Resolving the role of carbonaceous material in gold precipitation in metasediment-hosted orogenic gold deposits

Carbonaceous material (CM) is commonly associated with gold and sulfides in metasediment-hosted orogenic gold deposits. The role of CM in Au deposition is controversial; CM has been proposed to contribute to gold deposition by reducing Au bisulfide complexes, or by facilitating sulfidation, which destabilizes Au in bisulfide complexes with resultant Au deposition. Integration of petrographic observations, thermodynamic models, and geochemical data from metasediment-hosted orogenic gold deposits in New Zealand, Australia, Canada, and West Africa reveals genetic links between sulfides, CM, and mineralization. The results are consistent with the coexistence of CM and pyrite as a consequence of their codeposition from ore fluids, with a minor proportion of CM originally in situ in the host rocks. Au is deposited when pyrite and CM deposition decreases H2S concentration in ore fluids, destabilizing Au(HS)2-complexes. Most CM in gold deposits is deposited from CO2 and CH4 in ore fluids. These findings are applicable to similar deposits worldwide

Late Jurassic to Early Cretaceous age of the Daqiao gold deposit, West Qinling Orogen, China: implications for regional metallogeny

The West Qinling Orogen is endowed with more than 100 sediment-hosted gold deposits with an estimated resource of > 2000 t Au. Previous radiometric dating results have shown that most deposits formed during a Late Triassic to Early Jurassic period of contractional deformation over the orogen. However, here we show that the newly discovered Daqiao gold deposit (> 105 t at 3–4 g/t) in the southern belt of the West Qinling Orogen formed in latest Jurassic to Early Cretaceous under a different tectonic regime. The Daqiao gold deposit is hosted in weakly metamorphosed Triassic turbidites and is spatially associated with hydrothermally altered granodiorite and diorite porphyry dykes. Six granodiorite dykes have similar zircon U–Pb ages ranging from 215.0 ± 1.1 to 211.5 ± 1.5 Ma (1s), whereas one diorite porphyry dyke has a zircon U–Pb age of 187.5 ± 2.1 Ma (1s). The age of gold mineralization is constrained by two types of sericite: sericite aggregates coexisting with disseminated auriferous pyrite in relatively high-grade breccia ores and sericite coexisting with auriferous pyrite in weakly mineralized granodiorite dykes. Sericite aggregates from the breccia ores have 40Ar/39Ar plateau ages ranging from 150.7 ± 3.1 to 142.3 ± 2.5 Ma (2s), whereas grains from the altered granodiorite dykes and low-grade breccia ores have 40Ar/39Ar plateau ages of 130.8 ± 3.1 to 127.2 ± 0.6 Ma (2s). The 40Ar/39Ar ages thus suggest two periods of gold mineralization in the latest Jurassic and Early Jurassic that are likely related to repeated brecciation at Daqiao. These Jurassic-Cretaceous mineralization ages coincide with discounted ages from several other gold deposits in the region and suggest that there is an underappreciated gold event in the West Qinling Orogen that may not have been associated with the orogenic deformation but is genetically related to the far-field effects of plate reorganization during Paleo-Pacific subduction beneath the eastern Eurasian continent

Sequestration of Zn into mixed pyrite-zinc sulfide framboids: A key to Zn cycling in the ocean?

Zinc (Zn) is an important micronutrient in the ocean, and fixation of Zn into organic, trace element-rich sediments is an important contributor to Zn cycling in the ocean. Framboidal sulfides are considered to be the major host for Zn in such settings. The sequestration of Zn into framboids via biotic or abiotic processes is not fully understood, which presents difficulties for interpretation of Zn isotope values in sediments. In this work, we describe a novel type of framboid with mixed pyrite and zinc sulfide (sphalerite or wurtzite) microcrystals from meta-pelites of the Otago Schist, New Zealand. A combination of optical microscopy, scanning electron microscopy (SEM) and nanoscale secondary ion mass spectrometry (NanoSIMS) were utilized to assess the association between Zn, pyrite and organic matter in framboids. The distribution of Zn in framboids is variable. Most pyrite microcrystals include minor amounts of Zn. Trace Zn is also observed to co-locate with organic matter, which occurs on the boundaries of pyrite microcrystals. Finally, Zn is found as single zinc sulfide microcrystals or zinc sulfide rims around pyrite microcrystals within individual framboids. These textures have not been recorded before, to our knowledge. The sequence of events that sequesters Zn into framboids may affect Zn isotope fractionation from seawater to continental margin sediments

