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Belogubite CuZn(SO4)2 ⋅ 10H2O, a new mineral of the chalcanthite group, is found in the Gai (Gaiskoe) massive sulfide deposit, South Urals, Russia. This mineral forms aggregates of blue grains up to 1 mm. It is optically biaxial (–), np = 1.512(2), nm = 1.525(2), ng = 1.531(2), 2V = 70(10)°. The chemical composition of the holotype sample is as follows (wt %): 1.12 MgO, 0.10 MnO, 3.15 FeO, 8.98 CuO, 18.02 ZnO, 32.49 SO3, and 36.75 H2O, total 100.61. The empirical formula is (Cu0.55Zn0.45)Σ1.00(Zn0.64Fe0.22Mg0.14Mn0.01)Σ1.01S1.99O7.98 ⋅ 10.02H2O. The crystal structure of belogubite is studied using the single crystal method, R = 0.016. The mineral is triclinic, P $${{\bar {1}}}{\text{.}}$$ The unit cell parameters are: a = 6.2548(1), b = 10.6112(2), c = 6.0439(1) A, α = 82.587(1), β = 109.625(1), γ = 104.848(1)°, V = 364.81(1) A3, and Z = 1. The strongest reflections of the powder XRD pattern [dmeas., A (I, %) (hkl) are: 5.73 (35) (100), 5.576 (47) (–110), 4.873 (100) (–111), 3.907 (31) (021), 3.719 (45) (0 –21), 3.229 (27) (111), 2.915 (25) (–221), and 2.684 (26) (130).

The Sao Domingos area (Corte do Pinto, Portugal) represents a large sulfide ore deposit in the Iberian Pyrite Belt that was mined primarily for copper and sulfur in the past. Currently, the deserted mine and mine wastes are the reason for the production of acid mining drainage releasing potentially harmful elements. Because metastable secondary sulfates may temporary sink toxic pollutants, the in situ monitoring of their distribution is required. In this work, we tested a handheld Raman spectrometer equipped with a 532 nm laser excitation for this task. Twelve selected samples of complex composition were analyzed directly in the field using the handheld Raman spectrometer. For comparison, the collected samples were additionally analyzed through laboratory-based Raman spectroscopy and X-ray diffraction. Based on the in situ measurements, rozenite, melanterite, coquimbite, jarosite, metavoltine, chalcanthite, bonattite, antlerite, halotrichite-group minerals, gypsum, and sulfur were detected. The results show that handheld Raman spectrometer is comparable with other laboratory techniques and such handheld systems can be deployed successfully for monitoring of sulfate distribution directly on site.

Converter slags are by-products of pyrometallurgical processing of copper concentrates in Chile, which contain significant amounts of copper (close to 40.0% in the material considered here), converting them from a passive material (material that is not feasible to process) to an active material (it can be processed). This study analyses column leaching of converter slag with the use of ammonium hydroxide. A preliminary analysis was carried out on acid leaching (in an agitated system). Later, in ammonia medium, several variables were assessed, including particle size and NH4OH concentration, as well as different grades of acid purity to adjust the pH of the leaching solution. The experiments were carried out in 1.2 m high columns with a cross-section diameter of 7.5 × 10−2 m, using 2.0 kg of slag. The results show that using an acid system (i.e. ordinary leaching), reagent consumption reached 473.9 kg H2SO4/ton of slag, with copper recovery of only 50.8% and Fe recovery of over 67.0%. On the other hand, using an ammonia system, the recovery values reached 87.7% for Cu, with almost no impurities, with reagent consumption of 3.8 kg H2SO4/ton of slag. The working pH was 10.5. These recovery levels are due to the leaching of Cu2O and Cu° from the converter slag. When using an acid contaminated with impurities to adjust the pH, the copper extraction rate was increased. The impurities of antimony, bismuth and arsenic are not significant. The copper in pregnant solution (PLS) obtained was put into contact with NaSH to generate hydrated chalcanthite (CuSO4·5H2O) with a high grade of purity, while the remaining solution can be returned to the leaching stage due to its high level of ammonia content.

The Sarcheshmeh porphyry copper deposit (1.7 Gt @ 0.65% Cu, 0.02% Mo, 1.22 ppm Ag, 0.06 ppm Au) is one of the giant Miocene continental arc porphyry ore systems in the Tethyan metallogenic copper belt. The supergene sulfide ore zone (6 Mt. @ 2.43% Cu, 0.022% Mo, 1.55 ppm Ag and 0.114 ppm Au) is mainly capped by a hematitic gossan. This hematitic gossan is a possible surficial exploration target for unexposed porphyry copper ores. The total tonnage of waste rocks is about 2.6 G tonnes of gossanized as well as sulfide-bearing waste rocks with an average modal content of 10% pyrite-chalcopyrite. The gossanized waste rocks show boxwork texture and are composed of hematite, goethite, jarosite, malachite, chalcanthite, brochantite and delafossite. In order to assess the exploration, economic and environmental aspects of chalcophile and precious elements in the waste rocks, a total of 86 waste rocks and 10 residual gossan samples were collected by a systematic random sampling method, analysed by XRF and ICP-MS methods for major oxides and 50 minor and trace elements at ALS Minerals Lab, Ireland. The highly anomalous elements in immature residual gossans are Au (0.775 ppm), Ag (13.4 ppm) and Mo (122 ppm). The gossanized waste rocks are also enriched in Au (0.608 ppm), Ag (87 ppm) and Mo (2960 ppm). These geochemical signatures could be used as possible exploration guides for concealed porphyry copper deposits. The enrichment of Au, Ag and Mo is caused by the lower mobility of these elements in the immature gossans and gossanized waste rocks. The elemental enrichment factors normalized to the Sarcheshmeh ore zone are Au (2.50), Pd (1.05), Ag (4.67), Pb (4.6), Zn (17.34), Sn (2.64), W (1.47), Re (22.22), Se (5.38), Te (5.75), Tl (4.1), Bi (3.29), Ga (1.15), In (11.5), La (1.2), Ce (1.2) and Y (4.1), respectively. The mean contents of the most valuable by-product elements in the gossanized waste rocks include Cu (3168.2 ppm), Mo (180.22 ppm), Au (0.085 ppm), Ag (5.7 ppm), W (42.76 ppm), Re (0.01 ppm), Bi (10.87 ppm) and Se (13.45 ppm). The S-NNP diagram highlights that the sulfide-bearing waste rocks have also a negative impact on the environment, are prone to generate acid mine drainage (AMD) and release the potentially harmful metal (loids): Pb (107 ppm), Zn (365.3 ppm), As (83.53 ppm), Sb (10.24 ppm), In (0.44 ppm), and Se (13.45 ppm) into the surrounding area. These elemental values occurred at concentrations about 4–269 times greater than the crustal abundances and natural background of fresh granodiorite. As such, the heavy metal-rich gossans and sulfide-bearing waste rocks around the Sarcheshmeh mining areas may be considered as an exploration guide for valuable by-product elements as well as environmental concern.

Illicit trade in archaeology is a widespread phenomenon connected to the market of archaeological objects from clandestine excavations or faking manufacture, which includes bronze objects. As a consequence, authentication and provenance studies are required on objects of unknown provenance when they are recovered thanks to the investigation activity of the police, before returning them to the museums. Various strategies and approaches can be used to identify fake bronzes, as for instance patinas studies, since the corrosion can spontaneously occur over time, due to the interaction of the surface with the environment, or induced by artificial treatments, performed to mimic the archaeological aging effects in short time. The artificial patina has outward appearance and colours very similar to the natural patinas, but with different mineralogical composition. In this work, Raman spectroscopy is used to discriminate between artificial and natural patinas by a non-destructive approach, supported by the microanalysis SEM-EDS and optical microscope observations in the case of two ‘Etruscan-Roman’ bronze statuettes of illicit and unknown provenance, and demonstrates their recent and fake manufacture. Indeed, the patinas of both statuettes contain covellite, antlerite, langite, chalcanthite and rouaite, minerals or metastable chemical species traced back to corrosion induced by chemical attack and thermal treatment, as distinct from their stable polymorphs usually formed in burial condition. Moreover, we have not found evidence of the presence of malachite and azurite, typical of natural aged patinas. Finally, the abundance of Zn in the alloy suggest a modern manufacture.

