蔡家营铅锌银矿区CO2异常分布特征及其成因的讨论

本文介绍了蔡家营矿区壤中气CO₂和岩矿石中热释CO₂异常的分布特征。通过CO₂异常分布与矿体赋存关系的研究,对异常形成机理做了初步探讨,阐明了厚覆盖区CO₂异常的分布规律,以及在寻找隐伏矿、查明区域控矿构造中的作用。     

CO2气综合识别技术及应用

CO₂气藏由于其物理、化学性质的特殊性,CO₂气勘探与烃类气既有相同又有区别,综合应用多种资料和多种技术方法是识别CO₂气(层)藏的有效手段。利用区域地质分析、地球物理和地球化学勘探方法综合评价非烃气的分布,提出钻探目标,通过非烃色谱测量法和红外线CO₂气体浓度测量法实现CO₂气层钻井现场动态检测,利用气体色谱检测相关录井参数资料、核测井密度中子孔隙度差值综合解释CO₂气层,有效地识别CO₂气。主要介绍CO₂气藏综合勘探技术的关键的新技术方法,如地球化学方法、录井和测井综合识别的关键技术方法等。     

土壤温室气体昼夜变化及其环境影响因素研究

通过对北京东灵山草地和桦树林土壤气体CO₂,N₂O和CH₄浓度及其排放通量的昼夜连续观测,探讨了生长季节草地和森林土壤温室气体昼夜变化及其环境影响因素。研究表明:1)土壤CO₂排放通量昼高夜低,N₂O排放通量有明显小时尺度波动,但昼夜变化不突出;土壤CO₂和N₂O浓度昼夜变化不明显,且与排放通量波动不一致;土壤是大气CH₄的一个汇,相对厌氧的环境可能有利于土壤吸收CH₄。2)无雨时气温昼夜变化通过影响土壤表层的气体扩散和CO₂产生过程,来影响土壤CO₂和N₂O的地表排放通量,而对土壤10cm以下CO₂和N₂O的产生影响不大。小时尺度的土壤CO₂和N₂O浓度波动则可能还有其他影响因素或机制。3)降雨时土壤渗水引起的土壤空气对流取代气体浓度扩散成为土壤与大气空气交换的主要方式,导致土壤CO₂和N₂O排放通量的同步波动。降雨渗水较多时,较多的溶解氧随着雨水进入土壤内,会促进土壤CO₂的生成和抑制N₂O的产生。4)土壤CO₂与N₂O浓度存在显著的正相关关系,反映出土壤CO₂和N₂O有相对稳定的产率比。土壤有效碳可能是造成土壤CO₂与N₂O浓度正相关的主要原因,土壤空气的氧分压则可能是造成土壤CO₂和N₂O浓度波动不一致的重要因素。     

全球变化条件下的土壤呼吸效应

土壤呼吸是陆地植物固定CO₂尔后又释放CO₂返回大气的主要途径，是与全球变化有关的一个重要过程。综述了全球变化下CO₂浓度上升、全球增温、耕作方式的改变及氮沉降增加的土壤呼吸效应。大气CO₂浓度的上升将增加土壤中CO₂的释放通量，同时将促进土壤的碳吸存；在全球增温的情形下，土壤可能向大气中释放更多的CO₂，传统的土地利用方式可能是引发温室气体CO₂产生的重要原因，所有这些全球变化对土壤呼吸的作用具有不确定性。认为土壤碳库的碳储量增加并不能减缓21世纪大气CO₂浓度的上升。据此讨论了该问题的对策并提出了今后土壤呼吸的一些研究方向。其中强调，尽管森林土壤碳固定能力有限，但植树造林、森林保护是一项缓解大气CO₂上升的可行性对策；基于现有田间尺度CO₂通量测定在不确定性方面的进展，今后应继续朝大尺度田间和模拟程序方面努力；着重回答全球变化条件下的土壤呼吸过程机理；区分土壤呼吸的不同来源以及弄清土壤呼吸黑箱系统中土壤微生物及土壤动物的功能。当然，土壤呼吸的测定方法尚有待改善。     

