Anhydrite pseudomorphs and the origin of stratiform Cu–Co ores in the Katangan Copperbelt (Democratic Republic of Congo)

The stratiform Cu–Co ore mineralisation in the Katangan Copperbelt consists of dispersed sulphides and sulphides in nodules and lenses, which are often pseudomorphs after evaporites. Two types of pseudomorphs can be distinguished in the nodules and lenses. In type 1 examples, dolomite precipitated first and was subsequently replaced by Cu–Co sulphides and authigenic quartz, whereas in type 2 examples, authigenic quartz and Cu–Co sulphides precipitated prior to dolomite and are coarse-grained. The sulphur isotopic composition of the copper–cobalt sulphides in the type 1 pseudomorphs is between −10.3 and 3.1‰ relative to the Vienna Canyon Diablo Troilite, indicating that the sulphide component was derived from bacterial sulphate reduction (BSR). The generation of during this process caused the precipitation and replacement of anhydrite by dolomite. A second product of BSR is the generation of H₂S, resulting in the precipitation of Cu–Co sulphides from the mineralising fluids. Initial sulphide precipitation occurred along the rim of the pseudomorphs and continued towards the core. Precipitation of authigenic quartz was most likely induced by a pH decrease during sulphide precipitation. Fluid inclusion data from quartz indicate the presence of a high-salinity (8–18 eq. wt.% NaCl) fluid, possibly derived from evaporated seawater which migrated through the deep subsurface. ⁸⁷Sr/⁸⁶Sr ratios of dolomite in type 1 nodules range between 0.71012 and 0.73576, significantly more radiogenic than the strontium isotopic composition of Neoproterozoic marine carbonates (⁸⁷Sr/⁸⁶Sr = 0.7056–0.7087). This suggests intense interaction with siliciclastic sedimentary rocks and/or the granitic basement. The low carbon isotopic composition of the dolomite in the pseudomorphs (−7.02 and −9.93‰ relative to the Vienna Pee Dee Belemnite, V-PDB) compared to the host rock dolomite (−4.90 and +1.31‰ V-PDB) resulted from the oxidation of organic matter during BSR.     

The sandstone-hosted stratiform copper mineralization at Mwitapile and its relation to the mineralization at Lufukwe, Lufilian foreland, Democratic Republic of Congo

