Accumulation of heavy metals in Oostriku peat bog,Estonia: -site description,conceptual modelling and geochemical modelling of the source of the metals

Oxidation of sulphides leads to the dissolution of metals, which are transported with water and accumulate at geochemical barriers. Such barriers can form in peat bogs. This paper gives an introduction into the long-term processes in Oostriku peat bog where high accumulations of heavy metals are observed. Peat and water samples are analysed for Fe, As and heavy metals (Cd, Cu, Mn, Ni, Pb and Zn) using different methods. A concept is based on the observations. Metals are leached by sulphide oxidation in the carbonate rocks upstream of the peat. The water feeds the peat from below. The metals are sorbed and precipitated in the peat. The sulphide oxidation is simulated to examine the origin and metal speciation in the water. The simulated solution is compared with the groundwater entering the peat. The results showed a fair agreement for the major constituents. There were considerable differences for species with low concentrations.     

Mineralogy and textures of the Lahanos and Kızılkaya massive sulphide deposits,northeastern Turkey,and their similarity to Kuroko ores

A distinct vertical zonation very similar to that described for the Kuroko deposits of Japan, is displayed by both mineralogy and textures of sulphides from the Lahanos and Kzlkaya massive sulphide deposits of northeastern Turkey. A deeper erosional level is exposed at the Kzlkaya deposit, so that only remnants of the massive sulphide ore zone are present. The zonation is from an upper zone of massive Cu and Zn sulphides (black and yellow ore) with fine-grained, colloform, banded, framboidal, and spherulitic textures, downwards through an intermediate zone of low Cu-Zn massive pyrite with transitional textures, to a lower zone of stockwork and impregnated pyrite displaying euhedral, zoned textures. The fine-grained and colloform pyrite of the upper zones is progressively overgrown by, and recrystallized to, the massive and euhedral pyrite of lower zones. The original textures of these deposits are best preserved by pyrite. The previous interpretation of these textures, of sulphide deposition from colloidal solutions ponded by an impermeable pyroclastic horizon, is reexamined in the light of present observations. Although ultra-fine-grained sulphides, framboids, and radially-cracked spherules could have formed by replacement of pre-existing minerals by a colloidal solution, the colloform and banded textures are indicative of growth in open spaces. It thus seems likely that the fine-grained colloform sulphides, including chalcopyrite, sphalerite, and tennantite as well as pyrite, were initially deposited on or near the surface of the sea-floor. Additional evidence for this interpretation is seen in the progressive recrystallization of the sulphide textures to massive, much coarser, pyrite in the lower zones. This recrystallization may in part be due to diagenetic and hydrothermal processes operating after formation of the original layered sulphides. These conclusions are in agreement with those reached for the similar, but larger Madenköy deposit 100 km to the east.     

High-pressure metamorphism of stratiform sulphide deposits from the Diahot region,New Caledonia

Stratiform Cu-Pb-Zn (-Au-Ag) mineralization associated with black carbonaceous schists and acid metatuffs is restricted to distinct horizons within the Cretaceous sequence of the Diahot region. The sulphides occur in sharply bounded lenses which show varying degrees of compositional banding conformable with the foliation of the country schists. The deposits are sedimentary-exhalative of the Rio Tinto-type and have been modified by mid-Tertiary high-pressure metamorphism (lawsonite-albite and glaucophanitic greenschist facies). The ores are not strongly deformed by the metamorphism and sedimentary structures, pyrite framboids and atoll structures are preserved in some deposits. With increasing metamorphic grade sphalerite becomes more iron-rich, pyrrhotite becomes more abundant, and the sulphides show a general increase in grain-size which parallels that of the silicates in the enclosing rocks. In the more highly metamorphosed deposits the sulphide associations are retrograde assemblages. There is no evidence of large-scale metamorphic remobilization of sulphides. No differences were observed in either the sulphide assemblages or in the composition of the sulphides to indicate that the metamorphism was of the high pressure rather than the low pressure type.     

Iron sulphide formation in an exhalative-sedimentary environment,Talasea, New Britain,P.N.G.

