海底沉积物孔隙水钡循环对天然气渗漏的指示

冷泉流体的渗漏活动强烈地影响着海底沉积物孔隙水钡循环。冷泉流体中的Ba2+ 向上扩散与孔隙水硫酸盐反应,在硫酸盐—碳氢化合物转化带（SHT）之上沉淀重晶石。随着沉积物的埋藏,先前沉淀的重晶石被埋藏于SHT之下的硫酸盐亏损带,将发生溶解,溶解的钡向上扩散,在SHT之上再次沉淀重晶石。当体系中向上扩散的Ba2+超过埋藏的重晶石中的钡时,在剖面上形成“钡锋”。向上渗漏的碳氢化合物（甲烷为主）通量控制了SHT的深度,二者之间存在很好的地球化学耦合关系,从而,可以用“钡锋”来评价天然气渗漏活动的特征。在总结和分析国际海底冷泉渗漏活动区沉积物孔隙水的甲烷和钡循环的研究进展基础上,综述了海底沉积物孔隙水钡循环对现在和过去天然气渗漏的指示,总结了渗漏成因重晶石的地质和地球化学特征。     

Microbial mobilization of barite

Bacteria from lake mud grown under anaerobic conditions with powdered barite present significantly increase the amount of barium that dissolves in the culture medium. Innocula of lake mud were added to a growth medium specified for sulfate-reducing bacteria. Powdered barite was added to each culture flask and flasks were purged with nitrogen, sealed and maintained at 20°C for 17 days. When the cultures were opened for analysis, hydrogen sulfide and iron sulfide had formed in all growing cultures. In cultures containing barite as the only sulfate, the barium content of the culture solutions had risen to an average of 3.3 ppm (maximum = 3.8 ppm, minimum = 1.8 ppm). Cultures containing ferrous sulfate and barite showed less than 0.1 ppm barium in solution. Cultures that had been sterilized by poisoning or autoclaving showed approximately 0.5 ppm barium in solution. Sulfate-reducing bacteria may be responsible for the high barium concentrations recorded in streams draining barite mining areas.     

南秦岭大型钡成矿带有机地球化学特征与生物标示物研究

在南秦岭一带的下寒武统硅岩建造中,既存在一大批重晶石矿床,又发育大量毒重石矿床,构成世界上极为罕见的大型钡成矿带。通过对矿床中岩矿石的热解、有机碳分析、氯仿沥青"A"抽提及生物标志化合物等研究,认为含矿地层中有机质的先质母体为菌藻类生物,某些生物标志物指标指示了沉积环境为封闭的缺氧环境。有机质演化受热和生物降解双重作用影响,接近和达到了成熟阶段。在含矿岩石与矿石中,Ba与有机碳含量具有不协调的负相关趋势,有机质成熟度越高,越利于Ba的富集。钡的超常富集,不仅是一个消耗大量有机碳的过程,而且是有机质成熟度不断加深的过程。     

Petrography and textural development of inorganic and biogenic lithotypes in a relict barite tufa deposit at Flybye Springs, NT, Canada

A relict mound of Holocene barite (BaSO₄) tufa underlies the Flybye Springs, a small, barium‐rich, cold sulphur spring system in the Northwest Territories of Canada. The tufa is composed of relatively pure barite with ≤0·34 wt% Ca²⁺ and ≤0·77 wt% Sr²⁺. The mound is made up of coated bubble, raft, undulatory sheet, stromatolitic, coated grain and detrital conglomerate barite tufa. Although previously unreported in barite, these lithotypes are akin to facies found in many carbonate spring deposits. Raft and ooid‐coated grain tufa was formed via ‘inorganic’ barite precipitation in spring water ponds and tributaries where rapid oxidation of sulphide to sulphate established barite supersaturation. Undulatory sheet tufa may have formed by the reaction of dissolved barium with sulphate derived from the oxidation of extracellular polysaccharide‐rich colloidal sulphur films floating in oxygenated, barite‐saturated spring water ponds. Coated bubble, oncoid‐coated grain and stromatolitic tufa with filamentous microfossils was formed in close association with sulphur‐tolerant microbes inhabiting dysoxic and oxygenated spring water tributaries and ponds. Adsorption of dissolved barium to microbial extracellular polysaccharide probably facilitated the development of these ‘biogenic’ lithotypes. Detrital conglomerate tufa was formed by barite cementation of microdetrital tufa, allochthonous lithoclasts and organic detritus, including caribou hair. Biogenic textures, organic artefacts and microfossils in the Flybye barite tufa have survived diagenetic aggradational recrystallization and precipitation of secondary cements, indicating the potential for palaeoecological information to be preserved in barite in the geological record. Similarities between the Flybye barite tufa and carbonate spring deposits demonstrate that analogous textures can develop in chemical sedimentary systems with distinct mineralogy, biology and physiochemistry.     

