Methane‐related microbial gypsum calcitization in stromatolites of a marine evaporative setting (Münder Formation,Upper Jurassic,Hils Syncline,north Germany)

Fossil stromatolites may reveal information about their hydrochemical palaeoenvironment, provided that assignment to a specific microbial community and a corresponding biogeochemical mechanism of formation can be made. Tithonian stromatolites of the Münder Formation at Thüste, north Germany, have traditionally been considered as formed by intertidal cyanobacterial communities. However, thin sections of the stromatolites show elongated angular traces of former gypsum crystals in a dense arrangement, but no algal or cyanobacterial filament traces. Moreover, high Fe²⁺ and Mn²⁺ contents, oxygen‐isotope and sulphur‐isotope ratios of carbonate‐bound sulphates, and sulphurized hydrocarbon biomarkers of the stromatolitic carbonate indicate that CaCO₃ precipitation occurred near the oxic–anoxic interface as a result of intensive bacterial sulphur cycling rather than photosynthetic activity. Furthermore, anaerobic oxidation of methane by Archaea may have driven CaCO₃ precipitation in deeper parts of the biofilm community, as reflected by high concentrations of squalane with a strongly negative δ¹³C in conjunction with evaporite pseudomorphs showing extremely low δ¹³C_Carb ratios. Consequently, the Thüste stromatolites are now interpreted as having initially formed by gypsum impregnation of biofilms. Subsequently, early Mg‐calcitic calcitization within the biofilms occurred because of combined bacterial iron, manganese and sulphate reduction, with an increasing contribution of anaerobic oxidation of methane with depth. This model plausibly explains the prominent preservation of signals derived from oxygen‐independent metabolic pathways, whereas virtually no geochemical record exists for an aerobic community that may, nevertheless, have prevailed at the stromatolite surface. Photic‐zone stromatolites with a prominent signal of anaerobic oxidation of methane may be common in, and indicative of, oxygen‐depleted sulphate‐bearing environments with high rates of methane production, conditions that possibly were fulfilled at the Archaean to Proterozoic transition.     

Carbonate aeolianites of western Saurashtra,India: experimental decipherment of the depositional mechanisms

Granular carbonate deposits of Late Pleistocene to Early Holocene age, commonly referred to as ‘miliolite limestone’, occur in a linear belt, parallel to the southern coast of Saurashtra, India. In the present study area these carbonate deposits are found in select valleys between ridges and mounds of pyroclastic material present in the Deccan trap plateau. Two different depositional histories have been proposed for these sediments. The presence of marine bioclasts led to the postulation of a marine origin for these deposits. The second school of thought propounded redeposition of the coastal sediments by aeolian processes. Although a few features could not be explained by the proposed aeolian model, critical comparison of these two views favoured the aeolian origin. The mode of occurrence, lithological and structural attributes, and microscopic evidence presented here, also support a possible aeolian origin for these deposits. Experimental observation indicates that these carbonate aeolianites represent backflow deposits, which accumulated because of the flow separation caused by the presence of topographic highs. The conspicuous concave‐up geometry of the deposit conformed to the shape of the separation bulb. In view of the inferred depositional mechanism, the disposition of the deposits and the signature of the palaeoflow direction suggest that the carbonate particles were derived from the north‐western coast of Saurashtra by strong south‐easterly winds. Massive granular carbonates with outsized basement clasts appear to be the product of avalanching of granular material from the higher contours because of oversteepening of the primary deposit.     

