Nickel sulfide deposits in Australia: Characteristics,resources, and potential

Australia's nickel sulfide industry has had a fluctuating history since the discovery in 1966 of massive sulfides at Kambalda in the Eastern Goldfields of Western Australia. Periods of buoyant nickel prices and high demand, speculative exploration, and frenetic investment (the ‘nickel boom’ years) have been interspersed by protracted periods of relatively depressed metal prices, exploration inactivity, and low discovery rates. Despite this unpredictable evolution, the industry has had a significant impact on the world nickel scene with Australia having a global resource of nickel metal from sulfide ores of ∼ 12.9 Mt, five world-class deposits (> 1 Mt contained Ni), and a production status of number three after Russia and Canada. More than 90% of the nation's known global resources of nickel metal from sulfide sources were discovered during the relative short period of 1966 to 1973. Australia's nickel sulfide deposits are associated with ultramafic and/or mafic igneous rocks in three major geotectonic settings: (1) Archean komatiites emplaced in rift zones of granite–greenstone belts; (2) Precambrian tholeiitic mafic–ultramafic intrusions emplaced in rift zones of Archean cratons and Proterozoic orogens; and (3) hydrothermal-remobilized deposits of various ages and settings. The komatiitic association is economically by far the most important, accounting for more than 95% of the nation's identified nickel sulfide resources. The ages of Australian komatiitic- and tholeiitic-hosted deposits generally correlate with three major global-scale nickel-metallogenic events at ∼ 3000 Ma, ∼ 2700 Ma, and ∼ 1900 Ma. These events are interpreted to correspond to periods of juvenile crustal growth and the development of large volumes of primitive komatiitic and tholeiitic magmas caused by large-scale mantle overturn and mantle plume activities. There is considerable potential for the further discovery of komatiite-hosted deposits in Archean granite–greenstone terranes including both large, and smaller high-grade (5 to 9% Ni) deposits, that may be enriched in PGEs (2 to 5 g/t), especially where the host ultramafic sequences are poorly exposed.Analysis of the major komatiite provinces of the world reveals that fertile komatiitic sequences are generally of late Archean (∼ 2700 Ma) or Paleoproterozoic (∼ 1900 Ma) age, have dominantly Al-undepleted (Al₂O₃/TiO₂ = 15 to 25) chemical affinities, and often occur with sulfur-bearing country rocks in dynamic high-magma-flux environments, such as compound sheet flows with internal pathways facies (Kambalda-type) or dunitic compound sheet flow facies (Mt Keith-type). Most Precambrian provinces in Australia, particularly the Proterozoic orogenic belts, contain an abundance of sulfur-saturated tholeiitic mafic ± ultramafic intrusions that have not been fully investigated for their potential to host basal Ni–Cu sulfides (Voisey's Bay-type mineralization). The major exploration challenges for finding these deposits are to determine the pre-deformational geometries and younging directions of the intrusions, and to locate structural depressions in the basal contacts and feeder conduits under cover. Stratabound PGE–Ni–Cu ± Cr deposits hosted by large Archean–Proterozoic layered mafic–ultramafic intrusions (Munni Munni, Panton) of tholeiitic affinity have comparable global nickel resources to many komatiite deposits, but low-grades (< 0.2% Ni). There are also hydrothermal nickel sulfide deposits, including the unusual Avebury deposit in western Tasmania, and some potential for ‘Noril'sk-type’ Ni–Cu–PGE deposits associated with major flood basaltic provinces in western and northern Australia.     

Chemical weathering processes in the Yalong River draining the eastern Tibetan Plateau,China

To better understand chemical weathering and controlling processes in the Yalong River of the eastern Tibetan Plateau, this study presents major ion concentrations and stable isotopes of the dissolved loads. The isotopic compositions (δ¹³C-DIC, δ³⁴S and δ¹⁸O-SO₄) of the dissolved loads are very useful to quantify solute sources and define the carbon budget related with chemical weathering in riverine systems. The isotopic composition of sulphate demonstrates that most of the sulphate is derived from sulphide oxidation, particularly in the upper reach of the Yalong River. The correlations between δ¹³C-DIC, water chemistry and isotopes of sulphate, suggest that the carbon dynamics are mainly affected by carbonate weathering by sulphuric acid and equilibration processes. Approximately 13% of the dissolved inorganic carbon in the Yalong River originates from carbonate weathering by strong acid. The CO₂ consumption rates are estimated to be 2.8 × 10⁵ mol/km²/yr and 0.9 × 10⁵ mol/km²/yr via carbonate and silicate weathering in the Yalong River, respectively. In this study, the influence of sulphide oxidation and metamorphic CO₂ on the carbon budget is estimated for the Yalong River draining the eastern Tibetan Plateau.     

