Supergene sulphides and related minerals in the supergene profiles of VHMS deposits from the South Urals

The mineralogy and structure of the supergene profile in recently-exploited volcaniс hosted massive sulphide (VHMS) deposits of Cyprus, Uralian and Kuroko type in the South Urals, Russia, have been studied. Specific subzones enriched in secondary sulphides and associated minerals have been distinguished in residual pyrite and quartz–pyrite sands at the Gayskoye, Zapadno-Ozernoye, Dzhusinskoye and Alexandrinskoye deposits. Besides minerals which are common to the cementation subzones (covellite, chalcocite and acanthite), non-stoichiometric colloform and framboidal pyrite, pyrite–dzharkenite, pyrrhotite-like and jordanite-like minerals, metacinnabar, sphalerite, selenium-enriched tetrahedrite and unidentified As-, Sb sulphosalts of Pb or Hg and Ag, sulphur-bearing clausthalite, naumannite and tiemannite were also found. Secondary sulphide minerals in VHMS deposits of the South Urals region are characterized by light sulphur isotope compositions (− 8.1 to − 17.2‰). Superposition of the advanced oxidation of colloform pyrite, an enrichment in impurities (sphalerite, galena, and tennantite) from the primary ores, stagnant water conditions, an elevation of the water table during oxidation, and bacterial activity led to supergene concentrations of the base metals as sulphide, selenides or sulphosalts.     

A stable isotope study of the Garda lake, northern Italy: Its hydrological balance

Discontinuous measurements of the isotopic composition of surface water samples of the Garda lake carried out between 1998 and 2006 showed almost constant δ¹⁸O, δD and d-excess values through time. During 2006 and 2007 monthly vertical profiles of water samples were collected in the northernmost section of the lake, not far from the main inflow (Sarca river) to check whether there was any detectable influence from this inflowing river and whether there was a vertical isotopic stratification of the lake water. The isotopic measurement of water samples from the vertical profiles yielded isotopic values which were almost equal to those obtained from surface waters showing no detectable effect of the inflowing river water and no isotopic vertical stratification. The attempt to evaluate the evaporation rate of lake water by means of current models was totally unsuccessful. Despite the marked summer warming of the surface layer no isotopic fractionation related to evaporation processes could be detected. This anomalous behaviour may be related to the large amount of spring and summer precipitation characteristic of this area. The water balance of the lake calculated according to the amount of the inflowing water (Sarca river water plus rain water on the lake plus 20% of the precipitations on the whole catchment basin) and to the amount of outflowing water (Mincio river) showed a large imbalance, the river outflow alone resulting on average, during the last decade, at least double the inflow. To explain this imbalance of the lake, a large recharge by concealed groundwater is suggested: its isotopic composition should be quite close to the mean isotopic composition of precipitations over that area. This would be in agreement with the almost constant isotopic composition of both surface and deep waters and with the lack of vertical isotopic stratification. A few measurements of the tritium concentration carried out on lake water show values that are considerably higher than modern tritium values either in precipitation or in the Sarca river water: these results are in good agreement with the hypothesis of a recharge of the lake by deep aquifers.     

The Palaeoproterozoic Kristineberg VMS deposit, Skellefte district, northern Sweden, part I: geology

The Kristineberg volcanic-hosted massive sulphide (VMS) deposit, located in the westernmost part of the Palaeoproterozoic Skellefte district, northern Sweden, has yielded 22.4 Mt of ore, grading 1.0% Cu, 3.64% Zn, 0.24% Pb, 1.24 g/t Au, 36 g/t Ag and 25.9% S, since the mine opened in 1941, and is the largest past and present VMS mine in the district. The deposit is hosted in a thick pile of felsic to intermediate and minor mafic metavolcanic rocks of the Skellefte Group, which forms the lowest stratigraphic unit in the district and hosts more than 85 known massive sulphide deposits. The Kristineberg deposit is situated lower in the Skellefte Group than most other deposits. It comprises three main ore zones: (1) massive sulphide lenses of the A-ore (historically the main ore), having a strike length of about 1,400 m, and extending from surface to about 1,200 m depth, (2) massive sulphide lenses of the B-ore, situated 100–150 m structurally above the A-ore, and extending from surface to about 1,000 m depth, (3) the recently discovered Einarsson zone, which occurs in the vicinity of the B-ore at about 1,000 m depth, and consists mainly of Au–Cu-rich veins and heavily disseminated sulphides, together with massive sulphide lenses. On a regional scale the Kristineberg deposit is flanked by two major felsic rock units: massive rhyolite A to the south and the mine porphyry to the north. The three main ore zones lie within a schistose, deformed and metamorphosed package of hydrothermally altered, dominantly felsic volcanic rocks, which contain varying proportions of quartz, muscovite, chlorite, phlogopite, pyrite, cordierite and andalusite. The strongest alteration occurs within 5–10 m of the ore lenses. Stratigraphic younging within the mine area is uncertain as primary bedding and volcanic textures are absent due to strong alteration, and tectonic folding and shearing. In the vicinity of the ore lenses, hydrothermal alteration has produced both Mg-rich assemblages (Mg-chlorite, cordierite, phlogopite and locally talc) and quartz–muscovite–andalusite assemblages. Both types of assemblages commonly contain disseminated pyrite. The sequence of volcanic and ore-forming events at Kristineberg is poorly constrained, as the ages of the massive rhyolite and mine porphyry are unknown, and younging indicators are absent apart from local metal zoning in the A-ores. Regional structural trends, however, suggest that the sequence youngs to the south. The A- and B-ores are interpreted to have formed as synvolcanic sulphide sheets that were originally separated by some 100–150 m of volcanic rocks. The Einarsson zone, which is developed close to the 1,000 m level, is interpreted to have resulted in part from folding and dislocation of the B-ore sulphide sheet, and in part from remobilisation of sulphides into small Zn-rich massive sulphide lenses and late Au–Cu-rich veins. However, the abundance of strongly altered, andalusite-bearing rocks in the Einarsson zone, coupled with the occurrence of Au–Cu-rich disseminated sulphides in these rocks, suggests that some of the mineralisation was synvolcanic and formed from strongly acidic hydrothermal fluids. Editorial handling: P. Weihed     