Mining activity in Algares (Aljustrel Mine, Portuguese sector of the Iberian Pyrite Belt, IPB) stems prior to Roman times. As the orebody is vertical and relatively thin, mining was carried out mainly along underground adits (galleries). Nowadays, the deposit is considered exhausted and the area is being rehabilitated for a different use. The Algares +30 level adit intersects two volcanic units of the IPB Volcano-Sedimentary Complex. The massive sulphide and related stockwork zone are hosted by the Mine Tuff volcanic unit and are exposed in the walls of the gallery, showing intense hydrothermal alteration. Along the mine adit, the geological sequence is affected by strong oxidation and supergene alteration, giving rise to the formation of secondary minerals through the oxidation of the sulphides. The most common minerals found were melanterite (FeSO4&middot, 7H2O) and chalcanthite (CuSO4&middot, 5H2O), forming essentially massive or crystalline aggregates, ranging from greenish to bluish colours. Melanterite from the walls revealed to be Cu-rich by opposition to that from stalactites/stalagmites formed below the old ore storage silo revealing the low-copper-grade ores exploited underground. The mineralogy of the efflorescent salts was used to ascertain the processes involved in their formation, and moreover, the inventory of minerals is presented, as well as their principal characteristics.

Belogubite, ideally CuZn(SO 4 ) 2 ·10H 2 O, has been found in the supergene zone uncovered by the open pit at the Gayskoe massive sulfide Zn-Cu deposit (Orenburgskaya region, the South Urals, Russia). It is associated with dietrichite and may contain relics of quartz. Belogubite forms aggregates of blue grains up to 1 mm in size. The mineral is transparent with vitreous luster and white streak. Its color varies from pale equant to light blue. Cleavage and parting were not observed. The new mineral is brittle and has Mohsʼ hardness ca . 2½. Its density measured by floatation in bromoform+ethanol is 2.27(2) g/cm –3 , its calculated density is 2.249 g/cm –3 . Belogubite is biaxial (–), α = 1.512(2), β = 1.525(2), γ = 1.531(2); 2 V (meas.) = 70(10)°, 2 V (calc.) = 67.9°. Dispersion is noticeable, r

Voudourisite, Cd(SO4)·H2O, and lazaridisite, Cd3(SO4)3·8H2O, are two new minerals from the Esperanza Mine, Kaminiza Area, Lavrion Mining District, Greece. This small ancient mine is also the type locality of niedermayrite and katerinopoulosite. Further associated minerals are sphalerite, galena, edwardsite, chalcanthite, gypsum and greenockite. Both secondary minerals form tiny clusters or crusts and are among the latest to form in this paragenetic sequence. They are colourless or white, transparent to translucent, with a white streak and vitreous lustre. No fluorescence is observed. The minerals exhibit conchoidal fracture, no cleavage or preferred parting. The Mohs hardness is ~3 and both have brittle tenacity. Voudourisite is biaxial (–) with refractive indices at 589(1) nm of α = 1.580(2), β = 1.624(2), γ = 1.640(2), 2Vmeas.= 70(5)°, 2Vcalc.= 61° and β ~ || [010]. Lazaridisite is biaxial neutral with refractive indices at 589(1) nm of α = 1.552(2), β = 1.561(2), γ = 1.570(2), 2Vmeas.= 90(5)° and 2Vcalc.= 90°. The chemical compositions of voudourisite and lazaridisite are close to ideal with only minor amounts of copper detectable. The atomic arrangement in voudourisite (space groupP21/cwitha= 7.633(2),b= 7.458(2),c= 8.151(2) Å, β = 122.35(1)° andV= 392.0(2) Å3) is related to that of kieserite while lazaridisite (space groupC2/cwitha= 14.813(3),b= 11.902(2),c= 9.466(2) Å, β = 97.38(1)° andV= 1655.2(6) Å3) is a distinct structure-type. Calculated densities are 3.838 and 3.088 g/cm3, respectively.The strongest lines in the powder X-ray pattern [din Å (I) (hkl)] are: 4.890 (66) (110); 3.741 (25) (020); 3.578 (100) (11$\bar 2$); 3.230 (43) (200); 2.525 (33) (022); 2.395 (29) (112) for voudourisite and 6.860 (100) (200); 6.317 (72) (111); 5.965 (84) (020); 4.512 (58) (310); 3.727 (78) (202); 3.608(82)(13$\bar 1$); 3.109 (83) (40$\bar 2$); 3.020 (50) (33$\bar 1$) for lazaridisite, respectively.

Treating foot Odor infected with pathogenic fungus and bacteria has been a major concern for pharmaceutical companies. Finding a right treatment with minimum side effects has been of particular importance. This study configures a homemade topical powder mix in treating foot odor. The homemade topical powder mix is free of any harmful chemical constituents; its main constituents being Chalcanthite, Alum, and Clove. Energy dispersive X-ray fluorescence was used for the determination of the chemical composition component of Chalcanthite, Alum, Clove, and the powder mix of Chalcanthite, Alum, and Clove. XRF was able to measure elements such as Oxygen, Sulfur, Aluminum, Potassium, and Copper in kα line. The antimicrobial activity of the powder mix of Chalcanthite, Alum, and Clove was studied against two pathogenic fungi, which are Epidermophyton sp., and Trichophyton sp ., and two pathogenic bacteria, which are Brevibacterium sp., and Staphylococcus sp. Screening for antibacterial and antifungal was done using agar disk diffusion. The growth inhibition zone measured ranged from 16 to 28 mm for all the sensitive fungal, and ranged from 14 to 27 mm for the sensitive bacteria.

Secondary Cu and Cu-Ag sulphides are reported from altered metadiabases in the vicinity of a Neoproterozoic ophiolitic melange at the Zalm area in Saudi Arabia. The metadiabases occur in the form of NE-trending dykes forming resistant ridges with occasional chilled margins against a serpentinite host. Microscopic investigations revealed the occurrence of a peculiar assemblage of secondary Cu-bearing minerals down to the nanoscale. In most cases, secondary Cu and Cu-Ag sulphides formed at the expense of disseminated chalcopyrite (presumably argentian)± galena as the hypogene ore minerals. The most common textures are exclusively secondary and they are represented by “atoll” structure and rim replacement textures. The identification of ore minerals is based on combined ore microscopy and microchemistry of minerals. An assemblage of anilite-geerite-chalcocite intergrowth is recorded as the Cu sulphides, whereas mckinstryite (Ag1.18-1.19Cu0.80-0.81Fe0.01S) and stromeyerite (AgCu0.99Fe0.01S) are the extremely minute Cu-Ag sulphides that never exceed 5 μm in width. Ore fabrics and back-scattered electron (BSE) images clearly indicate that all phases of sulphides are secondary with some limited cationic substitution. Non-sulphides secondary Cu minerals are much more abundant and they are confined to rock fractures with visible hydrated Cu silicate (chrysocolla rimming hydrated Cu sulphate, as chalcanthite) that is either weakly crystalline or amorphous as indicated by the XRD data. Based on the chemical composition, ore textures and comparison with some world examples, it is believed that the Zalm Cu-Ag sulphides formed under oxidizing condition (pH = 5.8–7.2). As the temperature decreases, residual (stoichiometric) Ag2S is mobile in meteoric water. Precipitation of residual Ag continued down to 93.3 °C to form stromeyerite (i.e. late hydrothermal). During late stages of supergene alteration at the studied Zalm occurrence, loss of CO2 leads to the formation of Cu-bearing carbonates, sulphates and finally silicates at a very characteristic low S2 fugacity at shallow depths or at surface (i.e. supergene).