Dissolution kinetics of soil clays in sulfuric acid solutions: Ionic strength and temperature effects

Significant amounts of sulfuric acid (H₂SO₄) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline–acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline–acidic conditions (pH 1–4; ionic strengths = 0.01 and 0.25 M; 25 °C) and over a range of temperatures (25–45 °C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2–4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; R_Si, R_Al, R_Fe) increased with decreasing solution pH and increasing temperature. For example, the highest log R_Si value was obtained at pH 1 and 45 °C (−9.07 mol g⁻¹ s⁻¹), while the lowest log R_Si value was obtained at pH 4 and 25 °C (−11.20 mol g⁻¹ s⁻¹). A comparison of these results with pure mineral dissolution rates from the literature suggests that the BB clay dissolved at a much faster rate compared to the pure mineral samples. Apparent activation energies calculated for the clay sample varied over the range 76.6 kJ mol⁻¹ (pH 1) to 37.7 kJ mol⁻¹ (pH 4) which compare very well with the activation energy values for acidic dissolution of monomineralic samples e.g. montmorillonite from previous studies. The acid neutralisation capacity (ANC) of the clay sample was calculated from the release of all structural cations except Si (i.e. Al, Fe, K, Mg). According to these calculations an ANC of 1.11 kg H₂SO₄/tonne clay/day was provided by clay dissolution at pH 1 (I = 0.25 M, 25 °C) compared to an ANC of 0.21 kg H₂SO₄/tonne clay/day at pH 4 (I = 0.25 M, 25 °C). The highest ANC of 6.91 kg H₂SO₄/tonne clay/day was provided by clay dissolution at pH 1 and at 45 °C (I = 0.25 M), which is more than three times higher than the ANC provided under the similar solution conditions at 25 °C. In wetlands with little solid phase buffering available apart from clay minerals, it is imperative to consider the potential ANC provided by the dissolution of abundantly occurring phyllosilicate minerals in devising rehabilitation schemes.     

Leaching of metals from copper smelter flue dust (Mufulira,Zambian Copperbelt)

The leaching behaviour of electrostatic precipitator dust from the Mufulira Cu smelter (Copperbelt, Zambia) was studied using a 48-h pH-static leaching experiment (CEN/TS 14997). The release of metals (Cd, Co, Cu, Ni, Pb and Zn) and changes in mineralogical composition using X-ray diffraction and PHREEQC-2 modelling were investigated in the pH range of 3–7. The highest concentrations of metals were released at pH 3–4.5, which encompasses the natural pH of the dust suspension (～4.3). About 40% of the total Cu was leached at pH 3, yielding 107 g/kg. Chalcanthite (CuSO₄·5H₂O), magnetite (Fe₃O₄) and delafossite (CuFeO₂) represented the principal phases of the studied dust. In contact with water, chalcanthite was dissolved and hydrated Cu sulphates precipitated at pH 4–7. Gypsum (CaSO₄·2H₂O) and secondary Fe or Al phases were observed in the leached residues. Serious environmental impact due to leaching may occur in dust-contaminated soil systems in the vicinity of the smelting plants.     

Rare greenockite (CdS) within the chromite–PGE association in the Bangur Gabbro,Baula-Nuasahi Complex,Eastern India

We report the presence of greenockite from the chromite–PGE–base metal sulfide association in the Bangur Gabbro, Baula-Nuasahi mafic–ultramafic complex. The CdS phase occurs, sans any precursor Cd-bearing phase, as minute grains within siderite micro-veins in close proximity to chlorite in the chalcopyrite + pyrrhotite + pentlandite + violarite assemblage. Using various calibrations, chlorite compositions yielded temperature ranges of 245 to 325 °C. The associated siderite might have formed at or little below the above temperature. Electron probe micro-analyses (EPMA) of greenockite reveal small amounts of Fe (1.01–1.61 wt.%), Zn (1.89–4.54 wt.%), and substitution of Zn for Cd. Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis of chalcopyrite nearer to and away from siderite micro-veins that host greenockite confirms maximum Cd concentrations of 78 and 144 ppm, respectively, entailing possible derivation of Cd from chalcopyrite. We propose the transport of Cd as bisulfide complex in a low temperature alkaline and reducing fluid and the simultaneous precipitation of greenockite and siderite by reaction with Fe-rich minerals, aided by decrease in pH and/or increase in f_O2.     