A mapping of the electron localization function for earth materials

The electron localization function, ELF, generated for a number of geometry-optimized earth materials, provides a graphical representation of the spatial localization of the probability electron density distribution as embodied in domains ascribed to localized bond and lone pair electrons. The lone pair domains, displayed by the silica polymorphs quartz, coesite and cristobalite, are typically banana-shaped and oriented perpendicular to the plane of the SiOSi angle at ~0.60 Å from the O atom on the reflex side of the angle. With decreasing angle, the domains increase in magnitude, indicating an increase in the nucleophilic character of the O atom, rendering it more susceptible to potential electrophilic attack. The Laplacian isosurface maps of the experimental and theoretical electron density distribution for coesite substantiates the increase in the size of the domain with decreasing angle. Bond pair domains are displayed along each of the SiO bond vectors as discrete concave hemispherically-shaped domains at ~0.70 Å from the O atom. For more closed-shell ionic bonded interactions, the bond and lone pair domains are often coalesced, resulting in concave hemispherical toroidal-shaped domains with local maxima centered along the bond vectors. As the shared covalent character of the bonded interactions increases, the bond and lone pair domains are better developed as discrete domains. ELF isosurface maps generated for the earth materials tremolite, diopside, talc and dickite display banana-shaped lone pair domains associated with the bridging O atoms of SiOSi angles and concave hemispherical toroidal bond pair domains associated with the nonbridging ones. The lone pair domains in dickite and talc provide a basis for understanding the bonded interactions between the adjacent neutral layers. Maps were also generated for beryl, cordierite, quartz, low albite, forsterite, wadeite, åkermanite, pectolite, periclase, hurlbutite, thortveitite and vanthoffite. Strategies are reviewed for finding potential H docking sites in the silica polymorphs and related materials. As observed in an earlier study, the ELF is capable of generating bond and lone pair domains that are similar in number and arrangement to those provided by Laplacian and deformation electron density distributions. The formation of the bond and lone pair domains in the silica polymorphs and the progressive decrease in the SiO length as the value of the electron density at the bond critical point increases indicates that the SiO bonded interaction has a substantial component of covalent character.     

EK-Fenton process for removal of phenanthrene in a two-dimensional soil system

Feasibility of electrokinetic (EK) process combined with Fenton-like reaction was investigated for the removal of phenanthrene in a two-dimensional cell. Sandy soil and bentonite were selected as a model soil and a filling material to inhibit the leak of electrolyte solution within the electrode reservoirs into the soil by hydraulic pressure difference, respectively. The effects of parameters including current, electroosmotic flow (EOF), electrolyte pH, and moisture content on the removal efficiency were examined under constant voltage.

At the end of operation for 21 days, the concentration of phenanthrene near the anode was lower than the other positions of soil specimen and increased gradually towards the cathode because hydrogen peroxide solution was supplied from anode to cathode region following the direction of EOF. The concentration of phenanthrene at the bottom soil was lower than that at the top soil. Because capillary attraction in the sandy soil with high porosity was too low to maintain appropriate moisture at the top of the cell, EOF moved through the bottom soil with higher moisture content. Overall removal efficiency at 140 V was 81.6%, which was higher than 68.9% at 100 V because total EOF increased by a factor of 1.5 upon increase of the voltage from 100 to 140 V. In addition, power consumptions at 100 and 140 V were 7.2 and 19.4 kWh, respectively.     

