Hydrothermal alteration and the formation of aluminous haloes around sulfide deposits

The sulfide deposits of Chizeuil (Saone et Loire) occur in a Late Devonian volcano-sedimentary sequence within an acid volcanic unit and close to a Carboniferous granite batholith. Sulfide bodies, mainly pyrite, are enclosed in andalusite-bearing siliceous rocks lacking primary textures and recrystallized by the granitic thermal metamorphism.Several genetic interpretations were proposed for these siliceous rocks and the associated mineralization, i.e., as either being related to the granite intrusion or of volcanogenic derivation. Detailed studies led to their identification as hydrothermal alterites.A petrographic study of these siliceous alterites reveals that the main mineral phases are only constituted of silica and alumina: quartz, andalusite, kaolinite and minor contents of muscovite, diaspore and corundum. Neither K-feldspar or biotite are present with andalusite. This implies that thermal metamorphism occurred on an already alkali-, calcium- and magnesium-depleted rock.These siliceous alterites show less mobile-element (Al, Ti, V, Zr, Nb) concentration ranges similar to those of acid volcanic host rocks. A metasomatic model is computed from chemical data on surrounding soda dacites, assuming that acid hydrolysis was the only phenomenon involved, and that Al was stable in this process.Although altered rock types grading to soda dacites do not crop out, their existence may be deduced from surficial bedrock multielement geochemical data. The zoned distribution of elements agrees with that deduced from reactions and experimental phase diagrams.The pyrite bodies are surrounded by two distinct concentric alteration zones; the inner one is advanced argillic and the outer one is sericitic. Such a pattern is unusual for volcanogenic sulfide deposits but commonly associated with porphyry deposits. It may be related to the strong acidity (pH3) of hydrothermal solutions.These siliceous rocks were produced by an in-situ alteration of brecciated dacitic lavas, inside which a stockwork-type pyritic mineralization was deposited.     

蚀源区地质体铀浸出率与砂岩铀矿成矿关系

通过吐哈盆地南缘觉罗塔格山系和准噶尔盆地周缘（不包括准盆南缘北天山山脉）不同岩石浸出试验发现，同属中晚古生代的侵入岩、火山岩及变质岩，在相同条件下其铀浸出率有明显差异，即吐哈盆地南缘各类岩石的总浸出率在14.30%，而准噶尔盆地周缘（不包括准盆南缘北天山山脉）岩石的总浸出率仅为1.81%，这也许正是吐哈盆地南缘形成万吨级砂岩铀矿，而准盆北部（顶山地区）砂岩铀矿成矿前景欠佳，目前只有个别工业铀矿孔及部分矿化孔，而不具工业意义的原因之一。     

岩浆通道系统与岩浆硫化物成矿研究新进展

大型-超大型岩浆硫化物矿床的形成需要满足3个基本条件:(1)大量幔源岩浆参与成矿;(2)岩浆演化导致硫化物熔离;(3)硫化物在有限空间聚集。然而,除Sudbury矿床外,全球与镁铁质岩浆有关的超大型铜镍硫化物矿床都发现于小的镁铁-超镁铁岩体中。近10年来的研究表明这些含矿岩体实际上都是岩浆通道系统的一部分,中国金川、杨柳坪、喀拉通克、红旗岭等大型和超大型Ni-Cu-(PGE)硫化物矿床都形成于岩浆通道系统中,正是岩浆通道这样特殊的开放系统为大规模岩浆硫化物矿床提供了成矿条件。总结国内外最新研究结果,可以发现与成矿有关的岩浆通道系统都分布在深大断裂附近,大规模的幔源岩浆补充与地幔柱、大陆裂谷、碰撞造山后伸展等地质事件有密切的关系。尽管研究证明硫化物熔离都与地壳物质的混染有关,但矿石各种元素的品位却受母岩浆性质、硫化物熔离强度、与新注入镁铁质岩浆反应、以及硫化物本身结晶分异等多重因素的影响;含矿岩体和硫化物矿体的形态和大小都强烈地受围岩地质特征的控制。进一步明确这类矿床的地质特征、形成机制、成矿背景和成矿标志,对未来的研究和找矿工作都是非常必要的。     