The influence of citric acid,EDTA, and fulvic acid on U(VI) sorption onto kaolinite

Uranium(VI) sorption onto kaolinite was investigated as a function of pH (3–12), sorbate/sorbent ratio (1 × 10^?6–1 × 10^?4 M U(VI) with 2 g/L kaolinite), ionic strength (0.001–0.1 M NaNO₃), and pCO₂ (0–5%) in the presence or absence of 1 × 10^?2–1 × 10^?4 M citric acid, 1 × 10^?2–1 × 10^?4 M EDTA, and 10 or 20 mg/L fulvic acid. Control experiments without-solids, containing 1 × 10^?6–1 × 10^?4 M U(VI) in 0.01 M NaNO₃ were used to evaluate sorption to the container wall and precipitation of U phases as a function of pH. Control experiments demonstrate significant loss (up to 100%) of U from solution. Although some loss, particularly in 1 × 10^?5 and 1 × 10^?4 M U experiments, is expected due to precipitation of schoepite, adsorption on the container walls is significant, particularly in 1 × 10^?6 M U experiments. In the absence of ligands, U(VI) sorption on kaolinite increases from pH ～3 to 7 and decreases from pH ～7.5 to 12. Increasing ionic strength from 0.001 to 0.1 M produces only a slight decrease in U(VI) sorption at pH < 7, whereas 10% pCO₂ greatly diminishes U(VI) sorption between pH ～5.5 and 11. Addition of fulvic acid produces a small increase in U(VI) sorption at pH < 5; in contrast, between pH 5 and 10 fulvic acid, citric acid, and EDTA all decrease U(VI) sorption. This suggests that fulvic acid enhances U(VI) sorption slightly via formation of ternary ligand bridges at low pH, whereas EDTA and citric acid do not form ternary surface complexes with the U(VI), and that all three ligands, as well as carbonate, form aqueous uranyl complexes that keep U(VI) in solution at higher pH.     

Mercury mobility in unsaturated gold mine tailings,Murray Brook mine,New Brunswick,Canada

Elevated concentrations of Hg are present (averaging 36 μg/g), mainly as cinnabar, in the Murray Brook Au deposit, located in northern New Brunswick, Canada. After the mined ore was subjected to CN leaching, the tailings were deposited in an unsaturated pile, and 10 a after mine closure an estimated 4.7 × 10³ kg of CN and 1.1 × 10⁴ kg of Hg remain in the pile. Elevated Hg concentrations have been measured in the groundwater (up to 11,500 μg/L) and surface water (up to 32 μg/L) down-gradient of the tailings. To investigate the controls on Hg mobility and leaching persistence, laboratory experiments were conducted using unsaturated columns filled with tailings. Within the first 0.2 pore volumes (PV) eluted, the concentrations of Hg and CN increased to peak concentrations of 12,900 μg Hg/L and 16 mg CN/L, respectively. In the subsequent 0.9 PV, concentrations decreased to approximately 1300 μg Hg/L and 2.8 mg CN/L. Thermodynamic calculations demonstrate that >99.8% of the mobilized Hg in the tailings pore water is in the form of Hg–CN complexes, indicating that Hg mobility to the surrounding aquatic environment is directly dependent on the rate of CN leaching. One-dimensional transport simulations suggest that leached CN can be partitioned into conservative (24%) and non-conservative (76%) fractions. Extrapolation of simulation results to the field scale suggests that CN, and by extension Hg, will continue to elute from the tailings for at least an additional 130 a.     