The weathering processes of seafloor massive sulfide (SMS) deposits would significantly change the mineralogy and geochemistry of sulfides. The key to understanding the oxidation of SMS deposits lies in clarifying the metal mobilization during the oxidation of submarine sulfides by seawater and Fe-Si-rich hydrothermal fluids. We present the morphology, mineralogy, and geochemistry of secondary minerals and oxyhydroxides from the Xunmei hydrothermal field on the Southern Mid-Atlantic Ridge (SMAR) to illuminate their diverse characteristics and origins, further elaborating detailed submarine oxidation processes of sulfide mounds. Under the oxygenated seawater environments, the pyrite/marcasite and chalcopyrite were oxidized to Fe (oxyhydr)oxides and secondary Cu minerals (e.g., covellite, paratacamite/atacamite, and chalcanthite), respectively. The metal speciation in the sulfides (e.g., pyrite, marcasite, and chalcopyrite) controls the metal mobilization during oxidation. Cobalt and As in the crystal lattice of pyrite and marcasite vary over variations in Fe and S, respectively. Zinc, Ag, and Pb that occur as micron-inclusions in the pyrite, marcasite, and chalcopyrite are easily released during the galvanic interaction, of which mechanism is applicable to Cu-inclusions in the pyrite and marcasite. Compared to the enrichment of Zn and Ag in the secondary minerals via adsorption, Pb is depleted because of its high solubility in the seawater. The mineralization of amorphous oxyhydroxides includes low-temperature Si-rich precipitation and later oxidative weathering processes. The Si-rich hydrothermal fluids dissolve the basalt enriched in plagioclase and V-rich clay minerals to precipitate V-rich Si-Al oxyhydroxides. Subsequently, the flowing Si-rich hydrothermal fluids evoke precipitation of amorphous silica due to conductive cooling. As the alteration proceeds, a genetic scenario for the formation of Fe and Si oxyhydroxides is proposed. The Fe-Si-rich hydrothermal fluids alter the sulfides to Fe-Si oxyhydroxides and then Fe oxyhydroxides with an increasing trend of Fe, Cu, Zn, and Co. Our results unravel the metal mobilization during the weathering processes of submarine sulfides, establish a scenario for the formation of oxyhydroxides associated with sulfides, and predict the effect of oxidation on the economic values of sulfides.

This paper demonstrates the results of experiments for the determination of the composition of gases during the dehydration of sulfates (Na-jarosite, melanterite, and chalcanthite) collected at the surface of pyrometallurgical waste heaps. The volatilization of various elements, and vapor&ndash, gas phase transport from three sulfate groups were investigated by stepwise laboratory heating at 45, 55, and 65 &deg, C. The sample of yellow efflorescence mainly consisted of Na-jarosite, the white efflorescence contained melanterite as the major mineral, and the blue efflorescence sample consisted of chalcanthite. These all contained a few impurities up to 5 %. The highest total dissolved solids (TDS) was found in the gas condensates from melanterite (59 mg/L), followed by chalcanthite (29 mg/L) and Na-jarosite (17 mg/L). It was determined that major and trace elements in the condensate can be trapped by water vapor and can migrate with the vapor phase during the desorption and dehydration of hydrous sulfates. X-ray diffractograms showed that Na-jarosite remained stable throughout the temperature range, whilst the separation of melanterite&rsquo, s structural water occurred at 40 &deg, C, and chalcanthite completely lost two water molecules at 50 &deg, C. The gas condensates contained acetates and formates, which could be the fermentation products of bacterial communities. Some of the strains&mdash, Micrococcaceae sp., Bacillus sp., and Microbacteriaceae sp.&mdash, were cultivated.

The aim of this study is to investigate the potential of anti-osteoarthritis effects on egg white-chalcanthite (EC), purple bamboo salts (PBS), and a mixture of EC and PBS (EC+PBS). EC is a mixture of egg white and pulverized chalcanthite. PBS has been widely used as one of functional foods in Korea and shows unique features compared with common salt. Osteoarthritis was induced by intra-articular injection of monosodium iodoacetate (MIA, 4mg/kg bw) in Sprague-Dawley (SD) rats. Test substances were administered once daily for 6 weeks at doses of 10 mg EC, EC+100 mg PBS, EC+200 mg PBS before and after MIA injection. Each substance was assessed by blood chemistry parameters, and by serum cytokines including IL-1β and IL-6, and nitric oxide (NO) and prostaglandin-E2 (PGE2). Structural changes of articular cartilage were also evaluated by histopathological examination. As a result, body weight and blood chemistry parameter were not different in all experimental groups. EC+PBS mixture reduced the production of PGE2, NO, IL-1β, and IL-6. In histological grade of osteoarthritis, EC+PBS mixture had a tendency to ameliorate damage of articular cartilage induced by MIA in a dose-dependent manner. In conclusion, EC+PBS mixture was demonstrated to have a potential for anti-inflammatory effect against osteoarthritis induced by MIA in a dose-dependent manner.

The effect of the nature of the copper salt precursor anion and the pH of a solution on the morphology and the phase composition of CuS particles has been studied upon precipitation from thiourea solutions. It has been established that, irrespective of the precipitation conditions, generation of the CuS phase and the chalcanthite impurity phase CuSO4 • 5H2O is recorded according to the X-ray diffraction analysis data. At pH 8 and a c((NH2)2CS): c(Cu2+) ratio of 1: 1, from nitrate solutions a fine powder is formed that consists of spherical particles smaller than 100 nm in size. An increase in the c((NH2)2CS): c(Cu2+) ratio and in the precipitation pH results in coarser particles of up to 1.5 μm in size. The replacement of the salt precursor anion by SO42- facilitates the decrease in the spherical particle size to 1 μm and that by Cl– to 0.7 μm. The synthesis conditions of the CuS sorbent that control the latter’s morphological properties have an effect on the sorption of cadmium from aqueous solutions.

The new minerals fermiite (IMA2014-068), Na4(UO2)(SO4)3·3H2O and oppenheimerite (IMA2014-073), Na2(UO2)(SO4)2·3H2O, were found in the Blue Lizard mine, San Juan County, Utah, USA, where they occur together as secondary alteration phases in association with blödite, bluelizardite, chalcanthite, epsomite, gypsum, hexahydrite, kröhnkite, manganoblödite, sideronatrite, tamarugite and wetherillite.Fermiite descriptive details: pale greenish-yellow prisms; transparent; vitreous lustre; bright greenishwhite fluorescence; white streak; hardness (Mohs) 2½; brittle; conchoidal fracture; no cleavage; slightly deliquescent; easily soluble in RT H2O; densitymeas = 3.23(2) g cm–3; densitycalc = 3.313 g cm–3. Optically, biaxial (+), α = 1.527(1), β = 1.534(1), γ = 1.567(1) (white light); 2Vmeas.= 51(1)°, 2Vcalc.= 50°; dispersionr 3σI) contains [(UO2)(SO4)3] chains that are linked by bonds involving five different Na–O polyhedra to form a framework. The mineral is named for Italian-American theoretical and experimental physicist Dr. Enrico Fermi (1901–1954).Oppenheimerite descriptive details: pale greenish-yellow prisms; transparent; vitreous lustre; bright greenish-white fluorescence; white streak; hardness (Mohs) 2½; slightly sectile; three good cleavages, {110}, {011} and {101}; irregular fracture; slightly deliquescent; easily soluble in RT H2O; densitycalc = 3.360 g cm–3. Optically, biaxial (+), α = 1.537(1), β = 1.555(1), γ = 1.594(1) (white light); 2Vmeas.= 72(2)°, 2Vcalc.= 70°; dispersion isr>v, moderate, inclined; optical orientation:X≈ ⊥ {101},Z≈ [111]; pleochroism: X very pale greenish yellow, Y pale greenish yellow, Z greenish yellow; X < Y < Z. EDS analyses yielded the empirical formula Na1.94(U0.97O2)(S1.02O4)2(H2O)3. Oppenheimerite is triclinic,P1,a= 7.9576(6),b= 8.1952(6),c= 9.8051(7) Å, α = 65.967(5), β = 70.281(5), γ = 84.516(6)°,V= 549.10(8) Å3andZ= 2. The structure (R1= 3.07% for 2337Io> 3σI) contains [(UO2)(SO4)2(H2O)] chains that are linked by bonds involving two different Na–O polyhedra to form a framework. The mineral is named for American theoretical physicist Dr. J. Robert Oppenheimer (1904–1967).

The former Sherritt–Gordon sulfide deposit in Sherridon, Manitoba, Canada, was mined for zinc, copper, silver, and gold between 1930 and 1951. Since mine closure, two high-sulfide tailings impoundments underwent extensive oxidation, resulting in the release of very high concentrations of dissolved sulfate and metals to the tailings porewater. During precipitation events and Spring freshet, surface seeps develop along the flanks of the impoundments, discharging groundwater with a pH as low as 0.39 and dissolved concentrations of sulfate and iron up to 203 g L−1 and 68 g L−1, respectively, along with other metals at elevated concentrations. Several efflorescent minerals were observed within groundwater-seepage areas. Using a combination of powder X-ray diffraction and energy-dispersive spectroscopy, secondary efflorescent sulfate minerals at seepage zones were identified, including melanterite, rozenite, halotrichite, chalcanthite, alpersite, copiapite, hexahydrite, jurbanite, pickeringite, jarosite, and gypsum. According to geochemical modeling of seepage waters using a modified WATEQ4F database for ferrous and ferric sulfate minerals, the occurrence of most of the observed sulfate salts was favored. In the geochemical modeling, we used data available for seepage waters that were representative of discharging water after mineral precipitation had already occurred. Discrepancies between some of the observed and modeled results likely reflect the use of water compositions representative of the later stages in the reaction sequence rather than the composition during actual formation of the minerals. The formation of these secondary efflorescent minerals resulted in a temporary removal of sulfate and metals from solution. These minerals rapidly dissolved during laboratory dissolution tests; this would result in increased loading to receiving surface waters during precipitation events and Spring freshet.

