Metavolcanic host rocks,mineralization, and gossans of the Shaib al Tair and Rabathan volcanogenic massive sulphide deposits of the Wadi Bidah Mineral District,Saudi Arabia

The Wadi Bidah Mineral District of Saudi Arabia contains more than 16 small outcropping stratabound volcanogenic Cu–Zn–(Pb) ± Au-bearing massive sulphide deposits and associated zones of hydrothermal alteration. Here, we use major and trace element analyses of massive sulphides, gossans, and hydrothermally altered and least altered metamorphosed host rock (schist) from two of the deposits (Shaib al Tair and Rabathan) to interpret the geochemical and petrological evolution of the host rocks and gossanization of the mineralization. Tectonic interpretations utilize high-field-strength elements, including the rare earth elements (REE), because they are relatively immobile during hydrothermal alteration, low-grade metamorphism, and supergene weathering and therefore are useful in constraining the source, composition, and physicochemical parameters of the primary igneous rocks, the mineralizing hydrothermal fluid and subsequent supergene weathering processes. Positive Eu anomalies in some of the massive sulphide samples are consistent with a high temperature (>250°C) hydrothermal origin, consistent with the Cu contents (up to 2 wt.%) of the massive sulphides. The REE profiles of the gossans are topologically similar to nearby hydrothermally altered felsic schists (light REE (LREE)-enriched to concave-up REE profiles, with or without positive Eu anomalies) suggesting that the REE experienced little fractionation during metamorphism or supergene weathering. Hydrothermally altered rocks (now schists) close to the massive sulphide deposits have high base metals and Ba contents and have concave-up REE patterns, in contrast to the least altered host rocks, consistent with greater mobility of the middle REE compared to the light and heavy REE during hydrothermal alteration. The gossans are interpreted to represent relict massive sulphides that have undergone supergene weathering; ‘chert’ beds within these massive sulphide deposits may be leached wall-rock gossans that experienced silicification and Pb–Ba–Fe enrichment from acidic groundwaters generated during gossan formation.     

南秦岭古生代热水沉积盆地与热水沉积成矿

扬子地块北部被动边缘的南秦岭古生代沉积盆地中,发育一套自早古生代—中生代以来的碳酸盐岩夹细碎屑岩沉积建造,形成规模巨大独具特色的以铅锌金为主的多金属成矿带。伸展构造体制下形成的裂陷或断陷型盆地中,正常水成沉积与热水沉积同盆共存。正常水成沉积中叠加的热水沉积是一个"突发事件或灾变事件",具有特殊的物质组成和产态。通过对区内沉积成矿盆地的识别、分级,二级沉积盆地中边缘部位常发育多个三级构造热水沉积成矿盆地,它受控于沉积盆地中的同生断裂,具有沉积岩相、热水沉积岩组合、显著成矿作用及物化探异常广布的特点。三级构造热水沉积成矿盆地是矿床定位的构造空间,四级热水沉积洼地为矿体(矿层)的容纳空间。区内热水沉积岩主要为重晶石(毒重石)岩、硅质岩、钠长石岩和铁碳酸盐岩类,铅锌重晶石等矿产多产于热水沉积岩中或上盘。热水沉积形成一般由早期的热水喷发交代→主期热水喷流→晚期热水喷气演变。早期的热水喷发交代往往沿矿液喷发通道,形成网脉状、角砾状矿化;主期热水喷流主要形成多金属及热水喷流相,形成块状、条带状、层纹状矿石或热水沉积岩;晚期热水喷气主要形成浸染状矿石和热水喷气岩石。     

A magnetite-rich Cyprus-type VMS deposit in Ortaklar: A unique VMS style in the Tethyan metallogenic belt,Gaziantep, Turkey

