Weathering of the zinc-lead lode, Dugald River, northwest Queensland: II. surface mineralogy and geochemistry

Gossans associated with the Dugald River zinc-lead lode contain anomalous concentrations of Zn, Pb, Ag, As, Cd, Cu, Sb, Se, Tl and Ba and differ from those on the more pyritic Western Lode (Zn, Pb, Cu, As, Tl) and those associated with copper mineralization in the hanging wall (As, Bi, Co, Cu, Mo, Ni, Sb). Mineralogical and geochemical variations in gossans along strike reflect changes in primary ore and gangue mineralogy, particularly towards the north, where the Dugald River lode and hanging wall copper mineralization merge. Leaching of more soluble elements from the surface and re-precipitation below have resulted in large geochemical variations in the top metre of the profile.Dispersion into wall rocks has occurred over two distinct periods: hydromorphic dispersion, before erosion removed much of the gossan and surrounding Corella Formation, has resulted in very high Zn contents (up to 9%) in the footwall, whereas a more even dispersion of target and pathfinder elements into hanging and footwall rocks is from recent weathering of the slightly elevated gossan.     

法国比利牛斯山Trimouns滑石-绿泥石矿床地质与成因

位于法国比利牛斯山的Trimouns矿床是世界上最大的滑石-绿泥石矿床之一。对该矿床形成的条件及滑石和绿泥石矿石的含量已较清楚。它是由不同类型的岩石通过热液交代蚀变而形成的，主要包括白云岩蚀变为滑石为主的矿石和硅铝质岩石(云母片岩和伟晶岩)蚀变为绿泥石为主的矿石。滑石矿石显示片理化结构(滑石片岩)或压实块状结构(块滑石)。由伟晶岩蚀变而来的绿泥石矿石为呈绿色的球状矿体，而由云母片岩蚀变而来的绿泥石矿石呈块状或片理状、颜色为灰绿色和深灰色。本文对欧洲这个独一无二的滑石和绿泥石矿床的地质特征和成因进行了总结和讨论。流体包裹体研究表明成矿流体为高盐度(20to30％eq．wt％NaCl)、中温(320℃)、压为为2．5kbars。磷钇矿和独居石的U—Ph定年结果表明，成矿年代为112—97Ma，成矿作用可能持续了16Ma以上。     

Mineralogical and chemical Zonation around the Woodlawn Cu‐Pb‐Zn ore deposit,Southeastern New South Wales

The volcanogenic Woodlawn Cu‐Pb‐Zn sulphide mineralization occurs within a low‐grade metamorphosed sequence of Middle to Upper Silurian felsic volcanics and fine‐grained sedimentary rocks. Studies on a total of 234 rock samples from diamond drill holes have delineated zones of hydrothermally altered rocks extending more than ～500 m laterally from the main ore lens, at least ～100 m into the foot wall and up to ～200 m into the hanging wall. These altered rocks contain virtually no remnants of primary feldspars and ferromagnesian minerals, and they are variably chloritized, sericitized and silicified. Chlorite and disseminated sulphide minerals are most abundant in zone I, a restricted zone of intense alteration immediately around the main ore lens, whereas sericitic muscovite is most abundant in the relatively extensive zone II, further from the ore. Silicification is also a feature of volcanics well beyond the limits of observed phyllosilicate‐rich alteration zones. Chemical changes within the hydrothermally altered rocks include major enrichment of Fe, Mg, S, Si and H₂O, more sporadic enrichment of Ag, Ba, Bi, Cd, Cu, Mn, Pb, Sn and Zn, and major depletion of Ca, Na and Sr. K is depleted in zone I and shows considerable variation, but no overall depletion or enrichment, in zone II.

Lithological, mineralogical and geochemical features around the Woodlawn orebody are basically similar to those associated with the younger, unmetamorphosed Kuroko deposits.     

Determination of Ga,Ge, Mo,Ag, Cd,In, Sn,Sb, W,Tl and Bi in USGS Whole‐Rock Reference Materials by Standard Addition ICP‐MS

A procedure for determining a wide range of chalcophile and siderophile elements in typical crustal rocks using standard addition and ICP‐SFMS (inductively coupled plasma sector field mass spectrometry) is presented. New results for Ga, Ge, Mo, Ag, Cd, In, Sn, Sb, W, Tl and Bi abundances in USGS whole‐rock reference materials AGV‐2, BHVO‐1, BIR‐1, G‐2, GSP‐1 and W‐2 are reported using this analytical procedure. Intermediate precision of means based on multiple dissolved aliquots of each USGS reference material was 10% RSD or better for Ga, Ge, In and Sn in all, and similarly good for Ag, Cd, Sb, Tl and Bi in most reference materials. Poorer intermediate precision of Mo and W measurements in several reference materials is probably due to higher analytical blanks on these elements and powder heterogeneity due to a sulfide‐related nugget effect in the specific case of Mo in GSP‐1. Results for all elements fell within the range of available published data with the exception of Ag, which yielded systematically higher concentrations than found in the literature for five of the six reference materials, likely reflecting interference from unresolved polyatomic species.     

