热液脉型铅-锌-银矿床富铁闪锌矿中硫化物包裹体成因探讨

通过对热液脉型的铅－锌－银矿床（３个）和银矿床（１个）和闪锌矿中硫化物包囊体的特征研究表明,石英－硫化物阶段富铁闪锌矿（主矿物）的硫化物包裹体十分发育：沿生长带产出的乳滴状黄铜矿与主矿物为共同沉淀成因;沿穿切主矿物的黄铜矿或石英细脉两侧,和受粗粒黄铜矿溶蚀的富铁闪锌矿近接触部位发育的乳滴状黄铜矿为渗透－交代产物;沿解理（裂隙）或粒间、粒内产出的各种形态磁黄铁矿是充填－交代的结果;沿解理分布的脉状毒     

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.     

Fluorite deposition in hydrothermal systems

During the formation of fluorite deposits fluorite is precipitated either as a consequence of changes in temperature and pressure along the flow path of hydrothermal solutions or due to fluid mixing, or as the result of the interaction of hydrothermal solutions with wall rocks.A decrease in temperature in the flow direction is the most appealing, though still unproven, mechanism of fluorite deposition in Mississippi Valley fluorite deposits.Mixing can produce solutions which are either undersaturated or supersaturated with respect to fluorite. The most important parameters are the temperature, the salinity, and the calcium and fluoride concentration of the fluids prior to mixing.A variety of wall rock reactions can lead to fluorite precipitation. Among these reactions which increase the pH of initially rather acid (pH ≤ 3) hydrothermal solutions are apt to be particularly important.     

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.     

Computer reconstruction of the physicochemical conditions of sulfide formation for the Krasnov and Ashadze hydrothermal systems (Mid-Atlantic Ridge)

Computer-based reconstruction of the physicochemical conditions of formation of the Krasnov (16° N) and Ashadze (13° N) submarine systems in the Mid-Atlantic Ridge (MAR) has been performed using the equilibrium-thermodynamic approach to study samples from these sites. In the first case, a sphalerite-pyrite-barite association was considered, and in the second case, a sphalerite-pyrite association. In the modeling conducted, the composition of the sphalerite solid solution corresponding to the nonideal mixing of ZnS and FeS was used as a correlation parameter with the total composition of the Fe-Zn-Ba-S-H₂O-NaCl-HCl hydrothermal system depending on temperature (200-300 °C) and a given pressure of 100 bar. The calculation results predict that at an iron content of 0.17-0.36 wt.% in sphalerite, the minimum formation temperatures of the equilibrium sphalerite-pyrite-barite association should correspond to the interval of 280-300 °C (Krasnov site). As the iron content in sphalerite increases to 4.15-13.28 wt.%, the occurrence of barite in the systems studied becomes impossible and the formation temperatures of the sphalerite-pyrite association become equal to or higher than 300 °C (Ashadze site).     

闪锌矿的Cd含量与颜色关系

过去人们普遍认为黑色闪锌矿贫镉,浅色闪锌矿富镉。笔者统计了国内外74个矿床,385个Cd含量数据。其中33个矿床有不同颜色闪锌矿的Cd含量数据37组。闪锌矿从黑色到浅色,Cd含量依次降低的有15矿床,17组数据,占统计矿床的44.1%,数据组的48.6%;Cd含量逐渐增加有14个矿床,14组数据,分别占统计矿床的45.5%,数据组的38.9%;Cd含量先降后升,黑色闪锌矿含量最高的有2个矿床,2组数据,分别占统计矿床的6.1%,数据组的5.7%;Cd含量先减后增,浅色闪锌矿含量最高和先升后降,褐色闪锌矿含量最高的各有一个矿床,一组数据,分别各占统计矿床的3.0%,占数据组的2.9%。由此看来,黑色闪锌矿与浅色闪锌矿的Cd含量无明显差异,说明闪锌矿的Cd含量与其颜色无明显关系。     

Continuum model for simultaneous chemical reactions and mass transport in hydrothermal systems