高频红外碳硫仪测定重晶石和黄铁矿中的硫

硫酸盐矿石和硫化物矿石大部分是低电磁性的物质,利用高频红外碳硫仪测定这类矿石中的硫时,在燃烧过程中难以产生较大的电磁感应涡流,导致矿石中的硫释放不完全,造成硫的测定结果偏低。本文采用二氧化硅将重晶石精矿和黄铁矿精矿稀释成不同硫含量的重晶石和黄铁矿样品,通过优化称样量及助熔剂等测试条件,建立了使用高频红外碳硫仪测定重晶石和黄铁矿中硫含量的分析方法。结果表明:当样品中的硫含量高于2%时确定称样量为0.07 g,当硫含量低于2%时确定称样量为0.1 g,加入助熔剂0.4 g锡粒+0.4 g铁粒+1.5 g钨粒,可使重晶石和黄铁矿中的硫完全释放进入仪器红外吸收区域,硫的回收率提高至95.8%~104.2%(重晶石)和95.3%~105.1%(黄铁矿),分别高于常规红外碳硫仪的回收率(83.39%~91.1%和91.5~97.5%)。本方法精密度高(RSD5%),实现了硫含量的准确测定。     

中国南部湿润半湿润丘陵山区不同粒级水系沉积物地球化学特征对比研究

不同景观条件下选取合适的采样粒级是准确地获取地球化学信息,提升地质找矿效果的关键。为研究中国南部湿润半湿润中低山丘陵景观区水系沉积物测量最佳采样粒级,本文在安徽省南部胡乐司—宁国墩地区开展了区域化探采样粒度方法技术试验,采集-60目和-10目~+80目两种粒级样品,采用波长色散X射线荧光光谱法和电感耦合等离子体质谱法为主体的配套分析方案和测试技术获取了全国区域化探扫面规定的40种元素高精度数据。研究表明:两种粒级水系沉积物中造岩元素背景含量与区域岩石背景值基本接近,其他微量元素多呈富集状态,以-10~+80目粒级中As、Au、Hg、Mo、Pb、Sb等成矿元素富集程度最强;-10~+80目粒级受后期表生改造作用影响较弱,最大限度保留了原生地球化学分布特征,并在准确圈定与矿化有关的异常和清晰反映矿致异常特征等方面明显优于-60目粒级。因此,建议在安徽省南部中低山丘陵景观区,选择-10~+80目粒级为水系沉积物测量的最佳采样粒级,研究结果可以为中国相似景观区地球化学勘查找矿水系沉积物测量采样粒级的选择提供参考。     

Manganese and ferromanganese ores from different tectonic settings in the NW Himalayas,Pakistan

In Pakistan manganese and ferromanganese ores have been reported from the Hazara area of North West Frontier Province, Waziristan agencies in the Federally Administered Tribal Areas and the Lasbela-Khuzdar regions of Baluchistan. This study is focused on comparison of mineralogy and geochemistry of the continental ferromanganese ores of Hazara and the ophiolitic manganese ores of the Waziristan area of Pakistan. In the Hazara area, ferromanganese ores occur at Kakul, Galdanian and Chura Gali, near Abbottabad, within the Hazira Formation of the Kalachitta-Margala thrust belt of the NW Himalayas of the Indo-Pakistan Plate. The Cambrian Hazira Formation is composed of reddish-brown ferruginous siltstone, with variable amounts of clay, shale, ferromanganese ores, phosphorite and barite. In Waziristan, manganese ores occur at Shuidar, Mohammad Khel and Saidgi, within the Waziristan ophiolite complex, on the western margin of the Indo-Pakistan Plate in NW Pakistan. These banded and massive ores are hosted by metachert and overlie metavolcanics.The ferromanganese ores of the Hazara area contain variable amount of bixbyite, partridgeite, hollandite, pyrolusite and braunite. Bixbyite and partridgeite are the dominant Mn-bearing phases. Hematite dominates in Fe-rich ores. Gangue minerals are iron-rich clay, alumino-phosphate minerals, apatite, barite and glauconite are present in variable amounts, in both Fe-rich and Mn-rich varieties. The texture of the ore phases indicates greenschist facies metamorphism. The Waziristan ores are composed of braunite, with minor pyrolusite and hollandite. Hematite occurs as an additional minor phase in the Fe-rich ores of the Shuidar area. The only silicate phase in these ores is cryptocrystalline quartz.The chemical composition of the ferromanganese ores in Hazara suggests that the Mn–Fe was contributed by both hydrogenous and hydrothermal sources, while the manganese ores of Waziristan originated only from a hydrothermal source. It is suggested that the Fe–Mn ores of the Hazara area originated from a mixed hydrothermal–hydrogenetic source in shallow water in a ontinental shelf environment due to the transgression and regression of the sea, while the Mn ores of Waziristan were formed at sea-floor spreading centers within the Neo-Tethys Ocean, and were later obducted as part of the Waziristan ophiolite complex.     