The Ortaklar VMS deposit is hosted in the Koçali Complex consisting of basalts and deep sea pelagic sediments, which formed by rifting and continental break-up of the southern Neotethyan in Late Triassic. The basalts are of NMORB-type without notable crustal contamination. From the surface to depth, the Ortaklar deposit consists of a gossan zone, a thick massive ore zone and a poorly developed stockwork zone. Primary mineralisation is characterised by distinctive facies including sulphide breccias (proximal), graded beds (distal), stockworks and chimney fragments. Ore mineral abundances decrease in the order of pyrite, magnetite, chalcopyrite, and sphalerite. Two distinct phases of mineralisation, massive magnetite and massive sulphide, are present in the Ortaklar deposit. Textural evidence (e.g., magnetite replacing sulphides) and the spatial relationships with the host rocks indicate that magnetite and sulphide minerals were generated in different stages. The transition from sulphide to magnetite mineralisation is interpreted to relate to variation in H₂S content of ore fluids. The 1st stage massive sulphide ore might have formed by early hydrothermal fluids rich in Fe and H₂S. The 2nd stage massive magnetite might have formed by later neutral hydrothermal fluids rich in Fe but poor in H₂S, replacing the pre-existing sulphide ore.The alteration patterns, mineral paragenesis, lithological features (massive ore-stockwork ore-gossan) of the Ortaklar deposit together with its trace elements, Cu-Pb-Zn-Au-Ag and REE signatures are all consistent with a Cyprus-type VMS system. The δ³⁴S values in pyrite and chalcopyrite samples range from 2.6 to 5.7‰, indicating that the hydrothermal fluids were associated with sub-seafloor igneous activity, typical of Cyprus-type VMS deposits. However, magnetite formed later than sulphide minerals in the Ortaklar deposit, contrasting with typical Cyprus-type VMS deposits where magnetite generally occurs in lower sections. Consequently, although the Ortaklar deposit generally conforms to Cyprus-type deposits, it is distinguished from them by its late stage and high magnetite concentration. Thus, the Ortaklar deposit is thought to be an exceptional and perhaps unique Cyprus-type VMS deposit.     

REE and HFS element behaviour in the alteration facies of the Erenler Dağı Volcanics (Konya,Turkey) and kaolinite occurrence

Mainly high-K, calc-alkaline, Late Miocene to Pliocene volcanic rocks cropped out of the Konya area in Central Anatolia, Turkey. The volcanic rocks are predominantly andesitic to dacitic in composition and rarely basalt, basaltic andesite, basaltic trachyandesite and pyroclastics. Kaolinite, illite, Ca-montmorillonite, alunite, jarosite, minamiite and silica polymorphs were formed by widespread and intense hydrothermal alteration in or around the volcanic products. To investigate the effects of hydrothermal alteration on the chemistry of volcanic rocks, the whole rock chemical composition (major and trace elements, including rare-earth elements (REE) was analysed. The results of the study demonstrate notable differences in the REE behaviour in the different sample groups. REE trends of fresh parent rocks to weakly-, moderately-altered, kaolinitic and alunitic rocks are characterised by strong LREE enrichment ((La/Lu)_cn = 14.57, 11,8 to 15.20, 4.54 to 13.30, 12.5 to 24.2 and 34.6 to 47.26, respectively). Most of the samples have pronounced negative and/or weakly-negative Eu anomalies ranging from 0.75 to 0.98 while three samples have weakly-positive Eu anomalies. LRE element contents are higher than those of HREE in the samples. The LRE elements were strongly enriched in the kaolinitic and alunitic alteration; in weakly- and moderately-altered rocks. LREE are nearly immobile whereas HRE elements show different behaviour in different rock groups. The HFS and TRT elements are slightly mobilised in weakly-altered rocks, but enriched in other alteration types. Elements commonly assumed to be immobile (e.g. Y, Zr, Nb, Hf, TiO₂, Al₂O₃, REE) show variation in mass calculation. LIL elements showed enrichment over LREE and MREE, and similar behaviour, in contrast with HFSE. A clear increment of trans-transition elements (TRTE) was found mainly in alunitic and partly in kaolinitic samples.     

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.     

川西昌台勉戈组沉积岩系稀土特征

川西昌台地区上三叠统勉戈组中酸性火山岩之上主要为一套灰黑色至黑色沉积岩石组合,包括板岩、页岩和泥岩等。这套岩石组合可分为两类:底部为存在热水活动参与形成的沉积岩,厚度较薄;底部之上为无热水活动参与形成的沉积岩,厚度较大。本文取样上述两类岩石测得的稀土元素特征基本相似,无明显区别:两类样品稀土含量普遍偏高,与球粒陨石标准化的的配分曲线呈右倾型,LREE富集,基本无Ce正/负异常,具有明显的Eu负异常。有热水活动参与的沉积岩样品与太平洋SER地区现代海底典型热水沉积物的稀土元素特征明显不一致;与该区域内呷村矿区的典型热水沉积岩重晶石和硅质岩的稀土元素特征也不一致。但与秦岭志留系部分热水沉积岩样品和湘黔寒武系牛蹄塘组底部碳质伊利石页岩样品的稀土特征一致,呈现正常碎屑岩的稀土元素特征。综合分析认为,川西勉戈组碎屑页岩出现Eu负异常特征的主要原因是所测样品中的热液组分含量较少甚至无。     

