The speciation of mercury in hydrothermal systems,with applications to ore deposition

Hg in hydrothermal systems is generally thought to be transported as Hg-S complexes. However, the abundance of Hg⁰_vap, in geothermal emissions suggests that Hg⁰_eq, is present in the liquid phase of geothermal systems. Calculations for reducing fluids (HS^? dominant over SO⁼₄) in equilibrium with cinnabar indicate that Hg⁰_eq, can be quite abundant relative to other species at temperatures above 200°C. Increasing pH and temperature, and decreasing total S, ionic strength, and pO₂ all promote the abundance of Hg⁰_eq. When a vapor phase develops from a geothermal liquid, Hg partitions strongly into the vapor as Hg⁰_vap. Vapor transport at shallow level then results in the formation of Hg halos around shallow aquifers as well as in a flux of Hg to the atmosphere. Hg deposition may occur in response to mixing with oxidizing or acidic water, turning Hg⁰_eq, into Hg⁺⁺, with subsequent cinnabar precipitation. When pyrite is the stable Fe-sulfide, cinnabar solubility is at its lowest, so cinnabar + pyrite assemblages are common. Cinnabar + hematite ± pyrite can precipitate from more oxidized or S-poor water. Hg⁰_liq, can occur as a primary mineral, in coexistence with all common Fe-sulfides and oxides. Cinnabar ± Hg⁰_liq cannot coexist with pyrrhotite or magnetite at temperatures between 100° and 250°C. Evidence from Hg deposits indicates that many formed from dilute hydrothermal fluids in which Hg probably occurred as Hg⁰_eq. In S-rich systems, Hg may occur as Hg-S complexes, and in saline waters it can occur as Hg-Cl complexes.     

Titanium complexation in hydrothermal systems

The solubility of rutile in aqueous solutions of HCl, HF, H₂SO₄, NaOH, and NaF was determined at 500°C, 1000 bar, and hydrogen fugacity from 8 × 10⁻¹² to 10.3 bar (Mn₃O₄/Mn₂O₃ and Ni/NiO buffers, dissolution of an Al batch weight). The experimentally determined solubility values were used to calculate the constants of the following equilibria at 500°C and 1 kbar pressure: TiO₂(rutile) + H₂O + HCl⁰ = Ti(OH)₃Cl⁰ (pK = 4.89); TiO₂(rutile) + 2HCl⁰ = Ti(OH)₂Cl ₂ ⁰ (pK = 4.69), TiO₂(rutile) + HS O ₄ ⁻ + H⁺ = Ti(OH)₂SO ₄ ⁰ (pK = 1.98), TiO₂(rutile) + 2HSO ₄ ⁻ + 2H⁺ = Ti(SO₄) ₂ ⁰ + 2H₂O (pK = −1.50), TiO₂(rutile) + 2H₂O + OH⁻ = Ti(OH) ₅ ⁻ (pK = 3.17), TiO₂(rutile) + 2H₂O + 2OH⁻ = Ti(OH) ₆ ²⁻ (pK = 1.46), TiO₂(rutile) + 2H₂O + F⁻ = Ti(OH)₃F⁰ + OH⁻ (pK = 5.86), TiO₂(rutile) + 2HF⁰ = Ti(OH)₂F ₂ ⁰ (pK = 2.99), and TiO₂(rutile) + 2H₂O + F⁻ = Ti(OH)₄F⁻ (pK = 3.69). Based on the results obtained on the composition of volcanic emanations whose Ti concentrations were determined, we evaluated the constants of the equilibria TiO₂(rutile) + H₂O + HCl⁰ = Ti(OH)₃Cl⁰ (pK = 2.74) and TiO₂(rutile) + HSO ₄ ⁻ + H⁺ = Ti(OH)₂SO ₄ ⁰ (pK = 3.40) at 25°C. The electrostatic model of electrolyte ionization was used to calculate the ionization constants and the Gibbs free energy values for the following Ti species in aqueous fluids at the parameters of postmagmatic processes: Ti(OH) ₃ ⁺ , Ti(OH) ₄ ⁰ , Ti(OH) ₅ ⁻ , Ti(OH) ₆ ²⁻ , Ti(OH)₃F⁰, Ti(OH)₂F ₂ ⁰ , Ti(OH)₄F⁻, Ti(OH)₃Cl⁰, Ti(OH)₂Cl ₂ ⁰ , Ti(OH)₂SO ₄ ⁰ , and Ti(SO₄) ₂ ⁰ . As follows from our data on Ti complexation with Cl, F, and SO₄, fluids the most favorable for Ti migration are aqueous acid F-rich solutions with Ti concentrations of no higher than a few fractions of a milligram per kilogram of water. Original Russian Text ? B.N. Ryzhenko, N.I. Kovalenko, N.I. Prisyagina, 2006, published in Geokhimiya, 2006, No. 9, pp. 950–966.     

