辽宁红透山铜锌块状硫化物矿床的变质变形和成矿组分再活化

辽宁红透山铜-锌块状硫化物产在太古宙绿岩带中，矿床形成后经历了强烈的变形和变质，变质程度达高级角闪岩相。野外和显微镜研究表明，矿石在进变质过程中发生过强烈的机械再活化和重结晶，但各种进变质结构大部分已被变质峰期的全面重结晶所清除，目前保存着的结构主要是变质峰期和退变质过程的产物。退变质过程以黄铁矿变斑晶生长、矿石糜棱岩的形成、二次退火和化学再活化为特征。矿床中高度富集铜和金的矿石是韧性剪切形成的矿石糜棱岩受退变质流体叠加而成。磁黄铁矿主要是同生沉积后重结晶的产物，另有一部分由退变质热液形成，而黄铁矿变斑晶则有沉积一重结晶、磁黄铁矿退变质脱硫和热液叠加多种成因。世界各地块状硫化物矿床中的磁黄铁矿和黄铁矿各有三种成因类型。磁黄铁矿的类型有：同生沉积．变质重结晶、同生沉积黄铁矿变质和退变质热液充填或交代；黄铁矿的类型有：同生沉积-变质重结晶、磁黄铁矿退变质脱硫和退变质热液充填或交代。红透山矿区的退变质流体具有从早到晚氧逸度升高的趋势。     

Electrodialytic remediation of CCA-treated waste wood in pilot scale

When chromated copper arsenate (CCA)-treated wood is removed from service and turns into waste, the contents of Cu, Cr and As remain high due to the strong fixation of CCA in the wood. This high content of toxic compounds presents a disposal challenge. Incineration of CCA-treated waste wood is not allowed in Denmark; instead, the wood is to be land-filled until new methods for handling the wood are available. Since the amounts of CCA-treated wood being removed from service is expected to increase in the years to come, the need for finding alternative handling methods is very relevant. In this study, the usefulness of Electrodialytic Remediation was demonstrated for handling of CCA-treated waste wood in pilot scale. The electrodialytic remediation method, which uses a low-level direct current (DC) as the cleaning agent, combines electrokinetic movement of ions in the wood matrix with the principles of electrodialysis. It has previously been shown that it is possible to remove Cu, Cr and As from CCA-treated wood using electrodialytic remediation in laboratory scale, but until now, the method had not been studied in large scale. The pilot-scale plant used in this study was designed to contain up to 2 m³ wood chips. Six remediation experiments were carried out. In these experiments, the process was up-scaled stepwise by increasing the distance between the electrodes from initially 60 cm to finally 150 cm. The remediation time was varied between 11 and 21 days, and phosphoric acid and/or oxalic acid was used to facilitate the desorption of CCA from the wood. In the most successful of the experiments carried out, the concentration of CCA in the wood was reduced by up to 82% for Cr, 88% for Cu and at least 96% for As.     

Case study on the strategy and application of enhancement solutions to improve remediation of soils contaminated with Cu, Pb and Zn by means of electrodialysis

Numerous studies have been conducted with electrochemical removal of heavy metals from spiked kaolinite. Meanwhile, when moving from kaolinite to real soils, new factors must be taken into account—factors influencing, e.g., the buffering capacity of the soil against acidification and the adsorption/desorption processes of the heavy metals. The present study gives some examples where it is necessary to use an enhancement solution to aid desorption of Cu, Zn and Pb during electrodialytic treatment. Dependent on the composition of the pollution, different choices can be made. In the case of a Cu-polluted calcareous soil, ammonia may be used as enhancement solution, due to the formation of charged complexes between ammonia and Cu. Thus, Cu is mobile at high pH when ammonia is added and Cu can be removed without dissolving the calcareous parts. Zn is also mobilized by ammonia, but to a lesser extent than Cu. In the case of Cu, Zn and Pb at the same time, alkaline ammonium citrate may be a solution. It was shown that this enhancement solution could mobilize these three pollutants, but optimization of concentration and pH of the ammonium citrate is still needed. When choosing a remediation scheme for electrochemical treatment of an actual industrially polluted soil, this scheme must be chosen on basis of characterization of soil and pollution combination.     