东坪金矿床成矿过程中稀土元素活动性

尽管稀土元素常被认为是惰性元素,但在热液交代蚀变和化学风化作用过程中具有一定程度的活动性,河北省东坪与碱性岩有关的改进改造型热液金矿床成矿过程中,热液蚀变作用使近矿围岩ＬＲＥＥ／ＨＲＥＥ比值增大,并出现现铈正常异常;石英脉型金矿石的稀土元素分布模式呈出现明显的继承性,脉石矿物石英,钾长石的稀土元素组成相对富ＨＲＥＥ,且在脉石石英出现明显的铕正异常,研究结果表明在中,高温,近中性,较高氧逸度成矿流体     

热水沉积岩及矿物岩石标志

热水沉积物不同于普通沉积物 ,主要与热水流体类型有关。文中把热水流体划分为中高温热水流体与中低温热水流体。中高温热水沉积岩包括钾长石岩、硅质岩、电气石岩、钠长石岩、萤石岩 ;中低温热水沉积岩包括碳酸盐、硫酸盐等岩石。钾长石岩是文中确定的一种标准高温热水沉积岩 ,热水沉积钾长石以冰长石和钡长石为主 ;热水沉积碳酸盐矿物一般为铁、镁、锰、钙碳酸盐 ,碳酸盐的形成与CO2 和H2 O的不混溶温度有关 ,一般在不混溶温度 ,即 2 66℃以下生成 ,或在海水补偿线以上形成。热水沉积岩中有热水交代蚀变岩夹层 ,尤其是在高温热水活动区 ,可以交代泥质、钙泥质沉积物形成热水交代沉积岩 ,包括方柱石黑云母岩、透辉石透闪石岩、夕卡岩、绿泥石岩等。根据对霍各乞铜多金属矿床的研究 ,热水交代透辉石透闪石岩的稀土总量较低 ,表现为轻稀土富集 ,重稀土亏损 ,稀土配分模式表现为正Eu异常     

陕西柞山地区穆家庄铜矿稀土元素地球化学特征

尽管秦岭泥盆系铅锌金多金属成矿带成矿作用均与热水喷流沉积作用有关，柞山地区却有别于凤太地区，具有独特的铜矿成矿背景。本文通过对矿床的岩、矿石稀土元素地球化学研究，认为浸染状贫铜矿石和近矿围岩的稀土组成和配分曲线基本一致，表明浸染状贫铜矿石代表了泥盆纪时期热水沉积事件所形成的含少量硫化物的热水沉积岩初步富集的产物，泥盆纪时期形成了穆家庄铜矿的初始矿源层。嗣岩中的层纹状硅质岩可能代表了泥盆纪时期的热水沉积岩性质。块状富矿石的稀土组成代表了广泛的陆陆碰撞造山运动所产生的流体热液作用的结果，它既就地改造了初始矿源层，而且从异地可能带来了部分成矿物质，在合适的构造部位改造富集成矿。穆家庄铜矿的成因为改造型的。     

Mineralogy and geochemical behavior of trace elements of hydrothermal alteration types in the volcanogenic massive sulfide deposits,NE Turkey