The new minerals bobcookite (IMA 2014-030), NaAl(UO2)2(SO4)4·18H2O and wetherillite (IMA 2014-044), Na2Mg(UO2)2(SO4)4·18H2O, were found in the Blue Lizard mine, San Juan County, Utah, USA, where they occur together as secondary alteration phases in association with boyleite, chalcanthite, dietrichite, gypsum, hexahydrite, johannite, pickeringite and rozenite.Bobcookite descriptive details: lime green to greenish-yellow massive veins and columnar crystals; transparent; vitreous lustre; bright greenish-white fluorescence; pale greenish yellow streak; hardness (Mohs) 2½; brittle; conchoidal fracture; no cleavage; moderately hygroscopic; easily soluble in cold H2O; densitycalc= 2.669 g cm–3. Optically, biaxial (–), α = 1.501(1), β = 1.523(1), γ = 1.536(1) (white light); 2Vmeas.= 78(1)°; 2Vcalc.= 74°; dispersionr 4σF) contains [(UO2)(SO4)2(H2O)] chains linked by NaO4(H2O)2octahedra to form layers. Hydrogen bonds to insular Al(H2O)6 octahedra and isolated H2O groups hold the structure together. The mineral is named for Dr Robert (Bob) B. Cook of Auburn University, Alabama, USA.Wetherillite descriptive details: pale greenish-yellow blades; transparent; vitreous lustre; white streak; hardness (Mohs) 2; brittle; two cleavages, {101} perfect and {010} fair; conchoidal or curved fracture; easily soluble in cold H2O; densitycalc= 2.626 g cm–3. Optically, biaxial (+), α = 1.498(1), β = 1.508(1), γ = 1.519(1) (white light); 2Vmeas.= 88(1)°, 2Vcalc.= 87.9°; dispersion isr 4σF) contains [(UO2)(SO4)2(H2O)] sheets parallel to {100}. Edge-sharing chains of Na(H2O)5O polyhedra link adjacent uranyl sulfate sheets forming a weakly bonded three-layer sandwich. The sandwich layers are linked to one another by hydrogen bonds through insular Mg(H2O)6octahedra and isolated H2O groups. The mineral is named for John Wetherill (1866–1944) and George W. Wetherill (1925–2006).

A new mineral, hilarionite, ideally Fe 2 3+ (SO4)(AsO4)(OH) · 6H2O, has been found in the Hilarion Mine, Agios Konstantinos, Kamariza, Lavrion district, Attiki Prefecture, Greece. It was formed in the oxidation zone of a sulfide-rich orebody in association with goethite, gypsum, bukovskyite, jarosite, melanterite, chalcanthite, allophane, and azurite. Hilarionite occurs as light green (typically with an olive or grayish tint) to light yellowish green spherulites (up to 1 mm in size) and bunches of prismatic to acicular “individuals” up to 0.5 mm long that are in fact near-parallel or divergent aggregates of very thin, curved fibers up to 0.3 mm long and usually lesser than 2 μm thick. The luster is silky to vitreous. The Mohs’ hardness is ca. 2. Hilarionite is ductile, its “individuals” are flexible and inelastic; fracture is uneven or splintery. D(meas) = 2.40(5), D(calc) = 2.486 g/cm3. IR spectrum shows the presence of arsenate and sulfate groups and H2O molecules in significant amounts. The Mossbauer spectrum indicates the presence of Fe3+ at two six-fold coordinated sites and the absence of Fe2+. Hilarionite is optically biaxial (+), α = 1.575(2), γ = 1.64(2), 2V is large. The chemical composition (electron microprobe, average of 7 point analyses; H2O determined by modified Penfield method) is as follows, wt %: 0.03 MnO, 0.18 CuO, 0.17 ZnO, 33.83 Fe2O3, 0.22 P2O5, 18.92 As2O5, 22.19 SO3, 26.3 H2O, total is 101.82%. The empirical formula calculated on the basis of 15 O is: (Fe 1.90 3+ Cu0.01Zn0.01)Σ1.92[(SO4)1.24(AsO4)0.74(PO4)0.01]Σ1.99(OH)1.01 · 6.03H2O. The X-ray powder diffraction data show close structural relationship of hilarionite and kaňkite, Fe 2 3+ (AsO4)2 · 7H2O. Hilarionite is monoclinic, space group C2/m, Cm or C2, a = 18.53(4), b = 17.43(3), c = 7.56(1) A, β = 94.06(15)°, V = 2436(3) A3, Z = 8. The strongest reflections in the X-ray powder diffraction pattern (d, A-I[hkl]) are: 12.66–100[110], $$7.60 - 6[00\bar 1]$$ , 5.00–10[22l], $$4.70 - 10[31\bar 1]$$ , 4.33–7[040]. Hilarionite is named after its type locality.

*Corr esponding author Bluelizardite (IMA 2013-062), Na 7 (UO 2 )(SO 4 ) 4 Cl(H 2 O) 2 , is a new uranyl sulfate mineral from the Blue Lizard mine, San Juan County, Utah (USA). It was found in a sandstone matrix and is associated with chalcanthite, copiapite, ferrinatrite, gypsum, krohnkite, johannite, and several other new, unnamed Na- and Mg-containing uranyl sulfates. Bluelizardite is a supergene mineral formed by the post-mining weathering of uraninite. The mineral is monoclinic, C2/c, with a = 21.1507(6), b = 5.3469(12), c = 34.6711(9) A, β = 104.913(3)°, V = 3788.91(17) A 3 and Z = 8. Crystals are blades up to 0.4 mm long, flattened on {001}, elongated parallel to [010] and exhibiting the forms {100}, {001} and {111}. Bluel izardite is pale yellow and has a yellowish-white streak. It has good cleavage on {001} and uneven fracture. The Mohs hardness is estimated at 2. The calculated density based on the empirical formula is 3.116 g/cm 3 . Bluelizardite exhibits bright yellow-green fluorescence under both long- and short-wave UV radiation. The mineral is optically biaxial (–), with α = 1.515(1), β = 1.540(1) and γ = 1.545(1) (measured with white light). The measured 2V is 48(2)° and the calculated 2V is 47.6°. The mineral does not exhibit any dispersion or pleochroism. The optical orientation is X = b, Y ≈ a, Z ≈ c*. The empirical formula of bluelizardite is Na 6.94 (U 1.02 O 2 )(SO 4 ) 4.00 Cl 0.94 O 0.06 (H 2 O) 2 (based on 21 anions pfu). The Raman

Meisserite (IMA2013-039), Na5(UO2)(SO4)3(SO3OH)(H2O), is a new uranyl sulfate mineral from the Blue Lizard mine, San Juan County, Utah (USA). It is named in honour of the prominent Swiss mineralogist Nicolas Meisser. The new mineral was found in a sandstone matrix and is associated with chalcanthite, copiapite, ferrinatrite, gypsum, johannite and another new Na-bearing uranyl sulfate, belakovskiite (IMA2013-075). Meisserite is a secondary mineral formed by the post-mining weathering of uraninite. The mineral is triclinic,P,a= 5.32317(10),b= 11.5105(2),c= 13.5562(10) Å, α = 102.864(7)°, β = 97.414(7)°, γ = 91.461(6)°,V= 801.74(6) Å3, andZ= 2. Crystals are prisms elongated on [100], up to 0.3 mm long, exhibiting the forms {010} and {001}. Meisserite is pale green to yellowish green, translucent to transparent and has a very pale yellow streak. It is brittle, with fair cleavage on {100} and {001}, and uneven fracture. The Mohs hardness is estimated at 2. Meisserite is somewhat hygroscopic and easily soluble in water. The calculated density based on the empirical formula is 3.208 g/cm3. Meisserite exhibits bright yellow green fluorescence under both long- and shortwave UV radiation. The mineral is optically biaxial (–), with α = 1.514(1), β = 1.546(1), γ = 1.557(1) (measured in white light). The measured 2V is 60(2)° and the calculated 2V is 60°. Dispersion isr > v, perceptible, and the optical orientation isX≈a,Z≈c*. The mineral is pleochroic, withX(colourless) 3σI) is topologically unique among known structures of uranyl minerals and inorganic compounds. It contains uranyl pentagonal bipyramids linked by SO4groups to form chains. Na+cations bond to O atoms in the chains and to an SO3OH group and an H2>O group between the chains, thereby forming a heteropolyhedral framework.