Relationship between footwall composition,crustal contamination,and fluid–rock interaction in the Platreef,Bushveld Complex,South Africa

In the northern limb of the 2.06-Ga Bushveld Complex, the Platreef is a platinum group elements (PGE)-, Cu-, and Ni-mineralized zone of pyroxenite that developed at the intrusion margin. From north to south, the footwall rocks of the Platreef change from Archaean granite to dolomite, hornfels, and quartzite. Where the footwall is granite, the Sr-isotope system is more strongly perturbed than where the footwall is Sr-poor dolomite, in which samples show an approximate isochron relationship. The Nd-isotope system for samples of pyroxenite and hanging wall norite shows an approximate isochron relationship with an implied age of 2.17 ± 0.2 Ga and initial Nd-isotope ratio of 0.5095. Assuming an age of 2.06 Ga, the ɛNd values range from −6.2 to −9.6 (ave. −7.8, n = 17) and on average are slightly more negative than the Main Zone of the Bushveld. These data are consistent with local contamination of an already contaminated magma of Main Zone composition. The similarity in isotope composition between the Platreef pyroxenites and the hanging wall norites suggests a common origin. Where the country rock is dolomite, the Platreef has generally higher plagioclase and pyroxene δ ¹⁸O values, and this indicates assimilation of the immediate footwall. Throughout the Platreef, there is considerable petrographic evidence for sub-solidus interaction with fluids, and the Δ _{plagioclase–pyroxene} values range from −2 to +6, which indicates interaction at both high and low temperatures. Whole-rock and mineral δD values suggest that the Platreef interacted with both magmatic and meteoric water, and the lack of disturbance to the Sr-isotope system suggests that fluid–rock interaction took place soon after emplacement. Where the footwall is granite, less negative δD values suggest a greater involvement of meteoric water. Consistently higher values of Δ _{plagioclase–pyroxene} in the Platreef pyroxenites and hanging wall norites in contact with dolomite suggest prolonged interaction with CO₂-rich fluid derived from decarbonation of the footwall rocks. The overprint of post crystallization fluid–rock interaction is the probable cause of the previously documented lack of correlation between PGE and sulfide content on the small scale. The Platreef in contact with dolomite is the focus of the highest PGE grades, and this suggests that dolomite contamination played a role in PGE concentration and deposition, but the exact link remains obscure. It is a possibility that the CO₂ produced by decarbonation of assimilated dolomite enhanced the process of PGE scavenging by sulfide precipitation.     

Fluid and source magma evolution of the Questa porphyry Mo deposit,New Mexico,USA

Combined fluid inclusion microthermometry and microanalysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) are used to constrain the hydrothermal processes forming a typical Climax-type porphyry Mo deposit. Molybdenum mineralisation at Questa occurred in two superimposed hydrothermal stages, a magmatic-hydrothermal breccia and later stockwork veining. In both stages, texturally earliest fluids were single-phase, of low salinity (~7 wt.% NaCl_equiv.) and intermediate-density. Upon decompression to ~300 bar, they boiled off a vapour phase, leaving behind a residual brine (up to 45 wt.% NaCl_equiv) at temperatures of ~420°C. The highest average Mo concentrations in this hot brine were ~500 μg/g, exceeding the Mo content of the intermediate-density input fluid by about an order of magnitude and reflecting pre-concentration of Mo by fluid phase separation prior to MoS₂ deposition from the brine. Molybdenum concentrations in brine inclusions, then, decrease down to 5 μg/g, recording Mo precipitation in response to cooling of the saline liquid to ~360°C. Molybdenite precipitation from a dense, residual and probably sulphide-depleted brine is proposed to explain the tabular shape of the ore body and the absence of Cu-Fe sulphides in contrast to the more common Cu-Mo deposits related to porphyry stocks. Cesium and Rb concentrations in the single-phase fluids of the breccia range from 2 to 8 and from 40 to 65 μg/g, respectively. In the stockwork veins, Cs and Rb concentrations are significantly higher (45–90 and 110–230 μg/g, respectively). Because Cs and Rb are incompatible and hydrothermally non-reactive elements, the systematic increase in their concentration requires two distinct pulses of fluid exsolution from a progressively more fractionated magma. By contrast, major element and ore metal concentrations of these two fluid pulses remain essentially constant. Mass balance calculations using fluid chemical data from LA-ICPMS suggest that at least 25 km³ of melt and 7 Gt of deep input fluid were necessary to provide the amount of Mo contained in the stockwork vein stage alone. While the absolute amounts of fluid and melt are uncertain, the well-constrained element ratios in the fluids together with empirical fluid/melt partition coefficients derived from the inclusion analyses suggest a high water content of the source melt of ~10%. In line with other circumstantial evidence, these results suggest that initial fluid exsolution may have occurred at a confining pressure exceeding 5 kbar. The source of the molybdenum-mineralising fluids probably was a particularly large magma chamber that crystallised and fractionated in the lower crust or at mid-crustal level, well below the shallow intrusions immediately underlying Questa and other porphyry molybdenum deposits. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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.     

