Functioning of intertidal flats inferred from temporal and spatial dynamics of O<Subscript>2</Subscript>, H<Subscript>2</Subscript>S and pH in their surface sediment

In this article, we describe the dynamics of pH, O₂ and H₂S in the top 5–10 cm of an intertidal flat consisting of permeable sand. These dynamics were measured at the low water line and higher up the flat and during several seasons. Together with pore water nutrient data, the dynamics confirm that two types of transport act as driving forces for the cycling of elements (Billerbeck et al. 2006b): Fast surface dynamics of pore water chemistry occur only during inundation. Thus, they must be driven by hydraulics (tidal and wave action) and are highly dependent on weather conditions. This was demonstrated clearly by quick variation in oxygen penetration depth: Seeps are active at low tide only, indicating that the pore water flow in them is driven by a pressure head developing at low tide. The seeps are fed by slow transport of pore water over long distances in the deeper sediment. In the seeps, high concentrations of degradation products such as nutrients and sulphide were found, showing them to be the outlets of deep-seated degradation processes. The degradation products appear toxic for bioturbating/bioirrigating organisms, as a consequence of which, these were absent in the wider seep areas. These two mechanisms driving advection determine oxygen dynamics in these flats, whereas bioirrigation plays a minor role. The deep circulation causes a characteristic distribution of strongly reduced pore water near the low water line and rather more oxidised sediments in the centre of the flats. The two combined transport phenomena determine the fluxes of solutes and gases from the sediment to the surface water and in this way create specific niches for various types of microorganisms.     

Mineralogical and geochemical alteration of Hitura sulphide mine tailings with emphasis on nickel mobility and retention

Weathering of Hitura (W Finland) nickel sulphide mine tailings and release of heavy metals into pore water was studied with mineralogical (optical and electron microscopy, X-ray diffraction) and geochemical methods (selective extractions). Tailings were composed largely of serpentine, micas and amphiboles with only minor carbonates and sulphides. Sulphides, especially pyrrhotite, have oxidized intensively in the shallow tailings in 10–15 years, but a majority of the tailings have remained unchanged. Oxidation has resulted in depletion of carbonates, slightly decreased pH, and heavy metal (Ni, Zn) release in pore water as well as in the precipitation of secondary Fe precipitates. Nevertheless, in the middle of the tailings area, where the oxidation front moves primarily downward, released heavy metals have been adsorbed and immobilized with these precipitates deeper in the oxidation zone. In contrast to what was seen in pore water pH, but in accordance with static tests of the previous studies, the neutralisation potential ratio (NPR) calculated based on the mineralogical composition and the total sulphur content suggested that tailings are ‘not potentially acid mine drainage (AMD) generating’. However, the calculated buffering capacity of the tailings resulted largely from the abundant serpentine because of the low carbonate content. Despite its slow weathering rate, serpentine may buffer the acidity to some extent through ion exchange processes in fine ground tailings. Nevertheless, in practice, acid production capacity of the tailings depends primarily on the balance between Ca–Mg carbonates and iron sulphides. NPR calculation based on carbonate and sulphur contents suggested, that the Hitura tailings are ‘likely AMD generating’. The study shows that sulphide oxidation can be significant in mobilisation of heavy metals even in apparently non-acid producing, low sulphide tailings. Therefore, prevention of oxygen diffusion into tailings is also essential in this type of sulphide tailings.     

