基于美国国家地热数据的地热温度计案例分析与方法适宜性评价

热储温度评价是地热系统研究的关键内容.文章选取建设比较成熟的美国国家地热数据系统(National Geothermal Data System,NGDS),分别利用地球化学地热温度计、多矿物平衡法、冷热水混合模型及气体地热温度计对不同地热田的热储温度进行评价,确定不同热储温度评价方法的适用性和局限性,以期为热储温度评...     

腾冲热海地热田热储结构与岩浆热源的温度

腾冲热海地区是一个由幔源岩浆侵入形成的地热田, 地热流体排放受深浅不同的三组活动断裂控制, 具多层地热储结构特征。气体、 同位素、 水化学地球化学温标显示, 深层热储的温度约为250±7℃、中、浅层地热储温度的变化范围分别为241～190℃和195～154℃。根据岩浆来源CO     

地热系统气-水-岩石体系化学热力学平衡及其模拟计算

结合在冰岛地热田所取得的实际资料,本文讨论了影响地热井中地热流体样品代表性的因素,深入探讨了地热系统中气-液、气-气间的化学热力学平衡过程,认为Fischer-Tropsch反应在冰岛Krafla地热田部分热储(t>240℃)中是能够达到或接近平衡状态的。文中详细阐述了在气-水-岩石体系中对矿物组合和气体浓度关系进行化学热力学模拟计算的方法,提出黄铁矿+磁铁矿+绿帘石+葡萄石同样控制着一些热储(t<220℃,Cl~-<500ppm)中硫化氢的浓度,并对二氧化碳、硫化氢地热温度计作了热力学评价。     

一种改进的硫酸盐硫同位素制样方法

硫酸盐-氧化亚铜-石英砂直接热解法需要设置分离SO₂、H₂O和CO₂的冷阱。研究表明H₂O和CO₂主要来自试剂石英砂的气液包裹体。采取石英砂预处理措施能大大减少制样过程引入的H₂O和CO₂。改进后的制样系统简单、易操作,且与硫化物同位素样品制备兼容。     

地热系统气体地球化学研究进展

地热系统气体地球化学是迅速发展起来的一个新领域。本文综述了有关地热田气体组份来源的研究工作,回顾了气体地热温度计的阶段性发展,提出了气体地热温度计的分类,概述了地热系统气—水—岩石体系化学热力学模拟的意义,报道了应用气体地球化学研究和开发地热田的进展。     

新疆塔什库尔干谷地地热资源研究进展

归纳了新疆塔什库尔干谷地地热地质条件,分析了区内地质构造、地温分布、地热流体化学及同位素特征,研究了地热形成机理,计算了曲曼地热田的地热资源量和可开采量。结果表明: 研究区地热资源受断裂构造控制; 地温变化与盖层、完整基岩、断裂带(热储)表现出明显的一致性,目前实测最高热储温度为161 ℃,深部热储计算温度可达222~268 ℃,地温梯度最高为149.20 ℃/100 m; 地热流体具有深循环特征,与浅表冷水的水化学和同位素特征具有明显的差异; 地热流体来源于大气降水,在断裂及裂隙内储存、运移、富集,在侵入岩体放射性生热和结晶余热的热量供应下,地下流体不断与围岩进行热量及物质交换,在热储围岩和盖层中,热量以传导方式为主,在热储内,热量以对流方式为主; 曲曼地热田储存的热量为55.919×10¹¹ MJ,地热流体可开采量约为12 593 m³/d,产能(热能)约为77.9 MW。因此认为,塔什库尔干谷地热储埋藏深度浅,易开采,具有可观的直接和间接经济价值。     

应用SiO2地热温度计估算地热储温度——以赣南横泾地区若干温泉为例

本文重点讨论了应用SiO2地热温度计估算横泾地区若干温泉的地热储温度，讨论表明，应用上升热水与浅部冷水没有混合的绝热冷却的SiO2(石英）-焓图和传导冷却的石英地热温度计，计算的地热储的最低温度范围是78-134℃，而最高的温度范围是95-155℃；应用上升热水与浅部冷水产生混合，而混合之前蒸气已全部损失的SiO2(石英）-焓图，计算的地热储的最低温度范围是83-138℃，因此，可以认为横泾地区温泉水地热储的最低温度范围可能是78-138℃，而最高温度范围可能是95-155℃。     