Kinetics of selenium release in mine waste from the Meade Peak Phosphatic Shale,Phosphoria Formation,Wooley Valley,Idaho, USA

Phosphorite from the Meade Peak Phosphatic Shale member of the Permian Phosphoria Formation has been mined in southeastern Idaho since 1906. Dumps of waste rock from mining operations contain high concentrations of Se which readily leach into nearby streams and wetlands. While the most common mineralogical residence of Se in the phosphatic shale is elemental Se, Se(0), Se is also an integral component of sulfide phases (pyrite, sphalerite and vaesite–pyrite_ss) in the waste rock. It may also be present as adsorbed selenate and/or selenite, and FeSe₂ and organo-selenides.Se release from the waste rock has been observed in field and laboratory experiments. Release rates calculated from waste rock dump and column leachate solutions describe the net, overall Se release from all of the possible sources of Se listed above. In field studies, Se concentration in seepage water (pH 7.4–7.8) from the Wooley Valley Unit 4 dump ranges from 3600 µg/L in May to 10 µg/L by Sept. Surface water flow, Q, from the seep also declines over the summer, from 2 L/s in May to 0.03 L/s in Sept. Se flux ([Se] ? Q) reaches a steady-state of < 150 mg/day in 1–4 months, depending upon the volume of Q. Se release (mg/L) follows a first order reaction with a rate constant, k, = 1.35 – 6.35e?3 h^? 1 (11.8–55.6 yr^? 1).Laboratory experiments were performed with the waste shale in packed bed reactors; residence time varied from 0.09 to 400 h and outlet pH ～ 7.5. Here, Se concentration increased with increasing residence time and release was modeled with a first order reaction with k = 2.19e?3 h^? 1 (19.2 yr^? 1).Rate constants reported here fall within an order of magnitude of reported rate constants for oxidation of Se(0) formed by bacterial precipitation. This similarity among rate constants from both field and laboratory studies combined with the direct observation of Se(0) in waste shales of the Phosphoria Formation suggests that oxidation of Se(0) may control steady-state Se concentration in water draining the Wooley Valley waste dump.     

In situ U–Pb,Sr and Nd isotopic analysis of loparite by LA-(MC)-ICP-MS

This work describes the in situ analysis of loparite [(Na,REE)Ti₂O₆], a perovskite group mineral with extremely low Rb/Sr ratios and high rare earth contents, by LA-(MC)-ICP-MS for the determination of U–Pb ages together with Sr and Nd isotopic composition. The reliability of these data were validated by analysis of a loparite standard by TIMS solution methods. Data are given for loparite from the Lovozero and Khibiny peralkaline complexes of the Kola Alkaline Province (Russia). For Lovozero loparite the Tera–Wasserburg intercept age for 15 loparites analysed is 373 ± 11 Ma, and the weighted ²⁰⁷Pb corrected ²⁰⁶Pb/²³⁸U age is 373 ± 2 Ma. For Khibiny loparite, the intercept age for 5 loparites analysed is 375 ± 10 Ma, and the weighted ²⁰⁷Pb corrected ²⁰⁶Pb/²³⁸U age is 374 ± 3 Ma. The common Pb compositions for Lovozero and Khibiny loparites are identical i.e. ²⁰⁷Pb/²⁰⁶Pb = 0.898 ± 0.009 and 0.898 ± 0.007, respectively. The ⁸⁷Sr/⁸⁶Sr initial ratios of Lovozero loparite range from 0.703552 to 0.703682 (av. 0.703611), and εNd (t₃₇₀) from + 3.8 to + 4.4 (av. + 4.0). The ⁸⁷Sr/⁸⁶Sr initial ratios of Khibiny loparite range from 0.703560 to 0.703871, and εNd (t₇₃₀) from + 4.0 to + 4.8. Our data indicate that in situ LA-(MC)-ICP-MS analysis of loparite provides accurate and precise estimates of the intrusion ages and isotopic composition of peralkaline rocks.     

Synthesis and characterization of polycrystalline KAlSi3O8 hollandite [liebermannite]: Sound velocities vs. pressure to 13 GPa at room temperature

A polycrystalline specimen of liebermannite [KAlSi₃O₈ hollandite] was synthesized at 14.5 GPa and 1473 K using glass starting material in a uniaxial split-sphere apparatus. The recovered specimen is pure tetragonal hollandite [SG: I4/m] with bulk density of within 98% of the measured X-ray value. The specimen was also characterized by Raman spectroscopy and nuclear magnetic resonance spectroscopy. Sound velocities in this specimen were measured by ultrasonic interferometry to 13 GPa at room T in a uniaxial split-cylinder apparatus using Al₂O₃ as a pressure marker. Finite strain analysis of the ultrasonic data yielded K_S0 = 145(1) GPa, K₀′ = 4.9(2), G₀ = 92.3(3) GPa, G₀′ = 1.6(1) for the bulk and shear moduli and their pressure derivatives, corresponding to V_P0 = 8.4(1) km/s, V_S0 = 4.9(1) km/s for the sound wave velocities at room temperature. These elasticity data are compared to literature values obtained from static compression experiments and theoretical density functional calculations.     

