A study on gas inclusions in minerals. Analysis of the gases from micro-inclusions in allanite

In order to determine the chemical composition of the gases from micro-inclusions in allanite a comparative study, using the methods of heating to decrepitation and grinding in vacuum was undertaken. The dependence of gas composition on the grain size was studied, too. The analysis of gases was carried out in a vacuum apparatus for micro-analysis; the measurement was volumetric. The experiments using the decrepitation method were made in the temperature interval 200–1100°C. CO₂, H₂, CO, CH₄, N₂, He, and water were identified and determined. However, a considerable part of these gases is probably due to chemical reactions. By grinding in a vacuum ball mill, only small amounts of H₂, N₂, and He were evolved. Some experiments showed that CO₂ and H₂O are strongly adsorbed on the ground material, thus being lost for the analysis.The results obtained from these two methods were supplemented with data obtained from a new method for studying the composition of gas inclusions, by tracing the gas composition as a function of the sample grain size. Using an approximate model it was shown that this dependence should be non-linear (hyperbolic). The amount of gases, due to inclusions, decreases parallel to the decrease in size of the mineral grains down to a certain limiting size. This dependence could not be observed if the grains are smaller than this limiting value. The method offers a possibility for taking into account the amounts of gases having another origin (desorption, chemical interactions, etc.), using the experimental plots. The results from the three series of experiments showed that the gas phase of inclusions in examined allanite consists mainly of CO₂. The other gases which were found by the decrepitation method could not be unambiguously ascribed to inclusions.     

Application of soil-gas geochemistry to mineral exploration in Africa

Field methods of soil-gas analysis for CO₂, O₂, Rn and Tn are described and applied to the exploration for copper sulphide and gold/sulphide mineralisation in terrains ranging from tropical rain forest to sand desert in Africa. CO₂ concentrations are high in soil gases overlying sulphide-bearing mineralisation and the patterns can be followed under increasing cover of sand to a depth of several tens of metres. The radioactive gases show promise in the mapping of basic rocks which are potential hosts to gold mineralisation. Strong seasonal effects on the CO₂ distribution are noted in tropical rain forests, the absolute levels being much higher during or following the rainy season.     

A review of the occurrence, form and origin of C-bearing species in the Khibiny Alkaline Igneous Complex, Kola Peninsula, NW Russia

The Khibiny Complex hosts a wide variety of carbon-bearing species that include both oxidized and reduced varieties. Oxidised varieties include carbonate minerals, especially in the carbonatite complex at the eastern end of the pluton, and Na-carbonate phases. Reduced varieties include abiogenic hydrocarbon gases, particularly methane and ethane, dispersed bitumens, solid organic substances and graphite. The majority of the carbon in the Khibiny Complex is hosted in either the carbonatite complex or within the so-called “Central Arch”. The Central Arch is a ring-shaped structure which separates khibinites (coarse-grained eudialite-bearing nepheline-syenites) in the outer part of the complex from lyavochorrites (medium-grained nepheline-syenites) and foyaites in the inner part. The Central Arch is petrologically diverse and hosts the major REE-enriched apatite–nepheline deposits for which the complex is best known. It also hosts zones with elevated hydrocarbon (dominantly methane) gas content and zones of hydrothermally deposited Na-carbonate mineralisation. The hydrocarbon gases are most likely the product of a series of post-magmatic abiogenic reactions. It is likely that the concentration of apatite-nepheline deposits, hydrocarbon gases and Na-carbonate mineralisation, is a function of long lived fluid percolation through the Central Arch. Fluid migration was facilitated by stress release during cooling and uplift of the Khibiny Complex. As a result, carbon with a mantle signature was concentrated into a narrow ring-shaped zone.     