The Lufilian foreland is a triangular-shaped area located in the SE of the Democratic Republic of Congo and to the NE of the Lufilian arc, which hosts the well-known Central African Copperbelt. The Lufilian foreland recently became an interesting area with several vein-type (e.g., Dikulushi) and stratiform (e.g., Lufukwe and Mwitapile) copper occurrences. The Lufilian foreland stratiform Cu mineralization is, to date, observed in sandstone rock units belonging to the Nguba and Kundelungu Groups (Katanga Supergroup).The Mwitapile sandstone-hosted stratiform Cu prospect is located in the north eastern part of the Lufilian foreland. The host rock for the Cu mineralization is the Sonta Sandstone of the Ngule Subgroup (Kundelungu Group). A combined remote sensing, petrographic and fluid inclusion microthermometric analysis was performed at Mwitapile and compared with similar analysis previously carried out at Lufukwe to present a metallogenic model for the Mwitapile- and Lufukwe-type stratiform copper deposits. Interpretation of ETM+ satellite images for the Mwitapile prospect and the surrounding areas indicate the absence of NE–SW or ENE–WSW faults, similar to those observed controlling the mineralization at Lufukwe. Faults with these orientations are, however, present to the NW, W, SW and E of the Mwitapile prospect. At Mwitapile, the Sonta Sandstone host rock is intensely compacted, arkosic to calcareous with high silica cementation (first generation of authigenic quartz overgrowths). In the Sonta Sandstone, feldspar and calcite are present in disseminated, banded and nodular forms. Intense dissolution of these minerals caused the presence of disseminated rectangular, pipe-like and nodular dissolution cavities. Sulfide mineralization is mainly concentrated in these cavities. The hypogene sulfide minerals consist of two generations of pyrite, chalcopyrite, bornite and chalcocite, separated by a second generation of authigenic quartz overgrowth. The hypogene sulfide minerals are replaced by supergene digenite and covellite. Fluid inclusion microthermometry on the first authigenic quartz phase indicates silica precipitation from an H₂O–NaCl–CaCl₂ fluid with a minimum temperature between 111 and 182 °C and a salinity between 22.0 and 25.5 wt.% CaCl₂ equiv. Microthermometry on the second authigenic quartz overgrowths and in secondary trails related to the mineralization indicate that the mineralizing fluid is characterized by variable temperatures (Th = 120 to 280 °C) and salinities (2.4 to 19.8 wt.% NaCl equiv.) and by a general trend of increasing temperatures with increasing salinities.Comparison between Mwitapile and Lufukwe indicates that the stratiform Cu mineralization in the two deposits is controlled by similar sedimentary, diagenetic and structural factors and likely formed from a similar mineralizing fluid. A post-orogenic timing is proposed for the mineralization in both deposits. The main mineralization controlling factors are grain size, clay and pyrobitumen content, the amount and degree of feldspar and/or calcite dissolution and the presence of NE–SW to ENE–WSW faults. The data support a post-orogenic fluid-mixing model for the Mwitapile- and Lufukwe-type sandstone-hosted stratiform Cu deposits, in which the mineralization is related to the mixing between a Cu-rich hydrothermal fluid, with a temperature up to 280 °C and a maximum salinity of 19.8 wt.% NaCl equiv., with a colder low salinity reducing fluid present in the sandstone host rock. The mineralizing fluid likely migrated upwards to the sandstone source rocks along NE–SW to ENE–WSW orientated faults. At Lufukwe, the highest copper grades at surface outcrops and boreholes were found along and near to these faults. At Mwitapile, where such faults are 2 to 3 km away, the Cu grades are much lower than at Lufukwe. Copper precipitation was possibly promoted by reduction from pre-existing hydrocarbons and non-copper sulfides and by the decrease in fluid salinity and temperature during mixing. Based on this research, new Cu prospects were proposed at Lufukwe and Mwitapile and a set of recommendations for further Cu exploration in the Lufilian foreland is presented.     

Identification of ore extraction and metal working in ancient times: a case study of Sagalassos (SW Turkey)

The extensive territory of the ancient (Hellenistic to Byzantine) city of Sagalassos (SW Turkey) offered a rich variety in natural mineral resources. The frequent occurrence of iron slag in the excavations at the site proved the local working of metal. A geochemical prospection campaign was done in the territory of the ancient city in order to identify or discard the city and its territory as a self-sustaining metallurgical centre. Secondly, the geochemical impact of ancient metallurgy was investigated. Geochemical anomalies identified in stream sediments are explained by the presence of mineralised deposits and ancient metal working. Mg, Cr, Co and Ni anomalies point to chromite and chrysotile-magnetite deposits related to the basic rocks of the Lycian nappes in the area. Fe, V and Ti anomalies indicate the presence of iron mineralisations, which have been worked for iron production in ancient times. Finally, the association of P, Cu, Pb, Mn, As and Ag anomalies are an indicator of human activity at archaeological sites. Within the framework of this geochemical prospection, a metal working site apart from the city of Sagalassos was identified. Here, ore was both extracted and processed to workable iron.     