沉积岩中无机CO2热模拟实验研究

结合三水盆地的地质特点，分析了无机CO₂热模拟实验研究的可能性，进行了不同条件下的模拟试验和相关的分析测试，提出了无机CO₂生成量和转化率的概念和计算方法。从实验结果来看：含有一定量碳酸盐矿物的沉积岩，在一定温度下可转化形成相当数量的无机CO₂，无机CO₂转化率越高，岩石中碳酸盐矿物越容易转化生成无机CO₂；相同热成熟度条件下，Ⅱ型干酪根生成有机CO₂的量较Ⅲ型的少；CO₂中碳同位素与CO₂的成因密切相关，随有机质热成熟度的增加，同种类型有机质生成的有机CO₂相对富集¹³C；无机CO₂较有机CO₂的碳同位素明显富集¹³C，随水介质的pH值降低，无机CO₂气含量、模拟温度及时间的增加，无机CO₂相对富集¹³C。实验研究结果为CO₂成因研究及其资源评价提供了实验依据。     

腾冲新生代火山区温泉CO2气体排放通量研究

近期研究表明,不仅火山喷发期会向当时的大气圈输送大量的温室气体,火山间歇期同样会释放大量的温室气体。在火山活动间歇期,火山区主要以喷气孔、温(热)泉以及土壤微渗漏等形式向大气圈释放温室气体。腾冲是我国重要的新生代火山区,同时也是重要的水热活动区,那里出露大量的温泉,然而目前未见腾冲火山区温泉气体排放通量的研究报道。本文利用数字皂膜通量仪测量了腾冲新生代火山区温泉中CO₂的排放通量。研究结果表明,腾冲新生代火山区温泉向当今大气圈输送的CO₂通量达3.58×10³ t·a^-1,相当于意大利锡耶纳Bassoleto地热区温泉中CO₂的排放规模。腾冲火山区温泉的CO₂释放通量主要受深部岩浆囊、断裂分布、地下水循环、围岩成分等多方面因素的影响。本文根据温泉中CO₂的排放特征,将腾冲温泉分为南北两区,南区温泉CO₂通量远高于北区的温泉,热海地热区的通量为腾冲CO₂通量的最大值。在北温泉区,CO₂通量主要受控于断裂的分布;而在南温泉区,除受到断裂控制外,热海地热区底部的岩浆囊及其与围岩的相互作用成为CO₂气体的重要物质来源,同时高温的岩浆囊为温泉及CO₂的形成提供了重要热源。     

利用化探精查技术检测二氧化碳气藏

化探精查技术检测二氧化碳气藏异常方法是基于油气渗透理论,通过对CO₂(土壤或水中)和土壤全烃、碳酸钙、汞、同位素、荧光等地表地球化学指标组合异常的分析,结合地质—地球物理资料,预测CO₂气藏分布。笔者通过对济阳坳陷花沟地区化探方法、化探资料和气藏分布的综合分析,在区域地球化学背景分析研究基础上,指出区带异常,并结合油气地质、地球物理资料,对圈定的化探异常区进行分级评价,预测CO₂气藏聚集的有利区带,探索化探精查预测技术检测CO₂气藏的方法。     

卫星遥感探测大气CO2浓度研究最新进展

大气CO₂是一种重要的长寿命温室气体,卫星遥感探测大气CO₂浓度,可以连续地获得其全球时空分布变化情况,进而提高对大气CO₂源汇分布及区域和全球碳循环的认识,进一步增强对全球气候变化的研究和预测。卫星遥感探测大气CO₂浓度已经开始成为一个新的研究领域,文章综合论述了利用卫星平台遥感探测大气CO₂浓度分布的最新研究状况。首先简单地叙述了现阶段对大气CO₂浓度时空分布和变化情况的直接仪器观测结果,在此基础上比较全面地综述了卫星遥感测量大气CO₂浓度的主要方法及获得的结果,包括利用近红外反射太阳光谱或地气热红外发射辐射光谱及两者的组合进行得模拟和卫星实测反演研究,最后简单地进行了总结和展望。     

