Flotation of oxidized minerals of copper using a new synthetic chelating reagent as collector

A new synthetic reagent containing a mixed aliphatic-aromatic structure, with a hydrocarbon chain and an aminothiophenol chelating group, has proven to be an effective collector for the flotation of chrysocolla minerals. The flotation is optimum in the narrow pH range of 5.5 to 6, falls sharply at pH 5, and is moderate in the pH range 7 to 11. Infrared spectra indicate that copper aminothiophenolate chelates are formed on the surface of the chrysocolla under the conditions of maximum flotation.     

The flotation of chrysocolla by mercaptan

Laboratory experiments have demonstrated that chrysocolla and malachite can be floated with a mercaptan as collector. In contrast, even when used in large quantities, the higher xanthate homologs (hexyl, dodecyl) will float malachite but not chrysocolla. The flotation of chrysocolla with mercaptan is readily accomplished in a pristine system, but in the presence of finely ground gangue particles, additions of the mercaptan to the grinding mill gave superior recoveries to those achieved when the mercaptan is added to the flotation cell. A model for the attachment of the mercaptan to the chrysocolla surface is proposed which involves the reaction of molecular mercaptan with the copper sites. This results in the formation of copper mercaptide at the surface and the splitting off of a molecule of water. By extension, this model should describe the reaction of mercaptan with any base metal oxide or sulfide mineral where the metal mercaptide is relatively insoluble.     

Angélica Copper Deposit: Exotic Type Mineralization in the Tocopilla Plutonic Complex of the Coastal Cordillera, Northern Chile

The Angélica copper deposit is situated at the southernmost sector of the Jurassic Tocopilla plutonic complex in the North Chilean Coastal Cordillera. This deposit occurs in monzonitic to monzodioritic rocks, and has platelike orebodies with no appreciable hydrothermal alteration nor sulfide mineralization. The mineralized zones are located in the western side of the two main normal faults with NE and NW orientations, and are characterized principally by impregnation of supergene copper products of atacamite and minor amounts of chrysocolla, lavendulan and “black copper”. Generally, chrysocolla is more abundant at a distal NE sector of the deposit. The black copper is Cu‐Fe‐Mn‐Si‐Cl‐rich multimineral aggregates composed of atacamite with minor amounts of quartz, pseudomalachite, dioptase, neotocite, gypsum, paratacamite and melanothallite, and its surface exhibits nanometer‐sized cylindrical morphologies. All these characteristics suggest an exotic origin for the Angélica copper deposit. A few vein‐type copper deposits situated at the southwestern sector along the NE‐oriented fault are inferred as the possible source of the Angélica copper deposit.     

Sulphidizing reactions in the flotation of oxidized copper minerals,II. Role of the adsorption and oxidation of sodium sulphide in the flotation of chrysocolla and malachite

The rate of consumption of sulphide in the sulphidizing reactions of malachite and chrysocolla has been measured. The oxidation of sulphide ions at the surface of sulphidized chrysocolla was shown to take place. The influence of thiosulphate anions on the xanthate flotation of sulphidized malachite and chrysocolla was investigated and it was shown to depress the flotation of chrysocolla strongly.The result suggest, that the presence of thiosulphate as a product of simultaneous oxidation can be one of the reasons for the more difficult flotation of sulphidized chrysocolla.     

Characterization and pore structure analysis of a copper ore containing chrysocolla

The physical and chemical characteristics of a chrysocolla-bearing copper ore have been investigated with special emphasis on elucidation of its pore structure through gas adsorption techniques. The effect of such variables as particle size and outgassing temperature on the pore structure and size distribution has been investigated in detail. The results obtained show that the chrysocolla is a microporous solid and that its microporous nature can be considerably altered by heat treatment around 550°C. A possible reason for the so-called “thermal activation of chrysocolla” has been postulated.     