Ore-forming processes of the daqiao epizonal orogenic gold deposit, west qinling orogen, China: Constraints from textures, trace elements, and sulfur isotopes of pyrite and marcasite, and raman spectroscopy of carbonaceous material

The Daqiao gold deposit is hosted in organic-rich Triassic pumpellyite-actinolite facies metamorphosed turbidites in the West Qinling orogen, central China. Gold mineralization is characterized by high-grade hydraulic breccias (B and C ores) that overprint an earlier tectonic breccia (A ore). A complex paragenesis is defined by four sulfide stages: S1 diagenetic preore pyrite (py), S2 hydrothermal early ore disseminated pyrite and marcasite (mc), S3 main ore pyrite and marcasite aggregates, and S4 late ore coarse-grained marcasite with minor pyrite and stibnite. However, multiple generations of pyrite and marcasite may develop within one individual stage. Ore-related hydrothermal alteration is dominated by intensive silicification, sulfidation, sericitization, and generally distal minor carbonatization. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) trace element analyses show that the stage S1 py1 from the shale interlayers within turbidites contains low gold contents (mean of 0.05 ppm) and other trace elements (Mn, Co, Ni, Cu, Mo, Bi, and Pb), indicating an anoxic to euxinic sedimentary environment. Stage S2 contributed only minimally to the gold endowment with relatively low gold in various sulfides including py2 (mean of 0.09 ppm), py3 (0.84 ppm) to py4 (0.70 ppm), along with mc1 (0.02 ppm) and mc2 (0.14 ppm). Most of the gold was deposited in stage S3, which formed rapidly crystallized, irregular (e.g., framboids, colloform and cyclic zonation) cement-hosted py5a (mean of 27.35 ppm), py5b (9.71 ppm), and mc3 (5.94 ppm) during repeated hydraulic fracturing. Other trace elements (e.g., Ag, As, Sb, Hg, Tl, and W) are also significantly enriched in the main ore-stage pyrite and marcasite. Little or no gold is detected in the S4 py6 and mc4. Sulfur isotopes determined from in situ LA-multicollector (MC)-ICP-MS analyses of hydrothermal pyrite and marcasite from the Daqiao deposit vary significantly from –31.3 to 22.0 (d34S values) but fall mostly between –10 to 10 and provide important information on the source and evolution of sulfur and of the ore-forming fluids. The results show that S2 ore fluids (mean d34Ssulfide = –0.8 to 5.2) were most likely derived from deep-seated Paleozoic carbonaceous sediments during regional metamorphism associated with orogenesis of the West Qinling orogen. Main ore S3 fluids (mean d34Ssulfide = –9.7 to –6.0) are relatively depleted in34S relative to those of S2, presumably due to fluid oxidation associated with hydraulic fracturing caused by the overpressurized fluids. The textural, chemical, and isotopic data indicate two distinct gold-introducing episodes at Daqiao, forming sulfide disseminations during early ore S2 and cement-hosted sulfide aggregates during main ore S3. The S2 mineralization took place in a tectonic breccia beneath low-permeability shale seals that capped the flow of deep-seated metamorphic fluids, facilitating reaction with preexisting carbonaceous material and the host turbidites to form sulfide disseminations and pervasive silicification. Raman spectroscopy analysis suggests that carbonaceous material in the ores is poorly crystallized, with low maturity, giving estimated temperatures of 283° to 355°C that are much higher than those of the ore fluids (100°–240°C). This temperature difference indicates an in situ sedimentary origin modified by the regional pumpellyite-actinolite facies metamorphism for the carbonaceous material in the host rocks, rather than a hydrothermal origin. In S3, continuous flux of hydrothermal fluids caused fluid overpressure and consequent hydraulic fracturing of the competent silicified rocks. Subsequent rapid fluid pressure fluctuations led to phase separation and thus massive oxidation of ore fluids, which triggered fast precipitation of gold and other trace elements within the fine-grained irregular sulfides. Results presented here, in combination with geologic evidences, suggest that the Daqiao gold deposit can be best classified as the shallow-crustal epizonal orogenic type, genetically associated with orogenic deformation and regional metamorphism of the West Qinling orogen

The solubility and speciation of molybdenum in aqueous liquid and vapour : an experimental study