辽宁红透山块状硫化物矿床蚀变带元素迁移特征及定量计算

辽宁红透山块状硫化物矿床（MSD）位于华北地台东北部的浑北花岗岩-绿岩地体内,矿区岩石在30～28 亿年期间受到了600～650℃的高级角闪岩相变质。研究结果表明,广泛分布于红透山层状矿体下盘数百米处的和直接产于矿体下盘的堇青-直闪片麻岩,分别代表了变质后的MSD成矿系统以绿泥石化为特征的半整合和筒状不整合海底热液蚀变带。微量元素特征显示,层状堇青-直闪片麻岩的原岩并非同一种岩石,而是由5种不同岩性的岩石组成,筒状堇青-直闪片麻岩的原岩主要由流纹质岩石组成,而在堇青-直闪片麻岩走向上与之过渡的角闪片麻岩和黑云片麻岩则代表了不同岩性蚀变岩的未蚀变原岩。质量变化计算表明,相对于未蚀变原岩而言,两种蚀变岩的成分发生了显著变化,其中层状堇青-直闪片麻岩的Fe、Mg发生了富集,Na、K、Ca、Cu、Pb和Zn等元素被迁出,而筒状堇青-直闪片麻岩的Fe、Mg、Si、Na、Pb、Cu和Zn等元素则发生了富集,K被迁出。重稀土元素（HREE）和高场强元素(Zr、Ti、Nb、Hf和Ta)在海底热液蚀变过程中保持惰性,而Rb、Sr、Ba和轻稀土元素（LREE,尤其是Eu）则被强烈的迁出。这些元素变化特征表明海底热液蚀变以绿泥石化和硅化为特征,同时海底水-岩反应体系具有高水/岩比值。层状堇青-直闪片麻岩可作为红透山矿区成矿潜力评价的重要依据,而含硫化物石英脉的筒状堇青-直闪片麻岩不但本身可成为工业矿体,还可作为上覆层状矿体的近矿找矿标志。     

Oxidative dissolution of pyritic sludge from the Aznalcóllar mine (SW Spain)

As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m² g⁻¹).

The dissolution rate law of sludge obtained is r=10^{−6.1(±0.3)} [O₂(aq)]^0.41(±0.04) a_H+^0.09(±0.06) g_sludge m⁻² s⁻¹ (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10^{−7.8(±0.3)} [O₂(aq)]^0.50(±0.04) a_H+^0.10(±0.08) mol m⁻² s⁻¹ (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively.

A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O₂ onto pyrite surface is proposed.     

Lewis Ponds, a hybrid carbonate and volcanic-hosted polymetallic massive sulphide deposit, New South Wales, Australia

The Lewis Ponds Zn–Pb–Cu–Ag–Au deposit, located in the eastern Lachlan Fold Belt, central western New South Wales, exhibits the characteristics of both volcanic-hosted massive sulphide and carbonate-hosted replacement deposits. Two stratabound massive to disseminated sulphide zones, Main and Toms, occur in a tightly folded Upper Silurian sequence of marine felsic volcanic and sedimentary rocks. They have a combined indicated resource of 5.7 Mt grading 3.5% Zn, 2.0% Pb, 0.19% Cu, 97 g/t Ag and 1.9 g/t Au. Main Zone is hosted by a thick unit of poorly sorted mixed provenance breccia, limestone-clast breccia and quartz crystal-rich sandstone, whereas Toms Zone occurs in the overlying siltstone. Pretectonic carbonate–chalcopyrite–pyrite and quartz–pyrite stringer veins occur in the footwall porphyritic dacite, south of Toms Zone. Strongly sheared dolomite–chalcopyrite–pyrrhotite veins directly underlie the Toms massive sulphide lens. The mineralized zones consist predominantly of pyrite, sphalerite and galena. Paragenetically early framboidal, dendritic and botryoidal pyrite aggregates and tabular pyrrhotite pseudomorphs of sulphate occur throughout the breccia and sandstone beds that host Main Zone, but are rarely preserved in the annealed massive sulphide in Toms Zone. Main and Toms zones are associated with a semi-conformable hydrothermal alteration envelope, characterized by texturally destructive chlorite-, dolomite- and quartz-rich assemblages. Dolomite, chlorite, quartz, calcite and sulphides have selectively replaced breccia and sandstone beds in the Main Zone host sequence, whereas the underlying porphyritic dacite is weakly sericite altered. Vuggy and botryoidal textures resulted from partial dissolution of the dolomite-altered sedimentary rocks and unimpeded growth of base metal sulphides, carbonate and quartz into open cavities. The intense chlorite-rich alteration assemblage, underlying Toms Zone, grades outward into a weak pervasive sericite–quartz assemblage with distance from the massive sulphide lens. Limestone clasts and hydrothermal dolomite at Lewis Ponds are enriched in light carbon and oxygen isotopes. The dolomite yielded ¹³C_VPDB values of –11 to +1 and ¹⁸O_VSMOW values of 6 to 16. Liquid–vapour fluid inclusions in the dolomite have low salinities (1.4–7.7 equiv. wt% NaCl) and homogenization temperatures (166–232°C for 1,000 m water depth). Dolomitization probably involved fluid mixing or fluid–rock interactions between evolved heated seawater and the limestone-bearing facies, prior to and during mineralization. ³⁴S_VCDT values range from 2.0 to 5.0 in the massive sulphide and 3.9 to 7.4 in the footwall carbonate–chalcopyrite–pyrite stringer veins, indicating that the hydrothermal fluid may have contained mamgatic sulphur and a component of partially reduced seawater. The sulphide mineral assemblages at Lewis Ponds are consistent with moderate to strongly reduced conditions during diagenesis and mineralization. Low temperature dolomitization of limestone-bearing facies in the Main Zone host sequence created secondary porosity and provided a reactive host for fluid-rock interactions. Main Zone formed by lateral fluid flow and sub-seafloor replacement of the poorly sorted breccia and sandstone beds. Base metal sulphide deposition probably resulted from dissolution of dolomite, fluid mixing and increased fluid pH. Pyrite, sphalerite and galena precipitated from a relatively low temperature, 150–250°C hydrothermal fluid. In contrast, Toms Zone was emplaced into fine-grained sediment at or near the seafloor, above a zone of focused up-flowing hydrothermal fluids. Copper-rich assemblages were deposited in the Toms Zone footwall and massive sulphide lenses in Main and Toms zones as the hydrothermal system intensified. During the D₁ deformation, fracture-controlled fluids within the Lewis Ponds fault zone and adjacent footwall volcanic succession remobilized sulphides into syntectonic quartz veins. Lewis Ponds is a rare example of a synvolcanic sub-seafloor hydrothermal system developed within fossiliferous limestone-bearing facies. The close spatial association between limestone, hydrothermal dolomite, massive sulphide and dacite provides a basis for new exploration targets elsewhere in New South Wales.Editorial handling: D. Lentz     