青海木里三露天天然气水合物预判气测录井应用研究

气测录井以其可以灵敏、快速监测钻遇不同地层赋存烃类气体信息的优势而成为常规油气和非常规油气资源勘查的一种成熟技术手段。考虑到当钻具研磨赋存有天然气水合物的岩层时势必会导致其分解释放大量烃类气体并被气测录井仪器灵敏有效地监测,首次尝试利用气测录井方法在我国陆域冻土区-青海木里三露天天然气水合物调查区 进行钻探实时预判,建立天然气水合物的野外现场实时预判方法。最后,以DK8-19钻孔为例说明气测录井实时预判方法的应用、存在的问题及建议。实际应用结果表明,单一利用气测录井方法实时预判天然气水合物层段与地质和分析测试综合认识结果的吻合度可达到85.71%,而将上述三种方法结合可进一步提高野外识别天然气水合物的准确度。     

水中可溶气态烃和苯系物联测的新技术

地下水中的可溶气态烃和苯系物是水化学找油法的直接指标。应用直接抽取法,在色谱仪上同时测试C1—C4的烃类气体和苯系物,与传统的测试方法相比,具有无毒、无污染、简便、快速、灵敏度高、重现性好、自动化程度高的特点,有较高的实用价值。     

Isotopic signatures of CH4 and higher hydrocarbon gases from Precambrian Shield sites: A model for abiogenic polymerization of hydrocarbons

Previous studies of methane and higher hydrocarbon gases in Precambrian Shield rocks in Canada and the Witwatersrand Basin of South Africa identified two major gas types. Paleometeoric waters were dominated by hydrocarbon gases with compositional and isotopic characteristics consistent with production by methanogens utilizing the CO₂ reduction pathway. In contrast the deepest, most saline fracture waters contained gases that did not resemble the products of microbial methanogenesis and were dominated by both high concentrations of H₂ gas, and CH₄ and higher hydrocarbon gases with isotopic signatures attributed to abiogenic processes of water-rock reaction in these high rock/water ratio, hydrogeologically-isolated fracture waters. Based on new data obtained for the higher hydrocarbon gases in particular, a model is proposed to account for carbon isotope variation between CH₄ and the higher hydrocarbon gases (specifically ethane, propane, butane, and pentane) consistent with abiogenic polymerization. Values of δ¹³C for CH₄ and the higher hydrocarbon gases predicted by the model are shown to match proposed abiogenic hydrocarbon gas end-members identified at five field sites (two in Canada and three in South Africa) suggesting that the carbon isotope patterns between the hydrocarbon homologs reflect the reaction mechanism. In addition, the δ²H isotope data for these gases are shown to be out of isotopic equilibrium, suggesting the consistent apparent fractionation observed between the hydrocarbon homologs may also reflect reaction mechanisms involved in the formation of the gases. Recent experimental and field studies of proposed abiogenic hydrocarbons such as those found at mid-ocean spreading centers and off-axis hydrothermal fields such as Lost City have begun to focus not only on the origin of CH₄, but on the compositional and isotopic information contained in the higher hydrocarbon gases. The model explored in this paper suggests that while the extent of fractionation in the first step in the hydrocarbon synthesis reaction chain may vary as a function of different reaction parameters, δ¹³C values for the higher hydrocarbon gases may be predicted by a simple mass balance model from the δ¹³C values of the lower molecular weight precursors, consistent with abiogenic polymerization. Integration of isotopic data for the higher hydrocarbon gases in addition to CH₄ may be critical for delineation of the origin of the hydrocarbons and investigation of formation mechanisms.     

Galvanic interaction between grinding media and arsenopyrite and its effect on flotation: Part II. Effect of grinding on flotation

Arsenopyrite floatability was correlated with the galvanic current, calculated from polarization curves measured during grinding, as well as the amount of oxidized iron, measured by EDTA extraction, in the mill discharge. The adverse influence of galvanic interaction during grinding on arsenopyrite floatability was quantified.     

