Ore-forming Solutions Research Articles

Behaviours of Ore-forming Solutions in Seawater

Behaviours of Ore-forming Solutions in Seawater

Computer thermodynamic modeling of the transport and deposition of Sb and Au during the formation of Au-Sb deposits

Using the Chiller computer program, we performed modeling of the mechanisms of the joint transport and deposition of Au and Sb from various ore-forming solutions during the formation of Au-Sb deposits. Three models are considered by the example of the Uderei Au-Sb deposit in the Yenisei Ridge: (1) simple cooling (cooling only), (2) iso-enthalpy boiling ( P = f( T)), and (3) solution–rock interaction (rock titration model). The behavior of Sb(III) and Au(I) in the system Au–Sb–Fe–Cu–Pb–Zn–As–H 2O–Cl–H 2S–CO 2 under hydrothermal conditions was studied. It is shown that both weakly alkaline (near-neutral) and reduced acidic Fe aq 2+-enriched low-chloride high-CO 2 and high-chloride hydrothermal solutions play a crucial role in the formation of gold parageneses of Au-Sb ores.

Interaction of model F-bearing silicic melt with chloride fluid, uraninite, and columbite at 750°C and 1000–2000 bar and its implications for estimation of the ore-forming capability of the upper crustal magma chamber beneath the Strel’tsovka caldera, eastern Transbaikalia

The experimental study of an F-bearing silicic melt—U, Nb, Ta minerals—chloride-fluoride fluid system is focused on ascertaining the origin of uranium deposits spatially related to intraplate silicic volcanism. The first series of experiments on uranium solubility in silicic melts close in composition to ore-bearing rhyolite of the unique Strel’tsovka Mo-U ore field has been performed in order to determine more precisely the ore genesis. As starting solid phases, model homogeneous glass of the chemical composition (wt %) 72.18 SiO2, 12.19 Al2O3, 1.02 FeO, 0.20 MgO, 0.33 CaO, 4.78 Na2O, 3.82 K2O, 1.44 Li2O, and 2.4 F (LiF, NaF, KF, CaF2, MgF2); synthetic UO2 and UO3·0.33H2O; and natural columbite were used. The starting solutions contained 1.0 m Cl and 10−2m F. The runs were conducted in a gas vessel at a pressure of 1000 bar and in a high-pressure hydrothermal vessel at 2000 bar. The O2 (H2) fugacity was set by Ni-NiO, Co-CoO, Fe3O4-Fe2O3, and Cu-Cu2O buffers. The equilibrium between melt and solution for major elements is reached during the first day, whereas 5–7 days are required for ore elements (U, Nb, Ta) to come into equilibrium. The solubility of Nb and especially Ta in Cl-F solutions equilibrated with F-bearing melt is extremely low. The solubility of U is much higher (10−4−10−5 mol/kg H2O). The energy dispersive spectroscopy of run products allowed us to establish that columbite dissolved incongruently with formation of U- and F-bearing pyrochlores. The performed experiments have shown that a silicic melt close to the rhyolitic magma of the Strel’tsovka caldera in composition is not able to generate postmagmatic ore-forming solutions containing more than 10−6−10−5 mol U/kg H2O under the relatively low pressure necessary for the existence of the first type of fluid. The amount of uranium that could have precipitated from this fluid in the zone of ore deposition is estimated at 216–9000 t. This estimate is two orders of magnitude lower than the total uranium resources of the deposits localized in the Strel’tsovka caldera. Thus, the upper crustal silicic magma chamber hardly was a source of uranium for Mo-U deposits of the Strel’tsovka ore field.