Concentrations of iron sulphide minerals in sediments within and adjacent to a small intertidal thermal pool near Talasea township are forming and being modified under a wide range of exhalative-sedimentary conditions. A geochemical, mineralogical and bacteriological investigation of these iron sulphides has defined the major reactions leading to their formation and indicated aspects in which their mineralogies, textures and mechanisms of formation differ significantly from those of iron sulphides formed under “normal” sedimentary conditions. The main features of the thermal pool environment are: 1. the occurrence of relatively high iron sulphide concentrations; 2. the preservation, by the strongly anaerobic thermal spring waters, of hydrotroilite formed in the thermal pool sediments in the presence of excess sulphide; 3. the presence in the pool banks of major marcasite (which appears to replace its dimorph pyrite) formed as a result of the development of strongly acidic conditions; 4. the abundance in the pool banks of large euhedral crystals of pyrite and marcasite, and the scarcity of framboids; 5. the presence of sulphate-reducing bacteria in the thermal waters and sediments.     

Fabrics of deformed sulphides

Determination of preferred orientations in sulphide ores is an important facet in the analysis of the deformation and metamorphism in ore deposits. The methodology and problems of texture determinations in deformed sulphides are briefly reviewed. Deformation mechanisms and texture development in the common sulphide minerals are summarised. Axi-symmetric experimental deformation of galena, sphalerite and chalcopyrite produces similar pole figures with the (110) planes aligned normal to the compression axis. Deformation textures in naturally deformed sulphides however are best preserved in monomineralic ores which have undergone simple shear deformation. These textures can be correlated with the microstructures found in the sulphides. Computer simulations of deformation textures arising from dislocation mechanisms can be used to interpret the textures but the results to date are preliminary. These theoretical models emphasize the importance of the symmetry of the kinematic axes of the deformation, the operative glide systems and the strain history and the deformation path. Little is known, however, of the influence of static and dynamic recrystallisation on sulphide preferred orientations.     

Magma Mixing as a Trigger for Sulphide Saturation in the UG2 Chromitite (Bushveld): Evidence from the Silicate and Sulphide Melt Inclusions in Chromite

It is of great importance to understand the origin of UG2 chromitite reefs and reasons why some chromitite reefs contain relatively high contents of platinum group elements(PGEs: Os, Ir, Ru, Rh,Pt, Pd) or highly siderophile elements(HSEs: Au, Re, PGE). This paper documents sulphide-silicate assemblages enclosed in chromite grains from the UG2 chromitite. These are formed as a result of crystallisation of sulphide and silicate melts that are trapped during chromite crystallisation. The inclusions display negative crystal shapes ranging from several micrometres to 100 μm in size.Interstitial sulphide assemblages lack pyrrhotite and consist of chalcopyrite, pentlandite and some pyrite. The electron microprobe data of these sulphides show that the pentlandite grains present in some of the sulphide inclusions have a significantly higher iron(Fe) and lower nickel(Ni) content than the pentlandite in the rock matrix. Pyrite and chalcopyrite show no difference. The contrast in composition between inter-cumulus plagioclase(An_(68)) and plagioclase enclosed in chromite(An_(13)), as well as the presence of quartz, is consistent with the existence of a felsic melt at the time of chromite saturation.Detailed studies of HSE distribution in the sulphides and chromite were conducted by LA-ICP-MS(laser ablation-inductively coupled plasma-mass spectrometry), which showed the following.(Ⅰ) Chromite contained no detectable HSE in solid solution.(Ⅱ) HSE distribution in sulphide assemblages interstitial to chromite was variable. In general, Pd, Rh, Ru and Ir occurred dominantly in pentlandite, whereas Os,Pt and Au were detected only in matrix sulphide grains and were clearly associated with Bi and Te.(Ⅲ)In the sulphide inclusions,(a) pyrrhotite did not contain any significant amount of HSE,(b) chalcopyrite contained only some Rh compared to the other sulphides,(c) pentlandite was the main host for Pd,(d)pyrite contained most of the Ru, Os, Ir and Re,(e) Pt and Rh were closely associated with Bi forming a continuous rim between pyrite and pentlandite and(f) no Au was detected. These results show that the use of ArF excimer laser to produce high-resolution trace element maps provides information that cannot be obtained by conventional(spot) LA-ICP-MS analysis or trace element maps that use relatively large beam diameters.     