Geochemistry of natural gases in deep strata of the Songliao Basin, NE China

Chemical composition and stable carbon isotopic studies were undertaken for 27 gas samples from deep strata of the Xujiaweizi Depression in the Songliao Basin to investigate their origin. Gas molecular and carbon isotopic compositions show great variety. Methane is the main component for all studied samples and its content ranges from 57.4% to 98.2% with an average of 90.1%. Gas wetness ranges from 0.8% to 16.7% with an average of 2.7%. The main non-hydrocarbon gases are carbon dioxide and nitrogen with an average of 4.0% and 3.2%, respectively. Carbon isotope data suggest that these deep strata gases are mainly coal-type gases mixed with minor amounts of associated (oil-type) gases. Coal-type gases are characterized by heavier carbon isotopic values and drier chemical compositions. These gases were generated from the Lower Cretaceous Shahezi Formation coals interbedded shales with type III kerogen during the postmature stage of hydrocarbon generation. Oil-type gases are characterized by lighter carbon isotope and higher wetness, which were generated from the Lower Cretaceous shales with type II kerogen in the shallow strata during the early mature stage of hydrocarbon generation. Mixing of two different gases causes unusual carbon isotopic distribution patterns, with lighter isotopic values in higher numbered carbons in most gases. The discovery of coal-type gases in the Songliao Basin provides new prospects for the exploration in this region.     

油气化探样品酸解气中甲烷与氢气的相关性研究

酸解烃是油气化探方法中准确度相对较高的一项指标,已得到广泛的应用,深入研究酸解气有助于对其机理的进一步解释,并且有利于开发新的分析指标。本文利用气相色谱法测定了油气化探样品经盐酸分解后所得气体中烃类组分与非烃气体组分的含量,发现了酸解气中甲烷与氢气的含量具有正相关性。进而通过X射线荧光光谱和X射线衍射分析样品的元素和矿物组成、样品再粉碎分析以及激光拉曼光谱分析包裹体成分等实验,获得以下结论:(1)酸解气中的甲烷和氢气含量与样品元素组成无关,与碳酸盐矿物正相关,其含量可以反映深部油气的情况;(2)两种气体并不是以物理吸附形式存在于样品中,而是存在于更小的空间内,证明了酸解烃分析方法具有相当高的稳定性;(3)获得了甲烷和氢气同时存在于包裹体的直接证据,由此推测这两种气体可能具有同源性。由于甲烷和氢气含量相关性的存在,酸解脱气中氢气的含量测定有望成为油气化探的新指标,应用于油气资源调查。     

太原市大气颗粒物中有机物浓度的分布特征

首次研究了太原市大气颗粒物中的有机物分布特征。收集了太原市不同功能区冬夏两季的大气颗粒样品,经抽提分离取得饱和烃、芳香烃、非烃、沥青质4组馏分。分析结果表明:(1)大气颗粒中有机物浓度在取暖期高于非取暖期;(2)各功能区的有机污染程度不同,太钢工业区>长风剧场商业居民混合区>一电厂化工区、太行文化区。(3)各馏分浓度中沥青质含量普遍高,饱和烃含量最低,非烃、芳香烃馏分居中,且相对较低。(4)太原市整体污染主要为煤的燃烧和工业生产、尾气排放。     

Genetic classification of natural gases in the Bozhong Depression, Bohai Bay, China

The geochemical characteristics of natural gases discovered in the Bozhong Depression are systematically described in this paper. The natural gases are composed mainly of hydrocarbon gases. Natural gases occurring in the Paleogene and older reservoirs are wet gases, whereas those in the Neogene reservoirs are dry gases. Methane and ethane in the gases are significantly different in carbon isotopic composition. The methane carbon isotopic composition of the gases in structure BZ28-1 and the ethane carbon isotopic composition of the gases in structure QHD30-1 are characterized by the heaviest values, respectively. The natural gases are in the mature to highly mature stages. The hydrocarbon gases are of organic origin and can be classified as oil-type gases, coal-derived gases and mixed gases with the third one accounting for the major portion.     