A-type granites and related rocks: Petrogenesis and classification

The problems of identification of A-type granitoids are analyzed. These rocks occur in different geodynamic settings. Owing to their mantle nature, they show distinct REE specialization. These are acid intrusive rocks, whose volcanic products are of crucial scientific and practical significance. However, neither the great number of proposed classification schemes and diagrams, including those based on expensive analytical data, nor hot scientific discussions of their identification and the ambiguity of the term A-granitoids helped to determine their classification features in full measure. A principally new discriminant diagram is proposed for the classification of igneous A-type rocks, based on the analysis of earlier obtained results and the petrochemical composition of these rocks. A comparative analysis of subdivision of granites and related felsic volcanic rocks (SiO₂ > 67 wt.%), based on the ternary (Na₂O + K₂O)–Fe₂O₃* × 5–(CaO + MgO) × 5 and other widely applied diagrams, has shown the advantage of the proposed discriminant diagram for the classification of A-type granitoids from different geodynamic settings.     

Kinetics of Au (III) extraction by DBC from hydrochloric solution using Lewis cell

The kinetics of forward extraction [AuCl₄]^? from aqua regia medium by diethylene glycol dibutyl ether (DBC) have been investigated by the Lewis cell (LC) technique. At first gold extraction has been carried out under different experimental conditions for achieving the stoichiometry coefficients and the value of the extraction equilibrium constant (K = 0.1). For kinetic data treatment, flux ‘F’ method has been applied. Reaction order with respect to DBC, pH and [AuCl₄]^? was determined and then the rate constant was calculated. The rate of gold extraction from 2 M chloride medium can be expressed as F = 10^0.88[AuCl₄^?]^1.25 [DBC]^0.4 [H⁺]^?0.22. Kinetics data were treated by EVIEWS software and coefficients were obtained. The comparison of manual and software results indicated that the results had good conformity. Influence of temperature was studied and then activation energy, E_a, (11.17 kJ/mol), activation enthalpy (11.66 kJ/mol) and entropy (?187 J/mol K) were calculated by using Arrhenius and activation complex theory respectively. E_a value (< 20.9 kJ/mol) indicates that, the extraction of gold (III) in the investigated system is controlled by diffusion process.     

Metamorphic P–T path of mafic granulites from Eastern Hebei: Implications for the Neoarchean tectonics of the Eastern Block,North China Craton

This study documents the metamorphic evolution of mafic granulites from the Eastern Hebei Complex in the Eastern Block of the North China Craton. Mafic granulites from Eastern Hebei occur as boudins or enclaves within Neoarchean high-grade TTG gneisses. Petrographic observations reveal three characteristic metamorphic mineral assemblages in the mafic granulites: the pre-peak hornblende + plagioclase + ilmenite + quartz + sphene assemblage (M₁) existing as mineral inclusions within coarse-grained peak assemblage (M₂) represented by garnet + clinopyroxene + orthopyroxene + plagioclase + hornblende + ilmenite + quartz, and post-peak assemblage (M₃) marked by garnet + quartz ± ilmenite symplectites surrounding the peak pyroxene and plagioclase. Based on pseudosection modeling calculated in the NCFMASHTO model system using the program THERMOCALC, P–T conditions of the pre-peak (M₁), peak (M₂) and post-peak (M₃) assemblages are constrained at 600–715 °C/6.0 kbar or below, 860–900 °C/9.6–10.3 kbar, and 790–810 °C/9.6–10.4 kbar, respectively. These P–T estimates, combined with their mineral compositions and reaction relations, define an anticlockwise P–T path incorporating isobaric cooling subsequent to the peak medium-pressure granulite-facies metamorphism for the mafic granulites from Eastern Hebei. Such an anticlockwise P–T path suggests that the end-Neoarchean metamorphism of the Eastern Hebei Complex correlated closely with underplating and intrusion of voluminous mantle-derived magmas. In conjunction with other geological considerations, a mantle-plume model is favored to interpret the Neoarchean tectonothermal evolution of the Eastern Hebei Complex and other metamorphic complexes in the Eastern Block. The prograde amphibolite-facies metamorphism (M₁) was initiated due to the upwelling of the relatively cooler mantle plume head, followed by the peak medium-pressure granulite-facies metamorphism (M₂) as triggered by the uprising hotter plume “tail”, and finally when plume activity ceased, the heated metamorphic crust experienced nearly isobaric cooling (M₃).     