Setting,sulfur isotope variations,and metamorphism of Jurassic massive Zn‐Pb‐Ag sulfide mineralization associated with arc‐type volcanism (Skra,Vardar zone, Νorthern Greece)

Massive Zn‐Pb‐Ag sulfide mineralization appears conformable with felsic volcanism, developed in an Upper Jurassic volcanic arc to the Southwest (SW) of the Serbo‐Macedonian continent in Northern Greece. The host volcanic sequence of the mineralization comprises mylonitized rhyolitic to rhyodacitic lavas, pyroclastics, quartz‐feldspar porphyries, and cherty tuffs. A “white mica—quartz—pyrite” mineral assemblage characterizes the volcanic rocks in the footwall and hanging‐wall of massive sulfide ore layers, formed as a result of greenschist‐grade regional metamorphism on “clay‐quartz‐pyrite” hydrothermal alteration haloes. Massive ore lenses are usually underlain by deformed Cu‐pyrite and quartz‐pyrite stockworks. Most of the sulfide ore bodies have proximal‐type features. Ductile deformation and regional metamorphism have transformed many of the stockwork structures. The mineralization is characterized by high Zn, Pb, and Ag contents, while Cu and critical metals are low. Primary depositional textures, for example, layering, clastic pyrite, colloform, and atoll textures were identified. The overall textural features of the mineralization indicate it has undergone mechanical deformation. The most prominent features of the effects of metamorphism, folding and shearing, are modification of the ore body morphology toward flattened and boudinage structures and transformation of the ore textures toward the dominance of planar fabrics. Sulfur isotope analyses of sulfides along with textural observations are consistent with a dual source of sulfide sulfur. Sulfur isotope values for sphalerite, non‐colloform pyrite, galena, and chalcopyrite fall in a limited range from ?1.6 to +4.8‰ (mean δ³⁴S + 2‰), indicating a hydrothermal source derived from the reduction of coeval seawater sulfate in the convective system. Pyrites with colloform and atoll textures are characterized by a ³⁴S depletion, indicating a bacterial reduction of coeval seawater sulfate. The morphology of ore beds, the mineralogy, sulfide textures, and ore chemistry along with the petrology and tectonic setting of the host rocks can be attributed to typical of a bimodal‐felsic metallogenesis. Although similar in many respects to classic Kuroko‐type volcanogenic massive sulfide mineralization, it has some atypical features, like the absence of barite ore, which is possibly a result of significant temporal depletion in sulfate due to bacterial reduction, a conclusion supported by the widespread occurrence of colloidal and atoll textures of pyrite.     

Geochemical comparison of woodlawn and mount painter acid volcanics,Southeastern Australia

Major‐ and trace‐element chemistry (including rare‐earth elements), total‐rock Rb‐Sr and U‐Pb and zircon U‐Pb data are used in an attempt to distinguish between two essentially coeval, felsic volcanic suites: the predominantly submarine Woodlawn suite which is associated with massive Cu‐Pb‐Zn sulphide mineralization and the terrestrial Mt Painter suite, with minor vein‐type mineralization. The Woodlawn samples are the unmineralized equivalents of the volcanics in the immediate ore environment.

Alteration perturbs some of the major‐ and trace‐element chemistry, particularly Ca and alkalis, thereby precluding their usefulness. REE patterns exhibit a significant light to heavy rare‐earth enrichment with an average La/Yb of 12 in the Mt Painter volcanics compared with 5.6 in the Woodlawn volcanics. Both suites have a marked negative Eu anomaly, with that of the Woodlawn samples more pronounced (‐45.5) than in the Mt Painter volcanics (‐29.2). A hydrothermally‐altered sample from Woodlawn has apparently lost about 50% of its light rare‐earth elements.

Initial ⁸⁷Sr/⁸⁶Sr ratios at about 0.711 are the same for rocks from both suites and differences in initial lead‐isotopic ratios appear negligible.

Zircons from both suites are a mixture of clear euhedral crystals and rounded discrete crystals or rounded cores overgrown by clear zircon. The U‐Pb data substantiate the morphological features in that the zircon suites both contain older inherited Pb but the Mt Painter zircons contain a greater proportion.

Cs concentrations and Cs/Rb and Ti/Zr ratios can be used to distinguish between the Woodlawn suite and the Mt Painter suite.     

An Overview of Process Mineralogy of Tungsten and Its Associated Elements

China produces much tungsten metal every year. The tungsten deposits in China usually are low-grade and have complex mineralogy composition as well as many associated valuable elements. The associated elements include Sn, Mo, Bi, Cu, Pb, Zn, Sb, Be, Co, Au, Ag, Nb, Ta, Re, Sc, REE, Li, As, S, P and the nonmetallic minerals such as quartz, fluorite, feldspar, etc. Therefore, only the tungsten ore dressing is done in accordance with the ore properties based on the detailed and full process mineralogy study can the valuable elements be reasonably and fully recovered and the maximization of resource utilization as well as environment-friendly is achieved eventually. This paper summarizes the status quo of process mineralogy of tungsten and its associated elements in China, focuses on the process mineralogy studies on major tungsten ore types including tungsten-molybdenum associated ore, tungsten-tin polymetallic ore and tungsten-copper polymetallic ore, suggests the future process mineralogy research on tungsten and its associated elements.     