甘肃金川铜镍矿石中MgO对浮选的影响

金川铜镍矿浮选精矿中MgO高,影响闪速熔炼。对金川主力矿山二矿区矿石中MgO分布特征与赋存状态的研究,分析影响浮选过程中MgO难以抑制原因。认为矿石本身MgO含量高、矿石蚀变严重、含镁矿物自然可浮性的良好是造成精矿中MgO高的主要原因。提出研究含镁矿物的浮选特性和矿石的矿物组成特点是精矿降镁的前提。     

Mantle heterogeneity,plume-lithosphere interaction at rift controlled ocean-continent transition zone: Evidence from trace-PGE geochemistry of Vempalle flows,Cuddapah Basin,India

This study reports major, trace, rare earth and platinum group element compositions of lava flows from the Vempalle Formation of Cuddapah Basin through an integrated petrological and geochemical approach to address mantle conditions, magma generation processes and tectonic regimes involved in their formation. Six flows have been identified on the basis of morphological features and systematic three-tier arrangement of vesicular-entablature-colonnade zones. Petrographically, the studied flows are porphyritic basalts with plagioclase and clinopyroxene representing dominant phenocrystal phases.Major and trace element characteristics reflect moderate magmatic differentiation and fractional crystallization of tholeiitic magmas. Chondrite-normalized REE patterns corroborate pronounced LREE/HREE fractionation with LREE enrichment over MREE and HREE. Primitive mantle normalized trace element abundances are marked by LILE-LREE enrichment with relative HFSE depletion collectively conforming to intraplate magmatism with contributions from sub-continental lithospheric mantle(SCLM) and extensive melt-crust interaction. PGE compositions of Vempalle lavas attest to early sulphur-saturated nature of magmas with pronounced sulphide fractionation, while PPGE enrichment over IPGE and higher Pd/Ir ratios accord to the role of a metasomatized lithospheric mantle in the genesis of the lava flows. HFSEREE-PGE systematics invoke heterogeneous mantle sources comprising depleted asthenospheric MORB type components combined with plume type melts. HFSE-REE variations account for polybaric melting at variable depths ranging from garnet to spinel lherzolite compositional domains of mantle. Intraplate tectonic setting for the Vempalle flows with P-MORB affinity is further substantiated by(i) their origin from a rising mantle plume trapping depleted asthenospheric MORB mantle during ascent,(ii) interaction between plume-derived melts and SCLM,(iii) their rift-controlled intrabasinal emplacement through Archeane Proterozoic cratonic blocks in a subduction-unrelated ocean-continent transition zone(OCTZ). The present study is significant in light of the evolution of Cuddapah basin in the global tectonic framework in terms of its association with Antarctica, plume incubation, lithospheric melting and thinning, asthenospheric infiltration collectively affecting the rifted margin of eastern Dharwar Craton and serving as precursors to supercontinent disintegration.     