Remobilisation features and structural control on ore grade distribution at the Konkola stratiform Cu–Co ore deposit,Zambia

The Konkola deposit is a high grade stratiform Cu–Co ore deposit in the Central African Copperbelt in Zambia. Economic mineralisation is confined to the Ore Shale formation, part of the Neoproterozoic metasedimentary rocks of the Katanga Supergroup. Petrographic study reveals that the copper–cobalt ore minerals are disseminated within the host rock, sometimes concentrated along bedding planes, often associated with dolomitic bands or clustered in cemented lenses and in layer-parallel and irregular veins. The hypogene sulphide mineralogy consists predominantly of chalcopyrite, bornite and chalcocite. Based upon relationships with metamorphic biotite, vein sulphides and most of the sulphides in cemented lenses were precipitated during or after biotite zone greenschist facies metamorphism. New δ³⁴S values of sulphides from the Konkola deposit are presented. The sulphur isotope values range from −8.7‰ to +1.4‰ V-CDT for chalcopyrite from all mineralising phases and from −4.4‰ to +2.0‰ V-CDT for secondary chalcocite. Similarities in δ³⁴S for sulphides from different vein generations, earlier sulphides and secondary chalcocite can be explained by (re)mobilisation of S from earlier formed sulphide phases, an interpretation strongly supported by the petrographic evidence. Deep supergene enrichment and leaching occurs up to a km in depth, predominantly in the form of secondary chalcocite, goethite and malachite and is often associated with zones of high permeability. Detailed distribution maps of total copper and total cobalt contents of the Ore Shale formation show a close relationship between structural features and higher copper and lower cobalt contents, relative to other areas of the mine. Structural features include the Kirilabombwe anticline and fault zones along the axial plane and two fault zones in the southern limb of the anticline. Cobalt and copper behave differently in relation to these structural features. These structures are interpreted to have played a significant role in (re)mobilisation and concentration of the metals, in agreement with observations made elsewhere in the Zambian Copperbelt.     

Bismuth and cobalt minerals as indicators of stringer zones to massive sulphide deposits, Iberian Pyrite Belt

The stringer zones and commonly the interaction zone at the base of the massive sulphide mounds in the Iberian Pyrite Belt contain bismuth and cobalt minerals that are not found in the overlying massive sulphides. These are fairly rare cobalt sulphoarsenides (cobaltite, alloclasite, galucodot) that were formed at the beginning of the massive sulphide genesis, and fairly common bismuth sulphides (bismuthinite, hammarite, wittichenite, cosalite, kobellite, joseite, etc.), including species rare at world scale (nuffieldite, giessenite, jaskolskiite) that were deposited from last stage high-temperature (> 300 °C) copper-bearing fluids containing Bi (Te, Se). The last stage fluids precipitated chalcopyrite containing Cu, Bi, Te, (Se) sulphosalts at the base of the sulphide mound to form a high cupriferous zone. Their interaction with the massive sulphides is reflected by the formation of an exchange zone, a few metres thick, showing chalcopyrite disease textures, at the base of the mound; this zone forms the upper limit of potentially economic copper enrichment and of bismuth minerals. Gold is undoubtedly in part, if not totally, related to this last phase. The bismuth concentrations being equivalent in the massive sulphides and the stringers, the presence of bismuth minerals in the stringer zones results from high-temperature conditions combined with a rarity of galena, which impedes absorption of available Bi. The distribution of these bismuth minerals provides a basic mineralogical zoning in the stringer zone, with a deep, low-aS₂ zone containing native bismuth and tellurides and a shallow, higher-aS₂ zone in contact with the massive ore sensu stricto and containing complex bismuth sulphides. These results make it possible to distinguish between sulphide veinlets belonging to stockwork zones of massive orebodies and veinlets of an ambiguous nature, and provide mineralogical criteria for the proximity of copper-rich zones. They enrich the very complex mineralogy of the Iberian Pyrite Belt.     

The origin of framboidal pyrite as a surface effect of sulphur grains

Framboidal pyrite has been prepared by precipitation of oxyhydroxides of iron, peptized by humic acids using a solution of Na-sulphate or hydrogen sulphide, spherical grains of elemental sulphur being present. By peptization of iron oxyhydroxides using humic acids, a stable negatively charged colloidal system arises. At room temperature and a pressure of 1 atm., and at pH widely ranging between 6.5–7.5, sulphidation of this colloidal system gives rise to a monodispersive sulphidic sol whose stability depends on the concentration of iron in the solution, the amount of humic acids and the presence of electrolytes. In the presence of spherical grains of sulphur, arising by rapid oxidation (acidification) of Na₂S solution or a saturated solution of hydrogen sulphide, particles of the sulphidic sol precipitate on their surface and the grains become gradually replaced by sulphides of iron. At the same time, framboids of an average diameter of 14 μm are generated.     