云贵高原湖泊CO2的地球化学变化及其大气CO2源汇效应

湖泊是大气CO₂的源还是汇,长期以来一直都存有争议。云贵高原地区的湖泊由于受流域碳酸盐岩风化作用的影响,使这一问题就显得更特殊,也更复杂。本次研究通过化学平衡计算和气相色谱测定两种方法得到了比较一致的湖水CO₂浓度结果。研究发现,在夏季强烈的光合作用消耗了湖水CO₂,致使湖水中CO₂浓度降低。在贵州草海、百花湖以及云南的泸沽湖、杞麓湖,表层湖水CO₂分压(为便于与大气CO₂比较,文中湖水CO2用分压单位表示)小于200μatm,远低于大气CO₂分压,湖泊正不断地从大气中吸收CO₂,从而构成大气CO₂的汇。     

中国东部CO2气地球化学特征及其气藏分布

中国东部CO₂气田(藏)发育广泛,分布复杂。本文对中国东部松辽、渤海湾、苏北、三水、东海、珠江口、莺琼、北部湾等盆地和内蒙古商都地区以及部分现代构造岩浆活动区CO₂气田(藏)和气苗中CO₂的地球化学特征进行了分析和研究,探讨了中国东部CO₂气的成因、来源及分布。中国东部CO₂气的含量主要分布区间为0~10%,其次为90%~100%,呈现典型的U字型。δ¹³C_CO2值则呈现典型的单峰式分布,峰值区间为-6‰~-4‰。CO₂含量、δ¹³C_CO2值和R/Ra值综合表明,中国东部高含CO₂气以幔源无机成因为主,混有部分有机成因气和(或)壳源无机气。中国东部已发现的36个无机成因CO₂气田(藏)在空间分布上与新近纪及第四纪北西西向玄武岩活动带展布一致,深大断裂和岩浆活动是无机成因CO₂富集、运移和分布最重要、最直接的两大主控因素。     

Fluid inclusions in late minerals from the paleovalley-type uranium deposits of the West Siberian ore region: Thermochemical characteristics and genetic applications

Comprehensive microthermometric investigations revealed similar temperature ranges (280–120°C) for the formation of late carbonates in the Khokhlovskoe, Semizbai, and Malinovskoe deposits of the West Siberian uranium ore region. A close chemical similarity was definitely established between the solutions of fluid inclusions and thermal nitrogen-methane waters with elevated CO₂ concentrations typical of this region in general. It was noted that such CO₂-rich mineral waters (Yessentuki no. 4 type) are common in the Mesozoic sequences of the Shadrinsk region, where Transuralian uranium deposits occur, and are similar in composition and temperature to the modern CO₂-rich formation waters of the host sequences of the Khokhlovskoe deposit. The mineralogical and geochemical features of newly formed late minerals and uranium ores were considered as the most probable reflection of the exfiltration of such thermal solutions into the host levels. Two late mineral assemblages were distinguished: (1) hematite-calcite and (2) goethite-berthierine and goethite-smectite-chlorite with siderite or goethite-kaolinite-illite with siderite; they occur both in the host sequences and in the underlying basement rocks. The development of the latter assemblage causes a significant change in rock color (bleaching); it is widespread and was observed in all the deposits. It was shown that these altered rocks and uranium ores (especially high-grade) are very similar in mineral and chemical composition to the products of acid leaching and accompanying mineralization, which could be related to low-temperature argillization. It was suggested that exogenic epigenetic processes of ancient soil-bedrock oxidation contributed certainly to the development of uranium mineralization, and the modern character of the uranium ores and their host rocks is related to a large extent to the influence of hydrothermal CO₂-rich solutions related to the neotectonic activation of the region. This resulted in the development of their specific mineral and chemical compositions and corresponding technological characteristics. It seems expedient to estimate the possible contributions of exogenic and endogenic factors to the formation of the uranium mineralization rather than oppose the roles of these processes of different stages.     