Volcanogenic massive sulfide (VMS) deposits of the Eastern Pontides, Turkey, are hosted by the Maastrichtian–Eocene dacite and rhyodacite series, accompanied by lesser andesite and basalts, as well as their pyroclastic equivalents, with tholeiitic to calc-alkaline affinity. The ore mineral assemblages are chalcopyrite, sphalerite, galena, chalcocite, covellite, bornite, and tetrahedrite. Potassic-, phyllitic- (sericitic), argillic- (kaolinitic and smectitic), silicic-, propylitic- and hematitic-alteration is commonly associated with these deposits.HFSE, LILE, TRTE and REE contents show strong variability in different alteration types resulting from interaction with acid or alkaline fluids. Sample groups showed chondrite-normalized enrichment of LREE relative to HREE and sub-parallel trends, except for the hematitic- and phyllitic-alteration types. MREE are strongly depleted in the zones of most intense silicification and kaolinization. Most sample groups have strongly- to slightly-negative Eu anomalies, ranging from 0.35 to 0.88 (mean); hematitic- (1.45) and propylitic-altered rocks (1.11) have slightly- to moderately-positive anomalies. The negative Eu anomalies indicate the low temperatures of fluids (< 200 °C). In contrast, the positive Eu anomalies result from high-temperature hydrothermal conditions (> 200 °C). No Ce anomaly was observed, except for phyllitic alteration where a slight positive anomaly was noted. The chondrite-normalized trace and REE patterns of the altered rocks are similar to each other, suggesting that they were derived from a common felsic source. The alteration groups formed from acid, intermediate, and alkaline hydrothermal solutions. Some transition, base and precious metals and volatile elements were clearly enriched, especially in the hematitic-, silicic-, kaolinitic- and phyllitic-altered samples. The other elements exhibit different behaviors in different sample groups. REE behavior is relatively immobile in the silicic-, hematitic-, kaolinitic- and partially in moderately- and propylitic-altered rocks, based on mass-balance calculations. LILE and HFSE appear mobile in the altered sample groups, except in the propylitic-altered rocks. TRTE behave as relatively immobile in most of samples, except in some of the silicic- and phyllitic-altered rocks, and especially in the hematitic-altered samples. HFSE, most of the transition (W, Mo, Cu, and Sb) and some other trace elements (Pb, As, Hg, Bi, Se and Tl), are enriched in the hematitic-altered samples and in the some silicic-altered samples. The highest As, Bi, Mo, Se and Hg concentrations in the hematite-altered samples can be used to distinguish other alteration types and may be a useful indicator in a prospect-scale base metal exploration.     

6: Classification of VMS deposits: Lessons from the South Uralides

VMS deposits of the South Urals developed within the evolving Urals palaeo-ocean between Silurian and Late Devonian times. Arc-continent collision between Baltica and the Magnitogorsk Zone (arc) in the south-western Urals effectively terminated submarine volcanism in the Magnitogorsk Zone with which the bulk of the VMS deposits are associated. The majority of the Urals VMS deposits formed within volcanic-dominated sequences in deep seawater settings. Preservation of macro and micro vent fauna in the sulphide bodies is both testament to the seafloor setting for much of the sulphides but also the exceptional degree of preservation and lack of metamorphic overprint of the deposits and host rocks. The deposits in the Urals have previously been classified in terms of tectonic setting, host rock associations and metal ratios in line with recent tectono-stratigraphic classifications. In addition to these broad classes, it is clear that in a number of the Urals settings, an evolution of the host volcanic stratigraphy is accompanied by an associated change in the metal ratios of the VMS deposits, a situation previously discussed, for example, in the Noranda district of Canada.Two key structural settings are implicated in the South Urals. The first is seen in a preserved marginal allochthon west of the Main Urals Fault where early arc tholeiites host Cu–Zn mineralization in deposits including Yaman Kasy, which is host to the oldest macro vent fauna assembly known to science. The second tectonic setting for the South Urals VMS is the Magnitogorsk arc where study has highlighted the presence of a preserved early forearc assemblage, arc tholeiite to calc-alkaline sequences and rifted arc bimodal tholeiite sequences. The boninitc rocks of the forearc host Cu–(Zn) and Cu–Co VMS deposits, the latter hosted in fragments within the Main Urals Fault Zone (MUFZ) which marks the line of arc-continent collision in Late Devonian times. The arc tholeiites host Cu–Zn deposits with an evolution to more calc-alkaline felsic volcanic sequences matched with a change to Zn–Pb–Cu polymetallic deposits, often gold-rich. Large rifts in the arc sequence are filled by thick bimodal tholeiite sequences, themselves often showing an evolution to a more calc-alkaline nature. These thick bimodal sequences are host to the largest of the Cu–Zn VMS deposits.The exceptional degree of preservation in the Urals has permitted the identification of early seafloor clastic and hydrolytic modification (here termed halmyrolysis sensu lato) to the sulphide assemblages prior to diagenesis and this results in large-scale modification to the primary VMS body, resulting in distinctive morphological and mineralogical sub-types of sulphide body superimposed upon the tectonic association classification.It is proposed that a better classification of seafloor VMS systems is thus achievable using a three stage classification based on (a) tectonic (hence bulk volcanic chemistry) association, (b) local volcanic chemical evolution within a single edifice and (c) seafloor reworking and halmyrolysis.     