张掖盆地地热资源地质特征分析与研究

在野外实地调查张掖盆地地热资源的基础上,对研究区地热田特征、热储特征、热储温度以及温度场特征进行了分析和研究。研究结果表明:张掖盆地属张扭性盆地,有利地热运移和富集,属中低温地热资源;地热田热储为新近系及白垩系砂岩、砂砾岩、含砾砂岩等,厚度为536 m;经钾镁地热温标估算,热储温度60℃;盖层为新近系上新统疏勒河组泥岩、泥质砂岩层;热源来自地壳深部的热传导。通过对研究区地热田特征、热储特征、热储温度以及温度场特征的分析和研究,可以为当地政府进一步研究、勘探及开发地热资源提供依据。     

基于水文地球化学特征的辽宁丹东地区地热水成因模式研究

辽宁丹东地区地热资源丰富,阐明其地热田的成因模式对于区域热水资源的可持续开发利用具有重要意义。以区内北汤、东汤、五龙背地热田为研究对象,进行水化学和同位素分析。结果表明,北汤、东汤、五龙背地热水的水化学类型分别为SO₄·Cl-Na·Ca型、HCO₃·SO₄-Na型、 HCO₃-Na·Ca、HCO₃·SO₄-Na和HCO₃·Cl-Na型。研究区的热水来源为大气降水,北汤、东汤地热田的补给高程分别为678 m和376 m。根据¹⁴C测年方法,得出北汤、东汤和五龙背地热田地热水年龄分别为2 000~3 300 a B.P.、2 200~7 200 a B.P.和700~2 900 a B.P.。根据二氧化硅地温计和lg(Q/K)方法,北汤、东汤和五龙背地热田的热储温度分别为92 ℃、120 ℃和100~101 ℃,相应的地热水循环深度分别为1 900 m、3 000 m和800~1 800 m。地热水接收大气降水入渗补给,经断裂带深循环加热,于NNE和NW向两组断裂交汇处上涌进入浅部含水层或出露地表成泉,属中低温对流型地热系统。     

广东神灶海上温泉的流体地球化学特征及循环模式

广东神灶温泉出露于海水之中,揭示其流体循环机制对地热资源的可持续开发利用具有重要意义.通过采集神灶温泉区地热水、地热气体和海水样品,测试其流体地球化学组成及主要同位素组成,得到以下认识：神灶温泉水化学类型为Cl-Na·Ca型,主要由大气降水补给;水中盐分主要来自硅酸盐矿物溶解和现代海水混入,海水混入比例为29%～32%.利用化学温度计估算热储温度为130℃,地热水循环深度约4 km.地热气体以大气起源N₂为主要组分,CO₂、CH₄为壳内有机沉积物的热变质产物.此外,He同位素指示幔源组分占比不足5%,研究区大地热流值为67～69 mW/m².综上,神灶温泉区是以壳内放射性生热为主要热源的中温对流型地热系统.     

New gas geothermometers for geothermal exploration—calibration and application

Calibration of five gas geothermometers is presented, three of which used CO₂, H₂S and H₂ concentrations in fumarole steam, respectively. The remaining two use $\text{CO}{}_2\text{H}{}_2$ and $\text{H}{}_2\text{S}\text{H}{}_2$ ratios. The calibration is based on the relation between gas content of drillhole discharges and measured aquifer temperatures. After establishing the gas content in the aquifer, gas concentrations were calculated in steam formed by adiabatic boiling of this water to atmospheric pressure to obtain the gas geothermometry functions. It is shown that the concentrations of CO₂, H₂S and H₂ in geothermal reservoir waters are fixed through equilibria with mineral buffers. At temperatures above 230°C epidote + prehnite + calcite + quartz are considered to buffer CO₂. Two buffers are involved for H₂S and H₂ and two functions are, therefore, presented for the geothermometers involving these gases. For waters containing less than about 500 ppm chloride and in the range 230–300°C pyrite + pyrrholite + epidote + prehnite seem to be involved, but pyrite + epidote + prehnite + magnetite or chlorite for waters above 300°C and waters in the range 230–300°C, if containing over about 500 ppm.The gas geothermometers are useful for predicting subsurface temperatures in high-temperature geothermal systems. They are applicable to systems in basaltic to acidic rocks and in sediments with similar composition, but should be used with reservation for systems located in rocks which differ much in composition from the basaltic to acidic ones. The geothermometry results may be used to obtain information on steam condensation in upflow zones, or phase separation at elevated pressures.Measured aquifer temperatures in drillholes and gas geothermometry temperatures, based on data from nearby fumaroles, compare well in the five fields in Iceland considered specifically for the present study as well as in several fields in other countries for which data were inspected. The results of the gas geothermometers also compare well with the results of solute geothermometers and mixing models in three undrilled Icelandic fields.     