Complexation of Si in hydrothermal systems

The Au-SiO2 and Sn-SiO2 complexes have been experimentally calibrated at varying temperature,silica comcentration and pH: Au^ H2SiO4^-=AuH3SiO4 lgK=-1.65436 9611.21/T; Sn^4 4H3SiO4^-=Sn(H3SiO4)4 lgK200℃=42.73 Compared with Au-Cl,Au-HS and Sn-OH complexes,AuH3SiO4 and Sn(H3SiO4)4complexes can be recognized as the dominant transport forms in Si-bearing solurtions under pH and Eh conditions of general interest.The decrease of SiO2 concentration and oxygen fugacity would reverse the direction of dissolution-complexing reactions,resulting in the precipitation of gold and silica,as well as cassiterite and silica.This study illustrates the significance of SiO2-complexation in hydrothermal solutions for gold,tin and other metallizations.     

Iron isotope fractionation during hydrothermal ore deposition and alteration

Iron isotopes fractionate during hydrothermal processes. Therefore, the Fe isotope composition of ore-forming minerals characterizes either iron sources or fluid histories. The former potentially serves to distinguish between sedimentary, magmatic or metamorphic iron sources, and the latter allows the reconstruction of precipitation and redox processes. These processes take place during ore formation or alteration. The aim of this contribution is to investigate the suitability of this new isotope method as a probe of ore-related processes. For this purpose 51 samples of iron ores and iron mineral separates from the Schwarzwald region, southwest Germany, were analyzed for their iron isotope composition using multicollector ICP-MS. Further, the ore-forming and ore-altering processes were quantitatively modeled using reaction path calculations. The Schwarzwald mining district hosts mineralizations that formed discontinuously over almost 300 Ma of hydrothermal activity. Primary hematite, siderite and sulfides formed from mixing of meteoric fluids with deeper crustal brines. Later, these minerals were partly dissolved and oxidized, and secondary hematite, goethite and iron arsenates were precipitated. Two types of alteration products formed: (1) primary and high-temperature secondary Fe minerals formed between 120 and 300 °C, and (2) low-temperature secondary Fe minerals formed under supergene conditions (<100 °C). Measured iron isotope compositions are variable and cover a range in δ⁵⁶Fe between −2.3‰ and +1.3‰. Primary hematite (δ⁵⁶Fe: −0.5‰ to +0.5‰) precipitated by mixing oxidizing surface waters with a hydrothermal fluid that contained moderately light Fe (δ⁵⁶Fe: −0.5‰) leached from the crystalline basement. Occasional input of CO₂-rich waters resulted in precipitation of isotopically light siderite (δ⁵⁶Fe: −1.4 to −0.7‰). The difference between hematite and siderite is compatible with published Fe isotope fractionation factors. The observed range in isotopic compositions can be accounted for by variable fractions of Fe precipitating from the fluid. Therefore, both fluid processes and mass balance can be inferred from Fe isotopes. Supergene weathering of siderite by oxidizing surface waters led to replacement of isotopically light primary siderite by similarly light secondary hematite and goethite, respectively. Because this replacement entails quantitative transfer of iron from precursor mineral to product, no significant isotope fractionation is produced. Hence, Fe isotopes potentially serve to identify precursors in ore alteration products. Goethites from oolitic sedimentary iron ores were also analyzed. Their compositional range appears to indicate oxidative precipitation from relatively uniform Fe dissolved in coastal water. This comprehensive iron isotope study illustrates the potential of the new technique in deciphering ore formation and alteration processes. Isotope ratios are strongly dependent on and highly characteristic of fluid and precipitation histories. Therefore, they are less suitable to provide information on Fe sources. However, it will be possible to unravel the physico-chemical processes leading to the formation, dissolution and redeposition of ores in great detail.     