Camaronesite (IMA 2012-094), [Fe3+(H2O)2(PO3OH)]2(SO4)·1–2H2O, is a new mineral from near the village of Cuya in the Camarones Valley, Arica Province, Chile. The mineral is a low-temperature, secondary mineral occurring in a sulfate assemblage with anhydrite, botryogen, chalcanthite, copiapite, halotrichite, hexahydrite, hydroniumjarosite, pyrite, römerite, rozenite and szomolnokite. Lavender-coloured crystals up to several mm across form dense intergrowths. More rarely crystals occur as drusy aggregates of tablets up to 0.5 mm in diameter and 0.02 mm thick. Tablets are flattened on {001} and exhibit the forms {001}, {104}, {015} and {018}. The mineral is transparent with white streak and vitreous lustre. The Mohs hardness is 2½, the tenacity is brittle and the fracture is irregular, conchoidal and stepped. Camaronesite has one perfect cleavage on {001}. The measured and calculated densities are 2.43(1) and 2.383 g/cm3, respectively. The mineral is optically uniaxial (+) with ω = 1.612(1) and ε = 1.621(1) (white light). The pleochroism is O (pale lavender) > E (colourless). Electron-microprobe analyses provided Fe2O331.84, P2O529.22, SO315.74, H2O 23.94 (based on O analyses), total 100.74 wt.%. The empirical formula (based on 2 P a.p.f.u.) is: Fe1.94(PO3OH)2(S0.96O4)(H2O)4·1.46H2O. The mineral is slowly soluble in concentrated HCl and extremely slowly soluble in concentrated H2SO4. Camaronesite is trigonal, R32, with cell parameters:a = 9.0833(5), c = 42.944(3) Å, V = 3068.5(3) Å3 and Z = 9. The eight strongest lines in the X-ray powder diffraction pattern are [dobs Å (I)(hkl)]: 7.74(45)(101), 7.415(100)(012), 4.545(72)(110), 4.426(26)(018), 3.862(32)(021,202,116), 3.298(93)(027,119), 3.179(25)(208) and 2.818(25)(1·1·12,125). In the structure of camaronesite (R1 = 2.28% for 1138 Fo > 4σF), three types of Fe octahedra are linked by corner sharing with (PO3OH) tetrahedra to form polyhedral layers perpendicular to c with composition [Fe3+(H2O)2(PO3OH)]. Two such layers are joined through SO4 tetrahedra (in two half-occupied orientations) to form thick slabs of composition [Fe3+(H2O)2(PO3OH)]2(SO4). Between the slabs are partially occupied H2O groups. The only linkages between the slabs are hydrogen bonds. The most distinctive component in the structure consists of two Fe octahedra linked to one another by three PO4 tetrahedra yielding an [Fe2(PO4)3] unit. This unit is also the key component in the sodium super-ionic conductor (NASICON) structure and has been referred to as the lantern unit. The polyhedral layers in the structure of camaronesite are similar to those in the structure of taranakite. The Raman spectrum exhibits peaks consistent with sulfate, phosphate, water and OH groups.

A new mineral, yaroshevskite, ideally Cu9O2(VO4)4Cl2, occurs in sublimates collected from the Yadovitaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with euchlorine, fedotovite, hematite, tenorite, lyonsite, melanothallite, atlasovite, kamchatkite and secondary avdoninite, belloite and chalcanthite. Yaroshevskite forms isolated prismatic crystals, up to 0.1 × 0.15 × 0.3 mm in size, on the surface of euchlorine crusts. The mineral is opaque and black, with a reddish black streak and lustre between metallic and adamantine. Yaroshevskite is brittle, no cleavage was observed and the fracture is uneven. The Mohs hardness is ~3½ (corresponding to a mean VHN micro-indentation hardness of 172 kg mm -2) and the calculated density is 4.26 g cm-3. In reflected light, yaroshevskite is grey with a weak bluish hue. Pleochroism, internal reflections and bireflectance were not observed. Anisotropy is very weak. The composition (wt.%) determined by electron microprobe is: CuO 61.82, ZnO 0.53, Fe2O30.04, V2O531.07, As2O50.32, MoO31.56, Cl 6.23, O=Cl21.41; total 100.16. The empirical formula, calculated on the basis of 20 (O + Cl) anions is (Cu8.80Zn0.07Fe0.01)Σ 8.88(V3.87Mo0.12As0.03)σ 4.02O18.01Cl1.99. Yaroshevskite is triclinic, space groupP,a= 6.4344(11),b= 8.3232(13),c= 9.1726(16) Å , α = 105.338(14), β = 96.113(14), γ = 107.642(1)°,V= 442.05(13) Å3andZ= 1. The nine strongest reflections in the X-ray powder pattern [dobs in Å (I)(hkl)] are as follows: 8.65(100)(001); 6.84(83)(01); 6.01(75)(100); 5.52(60)(01); 4.965(55)(011); 4.198(67)(1); 4.055(65)(110); 3.120(55)(021); 2.896(60)(21,003,20). The crystal structure was solved by direct methods from single-crystal X-ray diffraction data and refined toR= 0.0737. The yaroshevskite structure is unique. It is based on corrugated layers made up of chains of edge-sharing flat squares with central Cu2+cations [Cu(1), Cu(4) and Cu(5)]; neighbouring chains are connected via groups consisting of three Cu2+-centred squares [two Cu(3) and Cu(6)]. Neighbouring layers are connected via pairs of Cu(2)O4Cl five-coordinate polyhedra and isolated VO4tetrahedra. The structure of yaroshevskite can also be considered in terms of oxygen-centred tetrahedra: O(7)Cu4tetrahedra are connected via common Cu(4) and Cu(5) vertices to form pyroxene-like chains [O2Cu6]∞. In this context, the structural formula can be written Cu3[O2Cu6][VO4]4Cl2. The mineral name honours the Russian geochemist Alexei A. Yaroshevsky (b. 1934) of Moscow State University.

This study describes geochemical barriers that have developed at three different localities in sulfiderich tailings in the Kemerovo region of Western Siberia, Russia. Iron oxyhydroxides, gypsum, malachite, chalcanthite, goslarite, bianchite, gunningite and copper and zinc chlorides crystallized in the sequence specified at an evaporative barrier around glassy slag produced by the Belovo zinc processing plant. A complex cemented barrier that has developed within the old Salair sulfide tailings contains two well defined layers: an upper layer containing Fe(III) minerals and gypsum as cements in which Pb, As, Mo, Ni and Co have been deposited; and (2) a lower calcite- and gypsum-bearing layer, in which phases containing Zn, Cd and Cu have been deposited. A complex organic-mineral barrier below the Ursk sulfide tailings consists of peaty organic matter, clay minerals and iron oxyhydroxides cemented by gypsum. Elements that have leached from the tailings are present in this barrier in a variety of different forms: Ca and Mn are present as water-soluble species; Cu, Fe and Zn are present as species produced by interaction with organic matter via ion-exchange, metal humate formation and cation bridging in organic-mineral complexes; Pb and As are co-precipitated with and/or adsorbed onto iron oxyhydroxides; gold has been deposited as minute particles of native metal. The mechanisms for the formation of the different geochemical barriers are discussed.

X-ray diffraction analysis was used to monitor patina composition on copper samples exposed during one-year period to different seawater zones (splash, tidal and full immersion) and marine atmospheric aerosols. Two phases contributed most to patina formation: cuprite (copper oxide) and atacamite (copper chloride compound). Their relative XRD spectra intensities were very similar in patina formed in the tidal sea zone, but atacamite became the sole majority phase in the full immersion zone. The cuprite phase decreased over time, and two minority copper sulfates phases appeared: posnjakite and chalcanthite (CuSO4). The results revealed that copper patina composition is strongly influenced by chloride pollution and specific zone conditions. Additional factors, such as wind-blown sand, continuous dredging in coastal areas and vessel docking, influenced degree of pollutant compound adherence to patinas and consequently their structure (porous or compact).