6: Classification of VMS deposits: Lessons from the South Uralides

VMS deposits of the South Urals developed within the evolving Urals palaeo-ocean between Silurian and Late Devonian times. Arc-continent collision between Baltica and the Magnitogorsk Zone (arc) in the south-western Urals effectively terminated submarine volcanism in the Magnitogorsk Zone with which the bulk of the VMS deposits are associated. The majority of the Urals VMS deposits formed within volcanic-dominated sequences in deep seawater settings. Preservation of macro and micro vent fauna in the sulphide bodies is both testament to the seafloor setting for much of the sulphides but also the exceptional degree of preservation and lack of metamorphic overprint of the deposits and host rocks. The deposits in the Urals have previously been classified in terms of tectonic setting, host rock associations and metal ratios in line with recent tectono-stratigraphic classifications. In addition to these broad classes, it is clear that in a number of the Urals settings, an evolution of the host volcanic stratigraphy is accompanied by an associated change in the metal ratios of the VMS deposits, a situation previously discussed, for example, in the Noranda district of Canada.Two key structural settings are implicated in the South Urals. The first is seen in a preserved marginal allochthon west of the Main Urals Fault where early arc tholeiites host Cu–Zn mineralization in deposits including Yaman Kasy, which is host to the oldest macro vent fauna assembly known to science. The second tectonic setting for the South Urals VMS is the Magnitogorsk arc where study has highlighted the presence of a preserved early forearc assemblage, arc tholeiite to calc-alkaline sequences and rifted arc bimodal tholeiite sequences. The boninitc rocks of the forearc host Cu–(Zn) and Cu–Co VMS deposits, the latter hosted in fragments within the Main Urals Fault Zone (MUFZ) which marks the line of arc-continent collision in Late Devonian times. The arc tholeiites host Cu–Zn deposits with an evolution to more calc-alkaline felsic volcanic sequences matched with a change to Zn–Pb–Cu polymetallic deposits, often gold-rich. Large rifts in the arc sequence are filled by thick bimodal tholeiite sequences, themselves often showing an evolution to a more calc-alkaline nature. These thick bimodal sequences are host to the largest of the Cu–Zn VMS deposits.The exceptional degree of preservation in the Urals has permitted the identification of early seafloor clastic and hydrolytic modification (here termed halmyrolysis sensu lato) to the sulphide assemblages prior to diagenesis and this results in large-scale modification to the primary VMS body, resulting in distinctive morphological and mineralogical sub-types of sulphide body superimposed upon the tectonic association classification.It is proposed that a better classification of seafloor VMS systems is thus achievable using a three stage classification based on (a) tectonic (hence bulk volcanic chemistry) association, (b) local volcanic chemical evolution within a single edifice and (c) seafloor reworking and halmyrolysis.     

鄂尔多斯盆地煤成烃潜力与成气热模拟实验

鄂尔多斯盆地煤的Ｒｏｃｋ Ｅｖａｌ分析结果表明，在肥煤—焦煤阶段，Ｓ１＋Ｓ２达最大值，随后生烃潜力减弱。煤的Ｐｙ ＧＣ分析及热模拟成气实验结果证实煤成气具有３个生气高峰，分别相应于Ｒｏ，ｍ０５％～０７％、１０％～１４％及２５％，表明煤成气具多阶段性的特点。这一规律性的认识有助于煤成气的勘探和开发。同时，随煤级增高，煤成烃特征亦发生有规律的变化：异构烃减少，正构烃增加；类异戊二烯烷烃分布亦存在多变性或多阶段的演化特点；苯系化合物具波动性变化特征。     

西天山元古界的热液沉积岩及其与成矿的关系

在西天山中元古界蓟县系首次发现硅质岩、钾长岩和透辉岩等热液沉积岩,其中钾长岩和透辉岩在国内外极为少见。通过对这些热液沉积岩的地球化学特征的综合研究,确定这些热液沉积岩为海底喷气—沉积成因。最后,表文还分析了该热液沉积岩形成的构造背景和沉积环境以及与铜矿化的成因联系。根据金属硫化物的硫同位素组成和微量元素组成特征进一步说明热液沉积岩和金属硫化物的主要物质来自深部地层中循环的同生热液。     