安徽铜陵冬瓜山铜、金矿床两阶段成矿模式

冬瓜山铜金矿床包括层状硫化物矿体、矽卡岩型和斑岩型矿体。层状硫化物矿体具层状形态和层控特征，矿石具块状、层纹状和揉皱状构造。燕山期岩浆岩及其岩浆流体对层状矿体进行了叠加和改造，改变了其结构构造、矿物组合和矿石成分，并在其上叠加蚀变和矿化。层状矿体中的铜是由含铜流体交代块状硫化物矿石形成的。冬瓜山铜金矿床经历了两次成矿作用：第一成矿阶段．在石炭纪中期，海底喷流作用形成了块状硫化物矿床，矿石成分以硫、铁矿为主；第二成矿阶段。燕山期岩浆侵人，一方面岩浆热液与围岩相互作用发生矽卡岩化、硅化、钾长石化、石英绢云母化和青磐岩化，形成矽卡岩型和斑岩型矿体，另一方面岩浆流体对块状硫化物矿体进行叠加改造，致使块状硫化物矿体富集铜等成矿物质。     

Fe–S mineralization in the Jurassic biogenic remains (Częstochowa,Poland)

Various Fe–S minerals of the mackinawite–greigite–pyrite association, ubiquitous in biogenic remains from Jurassic mudstones, have been described in detail in an SEM–EDS study. Two diagenetic stages of Fe sulphide formation and preservation in the Jurassic organic skeletons are identified. In the first stage, pyrite formed as euhedra and framboids shortly after deposition, mainly in the interiors of the skeletons which still contained labile organic matter. The second stage of iron sulphide formation was related to the later stages of diagenesis, when the influence of the surrounding sediment was more dominant, although some organic matter was still present in the biogenic skeletons. A Fe-rich carbonate–aluminosilicate cement was then introduced between the earliest iron sulphides and later subsequently sulphidized, to form a metastable iron monosulphide of mackinawite composition and then greigite.     

滨海红树林泥炭沉积物中硫的赋存特点及其控制因素

海南和厦门两地滨海红树林沉积物和埋藏泥炭中硫的成分分析表明,滨海红树林沉积物和泥炭中的硫以硫化铁硫为主,有机硫次之,硫酸盐硫含量最低。泥炭沉积物中硫的赋存形式和特点与沉积环境密切相关。海南福田地区红树林泥炭沉积物主要形成于红树林潮上坪和泥炭坪,硫含量较高,平均为2.60%,且有机硫含量与有机碳含量呈正相关,而硫化铁硫含量与有机碳含量没有明显的相关性;厦门海沧镇红树林泥炭沉积物形成于红树林潮间坪以及潮道环境,硫含量较低,平均值仅为0.43%,形态硫和有机质的相关性与海南红树林泥炭地沉积物相反。红树林泥炭沉积物中铁的硫化物主要以黄铁矿形式产出,且以莓球状形态为主。研究表明,黄铁矿与次生有机硫的生成与微生物活动密切相关,造成红树林泥炭中硫含量差异最主要的原因不是硫源,而是有机质的供给与沉积微环境的影响。现代滨海红树林泥炭沼泽中硫的赋存特征将对煤中硫成因的研究提供重要的科学依据。     

Laser ablation ICP-MS study of platinum-group elements in sulphides from the Platreef at Turfspruit,northern limb of the Bushveld Complex,South Africa