Chemical and isotopic evidence for secondary alteration of natural gases in the Hetianhe Field, Bachu Uplift of the Tarim Basin

H₂S and CO₂ are found in elevated concentrations in the reservoirs near the Carboniferous–Ordovician unconformity in the Hetianhe Field of the Tarim Basin, NW China. Chemical and isotopic analyses have been performed on produced gases, formation waters and reservoir rocks to determine the origin of CO₂ and H₂S and to explain the heterogeneous distribution of isotopic and geochemical characteristics of petroleum fluids. It is unlikely that H₂S and CO₂ had a mantle component since associated helium has an isotope ratio totally uncharacteristic of this source. Instead, H₂S and CO₂ are probably the result of sulphate reduction of the light hydrocarbon gases (LHG). Increasing H₂S concentrations and CO₂/(CO₂+ΣC_1–4) values to the west of the Hetianhe Field occur commensurately with increasingly heavy hydrocarbon gas δ¹³C values. However, thermochemical sulphate reduction is unlikely because the temperatures of the reservoirs are too low, no H₂S or rare pyrite was detected in deeper reservoirs (where more TSR should have occurred) and inferred δ³⁴S values of H₂S (from late-stage pyrite in the Carboniferous and Ordovician reservoirs) are as low as −24.9‰. Such low δ³⁴S values discount the decomposition of organic matter as a major source of H₂S and CO₂. Bacterial sulphate reduction of the light hydrocarbon gases in the reservoir, possibly coupled indirectly with the consumption of organic acids and anions is most likely. The result is the preferential oxidation of ¹²C-rich alkanes (due to the kinetic isotope effect) and decreasing concentration of organic acids and anions. Modern formation water stable isotope data reveal that it is possible that sulphate-reducing bacteria were introduced into the reservoir by an influx of meteoric water from the west by way of an inversion-related unconformity. This may account for the apparently stronger influence of bacterial sulphate reduction to the west of the Hetianhe Field, and the consequent greatest decrease of the δ¹³C-CO₂ values and the greatest increase in δ¹³C values of the alkane gases.     

微量轻烃气体快速分析方法及其在金属矿化探中的应用

金属矿化探, 过去主要用金属及非金属元素作指标。用有机气体作指标的试验是国外近几年报导的。国内过去未开展过烃气找金属矿的试验工作, 因此也尚未研制和试验过适合于金属矿勘探用的轻烃分析方法。本文报导新近研制的轻烃测试方法。样品在真空容器中, 用酸分解脱出烃气, 用气相色谱法测定。一次可向时完成C₁—C₅共九项烷烯烃测定。样品的测定下限低, 甲烷为0.1μl/kg, 报出率100%, 相对偏差在±20%内。本方法已经过3000余件样品分析考验, 证明方法可靠。已在铅锌矿、金矿和构造断裂地区进行了测量试验, 不仅普遍探测到轻烃气的存在, 而且均获得了明显的异常显示。初步表明, 轻烃气体是一个值得进一步深入研究的良好地球化学指标。在金属矿上进行烃气测量试验, 在国内尚属首次。     

Computational simulation of seepage instability problems in fluid-saturated porous rocks: Potential dynamic mechanisms for controlling mineralisation patterns

Pore-fluid flow associated with seepage instabilities can play an important role in controlling large mineralisation patterns within the upper crust of the Earth. To demonstrate this process, two kinds of seepage instability problems in fluid-saturated porous rocks are considered in this paper. The first kind of seepage instability problem is caused by the temperature-induced buoyancy of pore fluid, so that it can be called the buoyancy-driven seepage instability problem, while the second kind of seepage instability problem is caused by chemical dissolution reactions that are commonly encountered in the upper crust of the Earth, so that it can be called the chemical-dissolution-driven seepage instability problem. After the mathematical governing equations of and computational methods for these two kinds of seepage instability problems are introduced, two numerical examples are used to elucidate how and why these two kinds of seepage instabilities can provide favorable places for the formation of large mineralisation patterns within the upper crust of the Earth. The related computational simulation results have demonstrated that: (1) the convective pore-fluid flow caused by the buoyancy-driven seepage instability not only can dissolve minerals at the lower part of the upper crust, but also can transport the dissolved minerals from the lower part to the upper part of the upper crust, resulting in large mineralisation patterns near the surface of the Earth's upper crust. (2) The chemical-dissolution-driven seepage instability in fluid-saturated porous rock can provide some favorable places, such as finger-like channels created by porosity enhancement in the porous rock, for the formation of large mineralisation patterns within the upper crust of the Earth.     