The effect of Si and Al concentrations on the removal of U(VI) in the alkaline conditions created by NH3 gas

Remediation of uranium in the deep unsaturated zone is a challenging task, especially in the presence of oxygenated, high-carbonate alkalinity soil and pore water composition typical for arid and semi-arid environments of the western regions of the U.S. This study evaluates the effect of various pore water constituencies on changes of uranium concentrations in alkaline conditions, created in the presence of reactive gases such as NH₃ to effectively mitigate uranium contamination in the vadose zone sediments. This contaminant is a potential source for groundwater pollution through slow infiltration of soluble and highly mobile uranium species towards the water table. The objective of this research was to evaluate uranium sequestration efficiencies in the alkaline synthetic pore water solutions prepared in a broad range of Si, Al, and bicarbonate concentrations typically present in field systems of the western U.S. regions and identify solid uranium-bearing phases that result from ammonia gas treatment. In previous studies (Szecsody et al. 2012; Zhong et al. 2015), although uranium mobility was greatly decreased, solid phases could not be identified at the low uranium concentrations in field-contaminated sediments. The chemical composition of the synthetic pore water used in the experiments varied for silica (5–250 mM), Al³⁺ (2.8 or 5 mM), HCO₃⁻ (0–100 mM) and U(VI) (0.0021–0.0084 mM) in the solution mixture. Experiment results suggested that solutions with Si concentrations higher than 50 mM exhibited greater removal efficiencies of U(VI). Solutions with higher concentrations of bicarbonate also exhibited greater removal efficiencies for Si, Al, and U(VI). Overall, the silica polymerization reaction leading to the formation of Si gel correlated with the removal of U(VI), Si, and Al from the solution. If no Si polymerization was observed, there was no U removal from the supernatant solution. Speciation modeling indicated that the dominant uranium species in the presence of bicarbonate were anionic uranyl carbonate complexes (UO₂(CO₃)₂⁻² and UO₂(CO₃)₃⁻⁴) and in the absence of bicarbonate in the solution, U(VI) major species appeared as uranyl-hydroxide (UO₂(OH)₃⁻ and UO₂(OH)₄⁻²) species. The model also predicted the formation of uranium solid phases. Uranyl carbonates as rutherfordine [UO₂CO₃], cejkaite [Na₄(UO2)(CO₃)₃] and hydrated uranyl silicate phases as Na-boltwoodite [Na(UO₂)(SiO₄)·1.5H₂O] were anticipated for most of the synthetic pore water compositions amended from medium (2.9 mM) to high (100 mM) bicarbonate concentrations.     

刺猬沟金矿石英包体成矿溶液电导度和红外光谱找矿标型

石英是刺猬沟金矿重要的脉石矿物,也是金的主要载体.借助于成矿溶液电导度和红外光谱方法对刺猬沟金矿石英进行了分析,结果表明,成矿溶液电导度和红外光谱测定的DCO₂与石英中金含量呈正相关关系,成矿溶液电导度大于5.7 μS,DCO₂大于0.2矿化好.这对该找矿和矿床评价具有指导意义.     

Speciation and Precipitation of Uranium Complexes in Hydrothermal Solutions Related to Granite—type Uranium Deposits

Uranium-bearing hydrothermal solutions during the stage of ore deposition are weakly alkaline and of the Ca^2 -Na^ /HCO3^- -F^- type.UO2(CO3)2^2- and UO2F4^-, are dominant in the hydrothermal solutions with respect to their activity.Wall-rock hydrothermal alterations ,temperature and pressure drop and the reducing capability of rock assemblage (Δeh) led to a decrease in Eh of the hydrothermal solutions and an increase in Eh at which uranium began precipitating.Therefore,the mechanism of uranium precipitation is essentially the reduction of uranium complexes.The granite-type uranium deposits are the most important type of uranium resources in China.Discussions will be made in this paper concerning the hydrothermal speciation and precipitation mech-anisms of uranium complexes in the light of fluid inclusion and geological data from some major de-posits of this type in South China.     