塔里木陆块周缘岩浆Cu-Ni-Co硫化物矿床形成的探讨

因新发现的夏日哈木超大型岩浆铜镍钴硫化物矿床成岩成矿研究存在争议,对岩浆铜镍钴硫化物矿床的成因机制又引发新一轮的关注。中国造山带中铜镍钴硫化物矿床具有鲜明的分布特点,20世纪80年代东天山黄山东等一批岩浆铜镍钴硫化物矿床的发现,曾经提出蛇绿岩形成铜镍钴硫化物矿床的观点,而后出现了洋壳削减闭合陆-陆碰撞后新生陆壳裂陷槽环境形成铜镍钴矿的主流认识;进入21世纪后,随着塔里木早二叠世大火成岩省的提出,开始将东天山和新疆北山的岩浆铜镍钴硫化物矿床与塔里木大火成岩省的形成关联起来,并认为是地幔柱作用的结果。但随着研究的深入,由于含铜镍钴镁铁-超镁铁岩地球化学具有典型的岛弧特征,又将东天山铜镍钴矿床的形成与俯冲削减的板片再次联系了起来,导致岩浆型铜镍钴硫化物矿床形成背景还存在较大争议。我们认为岩石微量元素显示岛弧信息,是俯冲交代及地壳混染引起的地球化学屏蔽效应;铬尖晶石成分及所反映的氧逸度环境指示为张性环境,而非岛弧。塔里木陆块周缘3期岩浆铜镍钴硫化物矿床成矿代表了中国最重要的3期成镍事件,实际反映了塔里木陆块在全球大陆聚散演化中与超大陆之间关键的聚散事件:(1)新元古代金川Cu-Ni-PGE矿成矿代表了由于地幔柱作用以塔里木、扬子和西澳大利亚陆块之间的裂解为起点的罗迪尼亚超大陆裂解事件,直至早古生代形成原特提斯洋-古亚洲洋;(2)早古生代末夏日哈木Ni-Co矿则是代表冈瓦纳大陆南部裂解从而形成古特提斯洋的标志性事件;(3)晚古生代早二叠世坡一Cu-Ni矿应是地幔柱作用潘吉亚超大陆生长大火成岩省的深成相组成。本文系统总结了3个矿床的成矿特征,并对比了3个矿床的区别。尽管坡一在3个矿床中有基性程度最高的母岩浆,但坡一相对于夏日哈木、金川显示出低的地壳混染程度,特别是地壳硫混染程度,这可能是坡一成矿相对差的主要原因。此外坡一不仅地壳混染程度低,且其混染了较多的钙质,抑制了硫化物饱和。     

有机质在铀成矿过程中作用的实验模拟研究

沉积型铀矿的形成与有机质存在密切联系。实验模拟研究表明:芳香有机酸在弱酸到弱碱性条件下很容易和铀酰根离子发生配位反应,它能通过羧基上的氧原子以多种配位形式和铀形成配位键。此结果验证了前人的一些结论,并直观地展现了有机质的主要官能团与铀离子在溶液中的一些迁移形式。模拟实验结果也显示了烃类在水热条件下对铀成矿的还原作用,它能将六价铀还原成四价铀而沉淀下来。     

Uranium anomalies in paleo-aquifers near sandstone-type uranium deposits in the devonian catskill formation of Pennsylvania