Dissolution kinetics of Devonian carbonates at circum-neutral pH, 50 bar pCO2, 105 °C,and 0.4 M: The importance of complex brine chemistry on reaction rates

The dissolution kinetics of carbonate rocks sampled from the Keg River Formation in Northeast British Columbia were measured at 50 bar pCO₂ and 105 °C, in both natural and synthetic brines of 0.4 M ionic strength. Natural brines yielded reaction rates of −12.16 ± 0.11 mol cm⁻² s⁻¹ for Log R_Ca, and −12.64 ± 0.05 for Log R_Mg. Synthetic brine yielded faster rates of reaction than natural brines. Experiments performed on synthetic brines, spiked with 10 mmol of either Sr or Zn, suggest that enhanced reaction rates observed in synthetic brines are due to a lack of trace ion interaction with mineral surfaces. Results were interpreted within the surface complexation model framework, allowing for the discrimination of reactive surface sites, most importantly the hydration of the >MgOH surface site. Dissolution rates extrapolated from experiments predict that CO₂ injected into the Keg River Formation will dissolve a very minor portion of rock in contact with affected formation waters.     

Short-lived radioactive nuclides in meteorites and early solar system processes

Now extinct, short-lived radioactive nuclides, such as ⁷Be (T_1/2 = 53 days), ¹⁰Be (T_1/2 = 1.5 Ma), ²⁶Al (T_1/2 = 0.74 Ma), ³⁶Cl (T_1/2 = 0.3 Ma), ⁴¹Ca (T_1/2 = 0.1 Ma), ⁵³Mn (T_1/2 = 3.7 Ma) and ⁶⁰Fe (T_1/2 = 1.5 Ma), were present in the protosolar nebula when the various components of meteorites formed. The presence of these radioactive isotopes requires a ‘last-minute’ origin, either nucleosynthesis in a massive star dying close in space and time to the nascent solar system or production by local irradiation of part of the protosolar disk by high-energy solar cosmic rays. In this review, we list: (i) the different observations indicating the existence of multiple origins for short-lived radioactive nuclides, namely ⁷Be, ¹⁰Be and ³⁶Cl for irradiation scenario and ⁶⁰Fe for injection scenario; (ii) the constraints that exist on their distribution (homogeneous or heterogeneous) in the accretion disk; (iii) the constraints they brought on the timescales of nebular processes (from Ca–Al-rich inclusions to chondrules) and of the accretion and differentiation of planetesimals.     

Oxidative pre-treatment in thiosulphate leaching of sulphide gold ores

A diagnostic leaching showed that partial oxidation of the sulphide minerals in a gold ore was beneficial for thiosulphate leaching of gold. A pre-treatment process with oxidative ammoniacal solution enhanced the thiosulphate leaching of the sulphide ore, while the thiosulphate consumption was substantially reduced. The sulphide minerals partially decomposed in the pre-treatment process, exposing gold to the leach solution. Oxygen input by air bubbling and a longer contact time enhanced the oxidative ammonia pre-treatment process and hence accelerated subsequent thiosulphate leaching of the sulphide ore. Gold extraction in 0.8 M ammonia and 0.1 M thiosulphate solution after 24 h increased from 69% without pre-treatment to 81%, 84%, 90% and 94% respectively after 1, 3, 7 and 22 h pre-treatment. The consumption of sodium thiosulphate was 2.37 kg/t after 24 h leaching without pre-treatment, but was negligible after over 1 h oxidative ammonia pre-treatment. A counter-current leaching process was conducted in the leaching of the sulphide ore. The fresh leachant still gave higher leaching rates in contact with the pre-leached ore, while the pre-used leachant had significantly lower leaching kinetics and overall gold extraction in contact with the fresh ore. This 2-step counter-current leaching process proved that the leachant, other than the passivation, was the determinant factor causing the gold leaching rates to decrease after a certain time of leaching. The findings enable the thiosulphate leaching of high sulphide containing gold ores to be more efficient at lower thiosulphate consumption following the oxidative ammoniacal pre-treatment.     