Hazardous gas emissions from the flanks of the quiescent Colli Albani volcano (Rome,Italy)

Gas hazard was evaluated in the three most important cold gas emission zones on the flanks of the quiescent Colli Albani volcano. These zones are located above structural highs of the buried carbonate basement which represents the main regional aquifer and the main reservoir for gas rising from depth. All extensional faults affecting the limestone reservoir represent leaking pathways along which gas rises to the surface and locally accumulates in shallow permeable horizons forming pressurized pockets that may produce gas blowout when reached by wells. The gas, mainly composed of CO₂ (>90 vol.%), contains appreciable quantities of H₂S (0.35–6 vol.%), and both represent a potentially high local hazard. Both gases are denser than air and accumulate near ground where they may reach hazardous concentrations, and lethal accidents frequently occur to animals watering at local ponds. In order to evaluate the rate of degassing and the related hazard, CO₂ and H₂S diffuse soil flux surveys have been repeatedly carried out using an accumulation chamber. The viscous gas flux of some important discrete emissions has been evaluated and the CO₂ and H₂S air concentration measured by portable devices and by Tunable Diode Laser profiles. The minimum potential lethal concentration of the two gases (250 ppm for H₂S and 8 vol.% for CO₂) is 320 times higher for CO₂, whereas the CO₂/H₂S concentration ratio in the emitted natural gas is significantly lower (15–159). This explains why H₂S reaches hazardous, even lethal, concentrations more frequently than CO₂. A relevant hazard exists for both gases in the depressed zones (channels, excavations) particularly in the non-windy early hours of the day.     

An improved cubic model for the mutual solubilities of CO2–CH4–H2S–brine systems to high temperature,pressure and salinity

The phase behavior of CO₂–CH₄–H₂S–brine systems is of importance for geological storage of greenhouse gases, sour gas disposal and enhanced oil recovery (EOR). In such projects, reservoir simulations play a major role in assisting decision makings, while modeling the phase behavior of the relevant CO₂–CH₄–H₂S–brine system is a key part of the simulation. There is a need for an equation of state (EOS) for such system which is accurate, with wide application range (pressure, temperature and aqueous salinity), computationally efficient and easy for implementation in a reservoir simulator.In this study, an improved cubic EOS model of the system CO₂–CH₄–H₂S–brine is developed based on the modifications of the binary interaction parameters in Peng–Robinson EOS, which is widely implemented in reservoir simulators. Thus the new model is suited for numerical implementation in reservoir simulators.The available experimental data of pure gas brine equilibrium and gas mixture solubility in water/brine are carefully reviewed and compared with the new model. From the comparison, the new model can accurately reproduce (1) the CO₂–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 1000 bar and NaCl molality (mole number in 1 kg water, molal is used for short) from 0 to 6 molal, (2) CH₄–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 2000 bar and NaCl molality from 0 to 6 molal, (3) H₂S–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 200 bar and NaCl molality from 0 to 6 molal, and (4) has good accuracy for gas mixture solubility in brine.     