A comparison of selective extraction soil geochemistry and biogeochemistry in the Cobar area, New South Wales

In parts of the deeply weathered and semi-arid environments of the Cobar area (NSW, Australia), detection of mineralisation using conventional soil sampling and total metal analysis is impeded. This is due to the intense leaching of trace elements within the weathered profile, discontinuous coverage of transported materials and the existence of diffuse regional geochemical anomalies of ill-defined source. Selective chemical extractions, applied to various regolith components, and biogeochemistry offer a means of isolating localised geochemical patterns related to recent dispersion of trace elements through the overburden. Lag geochemical patterns across the McKinnons deposit (Au) and Mrangelli prospect (Pb–Zn–As) reflect mechanical dispersion processes and minor hydromorphic effects. Concentrations of more mobile elements tend to be higher in the non-magnetic fraction, due to higher proportions of goethite and poorly crystalline hematite than in the magnetic fraction. The subdued soil geochemical responses for metals extractable by cold 40% hydrochloric acid (CHX) and for total element concentration reflect the leached nature of the residual profile, low grade of mineralisation, dilution by aeolian components and disequilibrium of fine fractions with coarser, relict Fe-oxides. The stronger contrast for CHX for most metals, compared with total extraction, indicates surface accumulation of trace elements derived from underlying mineralisation. Enzyme leach element anomalies are intense but generally located directly over bedrock sources or major structural breaks, irrespective of the nature of the overburden. Though mechanisms for the dispersion of trace elements extracted by enzyme leaching are not well established, the lack of lateral transport suggests vertical migration of volatile metal species (atmimorphic dispersion). The strong, multi-element response to mineralisation in cypress pine needles indicates significant metal recycling during the present erosional cycle. However, a comparison of the trace element concentrations in vegetation (cypress pine needles) and selective extractions of soils indicates that recycling by the plants is not the dominant mechanism for transportation of metals through the overburden. The vegetation may be responding to hydromorphic dispersion patterns at depth. The use of selective extractions may be useful in detecting mineralisation through deeply leached profiles, but offers even greater potential when integrated with biogeochemistry to detect targets buried by significant thickness of transported cover.     

油、水、干层的地球化学识别

本文介绍一种判断油、水、干层的地球化学方法，根据储层样品中有机抽提的的含量和组成特征，结合油层物性，地层测试和试油资料编制织识别油、水，干层的图版，提出判别油、水、干层的地质／地球化学指标，确定油层的地球化学参数的下限，并运用此方法对松辽盆地新站油田主要油层分布段的油、水、干层进行判别。根据试油资料验证表明，地球化学判断结果比传统的地质录井及地球物理测井资料判断结果更符合实际情况。     

Biological marker characteristics of oils and asphalts from carbonate source rocks in a rapidly subsiding graben,Dead Sea,Israel

A detailed GC/MS study of biological marker compounds in the saturated and aromatic hydrocarbon fractions of oils and asphalts from the Dead Sea area, Israel, provided decisive information to the solution of a long-lasting controversy by showing that the asphalts are products of early generation in an immature stage from the same type of carbonate source rock which generated more mature oils. The asphalts are not biodegraded residues of the oils.Oils from six different wells, and asphalts from wells, outcrops, and a floating block from the Dead Sea all have very similar sterane and triterpane patterns. They all lack rearranged steranes (diasteranes) indicating a carbonate source matrix and compare reasonably well with a sample of Upper Cretaceous bituminous chalk from Nebi Musa. The main difference between the oils and the asphalts is a significantly higher triaromatic to mono- plus triaromatic steroid hydrocarbon ratio in the former. This is explained as a result of rapid subsidence and heating of their source rock close to the deep parts of the Dead Sea graben. The oils thus were generated in the more deeply buried source rock blocks under the graben fill, whereas the asphalts either originate from an immature source rock section closer to the graben rims or represent an earlier phase of generation and expulsion.This study also provides general information on the evolution of biological markers in carbonate source rocks. Low-activation-energy processes, like isomerisation of steranes, appear to occur much faster at low temperatures than in shales. The high sulfur content and less cross-linking of the biogenic organic matter into a complex kerogen structure are suggested to be responsible for this. Care should be taken when using only sterane isomerisation to assess the maturity of hydrocarbons from carbonate rocks and of carbonate-derived oils.     

