The occurrences of the rare earth elements and the platinum group elements in relation to base metal zoning in the vicinity of Rote Fäule in the Kupferschiefer of Poland

The concentrations of the lanthanide rare earth elements (REE) and Pt group elements (PGE) were measured in the Kupferschiefer from the Polish Zechstein Basin at, and in proximity to, the Rote Fäule near the Lubin Mining District. The Rote Fäule is a zone of post-depositional oxidation characterized by the presence of extensive amounts of Fe(III) oxides replacing syn-sedimentary framboidal pyrite. Outward from the Rote Fäule, the remainder of the Kupferschiefer is composed of Cu- and Pb/Zn-mineralized shale surrounding the Rote Fäule and a non-mineralized pyritic black shale in the central basin.The leading hypothesis explaining the high concentrations of PGE, and REE in the Kupferschiefer states that PGE, REE and the associated base metals were mobilized by oxidizing Cl⁻ brines which migrated outward from the Rote Fäule into the reduced Kupferschiefer. According to available thermodynamic data, PGE were in all likelihood present as chloro-complexes in these oxidizing brines, as geologically realistic concentrations of Pt, Pd and Au could be transported as chloro-complexes. The Eh of these brines decreased as they migrated further from the Rote Fäule and into the Kupferschiefer. Base metals and PGE were precipitated in the order of their decreased solubility in these brines. As a result, the concentrations of least soluble PGE (Pt) are highest in the Rote Fäule and in the transition zone adjacent to the Rote Fäule (e.g. [Pt]=202–537 ppb) while the concentrations of the more soluble metals in these brines (Ag, Cu, Pb, and Re) are highest in the reduced-mineralized Kupferschiefer. The sources of the PGE and REE are enigmatic. It is likely that the metals were derived either from the underlying Rotliegendes sandstones and volcanics, the Variscan basement rocks, or the Kupferschiefer shale whose metals were mobilized by saline, oxidizing fluids released during intra-continental rifting in the Triassic period.     

Origin of the gold deposit in the Polkowice-West Mine, Lubin-Sieroszowice Mining District, Poland

The recently discovered gold deposit in the Lubin-Sieroszowice district lies 0.0 to 1.5?m below the stratabound copper-silver orebody, mainly in the Polkowice-west mine. The deposit extends over 60?km², has a thickness of 20–80?cm and a conservative estimate of the average grade of 1.5?g/t gold, 0.3?g/t Pd and 0.2?g/t Pt. It contains gold and electrum in association with minor amounts (up to 0.4?vol%) of hematite, chalcocite, digenite, djurlite, bornite, chalcopyrite, pyrite, gersdorffite, rammelsbergite and clausthalite. The gold-bearing zone lies mainly in the Weissliegendes sandstone, but locally transgresses the stratigraphy into the overlying Kupferschiefer shale and Werra Dolomite of the Zechstein evaporite sequence. It lies within a transition zone between the oxidized, hematite-stained Rote Fäule facies and the overlying reduced organic carbon-bearing sediments. At the Polkowice-west mine, but only where gold is present, this zone is characterized by hematite-stained `patches' within grey to maroon sediment that contains little or no hematite or organic carbon. These textures were caused by downwelling reducing sulfur-rich solutions, flowing through previously oxidized sediments, and by gravitational instability between the reducing and oxidizing fluids. The oxidizing fluid originated within the Rote Fäule facies, whereas the reducing fluid originated in the overlying Zechstein sequence from which it was expelled downward during gypsum dehydration accompanying burial. Gold transport as the chloride complex in the oxidizing fluid is unlikely at the low temperature (?<100?°C) prevailing during mineralization. Some gold was probably transported as the bisulfide and, to a lesser extent, the polysulfide complexes, in the descending reducing fluid. However, the potential source rocks do not contain enough gold to account for the known deposit. Most of the gold was probably transported as the thiosulfate complex during replacement of reduced sediments by the Rote Fäule facies. Parts of the district where reduced fluids penetrated deeply into the Weissliegendes, and where the Rote Fäule facies transgressed the greatest volume of reduced sediments, should be evaluated for the presence of gold. We propose that the Polkowice-West mine represents a new class of gold deposit.     