Controlling factors on the morphology and spatial distribution of methane-related tubular concretions – Case study of an Early Eocene seep system

Up to 10 m in length and >1 m in diameter tubular, calcite-cemented sandstone concretions are hosted by the faulted Dikilitash unconsolidated sands and sandstones. These structures document shallow subsurface pathways of Early Eocene methane seepage in the Balkan Mountains foreland (NE Bulgaria). Their exceptional exposure allowed a unique study of the factors governing the morphology and spatial distribution of such fossilized fluid conduits. The large dimensions and subvertical, cylindrical shape of the most common tube type primarily reflects the buoyancy-driven, vertical path of an ascending gas-bearing fluid through permeable, mainly unconsolidated sandy host sediments. Tube morphology was also influenced by local stratigraphic anisotropies and might as well document differences in former seepage conditions. Mapping of >800 tubular concretions showed the NNW–NNE elongation and alignment of tube clusters and massive cemented sandstone structures. This suggests that Paleogene fault systems played a major role in directing the movement of fluids. However, within a single tube cluster, tubes are preferentially aligned, over distances up to 50 m along directions at an angle between 10° and 36° with respect to the inferred NNW–NNE, cluster parallel fault traces. In addition, cylindrical tubes of analogue dimensions are aligned over distances >100 m along N15° to N25°-oriented directions. It is hypothesized that this spatial geometry of tubular concretions reflects the complex geometry of deformations structures in fault damage zones along which fluids were preferentially channelled.     

Spatial Distribution of Elemental Enrichments around Archaeological Sites: Insights from the Ancient City of Sagalassos in Southwest Turkey

Ancient human activities have resulted in important elemental enrichments in soils at archaeological sites. Nevertheless, the spatial extent of such elemental enrichment signals is rarely studied. Our research addresses this theme by studying the characteristics and extent of the geochemical enrichment halo around the monumental Colonnaded Street of the Hellenistic to Byzantine city of Sagalassos in southwest Turkey. Given the complex geology of the area, a strategy applying multivariate statistical data analysis techniques is proposed to identify whether the enrichments have a geological or an anthropogenic source. In addition, we evaluate how a wide variety of natural and anthropogenic processes may influence the distribution of elements around the site. In this paper, it is shown that enrichments of P and Pb are present up to a distance of 450 m and 150 m away from the city, respectively. Hence, we conclude that the extent of chemical enrichment haloes around archaeological sites may be element specific.     

Biostratigraphy,sedimentology and sequence stratigraphy of the Tournaisian–Viséan transitional strata in South China (Guangxi)

The biostratigraphy and sedimentological evolution of the Tournaisian–Viséan (T–V) transitional strata in South China (Guangxi) have been investigated. The sediments were deposited on a carbonate platform and in slope and basinal environments. In the T–V transitional strata, six foraminiferal associations have been distinguished which allow correlation between the shallow and deep water deposits. A careful examination of the evolutionary stages of the foraminifer Eoparastaffella provides a more accurate criterion for the definition of the T–V boundary, but does not significantly modify the historical one. The distinction of two morphotypes is based on the elevation of the last whorl and the peripheral outline. Tournaisian specimens of Eoparastaffella have a well rounded periphery (morphotype 1) contrasting with the subangular periphery of younger Viséan specimens (morphotype 2). A coefficient can be deduced from simple biometric measurements for more precisely defining the T–V boundary. The sequence stratigraphy of the T–V strata in South China has been reconstructed by combining biostratigraphical and sedimentological data. It allowed the correlation of the T–V transitional strata between the platform area and the slope and basinal locations. Late Tournaisian strata were deposited during a highstand systems tract. Near the end of the Tournaisian, a major drop in relative sea-level led to the development of an unconformity in the platform area. Lowstand deposits formed during latest Tournaisian time in the basin where a detailed biostratigraphic framework has been devised. Sediments deposited during the ensuing transgressive systems tract overlie the late Tournaisian highstand sediments in the platform area and the latest Tournaisian lowstand deposits in the basin. A major drop in relative sea-level near the end of the Tournaisian has been recognized worldwide. Therefore, the possibility of using the sequence stratigraphy of the T–V strata in South China for worldwide correlations should be investigated. © 1997 John Wiley & Sons, Ltd.     

