Chemical speciation of redox sensitive elements during hydrocarbon leaching in the Junggar Basin,Northwest China

Bleaching related to seepage of petroleum fluids and subsurface migration of crude oil and natural gas can alter the chemical and mineralogical properties of rocks, while concurrently depleting hydrocarbon reservoirs. Mud volcanoes constitute one type of petroleum seepage present in several areas on the southern margin of the Junggar Basin in the Xinjiang Uygur Autonomous Region, NW China. The results of XRD, XRF, XANES, and Mössbauer spectroscopy on rock samples collected from areas affected by these mud volcanoes revealed an enrichment of certain minerals and elements, as well changes in mineralogical, molecular, or ionic carrier (“species”). After bleaching, reddish sedimentary rocks showed depletion in silica and enrichment of calcium, magnesium, manganese, and iron. Other elements, including aluminum, potassium, sodium, and titanium, were largely unchanged. Reduced iron and sulfur compounds predominated in the bleached rocks, producing changes in color from the original reddish into green, deep gray, and black. Iron and calcium were associated with carbonates, indicating carbonation of these elements during the bleaching processes. Manganese also appeared to be associated with carbonate, though not with sulfate even though sulfate was present in the bleached rocks. Alkaline conditions were apparently the dominant because reduced manganese would have been absent under acidic condition. The alteration of certain minerals, clay minerals in particular, was also observed in bleached rocks, the alteration of smectite-group minerals to chlorite and muscovite, for example. Mineralogical and geochemical changes in rocks bleached by hydrocarbon fluids could provide a better overall understanding of bleaching processes, and may have applications in surface geochemical exploitation and remote imaging.     

Neotectonic stage in the formation of the Khokhlovskoe uranium deposit, eastern Transural region: Structural, hydrochemical, mineralogical, and geochemical formation conditions

The structural, hydrochemical, mineralogical, and geochemical features of the Khokhlovskoe uranium deposit related to neotectonic processes are considered. The structural feature is expressed in neotectonic dislocations in the form of overall intense fragmentation of host rocks and widespread low-amplitude strike-slip faulting. The hydrochemical specificity is determined by the appearance of thermal carbonated formation water in ore-bearing aquifers. This water is similar in chemical and gas composition to hydrothermal solutions in fluid inclusions and mineral waters abundant in this district. The mineralogical and geochemical features comprise the occurrence of newly formed ferroan carbonates and late iron hydroxides in altered (bleached) pelitic rocks; the formation of silicic opal segregations in ore-bearing sand and sandstone; late sulfides, arsenides, and selenides of iron and other metals; and multiphase gel-pitchblende enriched in Zr especially typical of high-grade uranium ore. The age of high-grade ore determined by a precision uranium-ionium method coincides with the time when thermal carbonated water appeared in the host rocks. This time was estimated from a mathematical model of heat transfer and regional dynamics of underground water. This coincidence clearly indicates that the aforementioned processes are related to the late Quaternary neotectonic reactivation of the eastern Transural region.     

Genesis and formation conditions of deposits in the unique Strel’tsovka Molybdenum-Uranium ore field: New mineralogical,geochemical, and physicochemical evidence

The ambiguity of genetic interpretations of uranium ore formation at Mo-U deposits of the Strel’tsovka ore field led us to perform additional geochemical, mineralogical, and thermobarogeochemical studies. As a result, it has been established that closely related U and F were progressively gained in the Late Mesozoic volcanic rocks from the older basic volcanics (170 Ma) to the younger silicic igneous rocks (140 Ma). The Early Cretaceous postmagmatic hydrothermal epoch (140–125 Ma) is subdivided into preore, uranium ore, and first and second postore stages. The primary brannerite-pitchblende ore was formed in association with fluorite. At the first postore stage, this assemblage was replaced by a U-Si metagel, which was previously identified as coffinite. The metagel shows a wide compositional variation; its fine structure has been studied. The preore metasomatic alteration and related veined mineralization were formed under the effect of sodium (bicarbonate)-chloride solution at a temperature of 250–200°C. The uranium ore formation began with albitization and hematitization of rocks affected by supercritical fluid at 530–500°C; brannerite and pitchblende precipitated at 350–300°C. The chondrite-normalized REE patterns of pitchblende hosted in trachybasalt, trachydacite, and granite demonstrate a pronounced Sm-Nd discontinuity and a statistically significant tetrad effect of W type. These attributes were not established in REE patterns of rhyolites derived from the upper crustal magma chamber. This circumstance and a chronological gap of 5 Ma between silicic volcanism and ore formation do not allow us to suggest that uranium was derived from this magma chamber. According to the proposed model, the evolved silicic Li-F magma was a source of uranium. U⁴⁺, together with REE, was fractionated into the fluid phase as complex fluoride compounds. The uranium mineralization was deposited at a temperature barrier. It is suggested that hydromica alteration and the formation of molybdenum mineralization were genetically unrelated to the uranium ore formation.     