Geochemistry and genetic model of the ore-bearing sediments of the Parnok ferromanganese deposit, Polar Urals

The Parnok ferromanganese deposit is confined to the black shales of the western slope of the Polar Urals. The deposit area is made up of weakly metamorphosed terrigenous-carbonate rocks formed in a marine basin at a passive continental margin. Ore-bearing sequence is composed of coaliferous clayey-siliceous-calcareous shales comprising beds and lenses of pelitomorphic limestones, and iron and manganese ores. The iron ores practically completely consist of micrograined massive magnetite. The manganese ores are represented by lenticular-bedded rocks consisting of hausmannite, rhodochrosite, and diverse manganese silicates. With respect to relations between indicator elements (Fe, Mn, Al, Ti), the shales are ascribed to pelagic sediments with normal concentrations of Fe and Mn, the limestones correspond to metalliferous sediments, ferruginous sediments are ore-bearing sediments, while manganese rocks occupy an intermediate position. It was found that the concentrations of trace elements typical of submarine hydrothermal solutions (As, Ge, Ni, Pb, Sb, Zn, etc.) in both the ore types are in excess of those in lithogenic component. At the same time, the indicator elements of terrigenous material (Al, Ti, Hf, Nb, Th, Zr, and others) in the ores are several times lower than those in the host shales (background sediments). REE distribution patterns in iron ores show the positive Eu anomaly, while those in manganese ores, the positive Ce anomaly. In general, the chemical composition of the ores indicates their formation in the hydrothermal discharge zone. The peculiar feature of the studied object is the manifestation of hydrothermal vents in sedimentary basin without evident signs of volcanic activity. Hydrothermal solutions were formed in terrigenous-carbonate sequence mainly at the expense of buried sedimentation waters. The hydrothermal system was likely activated by rejuvenation of tectonic and magmatic processes at the basement of sedimentary sequences. Solutions leached iron, manganese, and other elements from sedimentary rocks and transported them to the seafloor. Their discharge occurred in relatively closed marine basin under intermittent anaerobic conditions. Eh-pH variations led to the differentiation of Fe and Mn and accumulation of chemically contrasting ore-bearing sediments.     

古代与现代火山成因块状硫化物矿床研究进展

    火山成因块状硫化物（VolcanogenicMas siveSulfide,简称VMS）矿床可见于前寒武纪至现代的各个地质时代。现代海底热液成矿作用为研究VMS矿床提供了一种新的途径,DSDP／ODP钻探资料揭示：①VMS矿床虽然可产生于不同环境,但均与张裂断陷有关。②成矿物质可能来源有 2种：一种是含矿火山岩系及下伏基底物质的淋滤;另一种是深部岩浆房挥发份的直接释放。③洋中脊海底热液循环呈双扩散对流模式。在有沉积物覆盖的洋中脊,热液循环更多地考虑流体与沉积物相互作用产生的效果。④从矿物组合的空间分布来看,热液硫化物堆积体上部以烟囱体为主,下部以块状硫化物为主,深部以网脉状硫化物为主,这在不同热液活动区似乎具有普遍性。
    VMS矿床的矿化模式反映的是一种热液成因,这种热液是深部（1～3 km）岩浆侵入所引起并通过海水在热穹隆之上循环产生的。VMS矿床的深入研究要求我们致力于发现新的矿产地,提高样品采集、分析技术,加强海底热液活动与构造、岩浆作用和环境演变的一体化研究。     