The Dynamic Mechanisms for the Formation of Primary Metal Zoning of Cassiterite-Sulfide Deposits in the Gejiu Metallogenic Province, Yunnan

Abstract Copper and tin in cassiterite-sulfide deposits of the Gejiu metallogenic province are intimately associated and show peculiar primary metal zoning. The authors made use of computer techniques to simulate numerically the zoning of these ore deposits. The study shows that the regular spatial zoning probably resulted from the succession of multiple, intermittent and pulsatory mineralizations. The successive transports with diverse velocities along channelways of the ore-forming solutions, taking place under conditions of definite difference between metal concentrations, in solutions and wallrocks, followed by differential deposition, constitute possible dynamic mechanisms for the primary metal zoning.

Genesis of Middle Miocene Yellowstone hotspot-related bonanza epithermal Au–Ag deposits, Northern Great Basin, USA

Epithermal deposits with bonanza Au–Ag veins in the northern Great Basin (NGB) are spatially and temporally associated with Middle Miocene bimodal volcanism that was related to a mantle plume that has now migrated to the Yellowstone National Park area. The Au–Ag deposits formed between 16.5 and 14 Ma, but exhibit different mineralogical compositions, the latter due to the nature of the country rocks hosting the deposits. Where host rocks were primarily of meta-sedimentary or granitic origin, adularia-rich gold mineralization formed. Where glassy rhyolitic country rocks host veins, colloidal silica textures and precious metal–colloid aggregation textures resulted. Where basalts are the country rocks, clay-rich mineralization (with silica minerals, adularia, and carbonate) developed. Oxygen isotope data from quartz (originally amorphous silica and gels) from super-high-grade banded ores from the Sleeper deposit show that ore-forming solutions had δ 18O values up to 10‰ heavier than mid-Miocene meteoric water. The geochemical signature of the ores (including their Se-rich nature) is interpreted here to reflect a mantle source for the “epithermal suite” elements (Au, Ag, Se, Te, As, Sb, Hg) and that signature is preserved to shallow crustal levels because of the similar volatility and aqueous geochemical behavior of the “epithermal suite” elements. A mantle source for the gold in the deposits is further supported by the Pb isotopic signature of the gold ores. Apparently the host rocks control the mineralization style and gangue mineralogy of ores. However, all deposits are considered to have derived precious metals and metalloids from mafic magmas related to the initial emergence of the Yellowstone hotspot. Basalt-derived volatiles and metal(loid)s are inferred to have been absorbed by meteoric-water-dominated geothermal systems heated by shallow rhyolitic magma chambers. Episodic discharge of volatiles and metal(loid)s from deep basaltic magmas mixed with heated meteoric water to create precious metal ore-forming fluids. Colloidal nanoparticles of Au–Ag alloy (electrum), naumannite (Ag2Se), silica, and adularia, likely nucleated at depth, traveled upward, and deposited where they grew large enough to aggregate along vein walls. Silica and gold colloids have been reported in hot springs from Yellowstone National Park, suggesting that such processes may continue to some extent to the present. However, it is possible that the initial development of the mantle plume led to a major but short-lived “distillation” process which led to the mid-Miocene bonanza ore-forming event.

Physicochemical modeling of the coupled behavior of gold and silver in hydrothermal processes: Gold fineness, Au/Ag ratios and their possible implications