Elimination of Swimming Pool Water Disinfection By‐products with Advanced Oxidation Processes (AOPs)

Ozonation is a treatment step which was first applied in the 1960s in pool water treatment for disinfection as well as for oxidation of pool water contaminants. Contact time between ozone and pool water was identified to be of significance with an increased elimination efficiency regarding chloramines, trihalogenmethane formation potential and the permanganate index for longer reaction times. Oxidation via OH radicals might be the dominating pathway. In this study ozonation was compared with the ozone based advanced oxidation processes ozone/UV and ozone/hydrogen peroxide regarding the elimination efficiency of both disinfection by‐products (DBPs) and DBP precursors. It was observed that AOPs in comparison to ozonation showed an increased elimination efficiency regarding total organic carbon (TOC), the organically bound halogens adsorbable on activated carbon (AOX) and AOX formation potential. A contact time of 3 minutes between pool water and oxidant turned out to be practically sufficient. Just for the trihalomethane (THM) formation potential ozonation showed a slight advantage compared to the AOPs because ozonation is a highly selective oxidant and OH radical reactions are known to produce small reactive molecules which are easier transformed to THMs. Combination of membrane filtration and AOPs resulted in an elimination of 10 to 90 % of the DBPs and their precursors. The ozone/hydrogen peroxide process is suggested for pool water treatment because of the higher elimination rates compared to ozonation and of economic reasons compared to the ozone/UV process.     

铂族元素中子活化分析的微型镍锍试金预富集方法研究

建立了适用于小样品(≤1g)中铂族元素分离富集的微型镍锍试金流程。讨论了试金熔剂、捕集剂的用量和比例,以及熔炼条件。化学回收实验显示铂族元素全流程回收率≥90%,分析精密度(RSD,n=6)为4.3%~7.7%。标准参考物质分析显示分析值与标准值基本吻合,表明所建立的微型镍锍试金流程是可靠的。     

Carbon and hydrogen isotope variation of plant biomarkers in a plant-soil system

Stable carbon (δ¹³C) and hydrogen (δD) isotopic compositions of n-alkanes, anteiso-alkanes, n-alkanoic acids, n-alkanols, phytol and sterols in raw leaves of Acer argutum and Acer carpinifolium, their fallen leaves, mold and soils from a natural Acer forest were measured in order to: (1) understand isotopic variation of the plant biomarkers in a plant-soil system and (2) evaluate which biomarker is the most effective recorder of soil vegetation. Long-chain (> C₂₄) n-alkanes, n-alkanoic acids and n-alkanols are gradually enriched in ¹³C up to 12.9‰ (average of 4.3‰) and depleted in D up to 94‰ (average of 55‰) from raw leaves to soils. However, anteiso-alkanes, phytol and sterols show little variation in both δ¹³C (< ± 1‰) and δD (< ± 2‰) from raw leaves to soils. These isotope signatures in a plant-soil system indicate that isoprenoid plant biomarkers such as sterols in soils faithfully preserve the isotopic compositions of dominant higher plants growing on the soils without a diagenetic effect upon the isotopic compositions. In contrast, long-chain n-alkyl molecules in soils undergo specific isotopic modification during biodegradation associated with early diagenesis and/or a significant contribution from heterotrophic reworking.     

Matching gasification technologies to coal properties

The gasification of coal to produce hydrogen for use either in power generation or/and for synthesis applications and transport is attracting considerable interest worldwide. Three types of generic gasifiers (entrained flow, fluidised bed and fixed bed gasifiers) presently in use in commercial gasification plants or under development worldwide are described. Their suitability for processing all types of coals is discussed. This includes an assessment of the impact of some of the major properties of coal on the design, performance and maintenance of gasification processes.     

Hydrogen from coal gasification: An economical pathway to a sustainable energy future

Although hydrogen is the most abundant element in the universe, it does not occur naturally in large quantities or high concentrations on Earth. Hydrogen must be produced from other compounds such as fossil fuels, biomass, or water and is therefore considered an energy carrier like electricity. Gasification of carbonaceous, hydrogen-containing fuels is an effective method of thermal hydrogen production and is considered to be a key technology in the transition to a hydrogen economy. However, for gasification to play a major role during the transition period, capital and operating cost must be reduced and reliability and performance must be improved.Analyses show that hydrogen produced from coal-based gasification can be competitive with production from natural gas provided the cost of natural gas remains above $4/10⁶ Btu and the high reliability of gasification-based processes can be demonstrated. But for coal to be considered in a carbon-constrained environment, the cost of natural gas would have to be greater than $5.50/10⁶ Btu. The development of advanced technologies, however, offers the potential for significant reductions in capital costs, improved thermal efficiencies, and increased reliability. If these advanced technologies are capable of achieving their goals, the cost of producing hydrogen from coal could be reduced by 25–50%, even with the capture and sequestration of CO₂. With these reductions, the cost of natural gas would have to be less than $2.50/10⁶ Btu to compete, a scenario that is very unlikely to occur in the future. This potential cost reduction provides considerable impetus for continuing research and development in the production of hydrogen from coal.