Metal accumulation during and after deposition of the Kupferschiefer from the Sangerhausen Basin,Germany

A densely sampled profile (58 cm in thickness) composed of 13 samples of the Kupferschiefer and overlying Zechstein carbonates from the Sangerhausen Basin, Germany has been analysed by various geochemical and microscopic methods in order to clarify the mechanism of base metal accumulation. In this location, the Kupferschiefer is only slightly influenced by the hematite-bearing, oxidized fluids calledRote Fäule.The determination of facies-dependent parameters along the profile indicates that Kupferschiefer from the Sangerhausen Basin was largely deposited in a marine environment; only at the beginning of Kupferschiefer sedimentation did euxinic conditions prevail. The bottom part of the profile is significantly enriched in trace elements such as Cu, Ph, Zn, As, Co, Ag and U. The Cu concentration amounts to 19.88 wt.%. Post-depositional oxidation of the organic matter is observed only in the transition zone between the Kupferschiefer and the Zechstein conglomerate indicating the influence of ascending, oxidizing brines. Microscopic analyses show that only Fe sulfides form framboidal textures; Cu minerals are present along the total profile preferentially in fractures and as patchy structures composed of chalcocite, chalcopyrite and bornite. In the highly mineralized bottom section, Cu sulfides are associated with pyrobitumen, sparry calcite and arsenopyrite. Results from maturation studies of organic matter suggest that the maximum temperature affecting the Kupferschiefer was approximately 130°C.A 3-step-process of metal accumulation is proposed. During deposition of the sediment, framboidal pyrite and pyrite precursors were precipitated by bacterial SO₄²⁻ reduction (BSR). During diagenesis the pyrite and pyrite precursors were largely replaced by mixed Cu/Fe minerals and by chalcocite (PR). In the section with very high Cu contents (> 8%) reduced sulfur from Fe-sulfides was not sufficient for precipitation of Cu and other trace metals from ascending solutions. In this part of the profile, thermochemical SO₄²⁻ reduction (TSR) occurred after pyrite replacement as indicated by the presence of pyrobitumen and sparry calcite.     

Geochemical and isotopic composition of organic matter in the Kupferschiefer of the Polish Zechstein basin: relation to maturity and base metal mineralization

max vs the present depth of the Kupferschiefer, soluble organic matter (SOM) yields, and relative proportions of saturated and aromatic hydrocarbons of the SOM provide evidence for an oxidative alteration of organic matter in highly mineralized Kupferschiefer samples near the Rote F?ule zones. This is confirmed by differences in the composition of the saturated and aromatic hydrocarbon fractions of the soluble organic matter: Saturated hydrocarbons from Rote F?ule samples are dominated by short-chain n-alkanes and higher abundances of pristane and phytane relative to heptadecane (n-C17) and octadecane (n-C18), respectively, compared with samples more distant to the Rote F?ule zone. Compositional changes of the aromatic hydrocarbon fractions with decreasing distance to that zone are characterized by the occurrence of polycyclic aromatic hydrocarbons and elevated ratios of phenanthrene to methylphenanthrenes that are attributed to demethylation reactions and resulted in a decrease of the methylphenanthrene index (MPI 1). Kupferschiefer samples from the barren zone of the Polish Basin do not show these alteration patterns. The observed variations in organic matter composition with burial depth are consistent with changes due to increasing thermal maturation. Maturity assessment is achieved from MPI 1 and the methyldibenzothiophene ratio (MDR). From the relationship between the maturity of organic matter in terms of vitrinite reflectance values and depth of the Kupferschiefer strata, a continuous increase in reflectance of vitrinite is obtained within the Polish Basin. The alteration pattern of organic matter related to base metal mineralization of the Kupferschiefer corresponds to changes in the isotopic composition of organic carbon and calcite. Kerogen within, or close to, Rote F?ule zone is enriched in ¹³C caused by the preferential release of isotopically light organic compounds through progressive degradation of organic matter. The opposite tendency towards lower δ ¹³C and δ ¹⁸O values of calcite provides evidence for isotopic exchange between carbonate and the oxidizing, ore-bearing solutions and for organic matter remineralization. In contrast, organic matter and calcite from the Kupferschiefer do not show regular trends in δ ¹³C with increasing thermal maturation. Received: 25 June 1999 / Accepted: 1 December 1999     

Paleomagnetism of the Cu�CZn�CPb-bearing Kupferschiefer black shale (Upper Permian) at Sangerhausen, Germany