An estimation of gold fineness deposited from aqueous sulphide–chloride solutions in pyritic ore with varying (Au/Ag) ore has been obtained using thermodynamic modeling (at T = 200–500 °C and P = 1000 bar). Silver sulphide with Au–Ag solid solution or Au–Ag solid solution are only stable under conditions of the Py–Po(–Mt) and Hem–Py (–Mt) buffers depending on Au and Ag concentrations in the ore-forming system. The predominant Au and Ag species in aqueous sulphide–chloride solutions depend on temperature, pH and chloride concentration and these solutions can be grouped as follows: Type I: Acid, high chloride ( m HCl > 0.0l, m NaCl = 1 to 5), high temperature (300–500 °C) solutions in which AgCl 2 − and AuCl 2 − are dominant; Type II: Weakly acidic, near-neutral, medium chloride ( m NaCl ≈ 1), moderate to high temperature (200–400 °С) solutions in which AgCl 2 − and AuHS 0 are dominant; Type III: Near-neutral, high chloride ( m NaCl = 1 to 5), high temperature (300–500 °С) solutions in which AgCl 2 − and Au(HS) 2 − are dominant; Type IV: Alkaline, variable chloride ( m NaOH > 0.01, m NaCl = 0 to 5), moderate to high temperature (200–500 °C) solutions in which Au(HS) 2 − and Ag(HS) 2 − are dominant; and Type V: Acid to near-neutral, low chloride ( m NaCl < 1), low to moderate temperature (< 300 °C) solutions in which AuHS 0 and AgHS 0 are dominant. The acid and near-neutral high- and medium chloride solutions (types I–III) are distinguished by high Ag-carrying capacity and low values of (Au/Ag) aq ≈ 10 − 7 to 10 − 2 . The highest Au-carrying capacity and high (Au/Ag) aq ratios (≈ 10 − 3 to 1) are typical of alkaline solutions of any chloride concentrations (type IV) and low chloride solutions of variable acidity (type V). Data on the physicochemical conditions of Au–Ag mineralization and mineralogical–geochemical characteristics of pyritic ores of hydrothermal gold deposits of different types are summarized. Wide ranges of gold fineness and low (Au/Ag) ore ratios of Au–Ag epithermal, Au–Cu-porphyry and Au–Cu-skarn deposits are related to the participation of acid or near-neutral high- or medium chloride ore-forming solutions (types I–III). High fineness gold and high values of (Au/Ag) ore ratio of Au–Te, Au–As, Au–Sb, Au orogenic and Carlin-type deposits are explained by participation of alkaline (type IV) or low chloride (type V) sulphide solutions. Gold fineness and (Au/Ag) ore ratios in the sulphide ores may be characteristics that determine the type of ore solution and its evolution in the process of hydrothermal deposit formation.

Wall-rock metasomatism of carbonaceous terrigenous rocks in the Lena gold district

The Lena gold district is situated in the fold-and-shear belt of the southern framework of the Siberian Platform. The gold deposits are hosted in the Riphean-Vendian Khomolkho and Aunakit formations, revealing the strict control of ore mineralization by folding and shearing. The microstructure of metasomatically altered ore-bearing carbonaceous sedimentary rocks at the Sukhoi Log, Golets Vysochaishy, and Verninsky deposits (the latter includes the Pervenets vein zone) testifies to parallelism in the development of shearing, foliation, and ore-forming metasomatism. The local pressure gradients are marked by removal of silica from pressured zones into opened cleavage fractures and pockets. Two metasomatic stages are recognized: (1) early sodic metasomatism, which is characterized by the assemblage of magnesian siderite and paragonite, and (2) late potassic metasomatism, with formation of muscovite in association with sideroplesite and ankerite. The rocks altered at the early stage are distinguished by elevated Ni, Cr, and probably PGE contents. The second stage, close in age to the emplacement of Hercynian granitic plutons, was accompanied by the gain of chalcophile metals and deposition of the bulk of gold. In mineral composition, the metasomatic rocks are close to beresites, but the alteration differed in somewhat elevated alkalinity, so that microveinlets of albite and potassium feldspar occur in the ore zone together with muscovite. The ratio of modal muscovite to paragonite contents in orebodies is substantially higher than in the surrounding metasomatized rocks. This ratio directly depends on the degree of rock permeability and the intensity of the flow of ore-forming solutions. Carbonaceous matter (CM) in the ore zone underwent reworking and redeposition. CM is graphitized to a lesser extent than in the rocks affected by regional metamorphism. The spatial distribution of CM containing nitro and amino groups indicates more oxidizing conditions in the zone of ore deposition than at a distance from this zone. The temperature of metasomatic processes estimated from the muscovite, muscovite-paragonite, and chlorite mineral thermometers and fluid inclusions in quartz was 300–350°C at a pressure of about 1 kbar. The S, O, and C isotopic compositions of ore-forming fluids that pertain to the second stage of metasomatism (δ34S= +8.5‰, δ18O = +10‰, and δ13C= −11 to −18‰) indicate their crustal origin. The generally similar conditions and products of the ore-forming metasomatic process at the giant Sukhoi Log deposit and at the small Golets Vysochaishy deposit are combined with some differences. The formation of the described deposits was related to the deep convection of fluids along shear zones followed by more local flows of postmagmatic solutions derived from the emplaced granitic magma.