Multiple Sources of Metals of Mineralization in Lower Cambrian Black Shales of South China: Evidence from Geochemical and Petrographic Study

Black shales of the Lower Cambrian Niutitang Formation in southern China (Huangjiawan mine, Zunyi region, northern part of the Guizhou Province) host regionally distributed stratiform polymetallic Ni‐Mo‐platinum group elements (PGE)‐Au phosphate‐ and sulfide‐rich ores. These are confined to a ≥0.2‐m thick ore horizon composed of mineralized bodies of algal onkolites, phosphate nodules, and sulfide and shale clasts in a mineralized phosphate‐ and organic matter‐rich matrix. Compared to footwall and hanging wall shales, the ore bed is strongly enriched in Ni (up to 100‐fold), As (up to 97‐fold), Mo (up to 95‐fold), Sb (up to 67‐fold), Rh (up to 49‐fold), Cu (up to 37‐fold), Pd (up to 33‐fold), Ru (up to 24‐fold), Zn (up to 23‐fold), Pt (up to 21‐fold), Ir (up to 15‐fold), Co (up to 14‐fold), and Pb (up to 13‐fold). Even footwall and hanging wall black shales are significantly enriched by Mo (21‐fold) and Ni (12‐fold) but depleted in Cr in comparison to average Cambrian black shale. Organic matter is represented by separate accumulations dispersed in the rock matrix or as biotic bitumen droplets and veinlets in ore clasts. Similar organic carbon (C_org) values in an ore bed and enclosing footwall and hanging wall shales of little mineralization indicate that metal accumulation was not controlled only by biogenic productivity and organic matter accumulation rate. Evaporitic conditions during sedimentation of the basal part of the Niutitang Formation were documented by an occurrence of preserved Ni‐, V‐, Cr‐, and Cu‐enriched phosphate‐rich hardground with halite and anhydrite pseudomorphs on the paleosurface of the underlying Neoproterozoic carbonates. Neoproterozoic black shales of the Doushantuo Formation are characterized by increased metal concentrations. Comparison of metal abundances in both hardground and Doushantuo black shales indicate that black shales could have become a source of metal‐rich hardground during weathering. The polymetallic Ni‐Mo‐PGE sulfide‐rich ore bed is interpreted to represent a remnant of shallow‐water hardground horizon rich in metals, which originated in a sediment‐starved, semi‐restricted, seawater environment. During the Early Cambrian transgression an influx of fresh seawater and intensive evaporation, together with the hydrothermal enrichment of seawater in a semi‐restricted basin, resulted in the formation of dense metalliferous brines; co‐precipitation of metals together with phosphates and sulfides occurred at or above the oxic–anoxic sediment interface. Metal‐enriched hardground was disintegrated by the action of waves or bottom currents and deposited in a deeper part of the anoxic basin. Contemporaneously with the formation of a polymetallic Ni‐Mo‐PGE‐Au sulfide ore bed, economic sedimentary exhalative (SEDEX)‐type barite deposits were forming in a stratigraphically and geotectonically similar setting. The results of geochemical study at the Shang Gongtang SEDEX‐type Ba deposit indicate that concentrations of Ag, As, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V, Zn and other metals decrease from top of the barite body toward the hanging wall black shale. Lower Cambrian black shales of the Niutitang Formation above the barite body also display similar element abundances as Neoproterozoic black shales of the Doushantuo Formation, developed in the footwall of the barite body. But the geochemical composition of the sulfide layer is different from the Ni‐Mo ore bed, showing only elevated Pb, Cu, Ni and Mo values. It is suggested that hydrothermal brines at Shang Gongtang might have leached metals from footwall Neoproterozoic sequences and became, after mixing with normal seawater, an additional source of Ag, Cr, Cu, Pb, Sb, Zn, Ni, PGE, V and other metals.     

On the relationship between auriferous talc deposits hosted in volcanic rocks and massive sulphide deposits in Egypt