Mapping Proterozoic unconformity-related uranium deposits in the Rockhole area, Northern Territory, Australia using landsat ETM+

The Rockhole area, Northern Territory, Australia, hosts a number of Proterozoic unconformity-related uranium deposits. The geology of the area features within Paleoproterozoic rocks of the Pine Creek Orogen, near the unconformity with overlying platform cover sandstone of the Paleo- to Mesoproterozoic McArthur Basin. Landsat Enhanced Thematic Mapper plus (ETM+) data was used in the Rockhole area to assist in mapping geological structures and lithology, and to identify anomalous concentrations of ferrous minerals, the product of alteration, which can be indicators of buried uranium mineralization. Several image-processing procedures were applied to the ETM+ data to identify, isolate and enhance mineralogical information as simple and complex false color composites. ETM+ 754 shown as red green and blue respectively was the best simple image. Overall, complex images based on Principal Component Analysis proved to be the most useful products. Sandstone, shale and siltstone, the target lithologies, Koolpin Formation, the target stratigraphic unit, and bleaching pattern due to the removal of iron(II) compounds, the target alteration pattern, were confidently mapped to provide information required by the mineral emplacement model, which ultimately identified areas of likely uranium mineralization. Thus the contrasting behavior of the two principle oxidation states of uranium and iron can be utilized to map/delineate bleached alteration zones associated with economic concentrations of uranium using multispectral sensors like Landsat or better hyperspectral sensors.     

A preliminary stable isotope study on Mogok Ruby, Myanmar

The primary occurrence of ruby in the Mogok area, northern Myanmar is exclusively found in marble along with spinel–forsterite-bearing marble and phlogopite–graphite marble. These marble units are enclosed within banded biotite–garnet–sillimanite–oligoclase gneisses. Samples of these marbles collected for C–O stable isotope analysis show two trends of δ¹³C–δ¹⁸O variation resulting most likely from fluid–rock interactions. Ruby-bearing marble and phlogopite–graphite marble follow a trend with coupled C–O depletion, whereas spinel–forsterite-bearing marble follows a δ¹⁸O depletion trend with relatively constant δ¹³C values. Ruby formation might have resulted from CO₂-rich fluid–rock interaction, while spinel–forsterite-bearing marble was genetically related to CO₂-poor fluid–rock interaction. Both fluids may have arisen from external sources. Based on graphite Raman spectral thermometry, the estimated temperature for phlogopite–graphite marble, and probably ruby-bearing marble, was lower than 607 °C, and for spinel–forsterite-bearing marble, lower than 710 °C. Contrasting C/O diffusion between graphite/ruby/spinel/forsterite and calcite, local variations of isotopic compositions of newly formed minerals as a result of non-pervasive fluid infiltration, and open-system isotopic disturbance during cooling may have affected C-/O-isotopic fractionations between minerals. The estimated high formation temperatures for ruby and spinel/forsterite imply that the parental fluids may have been related to nearby igneous intrusions and/or metamorphic processes. Whether these two types of fluid were genetically related is unclear based on the present data.     