Meridianiite, MgSO4·11H2O, is the most highly hydrated phase in the binary MgSO4–H2O system. Lower hydrates in the MgSO4–H2O system have end-member analogues containing alternative divalent metal cations (Ni2+, Zn2+, Mn2+, Cu2+, Fe2+, and Co2+) and exhibit extensive solid solution with MgSO4 and with one another, but no other undecahydrate is known. We have prepared aqueous MgSO4 solutions doped with these other cations in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. The solid products have been characterised by X-ray powder diffraction, and the onset of partial melting has been quantified using a thermal probe. We have established that of the seven end-member metal sulfates studied, only MgSO4 forms an undecahydrate; ZnSO4 forms an orthorhombic heptahydrate (synthetic goslarite), MnSO4, FeSO4, and CoSO4 form monoclinic heptahydrates (syn. mallardite, melanterite, bieberite, respectively), and CuSO4 crystallises as the well-known triclinic pentahydrate (syn. chalcanthite). NiSO4 forms a new hydrate which has been indexed with a triclinic unit cell of dimensions a = 6.1275(1) A, b = 6.8628(1) A, c = 12.6318(2) A, α = 92.904(2)°, β = 97.678(2)°, and γ = 96.618(2)°. The unit-cell volume of this crystal, V = 521.74(1) A3, is consistent with it being an octahydrate, NiSO4·8H2O. Further analysis of doped specimens has shown that synthetic meridianiite is able to accommodate significant quantities of foreign cations in its structure; of the order 50 mol. % Co2+ or Mn2+, 20–30 mol. % Ni2+ or Zn2+, but less than 10 mol. % of Cu2+ or Fe2+. In three of the systems we examined, an ‘intermediate’ phase occurred that differed in hydration state both from the Mg-bearing meridianiite end-member and the pure dopant end-member hydrate. In the case of CuSO4, we observed a melanterite-structured heptahydrate at Cu/(Cu + Mg) = 0.5, which we identify as synthetic alpersite [(Mg0.5Cu0.5)SO4·7H2O)]. In the NiSO4- and ZnSO4-doped systems we characterised an entirely new hydrate which could also be identified to a lesser degree in the CuSO4- and the FeSO4-doped systems. The Ni-doped substance has been indexed with a monoclinic unit-cell of dimensions a = 6.7488(2) A, b = 11.9613(4) A, c = 14.6321(5) A, and β = 95.047(3)°, systematic absences being indicative of space-group P21/c with Z = 4. The unit-cell volume, V = 1,176.59(5) A3, is consistent with it being an enneahydrate [i.e. (Mg0.5Ni0.5)SO4·9H2O)]. Similarly, the new Zn-bearing enneahydrate has refined unit cell dimensions of a = 6.7555(3) A, b = 11.9834(5) A, c = 14.6666(8) A, β = 95.020(4)°, V = 1,182.77(7) A3, and the new Fe-bearing enneahydrate has refined unit cell dimensions of a = 6.7726(3) A, b = 12.0077(3) A, c = 14.6920(5) A, β = 95.037(3)°, and V = 1,190.20(6) A3. The observation that synthetic meridianiite can form in the presence of, and accommodate significant quantities of other ions increases the likelihood that this mineral will occur naturally on Mars—and elsewhere in the outer solar system—in metalliferous brines.

A new mineral species, markascherite (IMA2010-051), ideally Cu3(MoO4)(OH)4, has been found at Copper Creek, Pinal County, Arizona, U.S.A. The mineral is of secondary origin and is associated with brochantite, antlerite, lindgrenite, wulfenite, natrojarosite, and chalcanthite. Markascherite crystals are bladed (elongated along the b axis), up to 0.50 × 0.10 × 0.05 mm. The dominant forms are {001}, {100}, and {010}. Twinning is found with the twofold twin axis along [101]. The mineral is green, transparent with green streak and vitreous luster. It is brittle and has a Mohs hardness of 3.5~4; cleavage is perfect on {100} and no parting was observed. The calculated density is 4.216 g/cm 3 . Optically, markascherite is biaxial (–), with nα >1.8, nβ > 1.8, and nγ >1.8. The dispersion is strong (r > v). It is insoluble in water, acetone, or hydrochloric acid. An electron microprobe analysis yielded an empirical formula Cu2.89(Mo1.04O4)(OH)4. Markascherite, polymorphic with szenicsite, is monoclinic, with space group P21/m and unit-cell parameters a = 9.9904(6), b = 5.9934(4), c = 5.5255(4) A, β = 97.428(4)°, and V = 328.04(4) A 3 . Its structure is composed of three nonequivalent, markedly distorted Cu 2+ (O,OH)6 octahedra and one MoO4 tetrahedron. The Cu1 and Cu2 octahedra share edges to form brucite-type layers parallel to (100), whereas the Cu3 octahedra share edges with one another to form rutile-type chains parallel to the b axis. These layers and chains alternate along [100] and are interlinked together by both MoO4 tetrahedra and hydrogen bonds. Topologically, the structure of markascherite exhibits a remarkable resemblance to that of deloryite, Cu4(UO2)(MoO4)2(OH)6, given the coupled substitution of [2Cu 2+ + 2(OH

Precipitated efflorescent salts in Cu–Co chemical leaching plant wastes in Kabwe, Zambia, have been studied using XRF analysis, powder X-ray diffraction, scanning electron microscopy (SEM), Raman spectroscopy, and evaporation experiments combined with geochemical modeling. Field samples of efflorescent salts contained up to 14.32 wt% Cu and 1.42 wt% Co. In the field, the principal minerals in the salts were gypsum (CaSO4·2H2O), moorhouseite (Co0.6Ni0.3 Mn 0.1 2 + (SO4)·6H2O), bloedite (Na2Mg(SO4)2·4H2O), starkeyite (MgSO4·4H2O), chalcanthite (CuSO4·5H2O) and kroehnkite (Na2Cu(SO4)2·2H2O). In the evaporation experiment, gypsum precipitated in the first and second evaporation steps, chalcanthite and bieberite (CoSO4·7H2O), started to precipitate in Step 3, after evaporation of 60% of water, and maximum amounts of Cu and Co sulfate salts accumulated in Step 4 after precipitation of 80% of water. Epsomite (MgSO4·7H2O), and hexahydrite (MgSO4·6H2O), precipitated only after evaporation of 97.5% of water in Step 5. Presence of chalcanthite, bloedite, and kroehnkite in precipitates of Step 4 was also confirmed by Raman spectroscopy. Magnesium and Na content in Cu and Co-sulfate phases gradually increased with evaporation progress, e.g. bieberite was replaced by Co-bloedite and chalcanthite was replaced by kroehnkite in later stages of evaporation. The precipitation order was consistent with results of geochemical modeling. The principal difference between field data and data obtained in the evaporation experiment was the presence of less hydrated sulfate phases in the field, which can be explained by different time scales available for evaporation and consecutive dehydration. Dissolution experiments using efflorescent salts collected in the field indicated fast dissolution with an instantaneous drop in pH to about 4.0 and a very fast increase of dissolved species concentrations. Such behavior may have a serious environmental impact at the beginning of the rainy period in November and December, when seepage through the impoundment dam was recorded. The wastes at the Kabwe site represent a long-term source of contamination, which may be especially significant as a consequence of on-going climatic change with increasing intensity of precipitation.

In the main frame of the research aimed to model the corrosion growth on bronze surface, the objective of the work here reported has been to characterize the corrosion products formed on laboratory samples of bronze alloy (Cu Sn12), during the early stage of exposure to moist air with sulfur dioxide. A cycling corrosion cabinet was used to control 200 ppm gas concentration, relative humidity (RH) and temperature, according to the DIN 50018 (Kesternich test).The method is designed to evaluate how well the surface resists to sulfur dioxide corrosion; the test cycle consists of 8 hours exposure to sulfur dioxide at 40°C temperature and 100% relative humidity, followed by 12 hours drying at room condition. Weight variation, Spectrophotometer, Scanning Electron Microscopy with X-ray microanalysis (SEM-EDS), X-ray Diffraction (XRD) analysis were carried out for the tarnish products characterization. Some of the compound identified were brochantite (Cu4(OH)6SO4), chalcanthite (CuSO4•5H2O) cuprite (Cu2O), cassiterite (SnO2) and ottemannite (Sn2O3).