The Platreef unit of the northern Bushveld Complex comprises a diverse package of pyroxenites, peridotites and mafic lithologies with associated Ni–Cu–platinum-group element (PGE) mineralisation. Base metal sulphides (BMS) are generally more abundant in the Platreef than in other Bushveld PGE deposits, such as the Merensky Reef and the UG2 chromitite, but the Platreef, though thicker, has lower overall PGE grades. Despite a commonly held belief that PGEs are closely associated with sulphide mineralisation, a detailed study by laser ablation ICP-MS (LA-ICP-MS) on a core through the Platreef at Turfspruit suggests that this is not strictly the case. While a significant proportion of the Pd, Os and Ir were found to be hosted by BMS, Pt, irrespective of its whole-rock concentration, was not. Only at the top of the Platreef is Pt directly associated with sulphide minerals where Pt–Pd–(±Sb)–Te–Bi-bearing inclusions were detected in the chalcopyrite portions of large composite sulphides. In contrast, Pd, Os, and Ir occur in solid solution and as discrete inclusions within the BMS throughout the core. For Os and Ir, this is usually in the form of Os–Ir alloys, whereas Pd forms a range of Pd–Te–Bi–(Sb) phases. Scanning electron microscope observations on samples from the top of the core revealed the presence of ≤0.2-mm-long (PtPd)₂(Sb,Te,Bi)₂ michenerite–maslovite laths within the chalcopyrite portions of large composite sulphides. Additional Pt-bearing minerals, including sperrylite and geversite, and a number of Pd(–Te–Bi–Sb) minerals were observed in, or close to, the alteration rims of these sulphides. This textural association was observed throughout the core. Similar platinum-group minerals (PGMs) were observed within the felsic assemblages composed of quartz, plagioclase, alkali feldspar and clinopyroxene produced by late-stage felsic melts that permeated the Platreef. Many of these PGMs occur a significant distance away from any sulphide minerals. We believe these features can all be linked to the introduction of As, Sb, Te and Bi into the magmatic system through assimilation of sedimentary footwall rocks and xenoliths. Where the degree of contamination was high, all of the Pt and some of the Pd formed As- and Sb-bearing PGM that were expelled to the edges of the sulphide droplets. Many of these were redistributed where they came into contact with late-stage felsic melts. Where no felsic melt interactions occurred, the expelled Pt- and Pd-arsenides and antimonides remained along the margins of the sulphides. At the top of the Platreef, where the effects of contamination were relatively low, some of the Pt remained within the sulphide liquids. On cooling, this formed the micro-inclusions and blade-like laths of Pt–Pd–(Sb)–Bi–Te in the chalcopyrite.     

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.     

Sulphur‐isotope study of the massive sulphide orebody at Woodlawn,New South Wales

³⁴S/³²S ratios have been measured in a suite of samples from the stratabound, volcanogenic massive sulphide deposit at Woodlawn, N.S.W. ³⁴S values for the sulphides vary as follows: in the ore horizon, pyrite +6.7 to +9.2%. (mean +8.1‰), sphalerite +5.2 to +8.6‰. (mean +6.9‰), chalcopyrite +6.4 to +7.0‰ (mean +6.7‰) and galena +2.8 to +5.5‰ (mean +4.4‰); in the vein mineralization, the host volcanics—pyrite +8.7 to +11.4%. (mean +9.8‰), sphalerite +7.8 to + 10.3‰ (mean +9.2‰), chalcopyrite; +8.8 to +10.1‰ (mean +9.2‰) and galena +6.9 to +7.2‰ (mean +7.1‰). Barite from the upper ore horizon levels has an isotopic composition of +30.0‰, consistent with its having originated from Silurian ocean sulphate. The general order of ³⁴S enrichment in the sulphides is pyrite > chalcopyrite ～ sphalerite > galena. Isotopic fractionations in the systems galena/sphalerite/pyrite and chalcopyrite/pyrite indicate an equilibration temperature of 275–300°C. This temperature is considered to represent that of sulphide deposition.     

Ni-Co sulphide segregation in the Mamb pyroxenite intrusion, Cameroon

The amphibole metapyroxenite intrusion from Mamb (Cameroon) consists of enstatite, diopside-augite, edenite, and traces of plagioclase, biotite and rutile. It contains notable amounts of sulphides (pyrrhotite, pentlandite, chalcopyrite, pyrite and Co-rich violarite). The sulphide phase segregated during magma crystallization as immiscible droplets (≤ 1 mm) included in growing ferromagnesian minerals or aggregated in the silicate crystal mush to form an interstitial phase. However, observed sulphide assemblages are likely to result from low-T (≤ 300 °C) re-equilibration of high-T monosulphide solid solutions, more particularly during the Pan-African metamorphic event. The Mamb amphibole pyroxenite intrusion is tentatively considered as a potential source for Ni and Co mineralization.     