Syngenetic, diagenetic and epigenetic models have been proposed for the Cu?CZn?CPb Kupferschiefer mineralization at Sangerhausen, Germany. Paleomagnetic and rock magnetic measurements have been made on 205 specimens from mine workings on the margin of the Sangerhausen Syncline. The mineralization is richest in the ??0.5-m-thick Upper Permian (258?±?2?Ma) Kupferschiefer black marly shale (nine sites) and dies out over ??0.2?m in the underlying Weisliegend sandstones (three sites) and overlying Zechstein carbonates (two sites). Except for one site of fault zone gypsum, characteristic remanent magnetization directions were isolated for all 14 sites using alternating field and thermal step demagnetization. These directions provide a negative fold test, indicating that the remanence postdates Jurassic fault block tilting. Rock magnetic measurements show that the Kupferschiefer shale marks a redox front between the oxidized Weissliegend sandstones and non-oxidized Zechstein carbonates. The 14 site directions give a Late Jurassic paleopole at 149?±?3?Ma. It is significantly different from the paleopole reported by E.C. Jowett and others for primary or early diagenetic Rote F?ule alteration that gives an age of 254?±?6?Ma on the current apparent polar wander path and is associated with Kupferschiefer mineralization. We suggest that the Late Jurassic extensional tectonic event that formed the nearby North German Basin also reactivated Variscan basement faults and extended them up through the overlying strata, thereby allowing hydrothermal basement fluids to ascend and epigenetically mineralize the Kupferschiefer shale. The possibility of a 53?±?3?Ma mineralization age is also considered.     

On the origin of copper mineralization in the Kupferschiefer: a suIphur isotope study*

Sulphur isotopic compositions of copper and iron sulphides (dispersed and vein mineralization) from the Polish part of the Kupferschiefer were determined and compared with data from the literature. Most of the δ³⁴S values of sulphides range from about -40 to -25%, indicating sulphide precipitation during bacterial sulphate reduction in an open system which gradually chanes into a closed system. Sulphides from veins are usually enriched in ³⁴S compared to finely dispersed mineralization and were probably formed in a more closed system. Copper sulphides are generally a few permil heavier than pyrite. Coupled with detailed microscopical observations the isotope data suggest that the mineralization is either syngenetic or early diagenetic.     

REE and their relevance to the development of the Kupferschiefer copper deposit in Poland

Over one hundred samples, representing mainly clayey-organic- and carbonate-rich shales (Kupferschiefer) but also other members of different ore sections, including hangingwall dolomites (Z1 Werra) and footwall Weissliegend sandstone (Lower Permian), have been collected in different mines of the Lubin–Głogów mining district, mainly near the contact (transitional zone) between the copper-mineralized zone and secondarily oxidized (Rote Fäule = RF) zone. In general, the Polish Kupferschiefer shales are enriched in MREE in comparison to NASC. In a typical copper-rich ore section the REE amounts and patterns depend on lithologies, being generally similar in shales and dolomite. ∑REE vary among sandstones, shales and dolomites (average 73, 143 and 85 ppm, respectively), probably reflecting mainly their clay contents. Sandstones have strongly convex REE patterns with positive Eu and negative Gd anomalies and depletion in LREE and enrichment in MREE relative to HREE. The REE patterns of shale and dolomite are similar to one another and rather flat, with strong negative Eu anomalies, and a small positive Gd anomaly in the case of shales.The REE patterns of shales from the mineralized Cu-zone are generally convex (MREE enriched) and have negative Eu anomalies. However, in a section with Cu-, Zn- and Pb-shales the REE pattern of Pb-bearing shales shows a positive Eu anomaly, in contrast to other shales and overlying dolomite. More oxidizing conditions of deposition can be assumed for Pb-shales.No significant differences between REE distributions in transitional and oxidized zones have been observed. Their REE patterns are more convex and are much higher (av. 247 ppm) than those in the mineralized zone and they do not show Eu anomalies. The strongly convex pattern may suggest either enrichment in MREE or relative depletion in LREE due to localized precipitation of light REE minerals, both in shales and in the uppermost part of the sandstones.Two unique sections, one Cu-rich and one Cu-lean (partly oxidized), comprising three shale beds interbedded with dolomites have been compared. Generally ∑REE contents are similar in these two sections. Also similar are changes in contents of REE between beds in both sections, which decrease significantly upwards (from 157–171 ppm to 54–60 ppm). The REE patterns of the lowermost beds (directly overlying sandstones) are ramp-like, with LREE enrichments. The upper beds have concave REE patterns. Comparison between sections shows generally stronger negative Eu and positive Gd anomalies in the highly-mineralized section.There is a highly significant positive relationship between Cu and ∑ REE contents in Cu-rich shales and slightly less significant negative relationship for their concentration in oxidized and transitional shales. There is a moderate significant positive correlation between P₂O₅ and ∑ REE contents in Cu-rich shales.The observed differences in REE contents cannot be provenance dependent but have been caused by diagenetic processes, possibly related to mineralization and oxidation processes. Europium anomalies, generally reflecting different Eh conditions in the deposit, can be eliminated by the prolonged oxidation. Strong enrichment of the RF zones in REE may result from their desorption from large volumes of oxidizing, including mineralizing, solutions which probably emerged from the underlying molasse lithologies into the Rote Fäule areas. Higher contents of REE in the lowermost shales suggest upward movement of solutions from the underlying sandstones also far away from the RF areas.     