REE geochemical characteristics of the No. 302 uranium deposit in northern Guangdong, South China

The No. 302 uranium deposit, located in Guangdong Province, is a typical granite-type uranium ore deposit. REE geochemical characteristics of the wall rocks, pitchblende, altered rocks, calcite and fluorite from this deposit have been systematically studied in this paper. The result showed that the alkali-metasomatic granites and other altered rocks have the same REE distribution patterns as Indosinian granites. It is indicated that the hydrothermal ore-forming solution had altered the Indosinian granites, and ore-forming materials may directly originate from the Indosinian granites. Calcite and fluorite of different stages are the products derived from the same source but different stages. The evolution and degassing of the mineralizing solution might induce LREE enrichment to varying degree. Mantle fluid and a large volume of mineralizer may be the crucial factors controlling uranium mineralization, and the hydrothermal solution with mineralizer played an important role in U transport and concentration. Meanwhile, the degassing of CO2 might promote U and REE precipitation.

Geochemistry of Apatite from the Apatite‐rich Iron Deposits in the Ningwu Region, East Central China

Abstract: Four types of apatite have been identified in the Ningwu region. The first type of apatite is widely distributed in the middle dark colored zones (i.e. iron ores) of individual deposits. The assemblage includes magnetite, apatite and actinolite (or diopside). The second type occurs within magnetite‐apatite veins in the iron ores. The third type is seen in magnetite‐apatite veins and (or) nodules in host rocks (i.e. gabbro‐diorite porphyry or gabbro‐diorite or pyroxene diorite). The fourth type occurs within apatite‐pyrite‐quartz veins filling fractures in the Xiangshan Group. Rare earth elements (REE) geochemistry of apatite of the four occurrences in porphyry iron deposits is presented. The REE distribution patterns of apatite are generally similar to those of apatites in the Kiruna‐type iron ores, nelsonites. They are enriched in light REE, with pronounced negative Eu anomalies. The similarity of REE distribution patterns in apatites from various deposits in different locations in the world indicates a common process of formation for various ore types, e.g. immiscibility. Early magmatic apatites contain 3031.48–12080 times 10−6 REE. Later hydrothermal apatite contains 1958 times 10−6 REE, indicating that the later hydrothermal ore‐forming solution contains lower REE. Although gabbro‐diorite porphyry and apatite show similar REE patterns, gabbro‐diorite porphyries have no europium anomalies or feeble positive or feeble negative europium anomalies, caused both by reduction environment of mantle source region and by fractionation and crystallization (immiscibility) under a high oxygen fugacity condition. Negative Eu anomalies of apatites were formed possibly due to acquisition of Eu2+ by earlier diopsite during ore magma cooling.The apatites in the Aoshan and Taishan iron deposits yield a narrow variation range of 87Sr/86Sr values from 0.7071 to 0.7073, similar to those of the volcanic and subvolcanic rocks, indicating that apatites were formed by liquid immiscibility and differentiation of intermediate and basic magmas.