Barium anomaly in Kupa River drainage basin

The objective of this work is to present an example of environmental impact of barite waste management observed in stream sediments of the western part of the Kupa River drainage basin. It is a significant water resource for Croatia and a part of Slovenia. In addition, it is for both countries a region of tourism, sport and fishing. Sediments (fraction < 63 μm) collected within the whole drainage basin have shown a significant barium anomaly in the western part. The highest concentration of total barium (5790 mg/kg) was determined in Kupica, a tributary of Kupa River. The barium anomaly was traced in Kupa River about 120 km downstream. Looking for the contamination source it was found that the anomaly originates from uncareful waste disposal into an abyss, after barite separation in Homer (Lokve), Gorski Kotar, Croatia. From there barite entered Kupica River subterraneous. Barite and albite were identified by XRD near the source of Kupica River as minor minerals, while quartz and dolomite ferroan were major minerals. This preliminary report does not give yet an answer about barium solubility in river water, about its bioavailability and consequently about barium pollution in the western part of the Kupa River drainage basin, however the possibility is highlighted and discussed.     

Barite concretions as evidence of pauses in sedimentation in the Marnes Bleues Formation of the Vocontian Basin (SE France)

Several intervals rich in barite nodules occur in the mid-Cretaceous marls of the Vocontian Trough (SE France). These concretions, which grew on heterogeneities in the sediment, are arranged as horizons parallel to the bedding, and are often associated with carbonate and phosphate nodules. Detailed sedimentological and stratigraphical observations suggest that they represent the consequence of short-term pauses in sedimentation during early diagenesis, but the most important occurrences of barite are below prominent discontinuities. This may be explained by the frequency of pauses in sedimentation caused by a progressive starvation, or an increase in the energy of bottom-water currents. The high number of barite occurrences on the basin margins is directly linked to the recurrence of sedimentary breaks. The geochemical data show that the host sediment corresponds to a pelagic setting, far from hydrothermal influences, but generally in a restricted, dysoxic to suboxic, depositional environment. The sulphur isotopic composition of the barite sulphate (+16 to +76‰ rel. CDT) supports the hypothesis of an early diagenetic origin of the barite nodules. Their genesis may be explained by the fixation of a diagenetic front corresponding to the penetration of a sulphate reduction zone from the seawater–sediment interface down in the sediment which is in contact with barium-rich porewaters expelled upwards as a consequence of compaction. The barium of biogenic origin, initially stored in the underlying black shale, was mobilized under strongly reducing conditions. Such fixation is normally induced by a pause or a stop in sedimentation due to starvation or renewed bottom-water circulation. Together with other concretions, the barite nodules mark condensed stratigraphic intervals and often represent major breaks. As such they shed light on variations in sedimentary activity and their importance in the sedimentology and stratigraphy of pelagic marly sequences cannot be ignored.     

Hydrogeochemical exploration for barite, Ouachita Mountains, U.S.A.

Approximately 100 springs were sampled as part of a general geochemical survey in a 130 by 140 km multi-mineralized area of the Ouachita Mountains. The study area was subdivided into Area I and Area II based on differences in lithology and mineralization. Area I is composed primarily of the Paleozoic Stanley Shale and the Arkansas Novaculite Formation, and has considerable manganese (often present as psilomelane) and barite mineralization. The barite occurs primarily as replacement deposits in shale in Area I. Area II is composed of Paleozoic and Cretaceous sedimentary rocks, and Quaternary alluvium. Mercury, antimony, strontium and barite mineralization is present. The barite mineralization occurs as cement in the Cretaceous sandstone and gravel in this area.The widely prevalent barite cement in Area II is reflected by higher median and upper range values of barium concentration and also higher median and threshold % BaSO₄ saturation values. The presence of barite as cement in the sediments of Area II tends to mask the detection of the barite deposits in this area. Approximately 83% of the sites within 1.7 km of known barite mineralization in Area I were characterized by anomalous barium concentration, and 67% within 3.4 km. Anomalous % BaSO₄ saturation values and Ba/Sr ratios produced success rates generally similar to those of anomalous barium concentrations. Anomalous strontium concentrations did not prove effective in detecting barite mineralization.     