Mechanisms of iron oxide transformations in hydrothermal systems

Coexistence of magnetite and hematite in hydrothermal systems has often been used to constrain the redox potential of fluids, assuming that the redox equilibrium is attained among all minerals and aqueous species. However, as temperature decreases, disequilibrium mineral assemblages may occur due to the slow kinetics of reaction involving the minerals and fluids. In this study, we conducted a series of experiments in which hematite or magnetite was reacted with an acidic solution under H₂-rich hydrothermal conditions (T = 100-250 °C, ) to investigate the kinetics of redox and non-redox transformations between hematite and magnetite, and the mechanisms of iron oxide transformation under hydrothermal conditions. The formation of euhedral crystals of hematite in 150 and 200 °C experiments, in which magnetite was used as the starting material, indicates that non-redox transformation of magnetite to hematite occurred within 24 h. The chemical composition of the experimental solutions was controlled by the non-redox transformation between magnetite and hematite throughout the experiments. While solution compositions were controlled by the non-redox transformation in the first 3 days in a 250 °C experiment, reductive dissolution of magnetite became important after 5 days and affected the solution chemistry. At 100 °C, the presence of maghemite was indicated in the first 7 days. Based on these results, equilibrium constants of non-redox transformation between magnetite and hematite and those of non-redox transformation between magnetite and maghemite were calculated. Our results suggest that the redox transformation of hematite to magnetite occurs in the following steps: (1) reductive dissolution of hematite to and (2) non-redox transformation of hematite and to magnetite.     

Advances in the microbial mineralization of seafloor hydrothermal systems

Research on the biomineralization in modern seafloor hydrothermal systems is conducive to unveiling the mysteries of the early Earth’s history, life evolution, subsurface biosphere and microbes in outer space. The hydrothermal biomineralization has become a focus of geo-biological research in the last decade, since the introduction of the microelectronic technology and molecular biology technology. Microorganisms play a critical role in the formations of oxide/hydroxides (e.g. Fe, Mn, S and Si oxide/hydroxides) and silicates on the seafloor hydrothermal systems globally. Furthermore, the biomineralization of modern chemolithoautotrophic microorganisms is regarded as a nexus between the geosphere and the biosphere, and as an essential complement of bioscience and geology. In this paper, we summarize the research progress of hydrothermal biomineralization, including the biogenic minerals, the microbial biodiversity, and also the interactions between minerals and microorganisms. In the foreseeable future, the research on hydrothermal biomineralization will inspire the development of geosciences and biosciences and thus enrich our knowledge of the Earth’s history, life evolution and even astrobiology.© 2019 China Geology Editorial Office.     

Dissolved organic carbon in ridge-axis and ridge-flank hydrothermal systems

The circulation of hydrothermal fluid through the upper oceanic crustal reservoir has a large impact on the chemistry of seawater, yet the impact on dissolved organic carbon (DOC) in the ocean has received almost no attention. To determine whether hydrothermal circulation is a source or a sink for DOC in the oceans, we measured DOC concentrations in hydrothermal fluids from several environments. Hydrothermal fluids were collected from high-temperature vents and diffuse, low-temperature vents on the basalt-hosted Juan de Fuca Ridge axis and also from low-temperature vents on the sedimented eastern flanks. High-temperature fluids from Main Endeavour Field (MEF) and Axial Volcano (AV) contain very low DOC concentrations (average = 15 and 17 μM, respectively) compared to background seawater (36 μM). At MEF and AV, average DOC concentrations in diffuse fluids (47 and 48 μM, respectively) were elevated over background seawater, and high DOC is correlated with high microbial cell counts in diffuse fluids. Fluids from off-axis hydrothermal systems located on 3.5-Ma-old crust at Baby Bare Seamount and Ocean Drilling Program (ODP) Hole 1026B had average DOC concentrations of 11 and 13 μM, respectively, and lowered DOC was correlated with low cell counts. The relative importance of heterotrophic uptake, abiotic sorption to mineral surfaces, thermal decomposition, and microbial production in fixing the DOC concentration in vent fluids remains uncertain. We calculated the potential effect of hydrothermal circulation on the deep-sea DOC cycle using our concentration data and published water flux estimates. Maximum calculated fluxes of DOC are minor compared to most oceanic DOC source and sink terms.     