The origin of rhythmic sulphide bands from the Permian sandstones (Weissliegendes) in the footwall of the Fore-Sudetic “Kupferschiefer” (Poland)

Rhythmic copper sulphide bands occur in the Weissliegendes sandstones, in the footwall of the Kupferschiefer in the mining district of SW Poland. The δ ³⁴S values of sulphides vary from −39 to — 44‰ (6–7‰ lighter than Kupferschiefer sulphides). The copper sulphides are represented mainly by digenite and chalcocite. According to microprobe results their Pb, Ni, Zn and Ag contents are similar to those in the Kupferschiefer. The bands are assumed to be formed by diffusion of bacterially produced hydrogen sulphide from the Kupferschiefer into the porous volume of the white sandstones containing dissolved copper. The sulphides were precipitated in almost equidistant bands, from top to bottom, probably according to the Ostwald-Prager supersaturation theory. The increase of isotopically heavier sulphur towards the lower levels in the sandstone might be explained by closing of the bacterial sulphate reduction system. Contribution to the IGCP Project No. 254     

Diagenesis of metal-organic complexes in sediments: Formation of metal sulphides from cystine complexes

Metal-cystine complexes of iron, lead, zinc, copper and nickel under mild artificial diagenesis give rise to crystalline metal sulphides and insoluble organic matter as well as gaseous and “oily” organic products. Under confined reducing conditions at 200°C for 100 h a virtual 100% conversion of metal complex to metal sulphide occurs, while < 10% of the associated organic material may remain as kerogen. Such a mechanism could account for the formation of metal sulphides and in particular pyrite from protein- or amino acid-rich material in carbonaceous sediments during diagenesis.     

A multistage origin for Kupferschiefer mineralization

New Re–Os age determinations on mineralized material from the Polish Kupferschiefer elucidate the timing of mineralization and thus the likely mechanisms of ore deposition. Three mineralization parageneses were analysed: (a) chalcocite as pore space filling in sandstone, (b) disseminated Cu–Mo mineralization in shale, and (c) massive, bedded copper sulphides. The resulting ages fall into two ranges: 245.2 (± 1.6)–264.7 (± 1.8) Ma and 162.3 (± 0.8)–184.3 (± 2.2) Ma. These results substantiate previous age determinations, although no Upper Triassic ages were found in this study. Some of the younger ages for the mineralization could represent alteration and recrystallization of existing sulphides. The results confirm that mineralization took place in several stages, from soon after Kupferschiefer sediment deposition in the Upper Permian and for at least 100 m.y. after, until at least the Cretaceous. The genesis of the mineralization can be explained by the episodic release of hydrothermal fluids from the subsiding adjacent Southern Permian sedimentary basin, although the relative importance of each successive mineralizing ‘event’ for introducing additional metals is as yet unknown.     