The volcanic-hosted massive sulphide (VHMS) deposits in the Eastern Desert of Egypt (e.g., Um Saki deposit) are associated with Precambrian coarse acid pyroclastic rocks. The upper contacts of the massive sulphide body are sharp and well-defined; while the keel zone to the mineralization is always associated with pervasive alteration, characterized by the presence of septechlorite and talc, associated with variable amounts of carbonate and tremolite. On the other hand, the economic talc deposits in Egypt are hosted intensively altered volcanic rocks. Besides talc, chlorite, carbonates and tremolite that occur in variable amounts in these deposits, anomalously high concentrations of gold are also present.The present study showed that alterations in the talc deposits of Darhib, El Atshan, Abu Gurdi, Egat, Um Selimat and Nikhira are similar to those occurring in the keel zone underlying the VHMS of Um Samuki and that the chemical modifications due to alteration processes (additions of Mg, Fe, Mn and Ca coupled with depletions in silica, alkalies, alumina and titanium) are comparable, even the host rocks are different, thus reflecting a genetic relationship. It is suggested that, the examined localities of talc deposits are hosted in the intensively altered volcanics in the keel zones of volcanogenic massive sulphide deposits. Recently, detailed geophysical prospecting program, including electric (resistivity, self-potential and induced polarization), electromagnetic and magnetic methods, was carried out at Darhib, Abu Gurdi and Um Selimat talc deposits. The quantitative interpretation of these geophysical measurements revealed the presence of subsurface bodies of sulphides. The present distribution of talc and allied minerals in Darhib, El Atshan, Abu Gurdi, Egat, Um Selimat and Nikhira could be explained by a tectonic process in which the coarse acid pyroclastic rocks with massive sulphides have tilted in such way that the footwall rock alterations (talc and allied minerals) are exposed on the present-day surface at these localities. Structural studies are currently under way in an attempt to explain the deformation regime that led to the present situation of talc deposits.Two distinct spatial and mineralogical associations of gold mineralization could be identified in the volcanogenic massive sulphide deposits and their footwall alterations (the keel zone) in the Eastern Desert of Egypt. These are (1) gold–silver–zinc association, and (2) gold–copper association. In the former, gold grades are very low and silver is anomalous. This association occurs typically in the upper levels of the VHMS deposit where low-temperature sulphides are abundant. Gold was deposited because of the mixing between the ascending hot solutions and the sulphate-rich seawater. The upper levels of Um Samuki sulphide body represent this association. Gold–copper association, on the other hand, typically occurs in the footwall altered rocks (the keel zone) and the lowest parts of the massive sulphide body. Gold grades reach up to 5.54 ppm, but the average is 1 ppm. Silver is very low, usually in the range of 4–10 ppm. Lead usually, but not always, accompanies gold in this association. Deposition of gold probably took place due to decreasing of temperature and/or increasing pH of the ascending hot brines. The keel zones at Darhib, Abu Gurdi, El Atshan, Um Selimat, Nikhira and Egat talc mines better represent this association.     

VHMS mineralisation at Erayinia in the Eastern Goldfields Superterrane: Geology and geochemistry of the metamorphosed King Zn deposit

Despite having been a target for volcanic-hosted massive sulfide (VHMS) deposits since the 1960s, few resources have been defined in the Archean Yilgarn Craton of Western Australia. Exploration challenges associated with regolith and deep cover exacerbate the already-difficult task of exploring for small, deformed deposits in stratigraphically complex, metamorphosed volcanic terranes. We present results of drill-core logging, petrography, whole-rock geochemistry and portable X-ray Fluorescence data from the King Zn deposit, to help refine mineralogical and geochemical halos associated with VHMS mineralisation in amphibolite-facies greenstone sequences of the Yilgarn Craton. The King Zn deposit (2.15?Mt at 3.47?wt% Zn) occurs as a 1–7 m-thick stratiform lens dominated by iron sulfides, in an overturned, metamorphosed volcanic rock-dominated sequence located ～140?km east of Kalgoorlie. The local stratigraphy is characterised by garnet-amphibolite and strongly banded intermediate to felsic schists, with rare horizons of graphitic schist and talc schist. Massive sulfide mineralisation is characterised by stratiform pyrite–pyrrhotite–sphalerite at the contact between quartz–muscovite schists (‘the footwall dacite’), and banded quartz–biotite and amphibole?±?garnet schists of the stratigraphic hanging-wall. A zone of pyrite–(sphalerite) and pyrrhotite–pyrite–(chalcopyrite) veining extends throughout the stratigraphic footwall. Footwall garnet-amphibolites are of sub-alkaline basaltic affinity, with a central zone dominated by chlorite?±?magnetite interpreted to represent the Cu-bearing feeder zone. SiO₂, CaO, Fe₂O_3T, MgO and Cu concentrations are highly variable, reflecting quartz–epidote?±?chlorite?±?magnetite?±?sulfide alteration. Hydrothermal alteration in stratigraphically overlying intermediate to felsic rocks is characterised by a mineral assemblage of quartz–muscovite?±?chlorite?±?albite?±?carbonate. Cordierite and anthophyllite are locally significant and indicative of zones of Mg-metasomatism prior to metamorphism. Increases in SiO₂, Fe₂O_3T, pathfinder elements (e.g. As, Sb, Tl), and depletions of Na₂O, CaO, Sr and MgO occur in quartz–muscovite schists approaching massive sulfide mineralisation. Within all strata (including the immediate hanging-wall), the following pathfinder elements are strongly correlated with Zn: Ag, As, Au, Bi, Cd, Eu/Eu*, Hg, In, Ni, Pb, Sb, Se and Tl. These geochemical halos resemble less metamorphosed VHMS deposits across the Yilgarn Craton and suggest that although metamorphism leads to element mobility and mineral segregation at the thin-section scale, assay samples of ～20?cm length are sufficient to vector to mineralisation in amphibolite facies greenstone belts. Recognition of minerals such as Mg-chlorite, muscovite, cordierite, anthophyllite, biotite/phlogopite, and abundant garnet are significant, in addition to Al-rich phases (i.e. kyanite, sillimanite, andalusite and/or staurolite) not identified at King. Chemographic diagrams may be used to identify and distinguish different alteration trends, along with several alteration indices (e.g. Alteration Index, Carbonate–Chlorite–Pyrite Index, Silicification Index) and the abundance of normative corundum and quartz.     