Concordant ages for the giant Kipushi base metal deposit (DR Congo) from direct Rb–Sr and Re–Os dating of sulfides

We report concordant ages of 451.1 ± 6.0 and 450.5 ± 3.4 Ma from direct Rb–Sr and Re–Os isochron dating, respectively, of ore-stage Zn–Cu–Ge sulfides, including sphalerite for the giant carbonate-hosted Kipushi base metal (+Ge) deposit in the Neoproterozoic Lufilian Arc, DR Congo. This is the first example of a world-class sulfide deposit being directly dated by two independent isotopic methods. The 451 Ma age for Kipushi suggests that the ore-forming solutions did not evolve from metamorphogenic fluids mobilized syntectonically during the Pan-African-Lufilian orogeny but rather were generated in a Late Ordovician postorogenic, extensional setting. The homogeneous Pb isotopic composition of the sulfides indicates that both Cu–Ge- and Zn-rich orebodies of the Kipushi deposit formed contemporaneously from the same fluid system. The sulfide Pb isotope signatures in combination with initial 87Sr/86Sr and 187Os/188Os ratios defined by the isochrons point to metal sources located in the (upper) crust. The concordant Re–Os and Rb–Sr ages obtained in this study provide independent proof of the geological significance of direct Rb–Sr dating of sphalerite.

Physicochemical formation conditions of banded iron formations and high-grade iron ores in the region of the Kursk Magnetic Anomaly: Evidence from isotopic data

The oxygen and carbon isotopic compositions of minerals from banded iron formations (BIFs) and high-grade ore in the region of the Kursk Magnetic Anomaly (KMA) were determined in order to estimate the temperature of regional metamorphism and the nature of rock-and ore-forming solutions. Magnetite and hematite of primary sedimentary or diagenetic origin have δ18O within the range from +2 to 6‰. During metamorphism, primary iron oxides, silicates, and carbonates were involved in thermal dissociation and other reactions to form magnetite with δ18O = +6 to +11‰. As follows from a low δ18Oav = −3.5‰ of mushketovite (magnetite pseudomorphs after hematite) in high-grade ore, this mineral was formed as a product of hematite reduction by organic matter. The comparison of δ18O of iron oxides, siderite, and quartz from BIFs formed at different stages of the evolution of the Kursk protogeosyncline revealed specific sedimentation (diagenesis) conditions and metamorphism of the BIFs belonging to the Kursk and Oskol groups. BIF of the Oskol Group is distinguished by a high δ18O of magnetite compared to other Proterozoic BIFs. Martite ore differs from host BIF by a low δ18O = −0.2 to −5.9‰. This implies that oxygen from infiltration water was incorporated into the magnetite lattice during the martite formation. Surface water penetrated to a significant depth through tectonic faults and fractures.

Physicochemical parameters of magmatic and hydrothermal processes at the Yaman-Kasy massive sulfide deposit, the southern Urals

Melt and fluid inclusions in minerals have been studied and physicochemical parameters of magmatic processes and hydrothermal systems estimated at the Yaman-Kasy copper massive sulfide deposit in the southern Urals. It was established that relatively low-temperature (910–945°C) rhyodacitic melts belonging to the tholeiitic series and containing 2.7–5.2 wt % water participated in the formation of the igneous complexes that host the Yaman-Kasy deposit. As follows from ion microprobe results, these silicic magmas had a primitive character. In the distribution of trace elements, including REE, the rhyodacites are closer to basaltic rather than silicic volcanic rocks, and they are distinguished in this respect from the igneous rocks from other massive sulfide deposits of the Urals and the Rudny Altai. Two types of solutions actively took part in the formation of hydrothermal systems: (1) solutions with a moderate salinity (5–10 wt % dissolved salts) and (2) solutions with a low salinity (a value close to that of seawater or even lower). Concentrated fluids with more than 11.5 wt % dissolved salts were much less abundant. Hydrothermal solutions heated to 130–160, 160–270, or occasionally 280–310°C predominated in ore formation. The sequence of mineral-forming processes at the Yaman-Kasy deposit is demonstrated. Mineral assemblages were formed with an inversion of the parameters characterizing ore-forming solutions. An increase in the temperature and salinity of solutions at the early stages was followed by a decrease at the final stages. The evolution of the hydrothermal system at the Yaman-Kasy deposit has much in common with the parameters of black smokers in the present-day Pacific backarc basins.