Background values of U and Th in 371 clastic sedimentary rocks from the Catskill Formation correlate negatively with Si and positively with Al and most other major elements because of the low content of U and Th in quartz and the relative enrichment in clays, Fe oxides, and other fine-grained components. Background U also correlates closely with Th. Similar results are obtained from 100 samples from western Colorado near the Uravan mineral belt. Weak anomalies in U are much more easily recognized by study of residuals or deviations from regressions of U against Al or Th than in the raw data.At Penn Haven Junction near Jim Thorpe, Pa., roll-type uranium deposits similar to those in Wyoming are localized around an iron-stained paleo-aquifer of conglomeratic sandstone. Twenty-four rock samples from this paleo-aquifer contain 1–12 ppm U; eight of the samples contain less than 4 ppm U, the background level for shales of the area. Uranium residuals from regressions against Al or Th are clearly anomalous for all samples. Experiments on another group of samples suggest that readily extractable U (H₂O₂-acetic acid leach) would also show the paleo-aquifer to be anomalous.Anomalies of this type in paleo-aquifers should be useful in evaluation of drill holes, outcrops, and radiometric data in prospective districts, especially when paleo-aquifers are difficult to recognize visually. The anomalies also indicate that U is added to sandstones of the paleo-aquifer rather than leached out to form the ore bodies in reduced rocks at the margins of a geochemical cell.     

Role of hydrodynamic factors in controlling the formation and location of unconformity-related uranium deposits: insights from reactive-flow modeling

The role of hydrodynamic factors in controlling the formation and location of unconformity-related uranium (URU) deposits in sedimentary basins during tectonically quiet periods is investigated. A number of reactive-flow modeling experiments at the deposit scale were carried out by assigning different dip angles and directions to a fault and various permeabilities to hydrostratigraphic units). The results show that the fault dip angle and direction, and permeability of the hydrostratigraphic units govern the convection pattern, temperature distribution, and uranium mineralization. A vertical fault results in uranium mineralization at the bottom of the fault within the basement, while a dipping fault leads to precipitation of uraninite below the unconformity either away from or along the plane of the fault, depending on the fault permeability. A more permeable fault causes uraninite precipitates along the fault plane, whereas a less permeable one gives rise to the precipitation of uraninite away from it. No economic ore mineralization can form when either very low or very high permeabilities are assigned to the sandstone or basement suggesting that these units seem to have an optimal window of permeability for the formation of uranium deposits. Physicochemical parameters also exert an additional control in both the location and grade of URU deposits. These results indicate that the difference in size and grade of different URU deposits may result from variation in fluid flow pattern and physicochemical conditions, caused by the change in structural features and hydraulic properties of the stratigraphic units involved.     

铀矿大型矿集区与成矿作用

大型矿集区的形成，是在地质历史演化进程中，多矿种大矿量超常聚集的结果。不同的矿集区有不同的典型矿种和典型矿床。本文仅以铀矿为例，在世界范围内厘定出14个铀矿大区矿集区。本文研究铀矿大型矿集区时空分布规律与地球动力学演化的关系，在此基础上探讨了铀矿大型矿集区元素超常聚集规律，提出多矿种“点区超常聚集”和“短时限爆发成矿”特征。本文按照“源、运、积”3个环节，探讨铀矿大型矿集区的成矿作用，其中有关深源成矿、特殊碱质流体的水岩反应以及元素沉积环境的研究，为建立铀矿大型矿集区的找矿模式奠定基础。     

The distribution of Hg, Ba, Cu and Zn in the vicinity of cupriferous sulfide deposits, Troodos complex, Cyprus

A geochemical rock- and soil-sampling program was carried out in the vicinity of eight concealed “Cyprus type” deposits, occurring in marginal mafic to intermediate metapillow lavas of the Troodos Ophiolite Complex. The mineralization of massive and stockwork sulfide ore is characterized by the predominance of pyrite, intergrown with less chalcopyrite and minor amounts of sphalerite.Background values of Hg are in the range of 8–12 ppb for soils and 3–6 ppb for surface rocks. Anomaly/background ratios of 10:1 (soils) and 5:1 (rocks) have been found only, where Hg migrated along channels formed by faults cutting shallow-seated mineralization. Here, Hg sometimes shows significant correlations with Cu, Zn, Ba and exceptionally with Co. However in one case an Hg anomaly in soils and surface rocks was detected directly over a deposit. The use of Hg as indicator element for these types of deposits is therefore limited. Buried mineralization may be delineated more distinctly by Cu, Zn and Ba.     