贵州威宁沉积型赤铁矿矿石工艺矿物学研究

对贵州威宁沉积型赤铁矿石进行了工艺矿物学研究,重点研究了该矿石的矿物组成、主要矿物嵌布特征和主要含铁矿物赤铁矿的单体解离情况。研究表明,该矿石属于低磷、低硫、微细粒嵌布的赤铁矿石;矿石中主要铁矿物以赤铁矿为主,其次为磁铁矿和褐铁矿,主要脉石矿物以石英为主,其次为绿泥石、云母、高岭石等粘土矿物;赤铁矿嵌布粒度极细,平均粒度0.015mm,且赤铁矿与脉石矿物嵌布关系复杂。本研究为该矿石的开发利用提供基础资料。     

Surface geochemical and biogeochemical expression of base‐metal mineralization at Woodlawn,New South Wales,Australia

The presence of base‐metal mineralization at Woodlawn was first recognised early in 1968 when a roadside reconnaissance geochemical sampling survey, conducted over felsic volcanic rocks in the Goulburn‐Tarago area, encountered anomalous B horizon soils containing up to 200 ppm Cu, 800 ppm Pb and 300 ppm Zn. Regional soil thresholds have been determined at 50 ppm Cu, 90 ppm Pb and 50 ppm Zn. Chip samples from the subsequently located gossan revealed up to 2000 ppm Cu, 8000 ppm Pb and 2000 ppm Zn, 500 ppm Sn, 25 ppm Ag and 3000 ppm As.

The first grid B horizon soil geochemical survey was conducted in 1968 over the gossan and surrounding area, and repeated with closer spaced sampling in the first half of 1970. The first survey delineated strong Cu (to 1000 ppm) and Pb (to 2500 ppm) anomalies coincident with the gossan zone, and intense hydromorphic zinc anomalies (to 3000 ppm) located down slope from the gossan in residual clay‐soils derived from dolerite bedrock. Threshold values have been determined at 140 ppm Cu, 700 ppm Pb and 580 ppm Zn. Ag and Sn in B horizon soils show pronounced anomalies coincident with the gossan and are suitable metals for geochemical target definition. Of fourteen trace elements determined in 1974 from B and C horizon soils on two lines across the ore zone Cu, Pb, Zn, Se, Ba, Sn and Ag show direct correlation with the mineralization, whereas Cd and Mn show moderate hydromorphic dispersion, having accumulated principally in clay soils derived from dolerite weathering. As, Sb and Bi, whilst responding over the ore zone, show elevated values in soils over hanging‐wall units; Ni and Co show maximum levels in soils over dolerite bedrock.

Bark and leaves of Acacia mearnsii, collected from a line across the gossan, contain anomalous levels of Cu, Pb, Zn, Sn and Ti near the ore zone, and weaker, but clearly anomalous Mn and Ni levels over dolerite bedrock. Both bark and leaves of Acacia mearnsii reflect the presence of concealed mineralization. The shrub Solanum linearifolium grows preferentially over and close to the Woodlawn ore zone, where it contains up to 840 ppm Cu, 250 ppm Pb, 7300 ppm Zn, 6 ppm Sn and 250 ppm Ti in leaf ash compared with levels of 200 ppm Cu, 2 ppm Pb, 400 ppm Zn, 0.8 ppm Sn and 60 ppm Ti in plants growing 1.5 km from the ore zone. This shrub has potential as an indicator of base‐metal mineralization.     

The Zn-Pb deposits of Casario (Ligurian Alps,NW Italy): Late Palaeozoic sedimentary-exhalative bodies affected by the alpine metamorphism

In the Ligurian Alps (South-Western Italian Alps), Zn-Pb deposits occur within late Palaeozoic meta-sedimentary units belonging to the Briançonnais Zone near Casario (Tanaro valley). Different types of sulphide-rich, lens-shaped mineralizations are recognized: sphalerite-galena massive sulphide bodies, pyrite-rich lenses and sulphide-rich quartz–carbonate-chloritoid granofels. Sulphide lenses and host rocks are affected by at least three ductile deformation phases and by a polyphase alpine metamorphism, whose climax conditions are estimated, based on P-T pseudosection calculations, at T = 300-325 °C and P = 0.55-0.60 GPa. In all the mineralized lenses the ore minerals are represented, in variable amount, by Fe-poor sphalerite, galena, pyrite and arsenopyrite (± tetrahedrite, chalcopyrite and pyrrhotite); the gangue consists of quartz, carbonate (sideritemagnesite ± rhodochrosite s.s.), Fe-chloritoid, muscovite-phengite and chlorite. The mineralizations are associated with chloritoid – carbonate micaschists displaying a finely bedded texture, with sharp between-bed compositional contrast, which suggests their exhalative origin.

In spite of the tectono-metamorphic overprint, some pre-metamorphic features of the hydrothermal system are still recognized, like relics of the hydrothermal feeding system, primary growth textures and sulphide-rich microbreccias. These massive sulphide lenses, which share many characters with the SEDEX deposits, testify to the occurrence of an exhalative event of Upper Carboniferous age previously unrecognized in the Ligurian Briançonnais Unit.     