纳米比亚欢乐谷地区白岗岩型铀矿床流体包裹体特征及成矿作用

文章对纳米比亚欢乐谷地区白岗岩型铀矿床流体包裹体的温度、盐度、密度和成分等进行了系统的分析研究,厘定了成矿流体的类型及基本性质,并对该地区铀成矿的物理化学条件和成矿流体来源进行了初步探讨。研究表明,该地区白岗岩型铀矿床的成矿流体可分为2个期次:主成矿期和叠加改造期。主成矿期的流体为岩浆晚期的残余高温、低盐度热液,其气相成分主要是CO2,含少量H2O、N2和CH4;叠加改造期的流体为中-低温、低盐度热液,其气相成分以CO2和H2O为主,含少量CH4和N2,来源于岩浆期后热液与大气水的混合。     

Uranium in supergene phosphorites

The distribution of uranium was studied in supergene phosphorites from the zones of the weathering of sedimentary and endogenous rocks, as well as in nonmarine coprolitic phosphorites and, to a lesser extent, phosphorites from ocean islands. These phosphorites show a diversity of the composition of their carbonate-apatite and structural characteristics. The uranium content ranges mostly from 5 to 100 ppm, with minimum and maximum values of 0.5 and 790 ppm. There is no correlation between the uranium content of a phosphorite and the type of rock with which it is connected. Lacustrine coprolitic phosphorites show elevated uranium contents (about 200 ppm). The maximum uranium content was detected in finely laminated phosphorite encrustations. The correlation analysis of the whole data set (63 samples) showed that uranium content is not correlated with any other component of phosphorites at a confidence level of 0.95. In contrast, there is a correlation between U and P₂O₅, CaO, and F for the combined set of samples from southern Siberian deposits. The significant correlation of U with Na₂O and CO₂ is variable both for southern Siberia on the whole and for particular deposits from this region.     

The effect of calcium on aqueous uranium(VI) speciation and adsorption to ferrihydrite and quartz

Recent studies of uranium(VI) geochemistry have focused on the potentially important role of the aqueous species, CaUO₂(CO₃)₃²⁻ and Ca₂UO₂(CO₃)₃⁰(aq), on inhibition of microbial reduction and uranium(VI) aqueous speciation in contaminated groundwater. However, to our knowledge, there have been no direct studies of the effects of these species on U(VI) adsorption by mineral phases. The sorption of U(VI) on quartz and ferrihydrite was investigated in NaNO₃ solutions equilibrated with either ambient air (430 ppm CO₂) or 2% CO₂ in the presence of 0, 1.8, or 8.9 mM Ca²⁺. Under conditions where the Ca₂UO₂(CO₃)₃⁰(aq) species predominates U(VI) aqueous speciation, the presence of Ca in solution lowered U(VI) adsorption on quartz from 77% in the absence of Ca to 42% and 10% at Ca concentrations of 1.8 and 8.9 mM, respectively. U(VI) adsorption to ferrihydrite decreased from 83% in the absence of Ca to 57% in the presence of 1.8 mM Ca. Surface complexation model predictions that included the formation constant for aqueous Ca₂UO₂(CO₃)₃⁰(aq) accurately simulated the effect of Ca²⁺ on U(VI) sorption onto quartz and ferrihydrite within the thermodynamic uncertainty of the stability constant value. This study confirms that Ca²⁺ can have a significant impact on the aqueous speciation of U(VI), and consequently, on the sorption and mobility of U(VI) in aquifers.     