Sulphur solubility in andesitic to basaltic melts: implications for Hekla volcano

The solubility of sulphur in sulphide-saturated, H₂O-bearing basaltic–andesitic and basaltic melts from Hekla volcano (Iceland) has been determined experimentally at 1,050°C, 300 and 200 MPa, and redox conditions with oxygen fugacity (logfO₂) between QFM−1.2 and QFM+1.1 (QFM is a quartz–fayalite–magnetite oxygen buffer) in the systems containing various amounts of S and H₂O. The S content of the H₂O-rich glasses saturated with pyrrhotite decreases from 2,500 ppm in basalt to 1,500 ppm in basaltic andesite at the investigated conditions. Furthermore, the reduction of water content in the melt at pyrrhotite saturation and fixed T, P and redox conditions leads to a decrease in S concentration from 2,500 to 1,400 ppm for basaltic experiments (for H₂O decrease from 7.8 to 1.4 wt%) and from 1,500 to 900 ppm (for H₂O decrease from 6.7 to 1.7 wt%) for basaltic andesitic experiments. Our experimental data, combined with silicate melt inclusion investigations and the available models on sulphide saturation in mafic magmas, indicate that the parental basaltic melts of Hekla were not saturated with respect to sulphide. During magmatic differentiation, the S content in the residual melts increased and might have reached sulphide saturation with 2,500 ppm dissolved S. With further magma crystallization, the S concentration in the melt was controlled by the sulphide saturation of the magma, decreasing from ~2,500 to 900 ppm S.     

连续流动分析法测定污水中阴离子表面活性剂、总氮、总磷、挥发酚、氰化物、硫化物的方法及实例

快速同时测定排污口样品中阴离子表面活性剂、总氮、总磷、挥发酚、氰化物、硫化物的分析方法。采用连续流动分析法,确定最佳实验方案。经多次试验验证,呈良好线性关系;质量控制样品测定值均在保证值范围内,样品回收率在95．2％～104％之间,RSD小于2％。     

The effect of hydrodynamic conditions on true flotation and entrainment in flotation of a complex sulphide ore

The separation efficiency and selectivity of flotation are directly proportional to recoveries of the mineral species in the feed due to true flotation and entrainment. In this study, effects of the hydrodynamic conditions on true flotation and entrainment were investigated by using a fractional factorial experimental design. A method previously described in the literature was applied to determine the contributions of true flotation and entrainment in flotation of a complex sulphide ore. In order to apply the method, the kinetic flotation tests were conducted under various hydrodynamic conditions defined by some physical variables. Some of these tests were conducted in the presence and absence of a collector to evaluate the self-induced floatability. The selectivity index of the mineral species for entrainment was seen to be suitable evaluation of the non-selectivity and efficiency of the entrainment. Furthermore, the results of the size-by-size analysis of the froth products indicated that the presence of the self-induced hydrophobic particles in the feed is as important as the presence of very fine particles for accurate estimation of true flotation and entrainment in flotation of a complex sulphide ore. In addition, the estimated results for entrainment in flotation of the complex sulphide ore can be misleading. Therefore, a new approach would be necessary to determine the contributions of true flotation and entrainment in flotation of a complex sulphide ore.