Dolomitization and the mineralization of the Marl Slate (N. E. England)

The Marl Slate, the English equivalent of the Kupferschiefer, has been studied with particular reference to the relationships between dolomitization and the origin of the metal sulphides. Dolomite occurs as: 1) discontinuous lenses of ferroan dolomicrite, 2) micronodules of finely crystalline dolospar in association with length-slow chalcedony and 3) discrete laminae of ferroan or non-ferroan dolospar. The ferroan dolomicrite has excess CaCO₃, and is more abundant in the lower, sapropelic facies of the Marl Slate. It is considered to have formed by the penecontemporaneous alteration of calcium carbonate under hypersaline conditions. Small micronodules (typically about 0.3 mm in diameter) are also more abundant in the sapropelic Marl Slate. These frequently contain cores of length-slow chalcedony (quartzine) fibres and sometimes quartz megacrysts. Textural observations clearly indicate that this silica is of authigenic origin and the dolomite/chalcedony micronodules are interpreted as diagenetic replacements of a calcium sulphate mineral such as anhydrite. The discrete laminae of finely crystalline dolospar are often inter-laminated with calcite in the upper part of the Marl Slate. This dolomite is also calcium rich and represents a replacement, possibly of anhydrite, during a later phase of diagenesis. Metal sulphides occur in two distinct forms: as disseminated framboidal pyrite and as discrete lenses of pyrite, chalcopyrite, galena, sphalerite and rarer sulphides. The framboidal pyrite originated during early diagenesis by reaction of sulphide, produced by reduction of sulphate by organic material and micro-organisms, with iron also released in the reducing environment. The sulphide lenses are often in intimate association with dolospar, length-slow chalcedony and authigenic quartz megacrysts. This indicates that the lenses were produced during diagenesis by the reduction and replacement of calcium sulphate (anhydrite). Various sources, such as co-precipitation with dolomite precursors and the underlying Yellow Sands, may have supplied metals which were mobilized and transported by connate brines as diagenesis progressed.     

Sulphide geochemistry and wall rock alteration as a guide to mineralization, mammoth area, NW Queensland, Australia

Stratabound mineralization in the Mammoth area of NW Queensland occurs in steeply dipping, faulted Proterozoic arenites and dolomitic rocks overlying basic volcanics. Both syngenetic/diagenetic and epigenetic sulphides are present, with the latter divided into Mammoth- and South Mammoth II-styles. Syngenetic/diagenetic pyrite is distinguished from epigenetic pyrite by higher Co and Ni, and lower As, Mo, Sb and Tl contents. Chalcopyrite is the major copper sulphide associated with syngenetic/diagenetic pyrite and is characterized by low Ag, Bi, Mo, Ni and Tl contents relative to epigenetic chalcopyrite. No substantial wall rock alteration is associated with such sulphides. Disseminated syngenetic/diagenetic sulphides in the mine sequence may have induced deposition of epigenetic Cu mineralization, but alone, even when remobilized, do not reach economic grades.The four epigenetic Mammoth orebodies are all richer in chalcocite and bornite than syngenetic/diagenetic mineralization and have wall rock alteration characterized by alkali depletion and Fe enrichment in the zone between the ore and the fault considered the conduit for the hydrothermal ore-forming fluids. Pyrite associated with Mammoth-style mineralization has high As, Mo, Sb and Tl contents and was formed subsequent to the copper sulphides.Thick, essentially barren, pyritic sequences occur at South Mammoth II where the moderate As, high Mo, Sb and Tl contents reflect their hydrothermal origin but distinguish them from Mammoth-style pyrite. Their low As/Sb ratio and lack of wall rock alteration imply a lower temperature of formation than the Mammoth-style pyrite and possibly such mineralization represents the pre-ore stage of the Mammoth mineralizing hydrothermal system.An essential feature of economic Cu mineralization in NW Queensland is the operation of a hydrothermal system. As all such systems may not necessarily give rise to extensive wall rock alteration, use of the high As, Mo, Sb and Tl contents of hydrothermal pyrite can aid evaluation of mineralization intersected during drilling.     

Stratigraphic and petrographic comparison of the Creta and Kupferschiefer copper shale deposits

Stratigraphic and petrographic characteristics of the Creta copper shale deposit in the Flowerpot Shale of southwestern Oklahoma are compared with the betterknown Rudna deposit in the Kupferschiefer of south-western Poland. At Creta, early diagenetic mineralization is indicated by: (1) copper sulfide replacement of large spores and of pyrite, (2) lack of compaction of replaced spores relative to unreplaced spores, (3) enclosure of uncompacted mud and copper sulfides by early matrix gypsum, and (4) location of the ore bed within a thick sequence of fine-grained, low-permeability sediments. This contrasts sharply with evidence of late-diagenetic copper mineralization in the Kupferschiefer at Rudna. Mineralization of copper shales appears to occur over a wide time scale relative to diagenesis of the host sediments.     