Lithospheric mantle xenoliths sampled by melts from upwelling asthenosphere: The Quaternary Tasse alkaline basalts of southeastern British Columbia,Canada

The Quaternary Tasse basalts are exposed near the north shore of Quesnel Lake in southeastern British Columbia. They host a variety of mantle xenoliths consisting predominantly of spinel lherzolite with minor dunite and pyroxenite. Mineralogically, the xenoliths are composed of olivine, orthopyroxene, clinopyroxene and spinel characterized by forsterite (Fo_87–93), enstatite (En_90–92), diopside (En_45–50–Wo_40–45–Fs₅), and Cr-spinel (6 − 11 wt.% Cr), respectively. All of the mantle xenoliths are coarse-grained and show granoblastic textures. Clinopyroxene and spinel display textural evidence for chemical reactions with percolating melts.The mantle xenoliths are characterized by restricted Mg-numbers (89 − 92) and low abundances of incompatible elements (Ba = 2 − 11 ppm; Sr = 3 − 31 ppm) and Yttrium (1 − 3 ppm). On the basis of REE patterns, the xenoliths are divided into three groups reflecting the various degrees of mantle metasomatism: (1) Group 1 consists of concave-up LREE patterns (La/Sm_cn = 0.48 − 1.16; Gd/Yb_cn = 0.71 − 0.92); (2) Group 2 possesses flat to moderately LREE-enriched patterns (La/Sm_cn = 1.14 − 1.92; Gd/Yb_cn = 0.87 − 1.09); and (3) Group 3 is characterized by strongly LREE-enriched patterns (La/Sm_cn = 1.53 − 2.45; Gd/Yb_cn = 1.00 − 1.32). On MORB-normalized trace element diagrams, the majority of the xenolith samples share the enrichment of LILE (Rb, Ba, K), U, Th, Pb, Sr and the depletion of HFSE (Nb, Ta, Ti, Y) relative to REE. These geochemical characteristics are consistent with a compositionally heterogeneous subcontinental lithospheric mantle source that originated as subarc mantle wedge peridotite at a convergent plate margin.The Tasse basalts have alkaline compositions characterized by low SiO₂ (44 − 46 wt.%) and high alkali (Na₂O + K₂O = 5.1 − 6.6 wt.%) contents. They are strongly enriched in incompatible elements (TiO₂ = 2.4 − 3.1 wt.%; Ba = 580 − 797 ppm; Sr = 872 − 993 ppm) and, display OIB-like trace element patterns (La/Sm_n = 3.15 − 3.85; Gd/Yb_n = 3.42 − 4.61). They have positive εNd (+ 3.8 to + 5.5) values, with 338 − 426 Ma depleted mantle model ages, and display uniform OIB-like Sr (⁸⁷Sr/⁸⁶Sr = 0.703346 − 0.703591) and Pb (²⁰⁶Pb/²⁰⁴Pb = 19.40 − 19.58; ²⁰⁷Pb/²⁰⁴Pb = 15.57 − 15.60; ²⁰⁸Pb/²⁰⁴Pb = 38.99 − 39.14) isotopic compositions. The basalts erupted discontinuously along a > 1000 km long SE-NW-trending linear belt with minimal compositional variation indicative of a homogenous mantle source. The Sr − Nd − Pb isotope and trace element systematics of the alkaline basalts suggests that they originated from partial melting of an upwelling asthenospheric mantle source. Melting of the asthenospheric mantle might have stemmed from extension of the overlying lithosphere in response to the early stages of back-arc basin opening in the Omineca and Intermontane belts. Ridge subduction beneath the Canadian Cordillera might have played an important role in the weakening of the lithospheric mantle prior to its extension. Alternatively, melting of the upwelling asthenosphere in response to the delamination of the lithospheric mantle beneath the Rocky Mountain Trench might have generated the alkaline lavas.     