Fluid evolution during burial and Variscan deformation in the Lower Devonian rocks of the High-Ardenne slate belt (Belgium): sources and causes of high-salinity and C–O–H–N fluids

Fluid inclusions in quartz veins of the High-Ardenne slate belt have preserved remnants of prograde and retrograde metamorphic fluids. These fluids were examined by petrography, microthermometry and Raman analysis to define the chemical and spatial evolution of the fluids that circulated through the metamorphic area of the High-Ardenne slate belt. The earliest fluid type was a mixed aqueous/gaseous fluid (H₂O–NaCl–CO₂–(CH₄–N₂)) occurring in growth zones and as isolated fluid inclusions in both the epizonal and anchizonal part of the metamorphic area. In the central part of the metamorphic area (epizone), in addition to this mixed aqueous/gaseous fluid, primary and isolated fluid inclusions are also filled with a purely gaseous fluid (CO₂–N₂–CH₄). During the Variscan orogeny, the chemical composition of gaseous fluids circulating through the Lower Devonian rocks in the epizonal part of the slate belt, evolved from an earlier CO₂–CH₄–N₂ composition to a later composition enriched in N₂. Finally, a late, Variscan aqueous fluid system with a H₂O–NaCl composition migrated through the Lower Devonian rocks. This latest type of fluid can be observed in and outside the epizonal metamorphic part of the High-Ardenne slate belt. The chemical composition of the fluids throughout the metamorphic area, shows a direct correlation with the metamorphic grade of the host rock. In general, the proportion of non-polar species (i.e. CO₂, CH₄, N₂) with respect to water and the proportion of non-polar species other than CO₂ increase with increasing metamorphic grade within the slate belt. In addition to this spatial evolution of the fluids, the temporal evolution of the gaseous fluids is indicative for a gradual maturation due to metamorphism in the central part of the basin. In addition to the maturity of the metamorphic fluids, the salinity of the aqueous fluids also shows a link with the metamorphic grade of the host-rock. For the earliest and latest fluid inclusions in the anchizonal part of the High-Ardenne slate belt the salinity varies respectively between 0 and 3.5 eq.wt% NaCl and between 0 and 2.7 eq.wt% NaCl, while in the epizonal part the salinity varies between 0.6 and 17 eq.wt% NaCl and between 3 and 10.6 eq.wt% for the earliest and latest aqueous fluid inclusions, respectively. Although high salinity fluids are often attributed to the original sedimentary setting, the increasing salinity of the fluids that circulated through the Lower Devonian rocks in the High-Ardenne slate belt can be directly attributed to regional metamorphism. More specifically the salinity of the primary fluid inclusions is related to hydrolysis reactions of Cl-bearing minerals during prograde metamorphism, while the salinity of the secondary fluid inclusions is rather related to hydration reactions during retrograde metamorphism. The temporal and spatial distribution of the fluids in the High-Ardenne slate belt are indicative for a closed fluid flow system present in the Lower Devonian rocks during burial and Variscan deformation, where fluids were in thermal and chemical equilibrium with the host rock. Such a closed fluid flow system is confirmed by stable isotope study of the veins and their adjacent host rock for which uniform δ¹⁸0 values of both the veins and their host rock demonstrate a rock-buffered fluid flow system.     

Geochemistry of highly saline fluids in siliciclastic sequences: genetic implications for post-Variscan fluid flow in the Moravosilesian Palaeozoic of the Czech Republic