Ferruginous and manganiferous haloes around massive sulphide deposits of the Urals

Proximal brecciform ferruginous and manganiferous rocks related to VMS deposits of the Urals are subdivided into jasperites, gossanites, and umbers, in addition to thin-bedded jaspers and cherts. The coherence of host rock composition and Mn–Fe-fertility of the sediments have been established. Fe-poor pink hematitic and gray sulphidic chert are typical of the felsic class of VMS deposits. In contrast the contents of Fe vary from high to moderate in ferruginous rocks enclosed in basaltic units associate with VMS deposits. Fe- and Mn-rich ferruginous rocks and umbers occur in association with limestones and calcareous sedimentary rocks in both types of volcanic sequences. A common feature of jasperites and umbers is the abundance of replacement textures of hyaloclastites and carbonates by hematite and silica. In addition, replacement of clastic sulphides by hematite and magnetite is a characteristic genetic feature of gossanites. All of these sedimentary rocks are accompanied by pseudomorphs of hematite and quartz formed after bacterial filaments. The abundance of replacement textures are supportive of the halmyrolysis model, in addition to hydrothermal sedimentary and sub-seafloor hydrothermal replacement theories. Study of chemical zonation of altered hyaloclasts shows depletion of their rims, not only in mobile Na, K, Mg, but also in immobile Al, Ti, and REE; whereas Si and Fe are concentrated in situ. The halmyrolysis model presented here, involving organic-rich calcareous hyaloclastic sediments, resolves the problem of subtraction of Al, Ti, REE and other elements, which are commonly immobile under hydrothermal conditions. The evolution of the halmyrolysis process from acidic reducing to alkaline oxidized conditions infers a possible range in transformation from Fe^II–Mg smectites to Fe-silicates and Fe-Si oxides as precursors of brecciform jasperite and thin-bedded jasper. The higher acidic, initial stage, of gossanite formation seems to be required for oxidation of organic matter and/or pyrite. The acidic condition facilitates the temporal preservation of “immobile” elements (Al, Ti, REE) in “immature”chlorite–hematite gossanites. Another peculiarity of the gossanite-forming processes is the likely sorption of P, U and V by iron hydroxides displacing sulphides. The general evolution of all ferruginous sediments results in complete Fe²⁺ oxidation and silicification accompanied by subtraction of other elements. The vertical diagenetic differentiation leads to concentration of Mn-carbonates, silicates and oxyhydroxides into the tops of jasperite and gossanite layers. Mn oxyhydroxides scavenge positively charged hydrated cations like Co and Ni. Near-vent bacterial communities may activate the processes of volcanic glass and sulphide degradation. The proposed processes of halmyrolysis followed by silicification, in situ, may resolve the enigma of silica-rich sediment formation in a silica undersaturated ocean. The discrimination between gossanite and jasperite is useful for elaboration of new criteria for local exploration of VMS- and Mn-deposits. Halo dispersion of gossanites covering an area about two to three times that of the massive sulphide deposit is a good vector for ore body discovery. Proximal gossanites can be differentiated from jasperites by presence of relic sulphide clasts or elevated contents of chalcophile elements (Cu, Fe, Zn, Pb, Bi, Te, As, Sb, Ba), noble metals (Au, Ag) and distinct REE patterns with La and Eu positive anomalies. The development of halmyrolysis and biomineralization models merit further elaboration and testing in on-going research, in order to add or revise theories of iron and manganese deposit formation.     