Partitioning of trace elements in co-crystallized sphalerite–galena–chalcopyrite hydrothermal ores

There is an abundance of published trace element data for sphalerite, galena and chalcopyrite in natural systems, yet for a co-crystallized assemblage comprising these base metal sulphides, there is no detailed understanding of the preferred host of many trace elements. Laser-ablation inductively-coupled plasma mass spectrometry trace element maps and spot analyses were generated on 17 assemblages containing co-crystallized sphalerite and/or galena and/or chalcopyrite from 9 different ore deposits. These deposits are representative of different ore types, geologic environments and physiochemical conditions of ore formation, as well as superimposed syn-metamorphic remobilisation and recrystallization. The primary factors that control the preferred base metal sulphide host of Mn, Fe, Co, Cu, Zn, Ga, As, Se, Ag, Cd, In, Sb, Te, Tl and Bi are element oxidation state, ionic radius of the substituting element, element availability and the maximum trace element budget that a given sulphide mineral can accommodate. Temperature, pressure, redox conditions at time of crystallization and metal source, do not generally appear to influence the preferred base metal sulphide host of all the trace elements. Exceptions are Ga, In and Sn recrystallized at high metamorphic grades, when the preferred host of Ga and Sn usually becomes chalcopyrite. In more typical lower temperature ores, the preferred host of Ga is sphalerite. Indium concentrations also increase in chalcopyrite during recrystallization. At lower temperatures the partitioning behaviour of Sn remains poorly constrained and shows little predictable pattern among the data here. The results obtained may be used as a tool to assess co-crystallization. If trace element distributions in a given base metal sulphide assemblage match those reported here, and assuming those distributions have not been significantly altered post (re-) crystallization, then it may be suggestive of a co-crystallized assemblage. Such information provides a foundation for novel attempts to develop trace element-in-sulphide geothermometers.     

Sulphur isotope constraints on formation conditions of the Luiswishi ore deposit, Democratic Republic of Congo (DRC)

Luiswishi is a Congo-type Neoproterozoic sediment-hosted stratiform Cu–Co ore deposit of the Central Africa Copperbelt, located northwest of Lubumbashi (DRC). The ores form two main Cu–Co orebodies hosted by the Mines Subgroup, one in the lower part of the Kamoto Formation and the other at the base of the Dolomitic Shales Formation. Sulphides occur essentially as early parallel layers of chalcopyrite and carrolite, and secondarily as late stockwork sulphides cross-cutting the bedding and the early sulphide generation. Both types of stratiform and stockwork chalcopyrite and carrolite were systematically analyzed for sulphur isotopes, along the lithostratigraphic succession of the Mine Series. The quite similar δ³⁴S values of stratiform sulphides and late stockwork sulphides suggest an in situ recrystallization or a slight remobilization of stockwork sulphides without attainment of isotopic equilibrium between different sulphide phases (chalcopyrite and carrolite). The distribution of δ³⁴S values (−14.4‰ to +17.5‰) combined with the lithology indicates a strong stratigraphic control of the sulphur isotope signature, supporting bacterial sulphate reduction during early diagenesis of the host sediments, in a shallow marine to lacustrine environment. Petrological features combined with sulphur isotopic data of sulphides at Luiswishi and previous results on nodules of anhydrite in the Mine Series indicate a dominant seawater/lacustrine origin for sulphates, precluding a possible hydrothermal participation. The high positive δ³⁴S values of sulphides in the lower orebody at Luiswishi, hosted in massive chloritic–dolomitic siltite (known as Grey R.A.T.), fine-grained stratified dolostone (D.Strat.) and silicified-stromatolitic dolomites alternating with chloritic–dolomitic silty beds (R.S.F.), suggest that they were probably deposited during a period of regression in a basin cut off from seawater. The variations of δ³⁴S values (i.e. the decrease of δ³⁴S values from the Kamoto Formation to the overlying Dolomitic Shales and then the slight increase from S.D.2d to S.D.3a and S.D.3b members) are in perfect agreement with the inferred lithological and transgressive–regressive evolution of the ore-hosting sedimentary rocks [Cailteux, J., 1994. Lithostratigraphy of the Neoproterozoic Shaba-type (Zaire) Roan Supergroup and metallogenesis of associated stratiform mineralization. In: Kampunzu A.B., Lubala, R.T. (Eds.), Neoproterozoic Belts of Zambia, Zaire and Namibia. Journal of African Earth Sciences 19, 279–301].     