Cyclic ore formation of some volcanogenic massive sulfide deposits in the skellefte district,Sweden

The Näsliden and Rävliden deposits in the Skellefte field consist of stratiform massive sulfide ores associated with submarine volcanic and clastic rocks. The ores are pretectonic. Consequently, the orebodies are considered to have formed syngenetically with deposition of the host rocks. Banding and interlayering with host sediments are common features. Cu : Zn and Zn : Pb ratios of the ores show stratigraphically and laterally defined trends. Cu : Pb : Zn ratios correspond with those found in other deposits of volcanogenic origin. Nonstratiform breccia Cu mineralizations occur directly under the massive stratiform ores in the footwall rocks where hydrothermal alteration is strongest. Ore formation took place intermittently resulting in clusters of ore systems occurring at slightly different stratigraphical levels within each deposit.     

The setting, style, and role of magmatism in the formation of volcanogenic massive sulfide deposits

Throughout Earth??s history, all volcanogenic massive sulfide (VMS)-hosting environments are associated with specific assemblages of mafic and felsic rocks with distinct petrochemistry (petrochemical assemblages) indicative of formation at anomalously high temperatures within extensional geodynamic environments. In mafic-dominated (juvenile/ophiolitic) VMS environments, there is a preferential association with mafic rocks with boninite and low-Ti tholeiite, mid-ocean ridge basalt (MORB), and/or back-arc basin basalt affinities representing forearc rifting or back-arc initiation, mid-ocean ridges or back-arc basin spreading, or back-arc basins, respectively. Felsic rocks in juvenile oceanic arc environments in Archean terrains are high field strength element (HFSE) and rare earth element (REE) enriched. In post-Archean juvenile oceanic arc terrains, felsic rocks are commonly HFSE and REE depleted and have boninite like to tholeiitic signatures. In VMS environments that are associated with continental crust (i.e., continental arc and back-arc) and dominated by felsic volcanic and/or sedimentary rocks (evolved environments), felsic rocks are the dominant hosts to mineralization and are generally HFSE and REE enriched with calc-alkalic, A-type, and/or peralkalic affinities, representing continental arc rifts, continental back-arcs, and continental back-arcs to continental rifts, respectively. Coeval mafic rocks in evolved environments have alkalic (within-plate/ocean island basalt like) and MORB signatures that represent arc to back-arc rift versus back-arc spreading, respectively. The high-temperature magmatic activity in VMS environments is directly related to the upwelling of mafic magma beneath rifts in extensional geodynamic environments (e.g., mid-ocean ridges, back-arc basins, and intra-arc rifts). Underplated basaltic magma provides the heat required to drive hydrothermal circulation. Extensional geodynamic activity also provides accommodation space at the base of the lithosphere that allows for the underplated basalt to drive hydrothermal circulation and induce crustal melting, the latter leading to the formation of VMS-associated rhyolites in felsic-dominated and bimodal VMS environments. Rifts also provide extensional faults and the permeability and porosity required for recharge and discharge of VMS-related hydrothermal fluids. Rifts are also critical in creating environments conducive to preservation of VMS mineralization, either through shielding massive sulfides from seafloor weathering and mass wasting or by creating environments conducive to the precipitation of subseafloor replacement-style mineralization in sedimented rifts. Subvolcanic intrusions are also products of the elevated heat flow regime common to VMS-forming environments. Shallow-level intrusive complexes (i.e., within 1?C3?km of the seafloor) may not be the main drivers of VMS-related hydrothermal circulation, but are likely the manifestation of deeper-seated mantle-derived heat (i.e., ~3?C10?km depth) that drives hydrothermal circulation. These shallower intrusive complexes are commonly long-lived (i.e., millions of years), and reflect a sustained thermally anomalous geodynamic environment. Such a thermally anomalous environment has the potential to drive significant hydrothermal circulation, and, therefore multi-phase, long-lived subvolcanic intrusive complexes are excellent indicators of a potentially fertile VMS environment. The absence of intrusive complexes, however, does not indicate an area of low potential, as they may have been moved or removed due to post-VMS tectonic activity. In some cases, shallow-level intrusive systems contribute metals to the VMS-hydrothermal system.     