广西木圭上泥盆统乳房状构造及其地质意义

产于泥质硅岩层中顺层分布的燧石结核,外形似乳头向下的乳房。结核下顶端有残余小孔,内部有与外形和残余小孔相对应的分带性。外带为不完全交代带,常残留被交代围岩的残余;内带是球粒化的完全交代带。有时还出现结晶充填为特征的核部带。地质和岩石学证据显示乳房状构造是沉积物尚未固结时,由富含硅质的热水溶液的交代作用、结晶充填作用所形成,可作为热水体系在盆地底面附近作用的标志,亦可作为示序构造。类似构造也见于锰矿、重晶石矿和盆地灰岩中。     

天柱大河边重晶石矿床铅同位素特征及来源探讨

对取自天柱大河边重晶石矿床的重晶石样品和含方铅矿黑色页岩样品进行了铅同位素测定与研究.结果表明,在 Zartman铅构造模式图中,重晶石矿石、含方铅矿黑色页岩和黑色页岩有大致相同的铅同位素分布区,均沿上地壳铅演化线分布,表明它们之间具有同源关系;重晶石矿石及其赋矿黑色页岩的铅同位素组成与基底地层的铅同位素组成在 Zartman铅构造模式图中具有完全不同的分布范围,表明重晶石矿石中的铅不大可能来源于基底地层;结合重晶石矿石及其赋矿黑色页岩的铅同位素组成在 Zartman铅构造模式图和Δγ-Δβ铅来源分类图的分布,天柱大河边重晶石矿床的铅主要具上地壳铅、壳幔混合的俯冲带铅和热水沉积作用铅的混合来源特点,这为天柱大河边重晶石矿床的热水沉积成因提供了铅同位素证据.     

Seasonal cycle of suspended barite in the mediterranean sea

Biogenic barium (Ba_xs) was measured in suspended particles at the DYFAMED site in the northwestern Mediterranean Sea, on a monthly basis between February and June 2003. The barium content of barite (BaSO₄) micro-crystals was investigated using Scanning Electron Microscopy (SEM). Suspended particles were collected by filtration of small volumes of seawater (∼10 L), as well as large volumes up to 2400 L in March and in May. The Ba_xs profiles obtained from small-volume filtration display the typical mesopelagic maximum reported by earlier studies at ∼200 m depth, with concentrations up to 595 pmol L⁻¹. In addition, suspended Ba_xs was found almost exclusively in the form of micro-crystalline barite, except in February. The Ba_xs profiles obtained from large-volume filtration are consistent with the small-volume filtration findings, but reveal a significant Ba_xs peak of 1698 pmol L⁻¹ in the surface waters in May. Seasonal sampling at the DYFAMED site shows a net increase in barite concentration during phytoplanktonic blooms, confirming the involvement of biological systems in barite formation, as well as the potential role of barite as a primary productivity tracer. In addition, the coincidence between the mesopelagic barite maximum and the oxygen minimum layer suggests that barite is primarily found at depths of intense remineralization, in agreement with the hypothesis that barite forms within microenvironments of decaying organic matter.     

Calcite and barite precipitation in CaCO<Subscript>3</Subscript>-BaSO<Subscript>4</Subscript>-NaCl and BaSO<Subscript>4</Subscript>-NaCl-CaCl<Subscript>2</Subscript> aqueous systems: kinetic and microstructural study

During the production of hydrocarbons from subterranean reservoirs, scaling with calcium carbonate and barium sulfate causes flux decline and dangerous problems in production facilities. This work is intended to study the effect of calcium ions on the precipitation of barium sulfate (barite); then, the effect of the formed barite on calcium carbonate crystallization. The conductometric and pH methods were used to follow the progress of the precipitation reaction in aqueous medium. The obtained precipitates were characterized by FTIR, RAMAN, SEM, and XRD. It was shown that Ca²⁺ in the reaction media does not affect the microstructure of barite even for higher calcium–barium molar ratio. It influences the precipitation kinetics and the solubility of barite by the formation of CaSO₄° ion pairing as a predominant role of complex formation (CaSO4) and the increase of the ionic strength. In Ca(HCO₃)₂-BaSO₄-NaCl aqueous system, experiments have showed that added or formed barite in the reaction media accelerates calcite precipitation. No effect on the microstructure of heterogeneous formed calcite which remain calcite shape. However the presence of carbonate ions affects slightly the microstructure of barite.     