Ubiquitous post-Variscan dolomites occur in Zn–Pb–Cu veins at the Nízký Jeseník Mountains and the Upper Silesian Basin (Lower and Upper Carboniferous siliciclastics at the eastern part of the Bohemian Massif). Crush–leach, stable isotope (oxygen and carbon) and microthermometry analysis of the fluid inclusions in dolomites enable understanding the geochemistry, origin and possible migration pathways of the fluids. Homogenisation temperatures of fluid inclusions range between 66 and 148°C, with generally higher temperatures in the Nízký Jeseník Mountains area than in the Upper Silesian Basin. The highest homogenisation temperatures (up to 148°C) have been found near major regional faults and the lowest in a distant position or at higher stratigraphic levels. Highly saline (16.6–28.4 eq. wt% NaCl) H₂O–NaCl–CaCl₂ ± MgCl₂ fluids occur in inclusions. Na–Cl–Br systematics of trapped fluids and a calculated oxygen isotopic fluid composition between ?0.9 and +3.0‰ V-SMOW indicate that the fluid was derived from evaporated seawater. Stable isotopic modelling has been used to explain stable isotopic trends. Isotopic values (δ¹³C = ?6.0/+2.0‰ V-PDB, δ¹⁸O = +15.5/+22.5‰ V-SMOW of dolomites) resulted from fractionation and crystallisation within an open system at temperatures between 80 and 160°C. Rock-buffering explains the isotopic composition at low w/r ratios. Organic matter maturation caused the presence of isotopically light carbon in the fluids and fluid–rock interactions largely controlled the fluid chemistry (K, Li, Br and Na contents, K/Cl, I/Cl and Li/Cl molar ratios). The fluid chemistry reflects well the interaction between the fluid and underlying limestones as well as with clay- and organic-rich siliciclastics. No regional trends in temperature or fluid geochemistry favour a fluid migration model characterised by an important vertical upward migration along major faults. A permeable basement and fractured sedimentary sequence enhanced the general nature of the fluid system. Fluid characteristics are comparable with the main post-Variscan fluid flow systems in the Polish (Cracow-Silesian ore district) and German sedimentary basins.     

Evolution of palaeofluids at the Variscan thrust front in eastern Belgium

The geochemical evolution of the fluids migra- ting at the Variscan thrust front in eastern Belgium has been investigated by a petrographic, mineralogical and geoche-mical study of ankerite, quartz and ferroan calcite veins hosted by lower Devonian rocks. Three vein generations have been recognized. The first generation consists of quartz, chlorite and ankerite filling pre- to early Variscan extensional fractures. The second generation is present as shear veins of Variscan age, and contains quartz, chlorite and ferroan calcite. The third generation consists of ankerite filling post-Variscan fractures. The oxygen and carbon isotopic composition of the two ankerite phases and of the ferroan calcites are respectively between –16.4 and –11.4‰ PDB between –17.8 and –1.7‰ PDB. This range is greater than that of calcite nodules in the lower Devonian siliciclastic sediments (δ¹⁸O= –15.6 to –11.1‰ PDB and δ¹³C= –13.4 to –10.2‰ PDB). This suggests precipitation of the carbonate veins from a fluid which was at most only partly isotopically buffered by the calcite nodules in the host rock. The calculated oxygen isotopic composition of the ambient fluid from which the calcite veins formed is between +7.8 and +10.0‰ SMOW. Two main fluid types have been recognized in fluid inclusions in the quartz and carbonates. The first fluid type is present as secondary fluid inclusions in the first and second vein generations. The fluid has a salinity of 0.5–7.2 eq. wt.% NaCl and a high, but variable, homogenization temperature (Th=124–188°C). Two origins can be proposed for this fluid. It could have been expelled from the lower Devonian or could have been derived from the metamorphic zone to the south of the area studied. Taking into account the microthermometric and stable-isotope data, and the regional geological setting, the fluid most likely originated from metamorphic rocks and interacted with the lower Devonian along its migration path. This is in agreement with numerical simulations of the palaeofluid and especially the palaeotempera-ture field, which is based on chlorite geothermometry and vitrinite reflectance data. The second fluid type occurs as secondary inclusions in the shear veins and as fluid inclusions of unknown origin in post-Variscan ankerite veins. Therefore, it has a post-Variscan age. The inclusions are characterized by a high salinity (18.6–22.9 eq. wt.% CaCl₂). The composition of the fluid is similar to that which caused the development of Mississippi Valley-type Pb–Zn deposits in Belgium.