Anhydrite-bearing rocks from the Rožná district (Moldanubian zone,Czech Republic): high-grade metamorphosed exhalites?

Several types of anhydrite-bearing rocks have been found in the amphibolite-facies metamorphosed rocks at the north-eastern margin of the Moldanubian Zone. Anhydrite either forms monomineralic bands up to 40 cm thick, or occurs in the form of disseminated grains in surrounding calc-silicate gneiss together with feldspar, scapolite, amphibole, pyroxene, epidote and pyrite. The isotopic composition of sulphur ('³⁴S=30.6 to 32.3‰) and strontium (⁸⁷Sr/⁸⁶Sr=0.70797 to 0.70781) in anhydrite may indicate a marine source of sulphate. The isotopic ratio of strontium is in the same range as that of metamorphosed strata-bound barite-sulphide ores, which have been previously described in the same area. The '³⁴S values of coexisting pyrite range from 21.4 to 22.5‰, the (³⁴S_{anhydrite-pyrite} corresponding to the metamorphic temperature of 600 to 660 °C. In contrast to many submarine-exhalative deposits, the oxygen isotopic compositions of anhydrite ('¹⁸O=9.3 to 10.2‰) are lighter than that of barite ('¹⁸O=10.4 to 13.8‰). This indicates that the both minerals are not in isotopic equilibrium. Therefore, it is probable that anhydrite and barite from the Ro—ná district were deposited from fluids that contained different proportions of seawater and hydrothermal fluids or from hydrothermal fluids that underwent variable extent of oxygen isotope exchange with seafloor rocks. The '¹³C values in calcite ('¹³C=-17.2 to -18.7‰) from anhydrite-bearing rock are lower than those in distant marbles. As graphite is absent in anhydrite- and calcite-bearing rocks, impoverishment in the ¹³C isotope cannot be attributed to the graphite-carbonate isotopic exchange during metamorphism. It is proposed that low '¹³C values in carbonates are caused by pre-metamorphic oxidation of organic matter in course of hydrothermal processes. Anhydrite and anhydrite-bearing calc-silicate gneiss from the north-eastern part of the Moldanubian Zone are interpreted to be the high-grade metamorphosed analogue of anhydrite-rich exhalites commonly found in submarine-exhalative hydrothermal deposits.     

Greenhouse Gas Emissions from Hydroelectric Reservoirs in Tropical Regions

This paper discusses emissions by power-dams in the tropics. Greenhouse gas emissions from tropical power-dams are produced underwater through biomass decomposition by bacteria. The gases produced in these dams are mainly nitrogen, carbon dioxide and methane. A methodology was established for measuring greenhouse gases emitted by various power-dams in Brazil. Experimental measurements of gas emissions by dams were made to determine accurately their emissions of methane (CH₄) and carbon dioxide (CO₂) gases through bubbles formed on the lake bottom by decomposing organic matter, as well as rising up the lake gradient by molecular diffusion.The main source of gas in power-dams reservoirs is the bacterial decomposition (aerobic and anaerobic) of autochthonous and allochthonous organic matter that basically produces CO₂ and CH₄. The types and modes of gas production and release in the tropics are reviewed.     

Organic geochemistry and petrology of barren and Mo–Ni–PGE mineralized marine black shales of the Lower Cambrian Niutitang Formation (South China)

Marine black shales of the Lower Cambrian Niutitang Formation in southern China host Mo–Ni–platinum group elements (PGE) mineralization confined to a phosphate- and pyrite-rich stratiform body (max. 20-cm thick). The H/C atomic ratio, carbon isotopic composition, FTIR spectra of bulk organic matter, and spectra of extractable part of organic matter indicate similar sources and thermal evolution of organic matter in barren and mineralized black shales.The morphology and relative abundance of organic particles in barren and mineralized shales are different. In barren black shales, organic particles comprise only elongated bodies and laminae 2–10 μm across or elongated larger bodies (> 10 μm) with R_max = 2.96–5.21% (Type I particles). Mineralized black shales contain Type I particles in rock matrix (90–95 vol%), small veinlets or irregular organic accumulations (Type II particles, 1–5 vol%) that display weak to well developed mosaic texture and a variable reflectance (R_max = 3.55–8.65%), and small (< 1 to 5 μm) rounded or irregular Type III organic particles (1–4 vol%) distributed within phosphate nodules and sulphide rip-up clasts. Type III particles show similar reflectance as particles of Type I in rock matrix. Type I particles are interpreted as remnants of in situ bacterially reworked organic matter of cyanobacteria/algal type, Type II as solidified products or oil-derived material (migrabitumen), and Type III particles as remnants of original organic matter in phosphatized or sulphidized algal/microbial oncolite-like bodies. Equivalent vitrinite reflectances of Type I and III particles in barren and mineralized rocks are similar and correspond to semi-anthracite and anthracite. Micro-Raman spectra of organic particles in rocks display a wide belt in the area of 1600 cm^− 1 (G belt) and approximately the same belt in the area of 1350 cm^− 1 (D belt). The ratio of integrated areas of the two belts correlate with R_max values.The Mo–Ni–PGE mineralized body is interpreted as to represent a remnant of phosphate- and sulphide-rich subaquatic hardground supplied with organic material derived from plankton and benthic communities as well as with algal/microbial oncolite-like bodies that originated in wave-agitated, shallow-water, nearshore environment.     