Geochemistry of shallow aquifers and soil gas surveys in a feasibility study at the Rivara natural gas storage site (Po Plain,Northern Italy)

A geochemical survey, in shallow aquifers and soils, has been carried out to evaluate the feasibility of natural gas (CH₄) storage in a deep saline aquifer at Rivara (MO), Northern Italy. This paper discusses the areal distribution of CO₂ and CH₄ fluxes and CO₂, CH₄, Rn, He, H₂ concentrations both in soils and shallow aquifers above the proposed storage reservoir. The distribution of pathfinder elements such as ²²²Rn, He and H₂ has been studied in order to identify potential faults and/or fractures related to preferential migration pathways and the possible interactions between the reservoir and surface. A geochemical and isotopic characterization of the ground waters circulating in the first 200 m has allowed to investigation of (i) the origin of the circulating fluids, (ii) the gas–water–rock interaction processes, (iii) the amount of dissolved gases and/or their saturation status. In the first 200 m, the presence of CH₄-rich reducing waters are probably related to organic matter (peat) bearing strata which generate shallow-derived CH₄, as elsewhere in the Po Plain. On the basis of isotopic analysis, no hints of thermogenic CH₄ gas leakage from a deeper reservoir have been shown. The δ¹³C(CO₂) both in ground waters and free gases suggests a prevalent shallow origin of CO₂ (i.e. organic and/or soil-derived). The acquisition of pre-injection data is strategic for the natural gas storage development project and as a baseline for future monitoring during the gas injection/withdrawing period. Such a geochemical approach is considered as a methodological reference model for future CO₂/CH₄ storage projects.     

Gas genetic type and origin of hydrogen sulfide in the Zhongba gas field of the western Sichuan Basin, China

Natural gases and associated condensate oils from the Zhongba gas field in the western Sichuan Basin, China were investigated for gas genetic types and origin of H₂S by integrating gaseous and light hydrocarbon geochemistry, formation water compositions, S isotopes (δ³⁴S) and geological data. There are two types of natural gas accumulations in the studied area. Gases from the third member of the Middle Triassic Leikoupo Formation (T₂l³) are reservoired in a marine carbonate sequence and are characterized by high gas dryness, high H₂S and CO₂ contents, slightly heavy C isotopic values of CH₄ and widely variable C isotopic values of wet gases. They are highly mature thermogenic gases mainly derived from the Permian type II kerogens mixed with a small proportion of the Triassic coal-type gases. Gases from the second member of the Upper Triassic Xujiahe Formation (T₃x²) are reservoired in continental sandstones and characterized by low gas dryness, free of H₂S, slightly light C isotopic values of CH₄, and heavy and less variable C isotopic values of wet gases. They are coal-type gases derived from coal in the Triassic Xujiahe Formation.The H₂S from the Leikoupo Formation is most likely formed by thermochemical SO₄ reduction (TSR) even though other possibilities cannot be fully ruled out. The proposed TSR origin of H₂S is supported by geochemical compositions and geological interpretations. The reservoir in the Leikoupo Formation is dolomite dominated carbonate that contains gypsum and anhydrite. Petroleum compounds dissolved in water react with aqueous SO₄ species, which are derived from the dissolution of anhydrite. Burial history analysis reveals that from the temperature at which TSR occurred it was in the Late Jurassic to Early Cretaceous and TSR ceased due to uplift and cooling thereafter. TSR alteration is incomplete and mainly occurs in wet gas components as indicated by near constant CH₄ δ¹³C values, wide range variations of ethane, propane and butane δ¹³C values, and moderately high gas dryness. The δ³⁴S values in SO₄, elemental S and H₂S fall within the fractionation scope of TSR-derived H₂S. High organo-S compound concentrations together with the occurrence of 2-thiaadamantanes in the T₂l reservoir provide supplementary evidence for TSR related alteration.     