A time-space continuum model for transport of hydrothermal fluids in porous media is presented which provides for simultaneous, reversible and irreversible chemical reactions involving liquids, gases and minerals. Homogeneous and heterogeneous reactions are incorporated in the model in a similar fashion through source/sink terms added to the continuity equation. The model provides for moving reaction fronts through surfaces of discontinuity across which occur jump discontinuities in the various field variables satisfying generalized Rankine-Hugoniot relations. Reversible reactions including aqueous complexing, oxidation-reduction reactions, mineral precipitation and dissolution reactions and adsorption are explicitly accounted for by imposing chemical equilibrium constraints in the form of mass action equations on the transport equations. This is facilitated by partitioning the reacting species into primary and secondary species corresponding to a particular representation of the stoichiometric reaction matrix referred to as the canonical representation. The transport equations for the primary species combined with homogeneous and heterogeneous equilibria result in a system of coupled, nonlinear algebraic/partial differential equations which completely describe the evolution of the system in time. Spatially separated phase assemblages are accommodated in the model by altering the set of independent variables across surfaces of discontinuity. Constitutive relations for the fluid flux corresponding to primary species are obtained describing transport of both neutral and charged species by advection, dispersion and diffusion. Numerical implementation of the transport equations is considered and both explicit and implicit finite difference algorithms are discussed. Analytical expressions for the change in porosity and permeability with time are obtained for an assemblage of minerals reacting reversibly with a hydrothermal fluid under quasi-steady state conditions. Fluid flow is described by Darcy's law employing a phenomenological expression relating permeability and porosity. Finally an expression for the local retardation factor of solute species is derived for the case of advective transport in a single spatial dimension which accounts for the effects of homogeneous and heterogeneous equilibria including adsorption on the rate of advance of a reaction front. The condition for the formation of shock waves is given.     

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.     

A simulation experimental study on oxidative kinetics of sphalerite under hypergene condition

The sphalerite oxidative kinetics under hypergene condition was simulated and studied by means of a mixed flow reactor over a pH range of 1.0 7.8,and at dissolution temperatures from 20 to 55℃,ferric ion concentrations from 1.0×10-5 to 1.0×10-2 mol/L,O 2 flux of 0.5 L/min,and oxidants of ferric ion and O 2.It is indicated that with ferric ion as oxidant,the oxidation rate of sphalerite increases with increasing ferric ion concentration,temperature and decreasing pH value,and under the studied conditions,the dissolution rates of Zn and Cd are approximately identical,with the values of activation energy being 41.75 and 42.51 kJ·mol-1,respectively,suggesting that the oxidation rate of sphalerite is controlled by chemical reactions on mineral surface.However,with O 2 as oxidant,the oxidation mechanism of sphalerite varies with pH value.Oxidation rate decreases with increasing pH value when pH is lower than 5.95,whereas the increase of pH value results in an increase in oxidation rate when pH value is higher than 7.The oxidation rate of sphalerite can be expressed as:R Zn =10 1.1663 [Fe3+] 0 0.154 ·[H+] 0.2659 ·e-41.75/RT or R Cd =10 1.7292 [Fe3+] 0 0.170 ·[H+] 0.2637 ·e-42.51/RT     

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.     

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.     

Electron-probe check of fe-distribution in sphalerite grains of the Nagybörzsöny hydrothermal ore deposits,Hungary

Micron-scale iron-distribution patterns in sphalerite grains derived from two contrasting mineral assemblages of the Nagybörzsöny hydrothermal ore deposits (high temperature stockwork and low temperature veins), were determined with electron microprobe, pointcounter and continuous chart-recorder measurements along radial profiles. A significant oscillation of iron-content ranging from 8.1 to 18 per cent for stockwork and 4.3 to 15.8 per cent for veins took place during crystal growth. Homogeneous crystal cores are characteristic for vein-filling, while replacement occurring in deeper levels of the stockwork results in mosaic cores. Frequent oscillation of iron content is relevant to top-sections of the ore bodies, copious supply being recorded in recurring shells, whereas scanty, unilateral ones produce crescents arranged in onion-like structure.