A wide range and variety of minerals are used in the pharmaceutical industry as active ingredients. Such minerals may be administered either orally as antacids, gastrointestinal protectors, antidiarrhoeaics, osmotic oral laxatives, homeostatics, direct emetics, antianemics and mineral supplements, or parenterally as antianemics and homeostatics. They may also be used topically as antiseptics, disinfectants, dermatological protectors, anti-inflammatories, local anesthetics, keratolytic reducers and decongestive eye drops. In all cases the LADME process of the minerals is described. In the cosmetic industry minerals are used as solar protectors as well as in toothpastes, creams, powder and emulsions, bathroom salts and deodorants. The minerals in use belong to the following groups: oxides (rutile, periclase, zincite), carbonates (calcite, magnesite, hydrocincite, smithsonite), sulphates (epsomite, mirabilite, melanterite, chalcanthite, zincosite, goslarite, alum), chlorides (halite, sylvite), hydroxides (brucite, gibbsite, hydrotalcite), elements (sulphur), sulphides (greenockite), phosphates (hydroxyapatite), nitrates (niter), borates (borax) and phyllosilicates (smectite, palygorskite, sepiolite, kaolinite, talc, mica). The therapeutic activity of these minerals is controlled by their physical and physico-chemical properties as well as their chemical composition. The important properties are high sorption capacity, large specific surface area, solubility in water, reactivity toward acids, high refractive index, high heat retention capacity, opacity, low hardness, astringency, and high reflectance.

Modeling the oxidation of pyrite copper-zinc ores under evaporization shows that structural features of ores influence the process kinetics, and displays new-formed mineral phases, namely, gannigite, biankite, chalcanthite, which relate with sulfate generating on evaporation from natural and process waters at pyrite deposits. The oxidation effect on the mineral flotation properties is described.

Zinc plant purification residue (ZPR), a typical Zn-hydrometallurgical waste, was collected from the Três Marias Zn plant (MG, Brazil). ZPR was characterized for its metal content and fractionation, mineralogy, toxicity and leachability. Toxicity characteristics leaching procedure (TCLP) and European Community Bureau of Reference (BCR) sequential extraction results revealed that this ZPR displays high percentages of metals (Cd, Cu, Zn and Pb) in the highly mobilizable fractions, increasing its hazardous potential. Bulk chemical analysis, pH dependent leaching and acid (H2SO4) leaching studies confirm that the ZPR is polymetallic, rich in Cd, Cu and Zn. The sulfuric acid concentration (1 M), agitation speed (450 rpm), temperature (40 °C) and pulp density (20 g L(-1)) were optimized to leach the maximum amount of heavy metals (Cd, Cu and Zn). Under optimum conditions, more than 50%, 70% and 60% of the total Cd, Cu and Zn present in the ZPR can be leached, respectively. The metals in the acid leachates were investigated for metal sulfide precipitation with an emphasis on selective Cu recovery. Metal sulfide precipitation process parameters such as initial pH and Cu to sulfide ratio were optimized as pH 1.5 and 1:0.5 (Cu:sulfide) mass ratio, respectively. Under optimum conditions, more than 95% of Cu can be selectively recovered from the polymetallic ZPR leachates. The Cu precipitates characterization studies reveal that they are approximately 0.1 μm in diameter and mainly consist of Cu and S. XRD analysis showed covellite (CuS), chalcanthite (CuSO4·5H2O) and natrochalcite (NaCu2(SO4)2(OH)·H2O) as the mineral phases. ZPRs can thus be considered as an alternative resource for copper production.

The blue colour in ancient soda-lime glasses has been attributed to the presence of copper and/or cobalt but the origin of different shades is not yet fully interpreted. As a contribution to this question, a non-destructive X-ray absorption study at [Cu]K-edge was undertaken on the blue (turquoise) layer from a “Nueva Cadiz” type tubular glass bead dated pre-XVII century where copper is the unique colouring agent. Minerals configuring two distinct blue tonalities due to Cu (2+) in similar square coordination were selected as basic model compounds: azurite, which is a classical navy-blue pigment used in ancient wall paintings over plaster, and chalcanthite, displaying exactly the same turquoise-blue tonality of tubular glass beads manufactured since the Egyptian Antiquity. Theoretical modelling of the XAFS spectra was undertaken using the FEFF code. The IFEFFIT software package was used for fitting the calculated spectra to experimental data. EXAFS results are discussed in view of the crystal structures of copper minerals chosen to model the speciation state and structural situation of that element prevailing in the turquoise-blue archaeological glass. Special attention is focused on the difficulties in theoretical modelling [Cu]K-XANES spectra of ancient glasses with different colourings.

Alpersite, Mg 0.58 Cu 0.37 Zn 0.02 Mn 0.02 Fe 0.01 SO 4 ·7H 2 O, a new mineral species with direct relevance to reactions in mine waste, occurs in a mineralogically zoned assemblage in sheltered areas at the abandoned Big Mike mine in central Nevada at a relative humidity of 65% and T = 4 °C. Blue alpersite, which is isostructural with melanterite (FeSO 4 ·7H 2 O), is overlain by a light blue to white layer dominated by pickeringite, alunogen, and epsomite. X-ray diffraction data (Mo K α radiation) from a single crystal of alpersite were refined in P 2 1 /c, resulting in w R = 0.05 and cell dimensions a = 14.166(4), b = 6.534(2), c = 10.838(3) A, β = 105.922(6)°, Z = 4. Site-occupancy refinement, constrained to be consistent with the compositional data, showed Mg to occupy the M1 site and Cu the M2 site. The octahedral distortion of M2 is consistent with 72% Cu occupancy when compared with the site-distortion data of substituted melanterite. Cuprian pentahydrite, with the formula (Mg 0.49 Cu 0.41 Mn 0.08 Zn 0.02 )SO 4 ·5H 2 O, was collected from an efflorescent rim on a depression that had held water in a large waste-rock area near Miami, Arizona. After dissolution of the efflorescence in de-ionized water, and evaporation of the supernatant liquid, alpersite precipitated and quickly dehydrated to cuprian pentahydrite. These observations are consistent with previous experimental studies of the system MgSO 4 -CuSO 4 -H 2 O. It is suspected that alpersite and cuprian pentahydrite are widespread in mine wastes that contain Cu-bearing sulfides, but in which solubilized Fe 2+ is not available for melanterite crystallization because of oxidation to Fe 3+ in surface waters of near-neutral pH. Alpersite has likely been overlooked in the past because of the close similarity of its physical properties to those of melanterite and chalcanthite. Alpersite is named after Charles N. Alpers, geochemist with the United States Geological Survey, who has made significant contributions to our understanding of the mineralogical controls of mine-water geochemistry.

Geological and microbiological examination of water and mineral samples collected primarily along the 5200 bench of the Metcalf pit within the Morenci copper deposit revealed that acidophilic iron oxidizing bacteria (thiobacilli) and sulfate-reducing bacteria have contributed to leaching and, in part, to the enrichment of copper in the supergene environment, respectively. The 5200 bench traverses a classic, but tilted, enrichment profile consisting of a 200-m-thick zone of leached capping (0.06% Cu, 0.06% S) that overlies a partially leached, 180-m-thick enriched blanket (0.42% Cu, 0.39% S). The modern climate in southwestern Arizona is semiarid and exhibits a biannual wet-dry cycle where active weathering zones, associated with fracture-flow regimes along the 5200 bench, provided a natural laboratory to study supergene processes. Samples from these weathering zones contained viable thiobacilli that thrived during wet periods of the year reaching populations >107 bacteria/ml within an environment where the pH was diluted to near-neutral conditions. The population of thiobacilli decreased during the dry periods, presumably due to low water activity. During dry periods, evaporative concentration of sulfuric acid also promoted sulfide mineral dissolution and the formation of sulfate salts (e.g., chalcanthite). During the subsequent wet phase, these salts dissolved, contributing to the soluble, mobile fraction of copper important to supergene enrichment. Acidification of the sulfide zone was also promoted by the formation of authigenic iron hydroxides such as goethite and jarosite, similar to acid mine drainage systems. Order of magnitude estimates of contemporary bacterial iron oxidation of a 100-m3 block in the active weathering environment reveals that an oxidized cap could be produced in as little as 9 × 102 to 5 × 103 yr. While it is interesting to think that leaching at Morenci could form on a time scale of several thousand years, it is incorrect to assume that an entire 100-m3 block could be active at one time (i.e., leaching occurs in discrete fractures). The most active fracture in the Metcalf pit, Morenci, which produces a few kilograms of bacteria/yr, could leach between 0.14 and 0.87 t of Cu annually. Small populations of viable sulfate-reducing bacteria (~103/g) occurred within this partially leached zone and at the ground-water interface (i.e., at the redox boundary). Even though the enriched blanket possesses viable sulfate-reducing bacteria, inorganic geochemical processes dominate supergene enrichment in this system. Comparing the annual carbon fixation occurring during biooxidation versus leaching, bacterial sulfate reduction could only fix between 0.2 and 1.1 percent of the copper being leached.