烃源岩解析气获取新方法研究

新研制的解析气脱气集气装置,避免了前人装置的缺点,具有样品适应范围广、进样量大,真空破碎时间短、温度低,高真空脱气,无水集气等明显优势,从而确保了获取气体样品能够真实反映烃源岩解析气的地球化学特征。获取的解析气主要以烃类气体及二氧化碳气体为主,烃类气体相对百分含量最高可达到80%以上,可稳定检测出δ13C₁~δ13C₃数据,部分样品检测出δ13C₄~δ13C₅数据,所含地化信息丰富,完全满足了解析气地球化学研究和应用的需要。本次研究利用上述新的解析气实验地球化学技术,把气-源对比研究提升到一个崭新的境界,建立天然气气源直接对比的新方法和新思路,证实前人运用天然气碳同位素间接进行气源对比是科学可行的。同时,反证了新的解析气脱气集气装置的科学性和可靠性,为烃源岩解析气的研究和应用打下了科学的实验基础。
关键词       

显微激光拉曼光谱测定天然气水合物的方法研究

天然气水合物是由烃类气体在一定的温度和压力下与水作用生成的一种非化学计量的笼型晶体化合物,显微激光拉曼光谱是测定其水合指数、笼占有率等结构参数的重要手段。天然气水合物极易分解,不能在常温常压下进行分析测试。本文针对天然气水合物的特性,研制了一套适合显微激光拉曼光谱法测定水合物的小型装置,将样品放入液氮罐中,定期加入液氮(-196℃)保存,确保在测定的过程中甲烷水合物保持稳定状态,解决了肉眼不可见水合物的微观识别问题。对实验合成的一系列不同体系的甲烷水合物和我国海域和陆域的水合物样品进行了分析,探讨了水合物样品的合成、保存和处理方法,研究了拉曼光谱测试条件,揭示不同条件下形成的水合物笼型结构特征。分析结果表明,对同一样品,测定水合指数的相对标准偏差小于1%,方法准确可靠,经分析南海神弧海域水合物为典型Ⅰ型结构的水合物,祁连山冻土区水合物为Ⅱ型结构的水合物,可为我国天然气水合物研究提供必要的结构信息。     

Biogeochemical sampling for mineral exploration in arid terrains: Tanami Gold Province,Australia

Vegetation sampling is an effective mineral exploration technique in areas of transported cover in the Tanami Gold Province where other techniques have been of limited success. This research tests the ability of plants to show signatures of mineralisation as well as the optimum scale of sampling for first-pass mineral exploration surveys. The semi-arid Tanami Gold Province in northern Australia encompasses nearly 160,000 km² and is a highly prospective yet under-explored region due to transported cover masking mineralisation. Various dominant plant species were sampled along transects across four sites of Au mineralisation in the Tanami (Larranganni, Hyperion, Coyote and Titania). Snappy gum (Eucalyptus brevifolia) gave a geobotanical (plant distribution) and lithological (S and Zn) signature of an underlying geological structure known to host Au mineralisation at the Coyote Prospect. Soft spinifex (Triodia pungens) provided an Au, As, ± Zn, ± S, and ± Ce expression of buried Au mineralisation at Coyote and Titania. At the Hyperion prospect, mineralisation is located at the contact between granite and dolerite, and biogeochemical signatures from snappy gum and dogwood (Acacia coriacea) show elevated ± Au, Ce, S and Zn that corresponded to the contact. Biogeochemistry is able to determine the location of mineralisation at each site, except at Hyperion where the sample density was too low. It is able to identify underlying substrate differences, however, background knowledge relating to regolith, geology, hydrology and geophysics are important in aiding the interpretation of the elemental data. It was found that having too few samples (at Hyperion) there was insufficient useful information for mineral exploration. Grid coverage of an area (at Titania) provided information on mineralisation and groundwater dispersion plumes; however, in this case a single transect over the same area would have been sufficient for a first-pass mineral exploration survey.