Some secondary ore formation features of the Sar-Cheshmeh porphyry copper-molybdenum deposit,Kerman, Iran

New secondary mineral features and the control of secondary molybdenum enrichment have now been recognized at the Sar-Cheshmeh copper deposit. In part of the deposit, copper is locally concentrated within a subvolcanic unit — the so-called Late Fine Porphyry in amounts that seem too great to have come from the primary phase of the same unit. Clay minerals are believed to have influenced the deposition of copper by through-flowing oxidized zone solutions within this otherwise subeconomic unit. These solutions have caused argillic alteration and copper concentration within the plagioclase phenocrysts. Fractures are filled with chrysocolla, but little chrysocolla was observed within the altered plagioclase phenocrysts. The scattered layers of sedimentary unroofing breccia — horizontal layers of Quaternary age accumulated within the depressions at the top of the deposit — contain minor amounts of native copper. The breccia consists of angular to subangular clasts of local derivation cemented by a matrix of hematite, limonite, geothite, and small rock fragments. Native copper, the only copper mineral associated with the breccia, mainly adhers to the cavity walls in the cementing materials. The amount of molybdenum within the leached capping of the Sar-Cheshmeh deposit is generally controlled by the amount of pyrite. Abundant pyrite has caused the retention of molybdenum within the leached capping of the pyritic halo as a result of the more acidic solution during weathering, in contrast to the leached zone of the pyrite-poor stock, where molybdenum is partially mobile.     

The effect of thermal treatment on the flotation of chrysocolla

Flotation studies using a Hallimond tube have been carried out on purified samples of chrysocolla. The results confirm that by heating the sample to 550°C, flotation of the sulphidized sample with amyl xanthate is considerably improved. Flotation with sodium dodecyl sulphate is also considerably higher. The recovery with cationic collectors is not modified by the thermal treatment.Electrophoretic mobility measurements and flotation studies using benzene instead of air for the collection of the particles suggest that the increase in flotation after thermal treatment is a consequence of (1) an increase in the solubility of copper ions and their adsorption on to the surface of the particles, and (2) an increase of the intrinsic hydrophobicity of the particles due to condensation of some of the free silanol groups on their surface.     

The stabilizing effect of Na2S on the collector coating of chrysocolla

The heterogeneous reaction between natural and sulphidized chrysocolla and potassium amyl xanthate in solution is investigated.It is found that, together with the consumption of large amounts of xanthate, particles composed of the reaction products are spontaneously released from the surface of chrysocolla giving rise to a colloidal dispersion. In principle the mechamism is related to the peptizing effect of the excess xanthate ions that are found when Cu²⁺ and X^? ions are made to react in a homogeneous phase.In sulphidized chrysocolla this phenomenon is markedly reduced, showing that Na₂S has a stabilizing effect on the collector coating.Flotation experiments performed with aqueous amyl dixanthogen emulsions show that stable adhesion occurs only on properly sulphidized chrysocolla. It is believed that the mechanism controlling adhesion in this case is similar to that which determines the stability of the collector layer.     

The geochemistry of gossans associated with Sarcheshmeh porphyry copper deposit,Rafsanjan, Kerman,Iran: Implications for exploration and the environment

The Sarcheshmeh copper deposit is one of the world's largest Oligo-Miocene porphyry copper deposits in a continental arc setting with a well developed supergene sulfide zone, covered mainly by a hematitic gossan. Supergene oxidation and leaching, have developed a chalcocite enrichment blanket averaging 1.99% Cu, more than twice that of hypogene zone (0.89% Cu). The mature gossans overlying the Sarcheshmeh porphyry copper ores contain abundant hematite with variable amounts of goethite and jarosite, whereas immature gossans consist of iron-oxides, malachite, azurite and chrysocolla. In mature gossans, Au, Mo and Ag give significant anomalies much higher than the background concentrations. However, Cu has been leached in mature gossans and gives values close or even less than the normal or crustal content (< 36.7 ppm). Immature gossans are enriched in Cu (160.3 ppm), Zn (826.7 ppm), and Pb (88.6 ppm). Jarosite- and goethite-bearing gossans may have developed over the pyritic shell of most Iranian porphyry copper deposits with pyrite–chalcopyrite ratios greater than 10 and therefore, do not necessarily indicate a promising sulfide-enriched ore (Kader and Ijo). Hematite-bearing gossans overlying nonreactive alteration halos with pyrite–chalcopyrite ratios about 1.5 and quartz stringers have significant supergene sulfide ores (Sarcheshmeh and Miduk). The copper grade in supergene sulfide zone of Sarcheshmeh copper deposit ranges from 0.78% in propylitized rocks to 3.4% in sericitized volcanic rocks, corresponding to the increasing chalcopyrite–pyrite or chalcocite–pyrite ratios from 0.3 to 3, respectively. Immature gossans with dominant malachite and chrysocolla associated with jarosite and goethite give the most weakly developed enrichment zone, as at God-e-Kolvari. The average anomalous values of Au (59.6 ppb), Mo (42.5 ppm) and Ag (2.6 ppm) in mature gossans associated with the Sarcheshmeh copper mine may be a criterion that provides a significant exploration target for regional metallogenic blind porphyry ore districts in central Iranian volcano–plutonic continental arc settings. Drilling for new porphyry ores should be targeted where hematitic gossans are well developed. The ongoing gossan formation may result in natural acidic rock drainage (ARD).     