Problems of Iron and Phosphorus Geochemistry in the Precambrian

The localization of economic sedimentary iron ore and phosphorite resources is discussed in comparative aspects. It is shown that the major economic resources of iron ore are hosted in Precambrian rocks, whereas the phosphorites are related to Upper Phanerozoic. High-temperature hydrothermal solutions served as an important source of iron for jaspilite ores. The low P₂O₅content therein indicates that the phosphorus deposition was only weakly related to the hydrothermal activity. Thus, the hydrothermal origin of phosphorite is denied from the geochemical standpoint.     

Metamorphic disturbances of magnetite chemistry and the Sm-Nd isotopic system of reworked Archean iron formations from NE Brazil

Iron formations are valuable archives of sedimentary conditions and post-depositional events. However, geochemical proxies commonly used to determine genetic characteristics can be variably modified during metamorphism and deformation, hampering their use as records of regional geological events. This work focuses on strongly reworked magnetite-quartz-rich rocks from the São José do Campestre Massif, one of the oldest fragments of preserved crust in South America. The genetic classification of these magnetite-quartz-rich rocks is not straightforward because primary assemblages and textures were variably modified by granulite facies metamorphism during a regional Paleoproterozoic migmatization event. To address genetic ambiguities, we analyzed their magnetite and pyroxene chemistry, whole-rock geochemistry, and Sm-Nd isotopes. Magnetite chemistry indicates that pyroxene-poor iron formations (Type B) are low in trace elements such as Ti, Al, V, and Mn, suggesting a chemical similarity to iron formations elsewhere. In contrast, magnetites from pyroxene-enriched Type A iron formations are rich in trace elements and more akin to magnetite crystallized from higher temperature systems, such as skarn and IOCG. The ¹⁴⁷Sm/¹⁴⁴Nd of these rocks show substantial variation even at the outcrop scale, indicating a locally-controlled, highly heterogeneous mixture of Archean, Paleoproterozoic, and Neoproterozoic sources. Therefore, our geochemical tools point out to heterogenous signatures of these magnetite-quartz rocks and proxies compatible with both low and high-temperature conditions and age of deposition spanning sources from the Archean to the Neoproterozoic. We interpret that the studied São José do Campestre magnetite-quartz rocks represent Archean iron formations with original magnetite chemistry and isotopic signatures variably modified by metamorphism and by at least one deformation-related hydrothermal event. These results contrast with similar examples from China and Greenland where iron formations either preserved the magnetite chemistry or the primary isotopic signatures. Our study indicates that metamorphism can selectively affect chemical proxies used to study iron formations and undermine the genetic classification of iron ores. Thus, these proxies should be carefully applied in the interpretation of syn-depositional environments of polydeformed belts.     

On the origin of bleaching phenomena in red bed sediments of Triassic Buntsandstein deposits in Central Germany

The Lower Triassic Buntsandstein in Central Germany comprises one of the major clastic, lithified hydrocarbon reservoirs, it is a major groundwater aquifer and it is considered as a potential underground gas storage lithology. Thus, sandstones of the Buntsandstein from Thuringia and NE Hesse were used to analyse their geochemical composition combined with mineralogical data in order to investigate the origin of several bleaching phenomena in primary red beds, since these give a hint for mineral alteration, mineral formation and mineral reactivity in the course of fluid-rock-interactions. This is relevant for e.g. recent Carbon Capture and Storage (CCS) efforts. The origin of the observed bleaching phenomena is diverse and it is linked to certain stages of diagenesis and different episodes of fluid flow: (1) eodiagenetic bleaching coupled with palaeosoil formation and iron mobilisation, (2) mesodiagenetic bleaching as a result of hydrocarbon migration, (3) Tertiary bleaching due to CO₂ degassing from Miocene volcanism, (4) Tertiary telodiagenetic bleaching due to weathering under humid climate conditions, and (5) weathering processes related to recent telodiagenesis/pedogenesis. This study emphasizes the multiple nature of fluids, which can induce iron mobilisation and bleaching of red beds.     