---

Zusammenfassung Bestimmungen der Eisenverteilung wurden an Zinkblendekörnern aus zwei verschiedenen Mineralparagenesen (Hochtemperatur-Stockwerk und Gangfüllungen niederiger Bildungstemperatur) der hydrothermalen Erzlagerstätte Nagybörzsöny im Mikronbereich durch Elektronen-Mikrosonde-Messungen (Punktzählung und kontinuierliche Band-Registrierung) entlang radialer Profile vorgenommen. Bedeutende Schwankungen des Eisengehaltes (8,1–18% für das Stockwerk und 4,3–15,8% für die Gänge) wurden registriert. Homogene Kristallkerne kennzeichnen die Gangfüllungen, wogegen in tieferen Horizonten des Stockwerks Verdrängungen zur Bildung von Kristallen mit Mosaik-Kernen führen. Allgemein ist in den Gipfel-Partien der Erzkörper Fluktuation des Eisengehaltes häufig. Gleichmäßiger Nachschub während des Kristallwachstums führte zu ringförmigen Zonen gleicher Eisengehalte, spärlicher oder einseitiger dagegen zu halbmondförmigen Hüllen mit Zwiebelstruktur.

     

磷灰石中磁黄铁矿出溶结构的发现

中国东部苏鲁地区(江苏赣榆)出露大理岩-榴辉岩块体,其菱镁矿大理岩中保存的白云石分解结构表明地壳物质俯冲深度达到-200公里。在与该大理岩共生的榴辉岩中,我们发现了磷灰石的磁黄铁矿出溶结构。磷灰石是该榴辉岩的主要副矿物,其自形程度较高,与石榴石共生。样品中几乎所有磷灰石均发育出溶结构,至少存在两组相互垂直的出溶棒,它们各自严格沿同一个方向分布。出溶棒形状规则,宽度相近(<1μm),但长度变化大(5-50μm)。利用高分辨能谱仪测定其能谱,结果表明,出溶棒主要由Fe和S两种元素组成,但不能准确地确定其Fe/S比值。我们把这种出溶棒初步确定为磁黄铁矿(Fe1-xS)。磷灰石由于含大量稀土元素和挥发性组分如OH、F、Cl等以及我们所观察到的S,它的深循环因此可能对地球的水、硫以及其它挥发性组分的全球平衡具有重要影响。本文报道的磷灰石中磁黄铁矿出溶结构为深入探讨这个基本科学问题提供了一个新的突破口。     

Formation and age of sphalerite mineralization in carbonate rocks of Bajocian age in the Swiss Jura Mountains: evidence of Mesozoic hydrothermal activity

A combination of petrographic and geochemical techniques was applied to better constrain the origin and evolution of the fluid systems responsible for the formation of disseminated, Cd-rich (up to 0.6 wt%), sphalerite (ZnS) mineralization in the northeastern part of the Jura Mountains, Switzerland. The Rb–Sr ages of sphalerite samples indicate that a main phase of sphalerite formation occurred near the boundary between the late Middle and early Late Jurassic, at around 162 Ma. The negative δ³⁴S values (?22.3 to ?5.3 ‰) suggest that biogenic sulfide sulfur was involved in ZnS precipitation. The strontium isotope composition is more radiogenic than that of contemporaneous seawater, reflecting the interaction of mineralizing fluids with silicate rocks. Lead isotope signatures are very uniform (²⁰⁶Pb^/204Pb = 18.63–18.67, ²⁰⁷Pb^/204Pb = 15.63–15.64, ²⁰⁸Pb^/204Pb = 38.51–38.63), indicating an isotopically well-homogenized fluid system. The basement rocks underlying the Jurassic strata are considered to be the main source of metals for the sphalerite mineralization. The migration of deep-sourced hydrothermal saline metal-bearing fluids into the Bajocian host carbonates containing sedimentary reduced sulfur resulted in the precipitation of sulfides. The period of sphalerite formation near the Middle–Late Jurassic boundary is characterized by enhanced tectonic and hydrothermal activity in Europe, related to the opening of the Central Atlantic and tectonic/thermal subsidence during spreading of the Alpine Tethys. Our study provides evidence that the Bajocian carbonate rocks in the Jura Mountains area were affected by the circulation of deep-sourced metal-bearing hydrothermal fluids in response to these continent-wide tectonothermal events. The presence of sphalerite mineralization and associated geochemical anomalies in Zn and Cd contents in carbonate rocks may also be used to trace basement features.     

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.