Subsea-floor replacement in volcanic-hosted massive sulfide deposits

Recent research on volcanic-hosted massive sulfide (VMS) deposits indicates that syngenetic subsea-floor replacement ores form an important component of many deposits. In the context of VMS deposits, subsea-floor replacement can be defined as the syn-volcanic formation of sulfide minerals within pre-existing volcanic or sedimentary deposits by infiltration and precipitation in open spaces (fractures, inter- and intra-granular porosity) as well as replacement of solid materials.There are five criteria for distinguishing subsea-floor replacement in massive sulfide deposits: (1) mineralized intervals are enclosed within rapidly emplaced volcanic or sedimentary facies (lavas, intrusions, subaqueous mass-flow deposits, pyroclastic fallout); (2) relics of the host facies occur within the mineral deposit; (3) replacement fronts occur between the mineral deposit and the host lithofacies; (4) the mineral deposit is discordant to bedding; and (5) strong hydrothermal alteration continues into the hanging wall without an abrupt break in intensity. Criteria 1–3 are diagnostic of replacement, whereas criteria 4 and 5 may suggest replacement but are not alone diagnostic. Because clastic sulfide ores contain accessory rock fragments collected by the parent sediment gravity flow(s) during transport, criteria 2 can only be applied to massive, semi-massive, disseminated or vein style deposits, and not clastic ores.The spectrum of VMS deposit types includes deposits that have accumulated largely subsea-floor, and others in which sedimentation and volcanism were synchronous with hydrothermal activity, and precipitation of sulfides occurred at and below the sea floor over the life of the hydrothermal system. Deposits that formed largely subsea-floor are mainly hosted by syn-eruptive or post-eruptive volcaniclastic facies (gravity flow deposits, water-settled fall, autoclastic breccia). However, some subsea-floor replacement VMS deposits are hosted by lavas and syn-volcanic intrusions (sills, domes, cryptodomes). Burial of sea-floor massive sulfide by lavas or sediment gravity flow deposits can interrupt sea-floor mineralization and promote subsea-floor replacement and zone-refining.The distance below the sea floor at which infiltration and replacement took place is rarely well constrained, with published estimates ranging from less than 1 to more than 500 m, but mainly in the range 10–200 m. The upper few tens to hundreds of metres in the volcano-sedimentary pile are the favoured position for replacement, as clastic facies are wet, porous and poorly consolidated in this zone, and at greater depths become progressively more compacted, dewatered, altered, and less amenable to large scale infiltration and replacement by hydrothermal fluids. Furthermore, sustained mixing between the upwelling hydrothermal fluid and cold seawater is regarded as a major cause of sulfide precipitation in VMS systems, and this mixing process generally becomes less effective with increasing depth in the volcanic pile.The relative importance of subsea-floor replacement in VMS systems is related principally to four factors: the permeability and porosity patterns of host lithofacies, sedimentation rate, the relative ease of replacement of host lithofacies (especially glassy materials) and early formed alteration minerals during hydrothermal attack, and physiochemical characteristics of the hydrothermal fluid.     

Tube fossils from gossanites of the Urals VHMS deposits,Russia: Authigenic mineral assemblages and trace element distributions

The occurrence, types, morphology, and mineralogical characteristics of tube microfossils were studied in gossanites from twelve VHMS deposits of the Urals. Several types of tube microfossils were recognized, including siboglinids, polychaetes and calcerous serpulids, replaced by a variety of minerals (e.g. hematite–quartz, hematite–chlorite, carbonate–hematite) depending on the nature of the substrate prior to the formation of the gossanites. Colonial hematite tube microfossils (~ 150 μm across,1–2 mm long) are composed of hematitic outer and inner walls, and may exhibit a cellular structure within their cavities. Spherical forms are saturated with Fe-oxidizing bacteria inside the tubes – probably analogues of trophosomes. Colloform stromatolitic outer wall surfaces are characterized by the presence of numerous interlaced filaments of hematite (2–3 μm diameter, up to 1–2 mm long). Between tube microfossils, the hematitized cement contains bundles of hematitized filaments with structures similar to the hyphae of fungi. Hematite–chlorite tube microfossils are scattered in gossanites, mostly as biological debris. They are typically 30 to 300 μm in diameter and 1 to 5 mm long. The layered structure of their tube walls is characterized by hematite–quartz and chlorite layers. Abundant filamentous bacteria coated by glycocalix and chlorite stromatolite are associated with hematite–chlorite tubes. The carbonate–hematite tube microfossils (up to 300 μm across, 2–3 mm long) occur in carbonate-rich gossanites. The tubes are characterized by fine (~ 10 μm thick) walls of hematite and cavities dominated by relatively dark carbonate or hematite. Carbonates may be present both in walls and cavities. Stromatolite-like leucoxene or hematite–carbonate aggregates were also found in association with tubes. Randomly oriented filaments are composed of ankerite. Single filaments are composed of individual cells, typically smaller than 100 nm across, similar to that of magnetotactic bacteria.Three dimensional tomographic images of all types of tube microfossils demonstrate a clear wavy microlayering from outer and inner walls, which may reflect segmentation of the tube worms. The traces of burrowing or fragments of glycocalix with relict spheres are typical of tube microfossils from gossanites.The carbon isotopic composition of carbonates associated with tube microfossils from hematite–quartz, hematite–carbonate, and hematite–chlorite gossanites average − 7.2, − 6.8, –22.8‰, PDB, respectively. These values are indicative of a biogenic origin for the carbonates. The oxygen isotopic composition of these carbonates is similar in all three gossanite types averaging + 13.5, + 14.2, + 13.0‰ (relative to SMOW), and indicative of active sulfate reduction during the diagenetic (and anadiagenetic) stages of the sediments evolution. The trace element characteristics of hematite from tube microfossils are characterized by high contents of following trace elements (average, ppm): Mn (1529), As (714), V (540), W (537), Mo (35), and U (5). Such high contents are most likely the result of metal and metalloid sorption by fine particles of precursor iron hydroxides during the oxidation of sulfides and decomposition of hyaloclasts via microbially-mediated reactions.     