年轻冰川沉积砾石的晒退特征及其对岩石释光埋藏测年的启示

不完全晒退/晒退不均现象是冰川沉积物释光测年所面临的巨大挑战,这一问题限制了传统颗粒沉积物释光方法在冰川沉积物测年方面的应用。最新发展的岩石释光埋藏测年技术,可以根据释光-深度曲线判断砾石是否经历过充分曝光,是解决冰川沉积晒退不均问题的有效途径之一。本工作选择青藏高原东部硬普沟现代冰川前沿为研究对象,采集130个年轻冰川沉积砾石样品,包括93个现代样品和37个小冰期样品,其中20个现代样品采自地表。首先,运用表_{~2 mm}/饱和信号法区分不同冰川沉积环境中砾石样品的晒退程度;再基于SAR和SGC法初步估算样品的等效剂量及其高估情况;然后,统计砾石样品的特征（磨圆度、球度、颜色、晶粒大小、晶粒相对大小、砾石大小等）与晒退程度的关系,找寻晒退良好的砾石及其特征。结果表明大部分采样点的砾石样品呈现了被晒退的特征,平均20.6%的埋藏砾石的岩芯晒退良好,剂量高估程度低;不同沉积类型样品的晒退程度不一,侧碛垄顶部砾石样品晒退程度最好,冰水阶地和现代冰河砾石样品次之,现代冰川后退碛垄间洼地的冰水沉积砾石样品晒退程度最差,剂量高估较严重;磨圆度较差、球度较低、浅色的花岗岩砾石晒退程度较好。综上,冰川沉积砾石的晒退程度与沉积环境、沉积过程、搬运距离、砾石特征等相关,在进行岩石释光埋藏测年采样时,应综合考虑上述情况。     

安徽庐枞盆地与正长岩有关的成矿作用

安徽庐枞盆地位于长江中下游成矿带内,定位于扬子板块、华北板块与大别造山带之间,为一中生代陆相火山岩断陷盆地。庐枞盆地内广泛发育中生代岩浆活动,包括龙门院、砖桥、双庙、浮山4个旋回的火山岩及同期次侵入的中酸性岩体。盆地中成矿作用类型丰富,矿种多样,与龙门院旋回有关的潜火山热液型铅锌矿床、与砖桥旋回有关的玢岩型铁矿床是盆地中重要的成矿作用系列,以往工作较为全面地对这两个成矿系列进行了研究。随着近几年找矿工作的突破,盆地中与正长岩类有关的铁氧化物-铜-铀矿床逐渐受到重视。本文以深部探测ZK01孔深部铀矿化、马口铁矿、黄梅尖岩体周边铀矿床为研究对象,初步探讨区域与正长岩类有关的铁氧化物-铜-铀矿化系列,为庐枞整装勘查区找矿工作提供新思路、新方向。     

The impact of diagenetic fluid–rock reactions on Rotliegend sandstone composition and petrophysical properties (Altmark area, central Germany)

In the framework of the German R&D joint project CLEAN (CO₂ large-scale enhanced gas recovery in the Altmark natural gas field), Rotliegend reservoir sandstones of the Altensalzwedel block in the Altmark area (Saxony-Anhalt, central Germany) have been studied to characterise litho- and diagenetic facies, mineral content, geochemical composition, and petrophysical properties. These sands have been deposited in a playa environment dominated by aeolian dunes, dry to wet sand flats and fluvial channel fills. The sediments exhibit distinct mineralogical, geochemical, and petrophysical features related to litho- and diagenetic facies types. In sandstones of the damp to wet sandflats, their pristine red colours are preserved and porosity and permeability are only low. Rocks of the aeolian environment and most of the channel fill deposits are preferentially bleached and exhibit moderate to high porosity and permeability. Although geochemical element whole rock content in these rocks is very similar, element correlations are different. Variations in porosity and permeability are mainly due to calcite and anhydrite dissolution and differences in clay coatings with Fe-bearing illitic-chloritic composition exposed to the pore space. Moreover, mineral dissolution patterns as well as compositions (of clays and carbonate) and morphotypes of authigenic minerals (chlorite, illite) are different in red and bleached rocks. Comparison of the geochemical composition and mineralogical features of diagenetically altered sandstones and samples exposed to CO₂-bearing fluids in laboratory batch experiments exhibit similar character. Experiments prove an increase in wettability and water binding capacity during CO₂ impact.     