Partizansky base-metal skarn deposit, Dal’negorsk ore district, Russia: Stages of ore formation, mineral assemblages, and typomorphism of fahlore

As indicated by mineralogical, geochemical, and structural-textural data, the base-metal skarn ore at the Partizansky deposit was formed during two stages (base-metal skarn and silver-sulfosalt), which were separated by intrusion of basaltic dikes. The bulk of the base-metal ore was deposited at the first stage, which comprises four sequential mineral assemblages: skarn-silicate, quartz-arsenopyrite, productive galena-sphalerite, and pyrrhotite-pyrite-chalcopyrite. The mineralization of the second stage was mainly confined to the upper margins of orebodies and pertains to the sulfosalt-galena-chalcopyrite assemblage, which was super-imposed on minerals of the first stage. The vertical mineralogical-geochemical zoning of the deposit is telescopic (related to the formation of the late silver-sulfosalt mineralization) and facies (typical of the early skarn and base-metal assemblages). The zoning of the skarn-silicate assemblage is expressed in the metasomatic replacement of skarn by quartz and calcite in the uppermost zone of skarn bodies and is emphasized by variation of the mineral composition throughout the skarn column, for instance, by the distinct updip enrichment of hedenbergite in manganese. The vertical zoning of the productive assemblage is emphasized by variations in the ratio of sphalerite to galena (the Pb/Zn ratio in the ore increases upward from 0.1 to 1), changes in mineral assemblages, and compositional variation of major ore-forming and minor minerals. In particular, galena from the deep levels is extremely enriched in Bi and Ag, while that from the upper levels is almost completely devoid of isomorphic admixtures. Fahlore displays updip enrichment in Sb, Ag, and Fe and corresponding depletion in Cu and Zn. The vertical chemical variations in fahlore are caused by the specific geological setting of ore deposition, the composition of the ore-forming solutions, and the physicochemical conditions of their transportation and ore deposition.

Synthetic Fluid Inclusions in the Systems NaCl‐H2O and NaCl‐CO2‐H2O: Dissolution Temperatures of Halite

Abstract. This study examined the effect of CO2 on NaCl solubility in hydrothermal fluid, with the synthetic fluid inclusion technique. Fluid inclusions of 30–40 wt% NaCl and 5 mol % CO2 were synthesized, and their halite dissolution temperatures, Tm(halite), were measured. The solubilities of NaCl in CO2‐bearing aqueous fluid were obtained at 160–320d̀C under vapor‐saturated pressures. The Tm(halite) value in aqueous fluid with 5 mol % CO2 obtained in this study agrees with that of Schmidt et al. (1995), showing that 5 mol % CO2 reduces the solubility of NaCl by about 1 wt%.Calculation of magnetite solubility suggests that 5–10 mol % CO2 decreases magnetite solubility by 4.5–8.9 % relative to the magnetite solubility in CO2‐free solution. Therefore, an increase of CO2 content in ore‐forming solutions may cause deposition of iron minerals and produce ore deposits.

Compositions of magmatic melts and evolution of mineral-forming fluids in the banska Stiavnica epithermal Au-Ag-Pb-Zn deposit, Slovakia: A study of inclusions in minerals