Magma evolution and the formation of porphyry Cu–Au ore fluids: evidence from silicate and sulfide melt inclusions

Silicate and sulfide melt inclusions from the andesitic Farallón Negro Volcanic Complex in NW Argentina were analyzed by laser ablation ICPMS to track the behavior of Cu and Au during magma evolution, and to identify the processes in the source of fluids responsible for porphyry-Cu-Au mineralization at the 600 Mt Bajo de la Alumbrera deposit. The combination of silicate and sulfide melt inclusion data with previously published geological and geochemical information indicates that the source of ore metals and water was a mantle-derived mafic magma that contained approximately 6 wt.% H₂O and 200 ppm Cu. This magma and a rhyodacitic magma mixed in an upper-crustal magma chamber, feeding the volcanic systems and associated subvolcanic intrusions over 2.6 million years. Generation of the ore fluid from this magma occurred towards the end of this protracted evolution and probably involved six important steps: (1) Generation of a sulfide melt upon magma mixing in some parts of the magma chamber. (2) Partitioning of Cu and Au into the sulfide melt (enrichment factor of 10,000 for Cu) leading to Cu and Au concentrations of several wt.% or ppm, respectively. (3) A change in the tectonic regime from local extension to compression at the end of protracted volcanism. (4) Intrusion of a dacitic magma stock from the upper part of the layered magma chamber. (5) Volatile exsolution and resorption of the sulfide melt from the lower and more mafic parts of the magma chamber, generating a fluid with a Cu/Au ratio equal to that of the precursor sulfide. (6) Focused fluid transport and precipitation of the two metals in the porphyry, yielding an ore body containing Au and Cu in the proportions dictated by the magmatic fluid source. The Cu/S ratio in the sulfide melt inclusions requires that approximately 4,000 ppm sulfur is extracted from the andesitic magma upon mixing. This exceeds the solubility of sulfide or sulfate in either of the silicate melts and implies an additional source for S. The extra sulfur could be added in the form of anhydrite phenocrysts present in the rhyodacitic magma. It appears, thus, that unusually sulfur-rich, not Cu-rich magmas are the key to the formation of porphyry-type ore deposits. Our observations imply that dacitic intrusions hosting the porphyry–Cu–Au mineralization are not representative of the magma from which the ore-fluid exsolved. The source of the ore fluid is the underlying more mafic magma, and unaltered andesitic dikes emplaced immediately after ore formation are more likely to represent the magma from which the fluids were generated. At Alumbrera, these andesitic dikes carry relicts of the sulfide melt as inclusions in amphibole. Sulfide inclusions in similar dykes of other, less explored magmatic complexes may be used to predict the Au/Cu ratio of potential ore-forming fluids and the expected metal ratio in any undiscovered porphyry deposit.Editorial handling: B. Lehmann     

浙江省绍兴市平水金矿体流体包裹体研究 与矿床成因

浙江平水铜矿位于钦杭成矿带北东段浙西北地区,是浙江省最大的铜矿床,前人研究表明其为典型的火山成因块状硫化物矿床（Chen 等, 2015）。平水铜矿体在新元古代形成之后,该地区经历了加里东的变质变形作用,在铜矿体的下盘普遍发育千糜岩带（韧性剪切带）,本项目组在研究过程中认为千糜岩带与铜矿无关,但明确提出本区可能存在造山型金矿,继而老矿山接替资源勘查在平水铜矿布置了10个坑内钻孔,其中9个见矿,成功的在平水深部发现两层金矿体和一层铜矿体。金矿体严格的受韧性剪切带的控制;金矿石有明显的宏观和微观韧性变形结构;矿石矿物主要是自然金和少量的黄铁矿,脉石矿物主要有石英、绢云母、绿泥石、碳酸盐和白云石。本文主要对平水金矿体开展流体包裹体研究,结合矿床地质特征,最终确定金矿体成因类型,为平水地区下一轮深边部找矿勘查提供依据。     

云南大红山地区铁、铜矿床类型及形成机理

大红山地区是云南省重要矿集区之一,已发现大红山大型铁铜矿床及东么、底巴都、底戛母、河口、坝达等多个中小型铁铜矿床（点）,区内分布多个磁异常及化探异常,成矿地质条件优越。近年云南省三年地质找矿行动计划项目“云南省新平县大红山外围铁、铜矿资源普查”经过勘查在大红山外围东么、底巴都矿区圈定多个工业铁、铜矿体及超贫磁铁矿体,取得一定找矿新进展。本文根据近年工作中观察到的新现象、取得的新资料,结合前人研究成果,对大红山地区铁、铜矿床成因类型及形成机理进行探讨。     