Accumulation of copper in the Permian Kupferschiefer: A result of post-depositional redox reactions

Within the Central European Zechstein Basin the Permian Kupferschiefer has been deposited under anoxic conditions. In most parts of the basin, the metal content does not exceed values commonly observed in black shales. However, in areas near to the Zechstein sea-shore which are simultaneously related to rift zones a significant base metal enrichment is observed. Organic geochemical analyses of the copper-mineralized sections in the Kupferschiefer from Southwest Poland show that significant changes in the composition of organic matter are associated with the metal enrichment processes. Porphyrins, commonly abundant constituents of the shale, have been decomposed by oxidizing fluids. Additionally, aliphatic hydrocarbons have been largely removed from the bitumen and alkylated aromatic systems were affected by side-chain degradation. This particular type of alteration is explained by ascending oxidizing solutions which transported high amounts of base metals from Lower Permian red beds into the Kupferschiefer horizon acting as a geochemical trap. The metal precipitation is suggested to be a result of thermochemical sulphide production with organic matter acting as hydrogen source. In areas such as the Lower Rhine Basin in the bottom section of the Kupferschiefer the base metals lead and zinc as well as barium have been accumulated from basinal Carboniferous formation waters. Copper enrichment is not observed because potential source rocks are missing in this area. However, the observed compositional changes of the organic matter do not point towards thermochemical redox processes.     

Alteration zones around Kupferschiefer-type base metal mineralization in West Germany

Several occurrences of red-colored rocks, which represent an unusual species within the lower Zechstein sediments as well as siderite ribbons and kaolinization have been reported from the West German lower Zechstein sequence. The red-colored rocks had been classified into two types, i.e., the stratiform red layers (SRL) and the Rote Fäule (RF). With regard to the gray beds, both types are characterized by enrichments and depletions of certain elements. As a result, ore-related Rote Fäule could be distinguished from insignificant stratiform red layers. Whereas Rote Fäule, which represents the alteration zone around diagenetic Kupferschiefer-type deposits, is chiefly characterized by apparent red coloring and enrichment in sulfate S, both the siderite ribbons and kaolinization of feldspars refer to formation of Cu-As sulfides and arsenides due to a hydrothermal, epigenetic process. Formation under more oxidizing, synsedimentary conditions is presumed for the stratiform red layers.     

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.     

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.     

Geological context,mineralization, and timing of the Juramento sediment-hosted stratiform copper–silver deposit,Salta district,northwestern Argentina

The Juramento deposit in northwestern Argentina exhibits several readily visible general characteristics of sediment-hosted stratiform copper (SSC) mineralization. It consists of fine-grained disseminated base-metal sulfides within marine to lacustrine graybeds (the basal whitish Late Cretaceous Lecho Sandstone and shallow-water carbonates of the overlying Maastrichtian Yacoraite Formation) that overlie a thick sequence of redbeds (the Pirgua Subgroup). The property has been examined and drilled in three successive exploration programs as a possible analog of world-class mineralization in the copperbelts of central Africa and the Kupferschiefer. The present report provides specific field and laboratory results that confirm the classification as SSC-type mineralization. The host graybeds are the basal sandstone and overlying oolitic and stromatolitic units of the Yacoraite Formation, which are shown from textural studies to be carbonaceous and to have initially contained very fine-grained, disseminated, syndiagenetic pyrite. These sediments would have been sufficiently porous and permeable in early diagenetic time to allow an infiltration of metalliferous fluids from the underlying redbeds, resulting in the observed progressive replacement of in situ pyrite by common base-metal sulfides (sphalerite, galena, argentiferous tetrahedrite, and copper-rich sulfides: first chalcopyrite, then bornite, and finally chalcocite). Sulfur isotope analyses indicate that a portion of the sulfur of ore-stage sulfides is isotopically heavier than that of pyrite, possibly due to a contribution from associated gypsum. Ore-stage sulfides are zoned vertically and obliquely through the mineralized zones, from cupriferous sulfides at low stratigraphic levels to lead- and zinc-rich mineralization above, with unreplaced pyrite remaining within upper Yacoraite strata. The zoned sulfides and their replacement textures, the peneconformable configuration of the mineralized zones, and the position of ore-stage mineralization adjacent to a stratigraphically defined redox transition from redbeds upward into graybeds indicate an overprint of copper (and accompanying ore-stage metals) on originally pyritic graybeds. The influx of ore-stage metals, presumably in an oxidized low-temperature brine, terminated with a silicification event that effectively sealed the host carbonates. These observations and the overall genetic interpretation are consistent with the general deposit-scale genetic model for early diagenetic SSC mineralization. The regional geologic context is also consistent with its classification as a SSC deposit: It is hosted by post-oxyatmoversion sediments and was formed in association with evaporites at a low paleolatitude in a major intracontinental rift system.