Fluid–rock interactions related to metamorphic reducing fluid flow in meta-sediments: example of the Pic-de-Port-Vieux thrust (Pyrenees,Spain)

In orogens, shortening is mainly accommodated by thrusts, which constitute preferential zones for fluid–rock interactions. Fluid flow, mass transfer, and mineralogical reactions taking place along thrusts have been intensely investigated, especially in sedimentary basins for petroleum and uranium research. This study combines petrological investigations, mineralogical quantifications, and geochemical characterizations with a wide range of analytical tools with the aim of defining the fluid properties (nature, origin, temperature, and redox) and fluid–host rock interactions (mass transfers, recrystallization mechanisms, and newly formed synkinematic mineralization) in the Pic-de-Port-Vieux thrust fault zone (Pyrenees, Spain). We demonstrate that two geochemically contrasted rocks have been transformed by fluid flow under low-grade metamorphism conditions during thrusting. The hanging-wall Triassic red pelite was locally bleached, while the footwall Cretaceous dolomitic limestone was mylonitized. The results suggest that thrusting was accompanied by a dynamic calcite recrystallization in the dolomitic limestone as well as by leaching of iron via destabilization of iron oxides and phyllosilicate crystallization in the pelite. Geochemical and physical changes highlighted in this study have strong implications on the understanding of the thrust behavior (tectonic and hydraulic), and improve our knowledge of fluid–rock interactions in open fluid systems in the crust.     

俄罗斯西西伯利亚和外贝加尔地区古河道型铀矿床

本文系统地介绍了俄罗斯 3个具有工业意义的古河道型铀矿化发育区 (外乌拉尔、西西伯利亚和外贝加尔 )的地质背景、铀矿化特征和铀成矿条件 ,指出切割到基底中的古河道型铀矿床 ,既可产于跨地区的造山带周围 ,也可产于活化的年青地台和古老地盾 ;既可形成于干燥的气候条件 ,也可形成于潮湿的气候条件。古河道型铀矿化可以从含矿层的沉积开始一直延续到被泥岩层或玄武岩层完全封盖。古河道的后成氧化分带有两种形式 :氧化带 铀矿化带 原生灰色岩石 ;氧化带 氧化铁再沉积带 漂白带 原生灰色岩石。古河道型铀矿床具宽广的元素谱 ,这主要是与含矿围岩富含有机质和在氧化带尖灭处存在各种地球化学障有关     

Comparison of the geochemical features of ore-bearing horizons at young and ancient hydrogenic uranium deposits (Hydrotechnological aspects)

Geochemical properties of ore-bearing horizons composed of alluvial aluminosilicate terrigenous rocks have been compared at young and ancient hydrogenic uranium deposits. It has been shown that the lithological setting at the young deposit has an elevated neutralization capacity in relation to sulfuric acid of leaching solutions and, in addition, has a rather low reducing capacity. The redox differentiation of ore substance at the deposit is in progress. It ensures an elevated degree of uranium oxidation in ores. Both ore and nonore sandy rocks contain a sufficient amount of natural oxidizer U(IV) in the form of trivalent iron. Ancient deposits, unlike young ones, contain ore-bearing and ore-hosting rocks with a low neutralizing but high reducing capacity and with an elevated degree of uranium and iron reducing, as the reducing environment dominates in all epigenetic geochemical zones. It is suggested that, in this geochemical setting, the process of in situ leaching (ISL) is not effective without addition of artificial oxidizer to the working sulfuric acid solutions.     

一个与超基性岩有关的矽卡岩铁矿

超基性岩同围岩接触,一般都很少见到明显的接触变质和接触交代现象,特別是后者更为少见。造成这一情况的原因可能有二:首先,超基性岩浆本身“活动组分”较少,如果沒有特殊有利的条件(包括岩体大小、侵入深度、接触面的形状产状、围岩成分以及构造条件等),这些组分不易集中,也就很难同围岩产生接触交代反应。     

Identification of ore extraction and metal working in ancient times: a case study of Sagalassos (SW Turkey)

The extensive territory of the ancient (Hellenistic to Byzantine) city of Sagalassos (SW Turkey) offered a rich variety in natural mineral resources. The frequent occurrence of iron slag in the excavations at the site proved the local working of metal. A geochemical prospection campaign was done in the territory of the ancient city in order to identify or discard the city and its territory as a self-sustaining metallurgical centre. Secondly, the geochemical impact of ancient metallurgy was investigated. Geochemical anomalies identified in stream sediments are explained by the presence of mineralised deposits and ancient metal working. Mg, Cr, Co and Ni anomalies point to chromite and chrysotile-magnetite deposits related to the basic rocks of the Lycian nappes in the area. Fe, V and Ti anomalies indicate the presence of iron mineralisations, which have been worked for iron production in ancient times. Finally, the association of P, Cu, Pb, Mn, As and Ag anomalies are an indicator of human activity at archaeological sites. Within the framework of this geochemical prospection, a metal working site apart from the city of Sagalassos was identified. Here, ore was both extracted and processed to workable iron.     