Leaching of metals from copper smelter flue dust (Mufulira,Zambian Copperbelt)

The leaching behaviour of electrostatic precipitator dust from the Mufulira Cu smelter (Copperbelt, Zambia) was studied using a 48-h pH-static leaching experiment (CEN/TS 14997). The release of metals (Cd, Co, Cu, Ni, Pb and Zn) and changes in mineralogical composition using X-ray diffraction and PHREEQC-2 modelling were investigated in the pH range of 3–7. The highest concentrations of metals were released at pH 3–4.5, which encompasses the natural pH of the dust suspension (～4.3). About 40% of the total Cu was leached at pH 3, yielding 107 g/kg. Chalcanthite (CuSO₄·5H₂O), magnetite (Fe₃O₄) and delafossite (CuFeO₂) represented the principal phases of the studied dust. In contact with water, chalcanthite was dissolved and hydrated Cu sulphates precipitated at pH 4–7. Gypsum (CaSO₄·2H₂O) and secondary Fe or Al phases were observed in the leached residues. Serious environmental impact due to leaching may occur in dust-contaminated soil systems in the vicinity of the smelting plants.     

An Assessment of Surface and Atmospheric Conditions Associated with the Extreme 2014 Wildfire Season in Canada’s Northwest Territories

Weather and climate are major factors influencing worldwide wildfire activity. This study assesses surface and atmospheric conditions associated with the 2014 extreme wildfires in the Northwest Territories (NWT) of Canada. Hot and dry conditions led to the NWT experiencing the most severe wildfire season in its recorded history. The season included a record number of cloud-to-ground lightning flashes and set a record for area burned. Lightning was the dominant ignition source and accounted for about 95% of the wildfires. Prolonged periods of smoke led to dramatic reductions in visibility, frequent road closures, and reduced air quality resulting in numerous health alerts. Temporal and spatial patterns of lightning characteristics in 2014, derived from Canadian Lightning Detection Network data, were different from those in other years with, for example, far more positive flashes from 0600 to 1200?utc (midnight to 6:00 am local time). The highest fraction of positive cloud-to-ground flashes (43.1%) occurred in the smoke-dominated North Slave region, which was more than in the Dehcho, South Slave, or Sahtu regions. Mid-tropospheric atmospheric circulation over a large region that included the NWT was classified into the six most common summer patterns. Results showed that ridging and ridge displacements occurred more frequently during 2014 although lightning was associated with all circulation patterns. This study has advanced the understanding of the roles of weather, lightning, and mid-tropospheric circulation patterns associated with extreme wildfires in northwestern Canada.     

Improved correlation between the variability and peak luminosity of gamma-ray bursts

A new procedure for smoothing a gamma-ray burst (GRB) light curve and calculating its variability is presented. Applying the procedure to a sample of 25 long GRBs, we have obtained a very tight correlation between the variability and the peak luminosity. The only significant outlier in the sample is GRB 030329. With this outlier excluded, the data scatter is reduced by a factor of ∼3 compared to that of Guidorzi et al., measured by the deviation of fit. Possible causes for the outlier are discussed.     