黏土矿物形成过程中元素的变化规律——以鄂尔多斯盆地东北部铀矿床为例

正1地质背景研究区位于鄂尔多斯盆地北部的伊蒙隆起区内,区内地层比较平缓,为向西南缓倾的单斜地层,倾角通常小于3°。出露的地层主要为侏罗系和白垩系,赋矿层位主要为中侏罗统直罗组下段的灰色中-粗砂岩。根据地层的岩性、颜色以及蚀变特点,可以将直罗组划分为两个岩性段:上段(J_2z~2)和下段(J_2z~1),其中下段又可以分为上亚段和下亚段。     

砂岩型铀矿床硫化物还原富集铀的机制

砂岩型铀矿中含大量不同形态、不同阶段的黄铁矿。仅凭矿相学对黄铁矿产状及电子探针对黄铁矿形态的观察难以准确地判别成矿期、成矿前及成矿后形成的黄铁矿。而成矿期黄铁矿是铀矿床成因和形成过程的重要信息载体,对其准确识别具有特别重要的意义。以往国内外研究采用激光剥蚀电感耦合等离子体质谱(LA-MC-ICP-MS)方法分析Pb同位素,但该方法对于低含量Pb样品分析精度较低且较难获得²⁰⁴Pb数据。本文对铀矿石中的黄铁矿利用微区原位的手段进行更加精准的飞秒级质谱(fs-LA-MC-ICP-MS)的Pb同位素测试,发现大量黄铁矿存在Pb同位素异常,从中可能区分出成矿期与非成矿期的黄铁矿。经U-Th-Pb放射性衰变原理分析并结合黄铁矿矿相学特点可以发现,矿相学镜下明确是成矿期的黄铁矿,其²⁰⁶Pb/²⁰⁴Pb比正常克拉克值大十几倍甚至数十倍,²⁰⁷Pb/²⁰⁴Pb稍有异常,而²⁰⁸Pb/²⁰⁴Pb基本不变。矿相学中产状呈草莓状,以及铀矿物围绕其生长但未有穿插关系的非成矿期黄铁矿,其²⁰⁶Pb/²⁰⁴Pb正常;矿相学镜下难以确定形成阶段的、与铀矿物没有任何接触关系的黄铁矿,其Pb同位素没有明显的规律性。这些结果证明了利用Pb同位素异常来判断黄铁矿形成阶段的准确性。因此,利用黄铁矿微区原位Pb同位素差异,适当配合矿相学形态和产状观察,可较为精准地识别出成矿期黄铁矿。

     

A possible origin of uranium deposits in granites in special reference to the formation of SL deposit

The tectonic destruction and hydrothermal alteration of the H granite massif resulted in the formation of the green alteration zone. During this process, infiltrating hydrothermal solutions would resorb uraninite in the rocks, leading to the mobilization and thus migration of uranium into fissures and grain interstices, or being adsorbed on clay minerals. As a result, the medium and space were provided for later mineralization. In the Cretaceous period, the upper part of the green alteration zone underwent strong oxidation, followed by the resorption and then the transformation of metallicsulfides into limonite and hydrogeothite. And uranium present both in uraninite and in fissures was further mobilized and concentrated to form uranium ore deposits of economic importance in the redox boundary between the green zone and the purple zone.     