Development of a Matrix‐Matched Sphalerite Reference Material (MUL‐ZnS‐1) for Calibration of In Situ Trace Element Measurements by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Sphalerite (ZnS) is an abundant ore mineral and an important carrier of elements such as Ge, Ga and In used in high‐technology applications. In situ measurements of trace elements in natural sphalerite samples using LA‐ICP‐MS are hampered by a lack of homogenous matrix‐matched sulfide reference materials available for calibration. The preparation of the MUL‐ZnS1 calibration material containing the trace elements V, Cr, Mn, Co, Ni, Cu, Ga, Ge, As, Se, Mo, Ag, Cd, In, Sn, Sb, Tl and Pb besides Zn, Fe and S is reported. Commercially available ZnS, FeS, CdS products were used as the major components, whereas the trace elements were added by doping with single‐element ICP‐MS standard solutions and natural mineral powders. The resulting powder mixture was pressed to pellets and sintered at 400 °C for 100 h using argon as an inert gas. To confirm the homogeneity of major and trace element distributions within the MUL‐ZnS1 calibration material, measurements were performed using EPMA, solution ICP‐MS, ICP‐OES and LA‐ICP‐MS. The results show that MUL‐ZnS‐1 is an appropriate material for calibrating trace element determination in sphalerite using LA‐ICP‐MS.     

Exploration rock geochemistry — detection of trace element halos at heath steele mines (N.B., Canada) by discriminant analysis

The Heath Steele massive sulphide deposit in northern New Brunswick lies conformably within a sedimentary-volcanic sequence of probable Ordovician age which has been metamorphosed to the greenschist stage. The dominant sulphide mineral is pyrite, and the main economic minerals are sphalerite, galena, and chalcopyrite; the general grade of the ore is 5% Zn, 2% Pb, and 1% Cu.The distribution of Pb and Zn in acid volcanic rocks stratigraphically above the massive sulphides is compared with the distribution in similar rocks stratigraphically below the sulphides. Whereas there are discernable differences in the populations, there is also considerable overlap between them. To enable individual samples to be classified, linear discriminant functions were calculated for the two groups; Pb and Zn were found to be the most useful variables to separate the two populations. The functions were then tested on hanging wall and footwall samples not used in computing the functions. A halo region, extending about 1,200 ft above the sulphides and 4,000 ft along the same stratigraphic horizon as the sulphides was outlined by samples classified as “hanging wall”. Beyond the halo zone there is no significant difference in the distribution of Pb and Zn between the hanging wall and footwall acid volcanic rocks.The results demonstrate that rocks at Heath Steele, which show no evidence of mineralogical alteration attributable to mineralization, have a trace element halo of considerable extent spatially associated with the sulphides. If similar halos can be shown to be a general feature of massive sulphide deposits, the technique described should have wide application for exploration for deeply buried deposits of this type.     

Geology and wall rock alteration at the Hercynian Draa Sfar Zn–Pb–Cu massive sulphide deposit, Morocco

Draa Sfar is a siliciclastic–felsic, volcanogenic massive sulphide (VMS) Zn–Pb–Cu deposit located 15 km north of Marrakesh within the Jebilet massif of the western Moroccan Meseta. The Draa Sfar deposit occurs within the Sarhlef series, a volcano-sedimentary succession that hosts other massive sulphide deposits (e.g., Hajar, Kettara) within the dominantly siliciclastic sedimentary succession of the lower Central Jebilet. At Draa Sfar, the footwall lithofacies are dominated by grey to black argillite, carbonaceous argillite and intercalated siltstone with localized rhyodacitic flows and domes, associated in situ and transported autoclastic deposits, and lesser dykes of aphanitic basalt and gabbro. Thin- to thick-bedded, black carbonaceous argillite, minor intercalated siltstone, and a large gabbro sill dominate the hanging wall lithofacies. The main lithologies strike NNE–SSW, parallel to a pronounced S1 foliation, and have a low-grade, chlorite–muscovite–quartz–albite–oligoclase metamorphic assemblage. The Draa Sfar deposit consists of two stratabound sulphide orebodies, Tazakourt to the south and Sidi M'Barek to the north. Both orebodies are hosted by argillite in the upper part of the lower volcano-sedimentary unit. The Tazakourt and Sidi M'Barek orebodies are highly deformed, sheet-like bodies of massive pyrrhotite (up to 95% pyrrhotite) with lesser sphalerite, galena, chalcopyrite, and pyrite. The Draa Sfar deposit formed within a restricted, sediment-starved, fault-controlled, anoxic, volcano-sedimentary rift basin. The deposit formed at and below the seafloor within anoxic, pelagic muds.The argillaceous sedimentary rocks that surround the Draa Sfar orebodies are characterized by a pronounced zonation of alteration assemblages and geochemical patterns. In the more proximal volcanic area to the south, the abundance of medium to dark green chlorite progressively increases within the argillite toward the base of the Tazakourt orebody. Chlorite alteration is manifested by the replacement of feldspar and a decrease in muscovite abundance related to a net addition of Fe and Mg and a loss of K and Na. In the volcanically distal and northern Sidi M'Barek orebody alteration within the footwall argillite is characterized by a modal increase of sericite relative to chlorite. A calcite–quartz–muscovite assemblage and a pronounced decrease in chlorite characterize argillite within the immediate hanging wall to the entire Draa Sfar deposit. The sympathetic lateral change from predominantly sericite to chlorite alteration within the footwall argillite with increasing volcanic proximity suggests that the higher temperature part of the hydrothermal system is coincident with a volcanic vent defined by localized rhyodacitic flow/domes within the footwall succession.     