Dependence of clinopyroxene composition on cooling rate in basaltic magmas: Implications for thermobarometry

The compositional variation of clinopyroxene and the partitioning of major elements between clinopyroxene and melt are estimated as a function of the cooling rate. Clinopyroxenes were crystallized under variable cooling regimes (15, 9.4, 3, 2.1, and 0.5 °C/min from 1250 down to 1000 °C) and at isothermal conditions of 1000 °C from a basaltic composition at a pressure of 500 MPa under anhydrous and hydrous (H₂O = 1.3 wt.%) conditions. The clinopyroxene chemistry shows that, as the cooling rate increases, crystals are progressively depleted in Ca, Mg, Fe²⁺ and Si and enriched in Na, Fe³⁺, Al (mainly Al^IV), and Ti. Di and Hd versus CaTs and CaFeTs form a continuous binary solid solution characterized by higher amounts of tschermakitic components with increasing cooling rate. Two parameters (DH = Di + Hd and TE = CaTs + CaFeTs + En) are calculated to describe the effect of cooling rate on the clinopyroxene composition. The variation of DH/TE with increasing cooling rate evidences the kinetic process induced by rapid cooling in basic rocks under hydrous and anhydrous conditions.Dynamic crystallization conditions affect the partitioning of major elements between clinopyroxene and melt; with increasing cooling rate, the value of crystal–melt partition coefficient departs from that obtained at the isothermal condition. However, in spite of these variations, the values of ^cpx–meltKd_Fe–Mg remain almost constant. Therefore, the Fe²–Mg exchange between clinopyroxene and melt is not suitable to prove the (dis)equilibrium conditions in basaltic cooling magmas, giving rise to possible mismatches in the application of thermobarometers. The results of our study are consistent with that observed at the margin of dikes or in the exterior portions of lavas, where the cooling rate is maximized and disequilibrium compositions of clinopyroxene have been found.     

Geochemistry,zircon UPb geochronology and LuHf isotopic composition of eclogites and their host gneisses in the Dulan area,North Qaidam UHP terrane: New evidence for deep continental subduction

In this study, we link zircon UPb SHRIMP and LA-ICP-MS geochronology and the LuHf isotopic composition of eclogites and their host gneisses/schists with whole-rock geochemistry of eclogites in the Dulan area to constrain their protoliths and metamorphic relationships. UPb dating suggests that the protolith of one of the eclogites was a Neoproterozoic mafic intrusive rock (828 ± 58 Ma) and the protolith of enclosing orthogneiss was an early-Neoproterozoic granitoid (923 ± 12 Ma). Detrital zircons from Grt-bearing mica-schists yield ages of 0.9–2.5 Ga, with a dominant range of 1.0–1.8 Ga, indicating sedimentary sources from Neoproterozoic to Neoarchean crust and a depositional age ≤ 0.9 Ga. The matching metamorphic ages of eclogites (438 ± 5 Ma, 436 ± 4 Ma) and their country rocks (Grt-bearing mica-schists: 438 ± 4 Ma, 439 ± 8 Ma; orthogneiss: 427 ± 8 Ma) indicate that all studied samples experienced coeval Early Paleozoic HP/UHP metamorphism. The UPb ages and Hf isotopic compositions of the inherited magmatic zircon cores of an eclogite sample (ε_Hf (800) = 2.6–9.2, T_DM1 = 1.0–1.3 Ga, T_DM2 = 1.1–1.4 Ga) suggest that the protolith may be derived from Neoproterozoic depleted mantle with variable proportions of an older crustal component. The magmatic zircon cores of the orthogneiss (ε_Hf (900) = ? 7.3 to ? 0.2; T_DM2 = 1.8–2.1 Ga) suggest that the parental magma was derived from a Paleoproterozoic crustal source. Hf isotopic compositions of the detrital zircons from the metasediments (ε_Hf(t) = ? 19.4 to + 10.6) suggest three crust formation and reworking events: (1) Archean (T_DM2 = 2.7–2.9 Ga) juvenile crust reworked at ~ 2.5 Ga; (2) early Paleoproterozoic (T_DM2 = 2.3–2.5 Ga) juvenile crust reworked at ~ 1.8 Ga; and (3) late Paleoproterozoic (T_DM2 = 1.5–1.9 Ga) juvenile crust reworked in the Neoproterozoic.Whole-rock geochemical data suggest that the protoliths of the Dulan eclogites were probably derived from a continental rift or an incipient oceanic basin rather than a large, long-lived ocean basin. Thus, combined with field relationships, petrology, geochemistry, zircon UPb dating and the LuHf isotopic analysis presented in this paper and reported from previous studies, we suggest that the Dulan eclogites and their country rocks experienced a common UHP metamorphism during Late Ordovician deep continental subduction.