unit of the Mesoproterozoic Zhulazhagamaodao Formation (MZF), which is composed mainly of epimetamorphic sandstone and siltstone and partly of volcanic rocks. With high concentration of gold,the first lithological unit of the MZF became the source bed for the late-stage ore formation. Controlled by the interstratal fracture zones, the ore bodies mostly appear along the bedding with occurrence similar to that of the strata. The primitiveore types are predominantly the altered rock type with minor ore belonging to the quartz veins type. There are also some oxidized ore near the surface. The metallic minerals are composed mainly of pyrite, pyrrhotite and arsenopyrite with minor chalcopyrite, galena and limonite. Most gold minerals appear as native gold and electrum. Hydrothermal alterations associated with the ore formation are actinolitization, silicatization, sulfidation and carbonation. A total of 100 two-phase H2O-rich and 7 three-phase daughter crystal-beating inclusions were measured in seven goldbearing quartz samples from the Zhulazhaga gold deposit. The homogenization temperatures of the two-phase H2O-rich inclusions range from 155 to 401℃, with an average temperature of 284℃ and bimodal distributions from 240 to 260℃ and 300 to 320℃ respectively. The salinities of the two-phase H2O-rich inclusions vary from 9.22wt% to 24.30wt% NaCl eqniv, with a mode between 23 wt% and 24wt% NaC1 equiv. Comparatively, the homogenization temperatures of the threephase daughter crystal-beating inclusions vary from 210 to 435℃ and the salinities from 29.13wt% to 32.62wt% NaCl equiv. It indicates that the ore-forming fluid is meso-hypothermal and characterized by high salinity, which is apparently different from the metamorphic origin with low salinity. It suggests a magmatic origin of the gold-bearing fluid. The δ^18O values of quartz from auriferous veins range from 11.9 to 16.3 per mil, and the calculated δ^18OH2O values in equilibrium with quartz vary from 1.06 to 9.60 per mil, which fall between the values of meteoric water and magmatic water. It reflects that the ore-forming fluid may be the product of mixing of meteoric water and magmatic water.Based on geological and geochemical studies of the Zhulazhaga gold deposit, it is supposed that the volcanism in the Mesoproterozoic might make gold pre-concentrate in the strata. The extensive and intensive Hercynian tectono-magmatic activity not only brought along a large number of ore-forming materials, but also made the gold from the strata rework. It can be concluded that the ore bodies were mainly formed in late hydrothermal reworking stage. Compared with typical gold deposits associated with epimetamorphic clastic rocks, the Zhulazhaga deposit has similar features in occurrence of ore bodies, ore-controlling structure, wall-rock alterations and mineral assemblages. Therefore, the Zhulazhaga gold deposit belongs to the epimetamorphic clastic rock type.     

Degradation of petroleum contaminants in oil

The treatment of diesel-contaminated soil with hydrogen peroxide oxidation is investigated in this paper. The factors influencing reactions such as initial oil content, H2O2 dosage, pH-value, catalyst and so on are studied. The results indicate that it is feasible to remediate diesel-contaminated soil by adding oxidant directly at room temperature because of higher absolute removal content although the degradation efficiency is low for the contaminated soil of 1%, 2% and 5% initial oil content. The more the H2O2 dosage, the better the degradation efficiency; it is economical and efficient to add 4 mL H2O2 to 10 g diesel-contaminated soil （2% or so） directly in-situ chemical oxidation （ICO）. For the contaminated soil of 5% initial oil content, when pH-value is 5-8 and H202 dosage is 20 mL, the removal efficiency reaches more than 96%; when pH-value is 1-3 and volume ratios of H2O2 to Fe^2＋ are 1 ： 1, 2：2, the degradation efficiencies are all very high （i.e., 86%-88% or so）. It can be concluded that the degradation efficiencies are comparative when adding 1 mL or 2 mL H2O2 of Fenton Reagent or adding 4 mL of H2O2 only to 10 g diesel-contaminated soil.     

Hydrogen Isotope Study of Fluid Inclusions in Vein Quartz of the Hishikari Gold Deposits, Japan

Abstract: The origin of mineralizing fluids responsible for the Hishikari vein-type epithermal Au deposits was studied on the basis of the hydrogen isotopic ratio (δD) of the inclusion fluid from vein quartz and adularia. The origin of hydrothermal fluids was estimated by combination of the present δ values and the oxygen isotopic ratios (δ¹⁸O) previously reported by Shikazono and Nagayama (1993). The water in the fluid inclusions was extracted by means of decrepitation of quartz at 500°C. Hydrogen was obtained by reduction of the collected water with Zn shot at 450°C. The δD values were determined by mass spectrometer. The δD values of inclusion fluid obtained from quartz range from –61 to –114%. These are significantly lower than the δD value of the thermal water presently venting from the Hishikari deposits and that of local meteoric water. Hydrogen isotopic fractionation between water and amorphous silica, which might have initially precipitated from the hydrothermal fluids at least partly, is not a probable cause of this isotopic depletion, while some water might have been released from the initial hydrous amorphous silica during recrystallization to quartz observed presently. Thus, a part of ore fluids for the Hishikari deposits is supposed to have been originated from the water having anomalous δD values of lower than –100%. Such D depletion cannot be caused by simple oxygen-shift of meteoric water or by contribution of magmatic volatiles. The δD values of water released from the shale samples of the Shimanto–Supergroup, a major host to the Hishikari veins range from –132 to –148%. Therefore, the anomalous δD values of inclusion fluids from some vein quartz and adularia suggest that the water released from hydrous minerals of the sedimentary basement rocks by dehydration or the groundwater isotopically exchanged with sedimentary rocks at elevated temperatures during circulation, partly contributed to the hydrothermal fluids responsible for the Hishikari deposits.     

橄榄石热解氢释放过程的分析

采用分步法热法分析了不同粒度的橄榄石的Ｈ２的质量体系,实验表明,不同粒度的橄榄石释放出的Ｈ２的质量体积不同,随着温度或粒度的变化,Ｈ２的质量体积呈现出规律性的变化,进一步探讨了氢在橄榄石中的赋存状态。     

轻烃及硫化物气体测量找寻多金属隐伏矿方法试验

挥发性有机化合物及硫化物气体作指标勘查金属矿床的工作国内外均处于初试阶段。近几年我们用硫化氢、二氧化硫及轻烃气体(C₁—C₄烷烃和烯烃)作指标对十个不同景观条件不同地区的铅锌矿、铜钼矿、金矿、铜镍等多金属矿床进行了土壤及地表岩石测量勘查隐伏矿的方法试验,取得很好的结果。表明该方法是寻找多金属隐伏矿的一种有效的气体测量方法,它可用于寻找覆盖厚度几米到400多米运积物覆盖区隐伏矿及基岩面下埋藏400多米盲矿的地表土壤和岩石测量以及岩体评价找矿工作。试验结果还表明该方法用于岩石测量的效果优于土壤测量。