Mechanisms for anhydrite and gypsum formation in the Kuroko massive sulfide–sulfate deposits,north Japan

The Sr, Ba, and rare earth elements (REEs) concentrations and Sr isotopic composition of anhydrite and gypsum have been determined for samples from the Matsumine, Shakanai, and Hanaoka Kuroko-type massive sulfide–sulfate deposits of northern Japan to evaluate the mechanisms of sekko (anhydrite and gypsum) ore formation. The Sr isotopic compositions of the samples fall in the range of 0.7077–0.7087, intermediate between that for middle Miocene (13–15 Ma) seawater (0.7088) (Peterman et al., Geochim Cosmochim Acta, 34:105–120, 1970) and that for country rocks (e.g., 0.7030–0.7050) (Shuto, Assn Geol Collab Japan Monograph 18:91–105, 1974). The Kuroko anhydrite samples exhibit two types of chondrite-normalized REE patterns: one with a decrease from light REEs (LREEs) to heavy REEs (HREEs) (type I), and another with a LREE-depleted pattern (type II). Based on the Sr content and isotopic ratio (assuming an Sr/Ca (mM/M) of 8.7 for seawater), anhydrite is considered to have formed by mixing of preheated seawater with a hydrothermal solution of Sr/Ca (mM/M) = ca. 0.59–1.36 under the condition in which the partition coefficient (Kd) ranges between ca. 0.5 and 0.7. This results in the formation of anhydrite with higher Sr content with an Sr isotopic value close to that of seawater under seawater-dominant conditions. Larger crystals of type II anhydrite are partly replaced by smaller ones, indicating that anhydrite dissolution and recrystallization occurred after or during the formation of sekko ore. Gypsum, which partially replaces anhydrite in the Kuroko deposits, also exhibits two distinct chondrite-normalized REE patterns. Because LREEs are likely to be more readily mobilized during dissolution and recrystallization, it is hypothesized that LREEs are leached from type I anhydrite, resulting in the formation of type II anhydrite with LREE-depleted profiles.     

川北砂岩型铀矿稀土元素特征及铀成矿作用

在大量取样分析的基础上 ,本文系统分析研究了围岩、矿石、方解石脉和铀矿物的稀土元素组成 ,讨论了岩石、矿石沉积和成岩过程中的稀土元素变化规律 ,总结了川北砂岩型铀矿床的稀土元素地球化学特征。通过与典型的火山岩型和变质岩型热液成因铀矿床进行对比 ,认为川北砂岩型铀矿具有热液 (水 )改造成矿作用的稀土元素地球化学特点 ;铀矿化经历了沉积成岩和热液改造富集两个阶段。     

The role of the thermal convection of fluids in the formation of unconformity-type uranium deposits: the Athabasca Basin,Canada

In the global production of uranium, ~18% belong to the unconformity-type Canadian deposits localized in the Athabasca Basin. These deposits, which are unique in terms of their ore quality, were primarily studied by Canadian and French scientists. They have elaborated the diagenetic–hydrothermal hypothesis of ore formation, which suggests that (1) the deposits were formed within a sedimentary basin near an unconformity surface dividing the folded Archean–Proterozoic metamorphic basement and a gently dipping sedimentary cover, which is not affected by metamorphism; (2) the spatial accommodation of the deposits is controlled by the rejuvenated faults in the basement at their exit into the overlying sedimentary sequence; the ore bodies are localized above and below the unconformity surface; (3) the occurrence of graphite-bearing rocks is an important factor in controlling the local structural mineralization; (4) the ore bodies are the products of uranium precipitation on a reducing barrier. The mechanism that drives the circulation of ore-forming hydrothermal solutions has remained one of the main unclear questions in the general genetic concept. The ore was deposited above the surface of the unconformity due to the upflow discharge of the solution from the fault zones into the overlying conglomerate and sandstone. The ore formation below this surface is a result of the downflow migration of the solutions along the fault zones from sandstone into the basement rocks. A thermal convective system with the conjugated convection cells in the basement and sedimentary fill of the basin may be a possible explanation of why the hydrotherms circulate in the opposite directions. The results of our computations in the model setting of the free thermal convection of fluids are consistent with the conceptual reasoning about the conditions of the formation of unique uranium deposits in the Athabasca Basin. The calculated rates of the focused solution circulation through the fault zones in the upflow and downflow branches of a convection cell allow us to evaluate the time of ore formation up to the first hundreds of thousands years.