豫西嵩县上庄坪铅锌银矿床地球化学特征及地质意义

上庄坪铅锌银矿床是新一轮国土资源大调查中在北秦岭二郎坪群发现的硫化物矿床。笔者通过对矿床矿石、容矿同岩、重晶石岩的微量、稀土元素地球化学特征分析和地质特征研究,探讨成矿构造环境、成矿物质来源及矿床成因问题。研究表明.矿石和容矿围岩稀土元素球粒陨石标准化组成模式均为右倾型.矿石与围岩在Cu-Pb-Zn判别图解中投点区域一致.矿石Zn/(Zn Pb)与冲绳海槽和上向黑矿矿石特征相似、与TAG和EPR13°N区硫化物存在差异.矿石具较高As、Sb和Pb与低Cu、Cd和Se元素特征.认为该矿床成矿元素来源于壳幔混合、但以壳源为主的围岩变(石英)角斑岩和变细碧岩。矿石稀土元素、微量元素地球化学特征、矿床地质特征及与热水沉积重晶石岩和硅质岩的紧密共生关系说明,上庄坪矿床是弧后盆地构造环境海底热液喷流成岩成矿作用的产物。重晶石岩、硅质岩、矿床纵向和横向分带是寻找和勘探该类矿床的重要标志和依据。     

新疆阿舍勒铜矿区火山岩与成矿

阿舍勒铜矿曾被认为是次火山热液矿床。根据岩芯观察研究和同位素、微量元素及稀土元素地球化学研究,认为该矿属海相火山喷气沉积成因,成矿作用与双峰式火山岩密不可分,细碧岩是成矿金属元素的主要来源,而作为沉淀剂的硫主要由酸性火山喷气作用提供。     

The sedimentary structures of barite: examples from the Chaudfontaine ore deposit, Belgium

The Chaudfontaine ore deposit is composed mainly of barite and hosted in Frasnian shale and carbonate formations of Belgium. Thirteen sedimentary structures involving barite crystals are described and discussed. Many of these structures appear to have developed under gravity control. The role of mechanical and chemical ore apposition processes are detailed in each case. The study shows that two populations of barite were formed: (1) crystals which grew in brine above the water-sediment interface and (2) crystals which developed in the sediment during early diagenesis. The two modes of formation have specific sizes, habits and structures. Both populations crystallized under the control of the prevailing physico-chemical conditions, and the size and abundance of the barite crystals may be expressed as a function of the degree of barium supersaturation. High-energy currents and unstable sediment caused previously deposited crystals to be reworked. Morphological similarities were found between Chaudfontaine barite and gypsum from evaporites.     

重晶石矿石成分分析标准物质研制

研制了7个重晶石矿石成分分析标准物质。其中,GSO-1为铁矿型重晶石,GSO-2、GSO-3为萤石型重晶石,GSO-4、GSO-5为石英型重晶石,GSO-6为硫化物型重晶石,GSO-7为黏土型重晶石。样品采用陶瓷衬里的球磨机加工,加工后样品粒度达到-0.074 mm。采用X射线荧光光谱法检验了钡、铜、铅、锌、锆、铝、硅、铁和钙共9种元素的均匀性,并进行振动试验。8个实验室参加定值工作,提供了硫酸钡、氧化钡、三氧化硫和锶的7个标准值,全三氧化二铁的2个标准值,氟化钙的1个标准值及铜、铅、锌和水溶盐等标准值或参考值。2009年4月,7个样品已被国家质量监督检验检疫总局批准为国家一级标准物质,编号为GBW 07811~GBW 07817。     

Geological and geochemical constraints on the genesis of the Xiangquan Tl-only deposit,eastern China

The Xiangquan Tl deposit, located in the northern part of the Middle–Lower Yangtze Valley metallogenic belt, eastern China, is the only known Tl-only deposit. It is hosted in micritic limestone, marl and mudstone of the Lower Ordovician Lunshan Formation. The orebodies are controlled by the Xiao–Xiaolongwang–Dalongwang anticline and two reverse faults, and are generally stratabound and lenticular. Tl is only ore metal contained in disseminated, massive, brecciated and banded ores. The ore is composed of Tl-bearing pyrite, and gangue minerals quartz, fluorite, barite and carbonate. Alteration minerals include fluorite, barite, fine grained quartz and carbonate. Tl occurs isomorphously replacing iron in the lattice of pyrite, and less commonly as tiny independent Tl-bearing minerals which may be lafossaite (TlAsS₂) or lorandite (TlCl) appearing as 0.1–1 μm-sized cubic crystals. Xiangquan is a submarine sedimentary deposit and demonstrates that Tl, as a normally dispersed element, can form not only part of poly-metallic deposits but also as independent Tl deposits.