Sulphide mineralization and wall-rock alteration in ophiolites and modern oceanic spreading centres

Massive and stockwork Fe-Cu-Zn (Cyprus type) sulphide deposits in the upper parts of ophiolite complexes represent hydrothermal mineralization at ancient accretionary plate boundaries. These deposits are probable metallogenic analogues of the polymetallic sulphide deposits recently discovered along modern oceanic spreading centres. Genetic models for these deposits suggest that mineralization results from large-scale circulation of sea-water through basaltic basement along the tectonically active axis of spreading, a zone of high heat flow. The high geothermal gradient above 1 to 2 km deep magma chambers emplaced below the ridge axis drives the convective circulation cell. Cold oxidizing sea-water penetrating the crust on the ridge flanks becomes heated and evolves into a highly reduced somewhat acidic hydrothermal solvent during interaction with basaltic wall-rock. Depending on the temperature and water/rock ratio, this fluid is capable of leaching and transporting iron, manganese, and base metals; dissolved sea-water sulphate is reduced to sulphide. At the ridge axis, the buoyant hydrothermal fluid rises through permeable wall-rocks, and fluid flow may be focussed along deep-seated fractures related to extensional tectonic processes. Metal sulphides are precipitated along channelways as the ascending fluid undergoes adiabatic expansion and then further cooling during mixing with ambient sub-sea-floor water. Vigorous fluid flow results in venting of reduced fluid at the sea-floor/sea-water interface and deposition of massive sulphide. A comparison of sulphide mineralization and wall-rock alteration in ancient and modern spreading centre environments supports this genetic concept.Massive sulphide deposits in ophiolites generally occur in clusters of closely spaced (< 1–5 km) deposits. Individual deposits are a composite of syngenetic massive sulphide and underlying epigenetic stockwork-vein mineralization. The massive sulphide occurs as concordant tabular, lenticular, or saucer-shaped bodies in pillow lavas and pillow-lava breccia; massive lava flows, hyalcoclastite, tuff, and bedded radolarian chert are less commonly associated rock types. These massive sulphide zones are as much as 700 m long, 200 m wide, and 50 m thick. The pipe-, funnel-, or keel-shaped stockwork zone may extend to a dehpth of 1 km in the sheeted-dike complex. Several deposits in Cyprus are confined to grabens or the hanging wall of premineralization normal faults.Polymetallic massive sulphide deposits and active hydrothermal vents at medium- to fast-rate spreading centres (the East Pacific Rise at lat. 21°N, the Galapagos Spreading Centre at long. 86°W, the Juan de Fuca Ridge at lat. 45°N., and the Southern Trough of Guaymas Basin, Gulf of California) have interdeposit spacings on a scale of tens or hundreds of metres, and are spatially associated with structural ridges or grabens within the narrow (< 5 km) axial valleys of the rift zones. Although the most common substrate for massive sulphide accumulations is stacked sequences of pillow basalt and sheet flows, the sea-floor underlying numerous deposits in Guaymas Basin consists of diatomaceous ooze and terrigenous clastic sediment that is intruded by diabase sills. Mound-like massive sulphide deposits, as much as 30 m wide and 5m high, occur over actively discharging vents on the East Pacific Rise, and many of these deposits serve as the base for narrow chimneys and spires of equal or greater height. Sulphides on the Juan de Fuca Ridge appear to form more widespread blanket deposits in the shallow axial-valley depression. The largest deposit found to date, along the axial ridge of the Galapagos Spreading Centre, has a tabular form and a length of 1000 m, a width of 200 m, and a height of 30 m.The sulphide assemblage in both massive and vein mineralization in Cyprus type deposits is characteristically simple: abundant pyrite or, less commonly, pyrrhotite accompanied by minor marcasite, chalcopyrite, and sphalerite. With few exceptions, the composition of massive sulphide ranges from 0.3 to 5 wt. % Cu, from 0.1 to 3 wt. % Zn, from 0.5 to 30 ppm Au, and from 1 to 50 ppm Ag. The only