Copper demand,supply, and associated energy use to 2050

To a set of well-regarded international scenarios (UNEP’s GEO-4), we have added consideration of the demand, supply, and energy implications related to copper production and use over the period 2010–2050. To our knowledge, these are the first comprehensive metal supply and demand scenarios to be developed. We find that copper demand increases by between 275 and 350% by 2050, depending on the scenario. The scenario with the highest prospective demand is not Market First (a “business as usual” vision), but Equitability First, a scenario of transition to a world of more equitable values and institutions. These copper demands exceed projected copper mineral resources by mid-century and thereafter. Energy demand for copper production also demonstrates strong increases, rising to as much as 2.4% of projected 2050 overall global energy demand. We investigate possible policy responses to these results, concluding that improving the efficiency of the copper cycle and encouraging the development of copper-free energy distribution on the demand side, and improving copper recycling rates on the supply side are the most promising of the possible options. Improving energy efficiency in primary copper production would lead to a reduction in the energy demand by 0.5% of projected 2050 overall global energy demand. In addition, encouraging the shift towards renewable technologies is important to minimize the impacts associated with copper production.     

Deciphering As and Cu cycling in sediment pore waters in a large marina (Port Camargue,southern France) using a multi-tracer (Fe,Mn, U,Mo) approach

The sediments of the Port Camargue marina (South of France) are highly polluted by Cu and As (Briant et al., 2013). The dynamics of these pollutants in pore waters was investigated using redox tracers (sulfides, Fe, Mn, U, Mo) to better constrain the redox conditions.In summer, pore water profiles showed a steep redox gradient in the top 24 cm with the reduction of Fe and Mn oxy-hydroxides at the sediment water interface (SWI) and of sulfate immediately below. Below a depth of 24 cm, the Fe, Mn, Mo and U profiles in pore waters reflected Fe and Mn reducing conditions and, unlike in the overlying levels, sulfidic conditions were not observed. This unusual redox zonation was attributed to the occurrence of two distinct sediment layers: an upper layer comprising muddy organic-rich sediments underlain by a layer of relatively sandy and organic-poor sediments. The sandy sediments were in place before the building of the marina, whereas the muddy layer was deposited later. In the muddy layer, large quantities of Fe and Mo were removed in summer linked to the formation of insoluble sulfide phases. Mn, which can adsorb on Fe-sulfides or precipitate with carbonates, was also removed from pore waters. Uranium was removed probably through reduction and adsorption onto particles. In winter, in the absence of detectable pore water sulfides, removal of Mo was moderate compared to summer.Cu was released into solution at the sediment water interface but was efficiently trapped by the muddy layer, probably by precipitation with sulfides. Due to efficient trapping, today the Cu sediment profile reflects the increase in its use as a biocide in antifouling paints over the last 40 years.In the sandy layer, Fe, Mn, Mo and As were released into solution and diffused toward the top of the profile. They precipitated at the boundary between the muddy and sandy layers. This precipitation accounts for the high (75 μg g⁻¹) As concentrations measured in the sediments at a depth of 24 cm.     

Oxidation of copper(I) in seawater at nanomolar levels

The oxidation and reduction of nanomolar levels of copper in air-saturated seawater and NaCl solutions has been measured as a function of pH (7.17–8.49), temperature (5–35 °C) and ionic strength (0.1–0.7 M). The oxidation rates were fitted to an equation valid at different pH and ionic strength conditions in sodium chloride and seawater solutions:

The reduction of Cu(II) was studied in both media for different initial concentrations of copper(II). When the initial Cu(II) concentration was 200 nM, the copper(I) productions were 20% and 9% for NaCl and seawater, respectively. The effect of speciation of copper(I) reduced from Cu(II) on the rates was studied. The Cu(I) speciation is dominated by the CuCl₂⁻ species. On the other hand, the neutral chloride CuCl species dominates the Cu(I) oxidation in the range of 0.1 M to 0.7 M chloride concentrations.     

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).