Fluorite stability in silicic magmas

Recent experimental evidence is used to assess the conditions under which fluorite forms an early crystallising phase in silicic magmas. Fluorite solubility primarily depends on the (Na + K)/Al balance in the coexisting silicic melt, reaching a minimum in metaluminous melts. It can display reaction relationships with topaz and titanite, depending on changes in melt composition during crystallisation. An empirical model of fluorite stability in Ca-poor peralkaline rhyolite melts is derived and applied to selected rocks:

Archean sea-floor hydrothermal systems: The third dimension

Mafic to felsic predominantly marine volcanic members on the west flank of the major volcanic vent of the relatively unmetamorphosed and undeformed Archean upper Blake River Group of the Noranda area were sampled at approximately 100 m centres in a 100 km² area for whole-rock analysis as part of an integrated exploration program during 1977–1980. Automatic processing of the resulting approximately 2000 analyses yielded not only the expected improved definition of primary rock types but also synvolcanic alteration patterns of varying intensity. Essentially two-dimensional sea floor “weathering” on paleo-bedding surfaces and the more fully three-dimensional, hydrothermal, volcanogenic, footwall alteration systems were discovered. The data, when integrated with existing drill and mining information provide a unique insight into the hidden shape of the sub-sea-floor plumbing of the recently discovered active hydrothermal, biologic systems observed in two dimensions at crustal spreading centres on today's ocean floor.Polarized compositional gradients observed within the footwall alteration patterns are interpreted to be potent exploration guides to proximal, polymetallic, sulphide facies exhalite deposits and their associated “stringer” zones.     

Mass transfer in hydrothermal alteration systems—A conceptual approach

At very low fluid/rock mass ratios the hydrothermal alteration process corresponds to isochemical recrystallisation of the primary rock. The resulting full equilibrium assemblage with the composition of an average crustal rock contains the phases albite, K-feldspar, K-mica, biotite, quartz and (depending on temperature) epidote, prehnite or one of the Ca-zeolites. Relative Na⁺, K⁺, Mg²⁺ and Ca²⁺—solution activities in such a rock-dominated alteration system are uniquely fixed and provide useful reference points with regard to the degree of attainment of full fluid/rock equilibrium. With increasing fluid/rock mass ratios the composition of now increasingly fluid-dominated alteration assemblages is determined by the interplay of three major processes: hydrogen metasomatism as a function of CO₂ reactivity increasing with the horizontal distance from major fluid upflow zones and leading to the formation of Al-enriched alteration assemblages; potassium metasomatism accompanied by silicification in or close to major fluid upflow zones leading to potassic and phyllic alteration; sodium, magnesium, calcium metasomatism associated with descending and heating solutions leading to propylytic alteration of recharge zones. Two new parameters, reactivity and exchangeability, determining the effectiveness of fluid components with respect to hydrothermal alteration are introduced.     

Movement of hydrothermal solutions and mechanism of crystal deposition,sub-Arctic Urals

The paper develops the argument that quartz crystal aggregates formed in vugs along the underside of quartz veins, filling faults, cut across the strike trend of the metasediments of the Northern Urals crystalline section. Crystal growth in the vugs was possible because hydrothermal solutions, presumably rich in carbon dioxide, were able to leach large quantities of silica out of the wall rock. It is noted, also, that the silica which was emplaced as thin sheets along the cleavage planes did not react with the country rock. Presumably, this was consequent upon the fact that this (earlier) generation of hydrothermal solutions was supersaturated with respect to silica, and was therefore incapable of supporting leaching reactions. The quartz in the sheets which follow the cleavage planes is amorphous; this may be evidence of the supersaturated state of the solutions. — M.E. Burgunker     

Geochemical constraints on chemolithoautotrophic metabolism by microorganisms in seafloor hydrothermal systems

Mixing of hydrothermal fluids and seawater at the ocean floor, combined with slow reaction kinetics for oxidation/reduction reactions, provides a source of metabolic energy for chemolithotrophic microorganisms which are the primary biomass producers for an extensive submarine ecosystem that is essentially independent of photosynthesis. Thermodynamic models are used to explore geochemical constraints on the amount of metabolic energy potentially available from chemosynthetic reactions involving S, C, Fe, and Mn compounds during mixing of hydrothermal fluids with seawater. For the vent fluid used in the calculations (EPR 21 degrees N OBS), the model indicates that mixing environments are favorable for oxidation of H2S, CH4, Fe2+ and Mn2+ only below approximately 38 degrees C, with methanogenesis and reduction of sulfate or S degrees favored at higher temperatures, suggesting that environments dominated by mixing provide habitats for mesophilic (but not thermophilic) aerobes and thermophilic (but not mesophilic) anaerobes. A maximum of approximately 760 cal per kilogram vent fluid is available from sulfide oxidation while between 8 and 35 cal/kg vent fluid is available from methanotrophy, methanogenesis, oxidation of Fe or Mn, or sulfate reduction. The total potential for chemosynthetic primary production at deep-sea hydrothermal vents globally is estimated to be about 10(13) g biomass per year, which represents approximately 0.02% of the global primary production by photosynthesis in the oceans. Thermophilic methanogens and sulfate- and S degree-reducers are likely to be the predominant organisms in the walls of vent chimneys and in the diffuse mixing zones beneath warm vents, where biological processes may contribute to the high methane concentrations of vent fluids and heavy 34S/32S ratios of vent sulfide minerals. The metabolic processes taking place in these systems may be analogs of the first living systems to evolve on the Earth.     

Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems

The rates of chemical reactions between aqueous sulfates and sulfides are essentially identical to sulfur isotopic exchange rates between them, because both the chemical and isotopic reactions involve simultaneous oxidation of sulfide-sulfur atoms and reduction of sulfate-sulfur. The rate of reaction can be expressed as a second order rate law: R = k·[∑SO₄^2?]·[∑S^2?], where R is the overall rate, k is the rate constant and [∑SO₄^2?] and [∑S^2?] are molal concentrations. We have computed the rate constants from the available experimental data on the partial exchange of sulfur isotopes between aqueous sulfates and sulfides using the rate law established by us: $\text{ln(}\text{α}{}^{\mathrm{e}}\text{? α}\text{α}{}^{\mathrm{e}}\text{? α}{}^0\text{) = ? kt([∑SO}{}_4{}^{\mathrm{2?}}\text{] + [∑S}{}^{\mathrm{2?}}\text{])}$, where t is time and α⁰, α, and α^e are, respectively, the fractionation factors at t = 0 (the initial condition), at the end of experiment, and at equilibrium. The equilibrium fractionation factor can be expressed as: $\text{1000 ln α}{}^{\mathrm{e}}\text{=}\text{6.463 × 10}{}^6\text{T}{}^2\text{+ 0.56 (±.5)}$ (T in Kelvin).The rate constants are strongly dependent on T and pH, but not in as simple a manner as suggested by Igumnov (1976). Our rate constants in Na-bearing hydrothermal solutions decrease by 1 order of magnitude with an increase in pH by 1 unit at pH's less than ~3, remain constant in the pH range of ~4 to ~7, and again decrease at pH >7. The activation energy for the reaction also depends on pH: 18.4 ± 1 kcal/mole at pH = 2, 29.6 ± 1 kcal/mole at pH = 4 to 7, and between 40 and 47 kcal/mole at pH around 9. The observed pH dependence of the rate constant and of the activation energy can be best explained by a model involving thiosulfate molecules as reaction intermediates, in which the intramolecular exchange of sulfur atoms in thiosulfates becomes the rate determining step.The rate constants obtained in this study were used to compute the changes in the isotopic fractionation factors between aqueous sulfates and sulfides during cooling of fluids. Comparisons with data of coexisting sulfate-sulfide minerals in hydrothermal deposits, suggest that simple cooling was not a likely mechanism for coprecipitation of sulfate and sulfide minerals at temperatures below 350°C. Mixing of sulfide-rich solutions with sulfate-rich solutions at or near the depositional sites is a more reasonable process for explaining the observed fractionation.The degree of attainment of chemical equilibrium between aqueous sulfates and sulfides in a hydrothermal system, and the applicability of a_O2-pH type diagrams to mineral deposits, depends on the ∑S content and the thermal history of the fluid, which in turn is controlled by the flow rate and the thermal gradient in the system.The rates of sulfate reduction by non-bacterial processes involving a variety of reductants are also dependent on T, pH, [∑SO₄^2?], and [∑S^2?], and appear to be fast enough to become geochemically important at temperatures above about 200°C.     

Composite synvolcanic intrusions associated with Precambrian VMS-related hydrothermal systems