The origin of tin deposits in the Mount Wells region,Pine Creek Geosyncline,Northern Territory

Tabular steeply dipping cassiterite‐bearing lodes in the Mount Wells region are hosted by lower greenschist fades metasediment of the Pine Creek Geosyncline within the contact aureole of late orogenic granitoids. The latter are predominantly I‐type, but S‐type phases are developed near the sediment‐granitoid contact.

Quartz, cassiterite, pyrite, arsenopyrite, chalcopyrite and pyrrhotite are the main minerals. Two types of lodes are present: (i) Sn‐quartz lodes containing 5–10 vol% sulphide minerals; and (ii) Sn‐sulphide lodes containing ～ 70 vol% sulphide minerals. At the surface, the former appear as normal quartz veins and the latter as hematite‐quartz breccia resulting from the collapse of original sulphide‐rich lodes as a consequence of volume reduction due to oxidation and leaching.

Two stages of quartz veining are recognized in both types of lodes. Cassiterite is present in stage I while stage II is composed of barren quartz with minor pyrite. Late stage III carbonate veinlets are present in Sn‐sulphide lodes. The lode‐wallrock contact is sharp with weak alteration effects confined to the fringe of the lodes. The alteration minerals include sericite, quartz, tourmaline, chlorite, pyrite and minor K‐feldspar.

Four types of fluid inclusions are present in vein quartz and cassiterite: Type A (CO₂ ± H₂O ± CH₄); Type B (H₂O+～ 20% vapour); Type C (H₂O+ < 15% vapour) and Type D (H₂O+ < 15% vapour + NaCl). Early ‘primary’ inclusions represented by Types A and B are present in stage I only and have a well‐defined temperature mode at ～300°C and a salinity range of 1–20 wt% eq NaCl. Types C and D inclusions are ‘secondary’ in stage I and primary in stage II and have a temperature mode at 120–160°C and salinities from about 1 to more than 26 wt% eq NaCl. Variable H₂O‐CO₂ ratios of Type A inclusions and homogenization in CO₂ or H₂O phase at near identical temperature indicate entrapment at the H₂O‐CO₂ solvus and define a pressure of ～ 100 MPa. The melting sequence of frozen inclusions suggests that the ore fluids were mainly H₂O‐CO₂‐CH₄‐Na‐Ca‐Cl brines. This is also confirmed by Raman Laser Spectrometry.

Oxygen and sulphur isotope data are consistent with a magmatic origin of the ore fluids. The δD values are up to 20%0 higher than those expected for magmatic fluids and probably resulted from interaction of the latter with the carbonaceous strata. This interpretation is supported by δ¹³C data on the fluid inclusion CO₂.

Fluid inclusions, stable isotope and mineralogical data are used to approximate the physico‐chemical parameters of the ore fluids which are as follows: T 300°C, m Cl～2, fO₂ ～ 10^‐35, mSS ～ 0.01, Sn ～ 1 ppm, Cu ～ 1 ppm and pH ～ 5.5.

It is suggested that fluids of granitic parentage interacted with the enclosing sediment and picked up CO₂, CH₄ and possibly Ca. The granitic phases became reduced due to this interaction and developed S‐type characteristics. Tin was probably partitioned into the CH₄‐bearing reduced fluids. At some stage the fluid overpressure exceeded the lithostatic lode enforcing failure of the carapace and the intruded rocks by hydraulic fracturing causing CH₄ and CO₂ loss resulting in the precipitation of the ore minerals.     

Chemistry and Sulfur Isotopes in a Chert-dominant Sequence around the Stratiform Manganese Deposit of the Noda-Tamagawa Mine, Northern Kitakami Terrane, Northeast Japan: Implication for Paleoceanographic Environmental Setting

Abstract. Chemistry and sulfur isotopes are analyzed for a series of rocks in the chert‐dominant sequence around the stratiform manganese ore deposit of the Noda‐Tamagawa mine in the northern Kitakami Terrane, northeast Japan. The sequence is litholog‐ically classified into six units in ascending order: lower bedded chert, lower black shale, massive chert, manganese ore, upper black shale, and upper bedded chert. The rocks around the manganese ore deposit exhibit anomalous enrichment in Ni (max. 337 ppm), Zn (102) and U (30) in the upper part of lower bedded chert, Mo (122), Tl (79) and Pb (33) in the lower black shale, MnO, Cu (786) and Co (62) in the manganese ore, and As (247) and Sb (17) in the upper black shale. The aluminum‐normalized profiles reveal zonal enrichment of redox‐sensitive elements around the manganese bed: Zn‐Ni‐Fe‐Mo‐U(‐Co), Tl‐Pb(‐Mo), Mn‐Fe‐Cu‐V‐Cr‐Co(‐Zn) and As‐Sb in ascending order. The uppermost part of the lower bedded chert and black shale exhibit negative Ce/Ce* values, whereas the massive chert, manganese ore and lower part of the upper bedded chert display positive values. The isotopic δ³⁴S values are 0±6 % in the lower part of the lower bedded chert, ‐19 to ‐42 % in the upper part of the lower bedded chert, ‐36 to ‐42 % in the lower black shale, ‐28 to ‐35 % in the massive chert, manganese ore and upper black shale, and ‐23±5 % in the upper bedded chert. Thus, there is a marked negative shift in δ³⁴S values in the lower bedded chert, and an upward‐increasing trend in δ³⁴S through the manganese ore horizon. The present data provide evidence for a change in the paleoceanographic environmental resulting from inflow of oxic deepwater into the stagnant anoxic ocean floor below the manganese ore horizon. This event is likely to have triggered the precipitation of manganese oxyhydroxides. The redistribution of redox‐sensitive elements through the formation of metalliferous black shale and manganese carbonate ore may have occurred in association with bacterial decomposition of organic matter during early diagenesis of initial manganese oxyhydroxides.     