我国主要硫矿床类型及成矿若干规律

我国硫矿资源丰富多采,有自然硫、硫化氢、硫铁矿、石膏、明矾石等。对于这些矿产中的主要矿床类型地质特征总结归纳,显然将有助于提高地质理论水平和扩大找矿远景。成矿规律是成矿地质条件的全面反映,矿质来源则为成矿地质的前提和物质基础。本文拟从物质来源探索出发,提出以下硫矿床的分类方案。     

中国含镓矿床的主要成因类型

一、前言元素镓自1875年发现迄今,虽已有一百余年历史,但其大量应用却很晚。近代工业和科学技术的发展,在很多部门已找到了镓的新用途,特别是它被认为是继锗、硅之后最有发展前途的半导体材料,因而自六十年代后期以来,其年产量和消费量都正在逐年迅速增加。     

胶东变质超镁铁—镁铁质岩石的地球化学特征及地幔源区性质

本文以地球化学方法为研究手段,结合野外宏观地质特征,论述了胶东地区前寒武纪变质建造中超镁铁—镁铁质岩石的地球化学性质及其成因。研究结果表明,该区超镁铁—镁铁质岩石为地幔不同程度熔融的产物,超镁铁质岩石相当于科马提岩类;镁铁质岩石为拉斑玄武岩类,并按橄榄质科马提岩→玄武质科马提岩→拉斑玄武岩演化系列的化学组成表现出连续的变化趋势。 拉斑玄武岩中的微量元素(主要是稀土元素)地球化学特征表明,其形成环境与现代板块构造的典型火山(岛)孤或孤后盆地环境相类似,并反映出地幔源区具有“富集型”地幔的特点,且存在着地幔不均一性。     

内蒙古新巴尔虎地区土壤地球化学异常特征与找矿方向

新巴尔虎左地区位于得尔布干成矿带西南端,现已在周边发现多个与火山岩、次火山岩有关的大型及超大型热液型矿床。但本区工作程度相对较低,本次研究在总结前人工作的基础上,对其开展1∶5万土壤地球化学测量。通过分析18种元素的土壤地球化学特征,发现本区Pb、Zn、Ag、Mo等元素具有较好的异常。本区异常多分布于成矿有利部位,具有良好的找矿潜力。综合考虑地球化学异常元素的组合及异常区成矿地质条件和地球化学条件,圈定综合异常12处,并确定4个找矿靶区,为下一步找矿工作提供了依据。     

Petrogeochemical characteristics of the kimberlites from the Middle Markha region with application to the problem of the geochemical heterogeneity of kimberlites

A comparative geochemical investigation of kimberlites from the Middle Markha region and traditional diamond-bearing areas of Yakutia supported the division of kimberlites into two geochemical types. One of them includes kimberlites from the traditional diamond-bearing areas of Yakutia, and the other is represented by the kimberlites of the Middle Markha region and the rocks of the Zolotitsa field and V. Grib pipe of the Arkhangelsk province. The obtained representative parameters of the two kimberlite types indicate a sharp geochemical contrast between them, and the individual features of correlation relationships between the elements in the rocks of the two types suggest that these differences are related to fundamental genetic factors, which concern primarily the group of highly charged incompatible trace and radioactive elements. The presence of geochemically contrasting rocks within a rather uniform petrochemical association and the geochemically specialized occurrences of kimberlites and related rocks are consequences of repeated metasomatic transformations of mantle rocks under the influence of deep-derived fluids or volatiles released during the recycling of subneous source and subsequent derivation of geochemically specialized types of deep magmas showing signatures of individual mantle sources.     

Facies types of sedimentary iron ore deposits and their geochemical features: Communication 2. Problems of the geochemistry of phanerozoic iron ores

Mineralogical-geochemical features of different facies types of sedimentary iron ore deposits are described. Particular attention is paid to deposits associated with the weathering crusts of ultramafic igneous rocks and to marine oolitic iron ores. The multistage formation of their geochemical properties is proved available geochemical models are considered.