The microdetermination of H2O,CO2, and SO2 in glass using a 1280°C microscope vacuum heating stage,cryopumping, and vapor pressure measurements from 77 to 273 K

A new microscope vacuum heating stage and gas analyzer has been developed for measurement of H₂O, CO₂, SO₂, and noncondensable gas (H₂, CO, N₂, Ar, CH₄, etc.) evolved from samples, particularly natural glass, at temperatures up to 1280°C. The gas evolved upon heating to 1280δC is collected in a liquid nitrogen cold trap. Gas components are identified by the characteristic vapor pressure and temperature ranges over which solid and vapor are in equilibrium during sublimation of individual components. The masses of CO₂, SO₂, and H₂O derived from samples and blanks are calculated using the ideal gas law, the molecular weights of the components, and the gauge constant (i.e. the ratio of the number of moles of a gas to its partial pressure in the constant volume). Results obtained by repeated determinations of H₂O, CO₂, and SO₂ evolved from a submarine basaltic glass from Kilauea volcano, Hawaii, (average sample mass = 3 × 10^?3 g) gave probable errors for the determinations of H₂O (0.23%), CO₂ (0.025%), and S (0.071%) equal to 4, 10, and 8% respectively, of the concentrations. Determinations of H₂O in smaller samples of H₂O-poor basaltic pumice show a linear proportionality (0.063%) between the measured H₂O and the sample mass over the range 0.1 × 10^?6 to 1.7 × 10^?6 g H₂O. Comparisons of H₂O determinations by this technique with those obtained by Penfield, gas chromatic, microcoulometric, and vacuum fusion techniques used elsewhere show reasonably good agreement. Determinations of SO₂ by this technique agree reasonably well X-ray fluorescence and electron microprobe determinations of sulfur. Determinations of CO₂ by the present technique are reproducible but cannot be compared directly to measurements made in other labs because of differences in samples analyzed. The principle advantages of this analytical technique are the very small sample required, the simultaneous determination of H₂O, CO₂, SO₂ and noncondensable gas, the avoidance of calibration procedures dependent on chemical standards, and the visual observations that can be made during sample outgassing.     

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.     

Carbon and hydrogen isotopic compositions of New Zealand geothermal gases

Carbon and hydrogen isotopic compositions are reported for methane, hydrogen and carbon dioxide from four New Zealand geothermal areas: Ngawha, Wairakei, Broadlands and Tikitere. Carbon-13 contents are between ?24.4 and ?29.5%. (PDB) for methane, and between ?3.2 and ?9.1%. for carbon dioxide. Deuterium contents are between ?142 and ?197%. (SMOW) for methane and between ?310 and ?600%. for hydrogen. The different areas have different isotopic compositions with some general relationships to reservoir temperature.The isotopic exchange of hydrogen with water indicates acceptable reservoir temperatures of 180–260°C from most spring samples but often higher than measured temperatures in well samples. Indicated temperatures assuming ¹³C equilibria between CH₄ and CO₂ are 100–200°C higher than measured maxima. This difference may be due to partial isotopic equilibration or may reflect the origin of the methane. Present evidence cannot identify whether the methane is primordial, or from decomposing sediments or from reduction of magmatic CO₂. The isotopic equilibria between CH₄, CO₂, H₂ and H₂O are reviewed and a new semi-empirical temperature scale proposed for deuterium exchange between methane and water.     

High temperature mass spectrometric gas-release studies of Hawaiian volcanic glass: Pele's tears

The identification of gaseous molecular species and mechanisms of their release from glassy lava have been investigated with a high temperature mass spectrometer. Using Pele's tears as representative of quenched liquids of Hawaiian tholeiitic basalts, it was found that volatiles are released at low temperatures by a rate-limiting diffusion mechanism and, at temperatures in the softening range of the glass, by bursting of bubbles trapped near the vaporizing surface of the sphere-like particles.Gases released by bursting gave pressure surges and were found to be water vapor, CO₂ and CO. Those released principally by diffusion, and in some cases generated by thermal degradation and further reaction with the sample, include H₂, O₂, N₂, S₂, H₂S, SO₂, SO₃, COS, HCl, HF and NH₃. Average mole percent compositions of the volatiles H₂O, CO₂ and SO₂ relative to the total gas released were found to be 95 per cent, 3·5 per cent and 1 per cent, respectively. Minor concentrations of organic constituents, previously unobserved in volcanic gas analyses, were also found. Fragmentation patterns and gas release behavior suggest that these are derived from a mixture of low-molecular weight saturated and unsaturated acyclic hydrocarbons (C₁-C₄).     

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.