自然铜、铜合金矿物及其矿床形成机理新探索

描述了自然铜、铜合金矿物及其矿床形成的新机制。在岩浆及热液中，铜及铜合金可呈氢化物、羧基配合物及纳米粒子活性、迁移、富集形成自然铜矿床，或经以后的地质事件，长期、多次迁移富集，叠加形成富而大的自然铜矿床。在表生条件下，铜的硫化矿物被氧化分解，可形成亚铜的硫代硫酸盐及氯配合物，部分可形成铜的硫酸盐配合物迁移，由于硫代硫酸盐被氧化，亚铜岐化可形成高纯度的自然铜，但它易氧化形成孔雀石、蓝铜矿、赤铜矿、黑铜矿、硅孔雀石等，因此很难形成自然铜矿床。     

Mineral Paragenesis and Fluid Inclusions of Some Pluton-hosted Vein-type Copper Deposits in the Coastal Cordillera, Northern Chile

Abstract. Formation conditions of some vein-type copper deposits of the Tocopilla district (Deseada, San Jose, Santa Rosa) and the Gatico district (Yohanita, Toldo-Velarde, Argentina) in the Coastal Cordillera of northern Chile were inferred from mineral paragenesis and fluid inclusion data, and were compared with those of neighboring stratiform copper deposits. The vein-type copper deposits are hosted in Late Jurassic dioritic to quartz-dioritic plutons intruding extensively an andesite-dominant volcanic pile of the Jurassic La Negra Formation. Primary mineralization is characterized by chalcopyrite + magnetite + pyrite + bornite, and supergene alteration of these minerals produced anilite, covellite, atacamite and chrysocolla. The hypogene mineral assemblage indicates relatively high sulfur fugacity and weakly oxidized conditions, distinct from the stratiform copper deposits formed under low sulfur fugacity and moderately oxidized conditions. Furthermore, the fluid inclusion data of the vein-type deposits indicate high temperature (401–560C) and high salinity (39–68 wt% NaCl equiv.) ranges in contrast to the stratiform deposits, suggesting that this type of deposits formed by magma-associated hypersaline ore fluids.     

Copper mineralization in sedimentary cover associated with tectonic elements and volcanism in Israel

Copper mineralization occurs within the thick Cretaceous to Neogene sedimentary cover of central and northern Israel. Two distinct types of copper-rich anomalies are encountered. One form of copper mineralization is characterized by the presence of copper minerals such as malachite, atacamite, paratacamite, chrysocolla, and/or chalcopyrite forming veins and concretions within the sedimentary host rocks. The second type of copper enrichment is found dispersed within iron oxide veins associated with enrichments of other trace metals such as Ni, V, Zn, Co, Mo, and As. Both forms of copper anomalies lie along and are confined to the vicinity of tectonic elements. These features may be the surface expression of the longitudinal faults of the Dead Sea Rift Valley, of the transverse shear zone of southern and central Negev, or of the EW-trending horsts and grabens of central Israel. In many cases the copper anomalies are found near to or at the contact of volcanic bodies of intermediate to basic composition; in others, they are found in the vicinity of thermal springs. The fault zones may have provided conduits along which solutions, in places possibly briny, could have risen and leached subsurface mineralized volcanic or sedimentary bodies.     

Silikatische Kupferlagerstätten in Nordchile

The formation of isolated silicateous copper deposits is controlled by two main conditions:

1. oversaturation of groundwaters in silica
2. lateral inflow of copper bearing and slightly acid solutions originating from the oxidation of primary sulfide deposits.

The basic copper silicate chrysocolla is formed by chemisorption of copper ions by disilicic acid with a net-like structure. Under favourable conditions copper silicate deposits are formed which contain up to several million tons of copper as for example the La Exotica deposit in Northern Chile. The copper values of these deposits sometimes exceed those of the primary sulfide deposits. Thus, the oxidation of sulfide deposits, the migration of copper bearing solutions and the chemisorption of copper ions by the disilicic acid can result in workable new copper concentrations originating from sulfide protores. High concentrations of silica in groundwaters and thus the chemisorption of copper ions by the disilicic acid as an ore forming process is restricted to arid or semiarid regions. Therefore it is proposed to call such deposits arid silicateous infiltration deposits. Infiltration deposits are related to weathering processes. “They comprise products of weathering by which valuable substances were leached from the host rocks, migrated in groundwaters and were redeposited in other neighbouring rocks” (Smirnov, 1970, p. 324).     