Mineralogy and environmental stability of slags from the Tsumeb smelter,Namibia

Three types of smelting slags originating from historically different smelting technologies in the Tsumeb area (Namibia) were studied: (i) slags from processing of carbonate/oxide ore in a Cu–Pb smelter (1907–1948), (ii) slags from Cu and Pb smelting of sulphide ores (1963–1970) and (iii) granulated Cu smelting slags (1980–2000). Bulk chemical analyses of slags were combined with detailed mineralogical investigation using X-ray diffraction analysis (XRD), scanning electron microscopy (SEM/EDS) and electron microprobe (EPMA). The slags are significantly enriched in metals and metalloids: Pb (0.97–18.4 wt.%), Cu (0.49–12.2 wt.%), Zn (2.82–12.09 wt.%), Cd (12–6940 mg/kg), As (930–75,870 mg/kg) and Sb (67–2175 mg/kg). Slags from the oldest technology are composed of primary Ca- and Pb-bearing feldspars, spinels, complex Cu–Fe and Cu–Cr oxides, delafossite–mcconnellite phases and Ca–Pb arsenates. The presence of arsenates indicates that these slags underwent long-term alteration. More recent slags are composed of high-temperature phases: Ca–Fe alumosilicates (olivine, melilite), Pb- and Zn-rich glass, spinel oxides and small sulphide/metallic inclusions embedded in glass. XRD and SEM/EDS were used to study secondary alteration products developed on the surface of slags exposed for decades to weathering on the dumps. Highly soluble complex Cu–Pb–(Ca) arsenates (bayldonite, lammerite, olivenite, lavendulan) associated with litharge and hydrocerussite were detected. To determine the mineralogical and geochemical parameters governing the release of inorganic contaminants from slags, two standardized short-term batch leaching tests (European norm EN 12457 and USEPA TCLP), coupled with speciation-solubility modelling using PHREEQC-2 were performed. Arsenic in the leachate exceeded the EU regulatory limit for hazardous waste materials (2.5 mg/L). The toxicity limits defined by USEPA for the TCLP test were exceeded for Cd, Pb and As. The PHREEQC-2 calculation predicted that complex arsenates are the most important solubility controls for metals and metalloids. Furthermore, these phases can readily dissolve during the rainy season (October to March) and flush significant amounts of As, Pb and Cu into the environment in the vicinity of slag dumps.     

The Rožná uranium deposit (Bohemian Massif, Czech Republic): shear zone-hosted, late Variscan and post-Variscan hydrothermal mineralization

Three major mineralization events are recorded at the Rožná uranium deposit (total mine production of 23,000 t U, average grade of 0.24% U): (1) pre-uranium quartz-sulfide and carbonate-sulfide mineralization, (2) uranium, and (3) post-uranium quartz-carbonate-sulfide mineralization. (1) K–Ar ages for white mica from wall rock alteration of the pre-uranium mineralization style range from 304.5 ± 5.8 to 307.6 ± 6.0 Ma coinciding with the post-orogenic exhumation of the Moldanubian orogenic root and retrograde-metamorphic equilibration of the high-grade metamorphic host rocks. The fluid inclusion record consists of low-salinity aqueous inclusions, together with H₂O-CO₂-CH₄, CO₂-CH₄, and pure CH₄ inclusions. The fluid inclusion, paragenetic, and isotope data suggest that the pre-uranium mineralization formed from a reduced low-salinity aqueous fluid at temperatures close to 300°C. (2) The uraniferous hydrothermal event is subdivided into the pre-ore, ore, and post-ore substages. K–Ar ages of pre-ore authigenic K-feldspar range from 296.3 ± 7.5 to 281.0 ± 5.4 Ma and coincide with the transcurrent reorganization of crustal blocks of the Bohemian Massif and with Late Stephanian to Early Permian rifting. Massive hematitization, albitization, and desilicification of the pre-ore altered rocks indicate an influx of oxidized basinal fluids to the crystalline rocks of the Moldanubian domain. The wide range of salinities of fluid inclusions is interpreted as a result of the large-scale mixing of basinal brines with meteoric water. The cationic composition of these fluids indicates extensive interaction with crystalline rocks. Chlorite thermometry yielded temperatures of 260°C to 310°C. During this substage, uranium was probably leached from the Moldanubian crystalline rocks. The hydrothermal alteration of the ore substage followed, or partly overlapped in time, the pre-ore substage alteration. K–Ar ages of illite from ore substage alteration range from 277.2 ± 5.5 to 264.0 ± 4.3 Ma and roughly correspond with the results of chemical U–Pb dating of authigenic monazite (268 ± 50 Ma). The uranium ore deposition was accompanied by large-scale decomposition of biotite and pre-ore chlorite to Fe-rich illite and iron hydrooxides. Therefore, it is proposed that the deposition of uranium ore was mostly in response to the reduction of the ore-bearing fluid by interaction with ferrous iron-bearing silicates (biotite and pre-ore chlorite). The Th data on primary, mostly aqueous, inclusions trapped in carbonates of the ore substage range between 152°C and 174°C and total salinity ranges over a relatively wide interval of 3.1 to 23.1 wt% NaCl eq. Gradual reduction of the fluid system during the post-ore substage is manifested by the appearance of a new generation of authigenic chlorite and pyrite. Chlorite thermometry yielded temperatures of 150°C to 170°C. Solid bitumens that post-date uranium mineralization indicate radiolytic polymerization of gaseous and liquid hydrocarbons and their derivatives. The origin of the organic compounds can be related to the diagenetic and catagenetic transformation of organic matter in Upper Stephanian and Permian sediments. (3) K–Ar ages on illite from post-uranium quartz-carbonate-sulfide mineralization range from 233.7 ± 4.7 to 227.5 ± 4.6 Ma and are consistent with the early Tethys-Central Atlantic rifting and tectonic reactivation of the Variscan structures of the Bohemian Massif. A minor part of the late Variscan uranium mineralization was remobilized during this hydrothermal event.     

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

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