Über Gehalte an Germanium,Zinn und einigen anderen Spurenelementen in ostalpinen Graphit- und Talkgesteinen

Zusammenfassung Es wurden Proben auf die Elemente Ge, Sn, Pb, Tl und Bi untersucht. Die Ergebnisse konnten durch eine emissionsspektrographische Doppelbogenmethode unter Verwendung sulfidierender Reagenzien gewonnen werden.Es werden in ostalpinen Graphit- und Talkgesteinen keine geochemisch bedeutenden Anreicherungen an Ge und Sn gefunden. Die relativ geringen Ge-Konzentrationen der aus karbonen Kohlen hervorgegangenen Graphitgesteine werden auf zwei Ursachen zurückgeführt: 1. die Chemofazies war germaniumarm, 2. bei der Graphitisation wird Ge in den Silikaten dispers verteilt. Ge findet sich in glimmerreichen Gesteinen bevorzugt angereichert.In Talken und Talkgesteinen, die in der Serie der Graphitgesteine liegen, nimmt Ge bis 13 ppm zu. Talke aus Ultrabasiten und Basiten enthalten Ge entsprechend der Häufigkeit in diesen Gesteinen.Sn- und Ge-Gehalte in den Graphitgesteinen sind mehr oder weniger korrelierbar. Die Sn-Verteilung ist lokalen Schwankungen unterworfen. Die Graphitgesteine der Grauwackenzone zeigen höhere Bi-Gehalte.

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Summary Samples of graphite and talc-bearing rocks of the Eastern Alps were examined for the elements Ge, Sn, Pb, Tl, and Bi. The results were obtained by means of spectro-chemical analysis using a double arc and sulphidizing reagents.No geochemically appreciable contents of Ge and Sn were found. The relatively low concentrations of Ge in graphitic rocks arising from carboniferous coals are traced back to two causes: (1) The chemofacies was poor in Ge; (2) during graphitization Ge is dispersed. Ge is found in higher concentration in rocks rich in micas.In talc and talc-bearing rocks associated with graphitic rocks Ge increases up to 13 ppm. Talcs derived from basic and ultrabasic rocks contain Ge according to its concentration in these rocks.Sn- and Ge-contents can be more or less correlated. The distribution of Sn is subject to local variations. The graphitic rocks of the Grauwackenzone show higher contents of Bi.

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Mit 6 Textabbildungen

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Herrn Professor Dr.F. Machatschki zum 70. Geburtstag gewidmet.     

X射线衍射-扫描电镜等技术研究秘鲁铜硫矿石选矿工艺矿物学特征

秘鲁铜硫矿石的主要回收对象是铜和硫矿物,由于铜矿物嵌布复杂、粒度过细以及与各种脉石矿物或金属矿物交生关系紧密,利用传统工艺矿物学研究方法如化学分析、光学显微镜检测等较难准确定量其工艺矿物学参数。本文采用化学分析、X射线衍射、扫描电镜、偏光显微镜及矿物参数自动分析系统(MLA)等技术手段,研究秘鲁铜硫矿石的化学成分、矿物组成和主要矿物的嵌布特征、粒度分布及单体解离特性等,并对影响选矿指标的主要矿物学因素进行分析。结果表明:矿石中主要元素为Cu(0.65%)和S(9.53%)。矿石中黄铁矿(16.57%)含量较高,形态较为规则,与其他矿物之间的交生关系相对简单,粒度普遍偏粗,其中粒径大于0.30mm的黄铁矿占95.06%。铜矿物主要以不规则粒状、皮壳状、网脉状、纤维状、尘粒状、斑点状分布于脉石中或与黄铁矿、闪锌矿、磁铁矿等金属矿物交生紧密,粒度极不均匀,使得铜矿物解离难度加大,且矿石中云母(12.51%)、绿泥石(3.74%)、滑石(3.34%)、高岭石、蒙脱石(3.59%)等黏土质矿物含量较高,在磨矿过程中易发生泥化从而恶化分选环境。根据该类型矿石的工艺矿物学特性,本文建议采用"粗磨-部分优先浮铜-铜硫混浮-混合精矿再磨再选分离"的工艺流程,可得到质量高的铜、硫精矿。