Large subvolcanic intrusions are recognized within most Precambrian VMS camps. Of these, 80% are quartz diorite–tonalite–trondhjemite composite intrusions. The VMS camps spatially associated with composite intrusions account for >90% of the aggregate sulfide tonnage of all the Precambrian, intrusion-related VMS camps. These low-alumina, low-K, and high-Na composite intrusions contain early phases of quartz diorite and tonalite, followed by more voluminous trondhjemite. They have a high proportion of high silica (>74% SiO ₂) trondhjemite which is compositionally similar to the VMS-hosting rhyolites within the volcanic host-rock successions. The quartz-diorite and possibly tonalite phases follow tholeiitic fractionation trends whereas the trondhjemites fall within the composition field for primitive crustal melts. These transitional M-I-type primitive intrusive suites are associated with extensional regimes within oceanic-arc environments. Subvolcanic composite intrusions related to the Archean Sturgeon Lake and Noranda, and Paleoproterozoic Snow Lake VMS camps range in volume from 300 to 1,000 km ³. Three have a sill morphology with strike lengths between 15 and 22 km and an average thickness between 1,500 and 2,000 m. The fourth has a gross stock-like shape. The VMS deposits are principally restricted to the volcanic strata above the strike length of the intrusions, as are areally extensive, thin exhalite units. The composite intrusions contain numerous internal phases which are commonly clustered within certain parts of the composite intrusion. These clusters underlie eruptive centers surrounded by areas of hydrothermal alteration and which contain most of the VMS deposits. Early quartz-diorite and tonalite phases appear to have intruded in rapid succession. Evidence includes gradational contacts, magma mixing and disequilibrium textures. They appear to have been emplaced as sill-dike swarms. These early phases are present as pendants and xenoliths within later trondhjemite phases. The trondhjemite phases contain numerous internal contacts indicating emplacement as composite sills. Common structural features of the composite intrusions include early xenolith phases, abundant small comagmatic dikes, fractures and veins and, in places, columnar jointing. Internal phases may differ greatly in texture from fine- to coarse-grained, aphyric and granophyric through seriate to porphyritic. Mineralogical and isotopic evidence indicates that early phases of each composite intrusion are affected by pervasive to fracture-controlled high-temperature (350–450 °C) alteration reflecting seawater-rock interaction. Trondhjemite phases contain hydrothermal-magmatic alteration assemblages within miarolitic cavities, hydrothermal breccias and veins. This hydrothermal-magmatic alteration may, in part, be inherited from previously altered wall rocks. Two of the four intrusions are host to Cu-Mo-rich intrusive breccias and porphyry-type mineralization which formed as much as 14 Ma after the main subvolcanic magmatic activity. The recognition of these Precambrian, subvolcanic composite intrusions is important for greenfields VMS exploration, as they define the location of thermal corridors within extensional oceanic-arc regimes which have the greatest potential for significant VMS mineralization. The VMS mineralization may occur for 2,000 m above the intrusions. In some cases, VMS mineralization has been truncated or enveloped by late trondhjemite phases of the composite intrusions. Evidence that much of the trondhjemitic magmatism postdates the principal VMS activity is a critical factor when developing heat and fluid flow models for these subseafloor magmatic-hydrothermal systems.     

Transport and deposition of uranium in hydrothermal ore fluids as exemplified by Uranium Deposit 302

Uranium Deposit 302 is a large hydrothermal uranium deposit occurring in fault zones within a granite. Pitchblende is the only primary uranium mineral found in the ore. The associated minerals include quartz, fluorite, hematite and pyrite. This paper focusses on the mechanism of transport and deposition of uranium in hydrothermal oreforming solutions responsible for the deposit. It is concluded that uranium might be not only oxidized in a relatively reducing environment, but also reduced in a relatively oxidizing environment, depending on the speciation of uranium in the solutions. The formation of pitchblende is closely related to uranium reduction at the stage of uranium mineralization.     

PGE fractionation in seafloor hydrothermal systems: examples from mafic- and ultramafic-hosted hydrothermal fields at the slow-spreading Mid-Atlantic Ridge

The distribution of platinum group elements (PGEs) in massive sulfides and hematite–magnetite±pyrite assemblages from the recently discovered basalt-hosted Turtle Pits hydrothermal field and in massive sulfides from the ultramafic-hosted Logatchev vent field both on the Mid-Atlantic Ridge was studied and compared to that from selected ancient volcanic-hosted massive sulfide (VHMS) deposits. Cu-rich samples from black smoker chimneys of both vent fields are enriched in Pd and Rh (Pd up to 227 ppb and Rh up to 149 ppb) when compared to hematite–magnetite-rich samples from Turtle Pits (Pd up to 10 ppb, Rh up to 1.9 ppb). A significant positive correlation was established between Cu and Rh in sulfide samples from Turtle Pits. PGE chondrite-normalized patterns (with a positive Rh anomaly and Pd and Au enrichment), Pd/Pt and Pd/Au ratios close to global MORB, and high values of Pd/Ir and Pt/Ir ratios indicate mafic source rock and seawater involvement in the hydrothermal system at Turtle Pits. Similarly shaped PGE chondrite-normalized patterns and high values of Pd/Pt and Pd/Ir ratios in Cu-rich sulfides at Logatchev likely reflect a similar mechanism of PGE enrichment but with involvement of ultramafic source rocks.