The vibrational (infrared and Raman) spectroscopy is used in order to identify and characterize the following amphibole minerals with general formula W0–1X2Y5Z8O22(OH)2 (W = Na, K; X = Na, Ca; Y = Mg, Fe2+, Fe3+, Al; Z = Si, Al) originating from the localities in the Republic of Macedonia: glaucophane, Na2(Mg,Fe2+)3(Fe3+,Al)2Si8O22(OH)2; tremolite–actinolite, Ca2(Mg,Fe2+)5Si8O22(OH)2; hornblende (Na,K)0–1Ca2(Mg,Fe2+,Fe3+,Al)5(Si,Al)8 O22(OH)2 and arfvedsonite, NaNa2(Mg,Fe2+)4(Fe3+,Al)Si8O22(OH)2. The chemical composition of these minerals is not necessarily fixed. It is due to the possibility to form solid solution series with other minerals being their end-members (for example, tremolite–ferro-actinolite series, Ca2Mg5Si8O22(OH)2–Ca2Fe2+5Si8O22(OH)2). In this context, it is shown that the intensity and especially the number of the IR bands in the ν(OH) region could serve as a tool for exact mineral identification. Namely, it is based on the presence of different Y cations in various octahedral sites (M1 and M3), which is manifested by different spectral view. On the other hand, the expressed similarities in the 1300–370 cm−1 (IR) and 1200–100 cm−1 regions (Raman) of the spectra are observed due to their common structural characteristics (double chains of SiO4 tetrahedra). Thus, the bands in this region are tentatively prescribed mostly to the vibrations of the SiO4 tetrahedra. The results of our study are compared with the corresponding literature data for the analogous mineral species originating all over the world.

Ion beam analysis (IBA) techniques were applied successfully to the investigation of non-corroded and artificially corroded patina layers grown on copper substrates in order to explore their potential use in the study of degradation phenomena of copper and copper alloys subjected to chemical treatment and exposed to selected environmental conditions. Rutherford backscattering spectroscopy (RBS) with deuterons as projectiles and the nuclear reactions 16O(d,p)17O and 32S(p,p′γ)32S were applied to the investigation of the depth distribution of oxygen and sulphur in near-surface layers of synthetic patina consisting of mineral phases corresponding to chalcanthite as well as to cuprite + chalcanthite and antlerite + brochantite + chalcanthite. Electrochemical techniques (potentiodynamic polarization and cyclic voltammetry in 0.5 M Na2SO4) were used for artificial acceleration and study of the corrosion processes, and scanning electron microscopy (SEM/EDS) was used for examination of the surface morphology of the samples. A patinated roof sample from the Vienna Hofburg also was investigated using the same techniques. The measurement showed that IBA can provide valuable information for the study of patina near-surface layers of thickness up to a few micrometres and indicated that cuprite was the mineral phase primarily formed on the copper substrates and the main component of the interface between the patina layer and the metallic substrate. The investigated copper patinas looked rather heterogeneous and were characterized by high porosity. Mixed patinas exhibited considerable stability to further corrosive attack. Copyright © 2005 John Wiley & Sons, Ltd.

Intermittent mining and processing of sulphide ore (pyrite–chalcopyrite) at the abandoned Mt Perry mine from the 1870s has resulted in numerousmine workings, waste dumps, a local drainage system contaminated by acid mine drainage (pH 3.3–4.5) and degradation of local soil and vegetation. Weatheringof sulphidic ore, oxidized waste material, tailings and slags (median of 32 samples: 0.65 ppm Au, 17 ppm Ag, 48 ppm As, 3090 ppm Cu, 3.5 wt% Fe, 138 ppm Mn, 19 ppm Mo, 55 ppm Pb, 39 ppm Zn) has led to the formation of secondary minerals (e.g. goethite, hematite, Cu carbonates, gypsum, jarosite, natrojarosite, chalcanthite) on waste materials, stream sediments and stream banks. Waters emanatingfrom underground workings and draining waste dumps have pH values as low as 3.3 and contain elevated contents of As, Cu, Fe, Zn and SO 4 . Dilution from uncontaminated tributaries and groundwaters causes decreasing Cu and Zn concentrations in stream waters, whereas Fe and As precipitate close to the mine site due to adsorption and coprecipitation processes. While much of the dissolved metal load derives from the mine site, Cu is also dissolved out of contaminated stream sediments. Soils in the mines area have elevated Cu and Fe values compared to background soils. The soils acquired their metal enrichments by hydromorphic dispersion from the dissolution of metal-rich particulates, transport of dust and physical erosion of metal-rich particulates from the dumps, and perhaps atmospheric fall-out from smelting plant emissions. Levels of Ag, As, Cu, Fe, and Zn in the fine fraction of stream sediments exceed background values by one to three orders of magnitude. This enrichment has been caused by physical erosion of metal-bearing minerals from abandoned ore and waste dumps and adsorption and coprecipitation of dissolved metals and metalloids in the stream bed. Areas disturbed by mining are characterized by lack of native vegetation, selective and non-selective bioaccumulation of metals and metalloids into plants (gold fern Pityrogramma austroamericana ; hickory wattle Acacia aulococarpa ; bunch speargrass Heteropogon contortus ; wiregrass Aristida benthamii , A. caput-medusae ), and partial recolonization by metal-tolerant plant species (gold fern; bunch speargrass; couch grass, Cynodon dactylon ; swordsedge, Lepidosperma sp.).

Sequential extractions are widely used for exploration purposes and to study element speciation in systems such as soil and sediments, and more recently to understand the complex biogeochemical element cycling in mine waste environments. This method is however often the focus of criticism due to uncertainty in the selectivity of specific leaches utilized. In this study, a procedure is presented how sequential extractions can be adapted to specific mineralogy in order to increase the selectivity and the accuracy of geochemical data interpretation. The application of dissolution kinetic tests and the control of dissolved phases in sequential extractions by X-ray diffraction (XRD) and differential X-ray diffraction (DXRD) indicate which minerals are dissolved in each leach. This information is crucial for the interpretation of geochemical data obtained from sequential extractions and enables to increase the selectivity of the sequence applied. A seven-step sequence was adapted to the specific secondary and primary mineralogy of mine tailings from Cu-sulfide ores, both from porphyry copper and from Fe-oxide Cu–Au deposits. As result of the study, the following seven-step sequence shows best selectivity for the aim of the study of Cu-sulfide mine waste: Step 1 liberates the water-soluble fraction (1.0-g sample into 50-ml deionized H2O shake for 1 h at room temperature [RT]) dissolving gypsum and metal salts (e.g., chalcanthite (CuSO4·5H2O), pickeringite (MgAl2(SO4)4·22H2O)). Step 2 liberates the exchangeable fraction (1 M NH4-acetate, pH 4.5, shaken for 2 h, RT) as adsorbed ions, but also dissolves calcite and breaks down a typical secondary vermiculite-type mixed-layer mineral from the low pH oxidation zone. Step 3 addresses the Fe(III) oxyhydroxides fraction (0.2 M NH4-oxalate, pH 3.0, shaken for 1 h in darkness, RT) and dissolves schwertmannite, two-line ferrihydrite, Mn-hydroxides, secondary jarosite partially, as well as goethite acid mine drainage formed. Step 4 dissolves the Fe(III) oxides fraction (0.2 M NH4-oxalate, pH 3.0, heat in water bath 80 °C for 2 h) and removes all secondary ferric minerals occurring as higher ordered ferrihydrite (e.g., six-line), goethite, primary and secondary jarosite, natrojarosite, and primary hematite. Step 5 consists of a change from reducing to oxidizing condition and is performed by a H2O2 leach (35% H2O2 heat in water bath for 1 h), which dissolves organic matter and supergene Cu-sulfides such as covellite and chalcocite–digenite. Step 6 (KClO3 and HCl, followed by 4 M HNO3 boiling) dissolves primary sulfides and Step 7 (HCl, HF, HClO4, HNO3) the residual fraction (silicates). The application of this extraction sequence to 5 Cu-sulfide mine tailings have shown that sequential extractions can be a powerful tool for detection of element mobilization and retention processes. This is especially the case in dry climates, where it is difficult to obtain pore-water geochemistry. A detailed mineralogical study should however go hand in hand with every geochemical study of mine waste to ensure the accuracy of the geochemical interpretations.