Epigenetic hydrothermal origin of native copper and supergene enrichment in the Vista Alegre district,Paraná basaltic province,southernmost Brazil

Native copper is widespread in the Lower Cretaceous Paraná basaltic province, southern Brazil, both as films in fractures and as massive balls in amygdules. The focus of this investigation is on the large concentration of occurrences (n = 85) that forms the Vista Alegre district in the border region of Rio Grande do Sul and Santa Catarina states. The high average of 220 ppm Cu content of the basalts resulted in ore of native copper, Cu oxides, abundant chrysocolla in the top of mineralizations, and minor malachite and azurite. Native copper is associated with dioctahedral and trioctahedral smectites, zeolites (heulandite and clinoptilonite), quartz, and calcite, typical of a low-T (100–150°C) hydrothermal alteration assembly. The PGE distribution shows enrichment in Pd in relation to Pt both in basalts and in native copper, supporting the hypothesis of hydrothermal origin of the mineralization. No evidence was found of direct precipitation of copper from the lava; based on field and petrographic evidence, integrated with BSE images, EPMA analyses, EGP contents of native copper, and bulk rock analyses, this is an epigenetic hydrothermal copper mineralization, followed by supergene enrichment.     

Pleistocene recycling of copper at a porphyry system,Atacama Desert,Chile: Cu isotope evidence

We present Cu isotope data of hypogene and supergene minerals from the Late Paleocene Spence Cu-Mo porphyry in the Atacama Desert of northern Chile. Chalcopyrite displays a restricted range of δ⁶⁵Cu values within the values reported for primary porphyry Cu sulfides (+ 0.28‰ to + 0.34‰, n = 6). Supergene chalcocite samples show heavier and remarkably homogeneous δ⁶⁵Cu values, between + 3.91‰ and + 3.95‰ (n = 6), consistent with previous models of Cu leaching and enrichment in porphyry systems. Secondary Cu minerals from the oxide zone show a wider range of composition, varying from + 1.28‰ and + 1.37‰ for chrysocolla (n = 6) to very light Cu isotope signatures reported for atacamite between -5.72‰ to -6.77‰ (n = 17). These data suggest redox cycling of Cu during supergene enrichment of the Spence Cu deposit, characterized by a first stage of supergene chalcocite formation from acidic, isotopically-heavy leach fluids of meteoric origin down-flowing in a semi-arid climate (44 to ~ 15-9 Ma). Reworking of the initial supergene copper assemblage, during the Pleistocene, by rising neutral and chlorine-rich deep formation waters under well-established hyper-arid climate conditions lead to the formation of atacamite with extremely fractionated Cu compositions. Essentially coeval chrysocolla formed by dissolution of atacamite during short episodes of wetter climatic conditions occurring in the latest Pleistocene.     

新疆库车盆地康村地区砂岩型铜矿成矿模式研究

新疆库车盆地分布着一系列砂岩型铜矿床和矿点,文章在野外调查的基础上开展康村地区铜矿沉积环境和成矿模式研究,总结了区内沉积环境、沉积相与铜矿化体的配置关系,进而探讨了矿化成因和成矿模式。结果表明：康村地区新近系中可以识别出主要的沉积相类型有冲积扇相、扇三角洲相和湖泊相,以及5种亚相和7种微相。砂岩型铜矿化与沉积环境相关,矿(化)体主要分布在扇三角洲平原相和扇三角洲前缘相。2件样品LA-ICP-MS测年数据分别为427.4±6.6 Ma、387.3±3.3 Ma和424.6±2.3 Ma、279.9±6.8 Ma,表明康村地区中新统吉迪克组(N₁j)含铜砂砾岩的物源主要来自于库车盆地北西南天山造山带古生代晚志留世至早二叠世地质演化所形成的地层和岩浆岩产物。康村地区的矿化类型为砂岩型铜矿化,深部铜富集为硫酸盐热化学还原作用(TSR)型矿化成因,近地表矿化为后期盆地地上和地下卤水改造成因。库车盆地康村地区的铜矿化形成于新近系砂岩成岩之后,为后生富集,主要受新近纪后期断裂构造及后生卤水控制。     

滇西北烂泥塘斑岩铜矿床原生晕异常结构研究

烂泥塘矿床是云南香格里拉地区典型的斑岩型铜矿床,主矿体产于在地表以下300～500米,地表矿化带仅见脉状铜矿体和铜矿化体.为研究云南香格里拉烂泥塘斑岩铜矿床的原生晕异常结构,本文以异常结构模式理论和方法为基础,对矿床地表和坑道岩矿石样品开展了元素组合、异常特征和水平分带规律研究.结果表明,烂泥塘铜矿床地球化学系统的结构...     