common gangue minerals — quartz, chlorite, calcite, and gypsum generally make up less than 10 percent of the massive zone.Sulphide assemblages in massive sulphide samples recovered from the Juan de Fuca Ridge (abundant sphalerite, wurtzite, and pyrite; minor marcasite, chalcopyrite, and galena), East Pacific Rise (abundant sphalerite, pyrite, and chalcopyrite; minor wurtzite, marcasite, and pyrrhotite), and Guaymas Basin (abundant pyrrhotite and sphalerite; minor chalcopyrite) contrast with ophiolitic deposits. Bulk analyses of two zinc-rich sulphide samples from the Juan de Fuca Ridge yield the following average values: Zn, 56.6 wt. %; Cu, 0.2 wt. %; Pb, 0.15 wt. %; Fe, 4.9 wt. %; Ag, 260 ppm; and Cd, 775 ppm. Other minerals precipitated with sulphides at hydrothermal-vent sites include anhydrite, barite, gypsum, Mg-hydroxysulphate-hydrate, talc, sulphur, and amorphous silica.Massive sulphide lenses in some Cyprus-type deposits are underlain by a silica-rich zone consisting of massive quartz, opaline silica, red jasper, or chert mixed with disseminated and veinlet Fe-Cu-Zn sulphides. Some deposits are overlain by ochre, a gossanous Mn-poor Fe-rich bedded deposit composed of goethite, maghemite, quartz, and finely disseminated sulphide. In the Solomon Islands, ochre is overlain by siliceous sinter containing anhydrite, barite, and sulphide; the sinter contains anomalous Ag, Au, Cu, Zn, and Hg, and grades upward into Fe-rich chert and manganiferous wad. Amorphous Fe-Mn deposits (umber) and Mn-bearing chert enriched in Ba, Co, Cu, Ni, Cr, Pb, and Zn are common features near the top of ophiolite sequences. Although their genetic relation to sulphide mineralization is uncertian, they probably formed during off-axis hydrothermal discharge.At modern, medium-rate spreading centres, thin blankets of unconsolidated hydrothermal sediment have been observed near hydrothermal sulphide deposits. Basalt fragments recovered with massive sulphide from the Juan de Fuca Ridge have surfaces coated with smectite, magnetite, hematite, opaline silica, and Fe---Mn-oxyhydroxides. Sediment mounds composed largely of nontronitic clay and hydrated Fe and Mn oxides, and more distal metalliferous (Fe, Mn, Cu, Ni, Pb, Zn) sediment on the flanks of ceanridges, are also products of off-axis hydrothermal processes.Pillow lavas, diabase dikes, and gabbro in ophiolite sequences, and deeper, layer 2 basalt and diabase recovered from oceanic ridges, are altered to greenschist-facies assemblages (albite + chlorite + actinolite ± sphene ± quartz ± pyrite) during high-temperature sub-sea-floor hydro-thermal metamorphism near the axis of spreading. Chemical changes in the wall-rock during this large-scale sea-water/rock interactive episode depend on the water/rock ratio and temperature but generally include gains in Mg, Na and H₂O and losses of Ca. Subsequent low temperature sea-water/rock interaction away from the axis of spreading results in fracture-controlled zeolitefacies alteration, characterized by smectite, caledonite, zeolite, calcite, prehnite, hematite, marcasite, and pyrite. This retrograde alteration involves increases in total Fe, K, and H₂O and decreases in Mg and Si in the wallrock; Ca may be lost or gained.Wall-rock alteration in Cyprus type stockwork zones is more striking, in that the basalt and diabase between veins of Fe---Cu-Zn sulphides, quartz, and chlorite have undergone partial to complete conversion to fine-grained aggregates of quartz + chlorite + illite + pyrite; kaolinite and palygorskite may be present in minor amounts. Calcium and Na are strongly depleted; K, Al, Ti, Mn, and Ni are leached to a lesser extent; and Fe, S, Cu, Zn, and Co are strongly enriched in the wall-rock underlying massive sulphide. Mafic rocks at depth in the volcanic pile may be enriched in K, Rb, and Li, and depleted in Cu, Co, and Zn. Lavas lateral to and overlying massive sulphide mineralization may have low concentrations of Cu and high concentrations of Zn and Co relative to background levels.Mutual consideration of hydrothermal sulphide deposits and associated wall-rock alteration in ophiolites and at modern oceanic spreading centres can provide useful criteria for the development of regional exploration models for ophiolitic terrains.