Biostratigraphic and isotopic record of the Cenomanian–Turonian deposits in the Ohaba-Ponor section (SW Haţeg, Romania)

The middle Cenomanian–lower Turonian deposits of Ohaba-Ponor section (Southern Carpathians) were studied from biostratigraphic and isotopic points of view. Both the qualitative and semiquantitative nannofloral analyses, as well as the stable isotope (δ¹³C and δ¹⁸O) data support significant palaeoenvironmental changes in the investigated interval. Two δ¹³C positive excursions were recognized: (1) an excursion up to 1.8‰ (PDB) within the middle/late Cenomanian boundary; (2) an excursion up to 2.2‰ (PDB) in the Cenomanian/Turonian boundary interval. The oldest δ¹³C positive excursion recorded (placed within the Acanthoceras jukes-brownei/Eucalycoceras pentagonum Ammonite Zone boundary interval, and in the NC11 Calcareous Nannofossil Zone respectively) could be assigned to the middle Cenomanian Event II (MCEII). During the above-mentioned event, significant increase in abundance of Watznaueria barnesae, followed by successive blooms of Biscutum constans and Eprolithus floralis, were observed. The youngest δ¹³C positive excursion was identified in the Cenomanian/Turonian boundary interval (in the NC12 and lower part of the NC13 Calcareous Nannofossil Zones). Even the amplitude of this δ¹³C positive excursion is lower in the Ohaba-Ponor section, as generally reported, this may represent the regional record of the OAE2. The successive peaks of the nannofossils Biscutum constans, Zeugrhabdotus erectus and Eprolithus floralis indicate episodes of cooler surface water and high fertility, which preceded and lasted the Cenomanian/Turonian boundary event. Additionally, fluctuations of δ¹⁸O values between −2 and −6‰ suggest also cooler conditions within the Cenomanian/Turonian boundary interval.     

Diagenesis, palaeoclimate and tectono-sedimentary influences on clay mineralogy and stable isotopes from Upper Cretaceous marine successions of the Basque-Cantabrian Basin (N Spain)

Clay mineralogy and whole-rock stable isotopes (δ¹⁸O and δ¹³C) of Upper Cretaceous marly sediments on the Basque-Cantabrian Basin have been integrated to determine the main effects of diagenesis, palaeoclimate and tectono-sedimentary factors in sections belonging to deep- (Barrika) and platform-marine (Isla de Castro, Villamartín and Olazagutía) settings.The mean values for the clay assemblages and δ¹⁸O exhibit notable differences among the sections, partially explainable by the influence of diagenesis. The Barrika sediments, with more diagenetically advanced illite-smectite (I-S) mixed-layer (R1, 70% illite), authigenic chlorite, and low δ¹⁸O (−4.05‰ PDB), experienced higher diagenetic grade than Isla de Castro and Olazagutía, which have R0 I-S (20% illite) and heavier δ¹⁸O. Villamartín was also affected by higher diagenesis than Isla de Castro and Olazagutía, given the occurrence of R1 I-S (60% illite) and low δ¹⁸O (−4.11‰ PDB). However, the absence of other clays in Villamartín (e.g. authigenic chlorite) is indicative of less diagenetic grade than Barrika. These results show the useful integration of clay mineralogy and stable isotopes to detect different diagenetic grades in distinct marine successions of the same basin.Despite being influenced by diagenesis, the clay mineralogy partially preserves its inherited signature. This allows detection of major contents of I-S and mica, and minor kaolinite, interpreted as indicative of warm palaeoclimatic conditions. High kaolinite content in Villamartín and absence of kaolinite in Isla de Castro, though, are considered to be a product of neither diagenesis nor palaeoclimatic influences. Instead, tectono-sedimentary causes, related to unsuitable conditions for clay formation and transport from the local source areas, contributed to original clay differences. The inferred effects of diagenesis, palaeoclimate and tectono-sedimentary factors make this work important to show the potentially great variety of controls on the clay mineralogy of marine sections, which are often uncritically treated in studies concerning the Late Cretaceous.