We have conducted an experimental investigation of the solubility and speciation of Mo in HCl-, NaCl-, and NaOH-bearing water vapour, and of the partitioning of Mo between coexisting aqueous liquid and vapour at 300 to 370°C and up to saturated pressure. Our results indicate that Mo concentration is enhanced in HCl-bearing water vapour at fHCl > 0.1 bar, and in NaOH-saturated water vapour, but is unaffected by the presence of NaCl. This suggests that Mo speciates as MoO3·nH2O in water vapour at equilibrium with NaCl or fHCl < 0.1 bar. The dependence of SigmafMo on fHCl at higher acidity points to the formation of Mo oxychloride (MoO2Cl 2). For the system MoO3-NaOH-H2O, log Sigma fMo increases with increasing fH2O, and with log SigmafNa in a ratio of 0.28+/-0.4, but Sigma fNa does not change with increasing fH2O. This suggests the formation of a small proportion of sodium molybdate (Na 2MoO4) in addition to MoO3·nH2O. Our partitioning experiments show that at lower temperature and fluid density, Mo partitions more strongly into the liquid than the vapour, but the Mo concentration in the vapour increases as the temperature-pressure conditions approach those of the critical point of water (374°C and 221 bar), surpassing that in the liquid at ∼360°C. The results of our experiments indicate that both the liquid and vapour phases may be important for the transport of Mo in porphyry ore-forming systems, and that vapour-phase solubility is enhanced in high fHCl magmatic gases

The solubility and speciation of molybdenum in water vapour at elevated temperatures and pressures : implications for ore genesis

The solubility of molybdenum trioxide in liquid-undersaturated water vapour has been investigated experimentally at 300, 320, and 360°C and 48 to 163 bars. Results of these experiments show that the solubility of MoO3 in the vapour phase is between 1 and 23 ppm, which is 19-20 orders of magnitude higher than that in a water-free system. Molybdenum solubilities increase linearly with fH2O , indicating that the metal forms a gaseous hydrated complex of the type MoO3·nH2O by the reaction: MoO3g+nH 2Og=MoO3· nH2Og A1 The hydration number, n, is interpreted to have a value of 2.6 at 300ºC, 2.5 at 320ºC, and 3.0 at 360ºC. Values of log K for this reaction are 16.9 at 300ºC, 16.5 at 320ºC, and 12.5 at 360ºC.Calculations based on the extrapolated solubility of MoO 3 in equilibrium with molybdenite at 600ºC and 500 bars, using average H2O and total S fluxes of actively degassing volcanoes, with fO2 and fS2 controlled by the assemblage hematite-magnetite-pyrite, indicate that the vapour phase can transport sufficient Mo in about 900,000 years (within the life of some geothermal systems) to form a deposit of 336 Mt, with an average grade of 0.087% Mo (e.g., the Endako Mo-porphyry deposit, Canada)

An experimental investigation of trace element dissolution in carbon dioxide: Applications to the geological storage of CO2

This paper presents the first experimental data for the fractionation of Fe, Cu and Zn between brine and carbon dioxide at pressure-temperature conditions applicable to the saline aquifers used for the geological storage of CO2, in order to evaluate the potential for trace element remobilization within the injected CO2 plume. The study was carried out at 6.5-16 MPa and 60 °C in a large-volume autoclave, which was loaded with pressurized CO2 and a 20 wt% NaCl solution having a known concentration of Fe, Cu or Zn. Paired samples of brine and CO2 were extracted from separate capillary lines and analyzed for metal concentrations

An experimental method for gold partitioning between two immiscible fluids: Brine and n-dodecane

Organic matter can be found in many different types of ore deposits, but its role in ore-forming processes is not yet fully understood. Here, we present an experimental method that can be used to determine the partition coefficient (DAuorg/aq: partition coefficient of Au between an hydrocarbon and an aqueous fluid) of gold between two immiscible liquids, and thus whether liquid hydrocarbon fluids such as petroleum can act as ore fluids and transport gold or other metals of interest. To investigate liquid hydrocarbons in the presence of an aqueous liquid doped with gold, we modified the HFS-340Z hydrothermal flow system (Coretest Systems, Inc.) to enable sampling at hydrothermal P-T conditions (=150 °C and ~5 bar) of each of two density-stratified immiscible liquids. A saline aqueous solution (10 wt% NaCl) was doped with gold and heated with n-dodecane (CH3(CH2)10CH3) to 105 °C and 150 °C. Each brine sample was directly followed by an organic sample until three samples of each liquid were taken. Aqua regia was added to the brine samples to stabilize the gold before ICP-MS analyses. Each organic sample was digested chemically with a mixture of ultra-pure nitric acid and hydrogen peroxide to generate carbon free solutions prior to ICP-MS analysis. This procedure generates reproducible partition coefficients for gold, or presumably any other metal, between hydrocarbon and aqueous liquids, if passivation procedures of the HFS-340Z hydrothermal flow system are strictly followed and error sources are monitored rigorously. The preferred DAuorg/aq between n-dodecane and the brine is 0.05 ± 0.04