Mineralogical controls on element dispersion in regolith over two mineralised shear zones near the Peak, Cobar, New South Wales

Effective exploration for polymetallic ore deposits in the Cobar region is hampered by incomplete knowledge of the mineralogical controls on element dispersion in the different regolith-landform settings throughout the area. A detailed mineralogical and geochemical study of regolith profiles over two major mineralised shear zones in a strongly weathered but dominantly erosional setting has delineated the important host minerals for a range of base metal cations. Iron oxides/oxyhydroxides, particularly goethite and to a much lesser extent hematite, are major hosts for Pb, Cu, and Zn as substituted/adsorbed cations and as constituents of associated or intergrown minerals, probably including members of the jarosite–alunite group. Correlations between elements and major regolith minerals suggest that goethite is also a host phase for As, Bi and Sb. Minor manganese minerals, including lithiophorite and cryptomelane group minerals, also host base metals in appreciable amounts. No clear association was found between gold and any particular secondary mineral. It is likely that gold is present largely as elemental gold particles associated with a range of minerals.Sampling strategies for geochemical exploration in variably leached and stripped regolith in the Cobar area should take into account the relative abundance of goethite and manganese oxides/oxyhydroxides within the profiles and overlying lag. Goethite would appear to be the preferred sampling medium for base metals. Highly ferruginous lag has a high proportion of hematite with variable maghemite and very low manganese oxide contents. Most of the base metal content in this surface material is strongly bound to the crystalline oxides/oxyhydroxides. More work is required to understand the effects of surface transformation of goethite to hematite and maghemite on the mobility and distribution of base metal cations in soil and ferruginous lags.     

Biomorphic textures in the ferruginous-siliceous rocks of massive sulfide-bearing paleohydrothermal fields in the urals

The work is dedicated to first finds of bacteriomorphic and microfaunal textures in the ferruginous-siliceous rocks that are widespread among volcanosedimentary complexes of the massive sulfide-bearing paleohydrothermal fields in the Urals. The bacteriomorphs are represented by: (1) single filaments with a diameter of 8–10 μm across and 80–90 μm long; (2) fascicles of branched or twisted-fibrous hematitequartz filaments 1–4 μm in diameter and up to 100 μm long; (3) microtubular textures, 20–30 μm across and up to 500 μm long, closely interlaced with thin hematite-quartz filaments (3–5 μm in diameter); (4)and hematite-quartz filaments (with the axial channel 1 μm across) formed by chains of elongated-oval lumps. These textures closely associate in the ferruginous-siliceous rocks with the fossilized tubular organisms (60–120 μm in diameter), tentaculites, remains of radiolarian skeletons, foraminifers, and others. It has been established that accumulation of various elements, such as Fe, Si, Ca, P, Mn, Ba, Ti, and K that are associated with biomorphic structures, was accompanied by the formation of their own mineral forms. Biomorphic textures in the gossanites (ferruginous-siliceous rocks forming haloes around destroyed massive sulphide mounds) differ from jasperites (not associating with sulfide ores ferruginouse-siliceous rocks), in terms of abundance, diversity, and development of tubular organisms and tentaculites. Biomineralization of different degrees of preservation in the Paleozoic ferruginous-siliceous rocks can indicate the microbial influence on geochemical processes during the decomposition of initial hyaloclastic sediments, which contain an admixture of sulfides and carbonates, under low-temperature conditions accompanied by the formation of iron and silica.