Chemical factors controlling the solubility of uraninite and their significance in the genesis of unconformity-related uranium deposits

A quantitative evaluation of the solubility of uraninite (UO₂) in aqueous solutions under hydrothermal conditions was made using previously reported thermodynamic data, so as to inquire into the controlling factors for Canadian unconformity-type ore mineralization as observed in the Athabasca uranium field. The results of solubility calculations suggest that uranyl carbonate complexes, such as UO₂CO ₃ ^o , UO₂(CO₃) ₂ ^2- and UO₂(CO₃) ₃ ^4- , predominate under relatively oxidizing and slightly acidic-alkaline conditions and that the uranyl chloride complex, UO₂Cl⁺ is dominant under acidic conditions. These features are predicted at temperatures up to 200 °C over reasonable ranges of CO₂ pressure (Pco₂) and salinity. Consequently, the physico-chemical parameters, such as oxygen activity (ao₂), and pH are regarded as the most important factors controlling uraninite solubility. Judging from the paragenetic sequences observed in most unconformity-type uranium deposits in the Athabasca district, appreciable decreases in the above variables are postulated to have occurred in the stage of principal uranium deposition. Such changes would be due to fluid-mixing phenomenon accompanied by the diagenetic-hydrothermal activity (Hoeve and Quirt 1987).     

Mechanism of mineralization in the Changjiang uranium ore field,South China: Evidence from fluid inclusions,hydrothermal alteration,and H–O isotopes

The Changjiang uranium ore field, which contains >10,000 tonnes of recoverable U with a grade of 0.1–0.5%, is hosted by Triassic two-mica and Jurassic biotite granites, and is one of the most important uranium ore fields in South China. The minerals associated with alteration and mineralization can be divided into two stages, namely syn-ore and post-ore. The syn-ore minerals are primarily quartz, pitchblende, hematite, hydromica, chlorite, fluorite, and pyrite; the post-ore minerals include quartz, calcite, fluorite, pyrite, and hematite. The fluid inclusions of the early syn-ore stage characteristically contain O₂, and those of the late syn-ore and post-ore stage contain H₂ and CH₄. The fluid inclusions in quartz of the syn-ore stage include H₂O, H₂O–CO₂, and CO₂ types, and they occur in clusters or along trails. Homogenization temperatures (T_h) for the H₂O–CO₂ and two-phase H₂O inclusions range from 106 °C to >350 °C and cluster in two distinct groups for each type; salinities are lower than 10 wt% NaCl equiv. The ore-forming fluids underwent CO₂ effervescence or phase separation at ∼250 °C under a pressure of 1000–1100 bar. The U/Th values of the altered granites are lowest close to the ore, increase outwards, but subsequently decrease close to unaltered granites. From the unaltered granites to the ore, the lowest Fe₂O₃/FeO values become lower and the highest values higher. The REE patterns of the altered granites and the ores are similar to each other. The U contents of the ores show a positive correlation with total REE contents but a negative correlation with LREE/HREE ratios, indicating the pitchblende is REE-bearing and selectively HREE-rich. The δEu values of the ore show a positive correlation with U contents, indicating the early syn-ore fluids were oxidizing. The δCe values show a negative correlation, indicating the later mineralization environment became reducing. The water–rock interactions of the early syn-ore stage resulted in oxidization of altered granites and reduction of the ore-forming fluids, and it was this reduction that led to the uranium mineralization. During alteration in the early syn-ore stage, the oxidizing fluids leached uranium from granites close to faults, and Fe₂O₃/FeO ratios increased in the alteration zones. The late syn-ore and post-ore alteration decreased the Fe₂O₃/FeO ratios in the alteration zones. The δ¹⁸O_W–SMOW values of the ore-forming fluids range from −1.8‰ to 5.4‰, and the δD_W–SMOW values range from −104.4‰ to −51.6‰, suggesting meteoric water. The meteoric water underwent at least two stages of water–rock interaction: the first caused the fluids to become uranium-bearing, and the second stage, which was primarily associated with ore-bearing faults, led to uranium deposition as pitchblende, accompanied by CO₂ effervescence.