青海祁漫塔格成矿带骆驼峰铜钼矿床地质特征及成因探讨

骆驼峰铜钼矿床是祁漫塔格成矿带新发现的斑岩型铜钼矿床,位于柴达木盆地西南缘,区内出露地层主要为古元古界金水口岩群片麻岩类;岩浆岩以印支期花岗闪长岩类为主,花岗闪长岩为区内主要含矿岩性;构造以北东向张性断裂为主,为区内主要的控矿构造。区内地表及外围矿体以热液脉型铜多金属矿为主,深部矿体以斑岩型钼矿为主,总体形成以含钼斑岩体为中心的斑岩型钼矿,外围为热液脉型铜多金属矿的岩浆热液成矿系列,从地表向深部总体具绿泥石化—钾化—硅化+绢英岩化的矿化蚀变分带特征,初步建立了“上铜下钼”的成矿模式,今后的找矿思路是加强对斑岩体时空分布、成矿物质来源及成矿对比的研究,进一步建立找矿模型,为祁漫塔格地区乃至东昆仑地区铜钼多金属矿床的找矿拓宽思路。     

An X-ray absorption spectroscopy study of the structure and reversibility of copper adsorbed to montmorillonite clay

X-ray absorption spectroscopy (XAS) and adsorption-desorption measurements have been performed to assess the relationship between the structure and reversibility of copper complexes on montmorillonite clay. By varying the solution pH and background electrolyte concentration, the adsorption of copper on either the edge sites or permanent charge sites of montmorillonite was controlled. This allowed the structure and reversibility of copper complexes on each of these site types to be assessed independently of each other. XAS analysis of copper adsorbed on the permanent charge sites indicated outer-sphere surface complexes, with these complexes showing sorption reversibility. For copper complexes formed on the edge sites of montmorillonite, XAS data confirmed the presence of monomer and dimer copper surface complexes. Sorption irreversibility at edge sites was noted at copper coverages less than 20 μmoles/g clay at pH=4.2 and at coverages greater than 50 μmoles/g clay at pH=6.8. At pH=6.8, higher Cu-Cu coordination numbers indicated the copper sorption irreversibility may be due, in part, to the formation of dimer surface complexes. The coordination numbers at pH=4.2 indicated the irreversibility could be due to the formation of dimers or due to formation of surface complexes on high energy edge sites.     

库车前陆盆地古－新近系铜矿化特征及铜的来源、富集分布初探

库车盆地铜成矿作用发生在新近纪,主要有砂岩型、泥岩型、灰岩型、含石英脉硫化物型铜矿化。矿化主要分布在盆地南部的秋里塔格构造带和北部的克拉苏构造带,基本位于背斜核部偏两翼部位,沿近东西向的断裂带呈带状分布,发育在盐丘附近。主要的地表铜矿物是氯铜矿,为干旱气候条件下含盐盆地的产物。盆地古近系蒸发岩电镜分析、石膏铜含量化学分析及新近系碎屑岩中铜含量变化分析结果表明：盐岩、膏岩,褐红色碎屑岩（粉砂岩、泥质粉砂岩、泥岩）为铜的矿源层,灰绿色粉砂岩、泥岩、灰白色（含砾）中粗砂岩为铜的含矿层。铜离子的运移载体为源自大气降水溶解蒸发岩所形成的卤水,卤水淋滤褐红色碎屑岩中的铜并下渗到地下,在以构造挤压为主及盐构造卸负作用产生流体上涌的驱动力下沿断裂向地表运移,随着卤水温度压力降低,在干旱气候条件下,在地表碎屑岩节理面、部分层理面上盐、膏、铜矿物析出,形成地表砂岩型、泥岩型、灰岩型铜矿化。如果含铜卤水经过被方解石交代的硬石膏带时,遇到由于TSR反应形成的还原硫、氧化－还原化学障,铜会发生富集,可能形成地下铜矿体。