Melt and fluid inclusions were investigated in minerals from igneous rocks and ore (Au-Ag-Pb-Zn) veins of the Stiavnica ore field in Central Slovakia. High H2O (7.1–12.0 wt %) and Cl (0.32–0.46 wt %) contents were found in silicate melt inclusions (65–69 wt % SiO2 and 5.2–5.6 wt % K2O) in plagioclase phenocrysts (An 68–36) from biotite-homblende andesites of the eastern part of the caldera. Similar high water contents are characteristic of magmatic melts (71–76 wt % SiO2 and 3.7–5.1 wt % K2O) forming the sanidine rhyolites of the Vyhne extrusive dome in the northwestern part of the Stiavnica caldera (up to 7.1 wt %) and the rhyolites of the Klotilda dike in the eastern part of the ore field (up to 11.5 wt %). The examination of primary inclusions in quartz and sanidine from the Vyhne rhyolites revealed high concentrations of N2 and CO2 in magmatic fluid (8.6 g/kg H2O and 59 g/kg H2O, respectively). Fluid pressure was estimated as 5.0 kbar on the basis of primary CO2 fluid inclusions in plagioclase phenocrysts from the Kalvari basanites. This value corresponds to a depth of 18 km and may be indicative of a deep CO2 source. Quartz from the granodiorites of the central part of the Stiavnica-Hodrusa complex crystallized from a melt with 4.2–6.1 wt % H2O and 0.24–0.80 wt % Cl. Magmatic fluid cogenetic with this silicate melt was represented by a chloride brine with a salinity of no less than 77–80 wt % NaCl equiv. Secondary inclusions in quartz of the igneous rocks recorded a continuous trend of temperature, pressure, and solution salinity, from the parameters of magmatic fluids to the conditions of formation of ore veins. The gold mineralization of the Svyatozar vein system was formed from boiling low-salinity fluids (0.3–8.0 wt % NaCl equv.) at temperatures of 365–160°C and pressures of 160–60 bar. The Terezia, Bieber, Viliam, Spitaler, and Rozalia epithermal gold-silver-base metal veins were also formed from heterogeneous low-salinity fluids (0.3–12.1 wt %) at temperatures of 380–58°C and pressures of 240–10 bar. It was found that the salt components of the solutions were dominated by chlorides (high content of fluorine, up to 0.45 mol/kg H2O, was also detected), and sulfate solutions appeared in the upper levels. The dissolved gas of ore-forming solutions was dominated by CO2 (0.1–8.4 mol %, averaging 1.3 wt %) and contained minor nitrogen (0.00–0.85 mol %, averaging 0.05 mol %) and negligible methane admixtures (0.00–0.05 mol %, averaging 0.004 mol %). These data allowed us to conclude that the magmatic melts could be sources of H2O, Cl, CO2, and N2. The formation of the epithermal mineralization of the Stiavnica ore field was associated with the mixing of magmatic fluid with low-concentration meteoric waters, and the fluid was in a heterogeneous state.

The μ2M project on quantifying the effects of biofilm growth on hydraulic properties of natural porous media and on sorption equilibria: an overview

Abstract The physical and chemical effects of bacterial biofilm formation upon hydraulic conductivity, mineral-solution interactions and the formation of biogenic mineral precipitates have been studied over a wide range of scales, from microscopic to macroscopic. Several novel pieces of equipment have been designed, constructed and commissioned in order to measure the physical effects of biofilms upon fluid flow through fractures and porous media, the overall effects of biofilm formation upon mineral surface reactivity, and the imaging and identification of mineral precipitates formed due to the presence of biofilm and bacterial cell surface polymers on a quartz surface. This paper presents an overview of key experimental methods and selected results; further experimental information is being published elsewhere. Biofilm formation with quartz sand in artificial groundwater resulted in a two orders of magnitude reduction in hydraulic conductivity under bench-scale constant head conditions. However, under quasi-environmental conditions within macroscopic centrifuge experiments, a reduction of 21% was measured, revealing differences in measurements and, hence, the value of the macroscopic experimental work in scaling from micro to macro. In-situ microscopic evaluation of biofilms within simulated quartz rock fractures and in porous media reveal only a small percentage of the biomass to be in direct contact with the mineral surface, allowing mineral chemistry to be predominantly controlled by mineral surface reactivity, rather than by a diffusion-limited mineral-biofilm-solution interface. This is true even when a mineral surface is apparently completely covered by biofilm. The alteration of mineral surface drastically increases the kinetics of surface-coordinated trace metal precipitate formation by providing nucleation sites upon extracellular biopolymers and cell wall polymers. Over geological time-scales, these processes, particularly the formation of thermodynamically stable pore-blocking mineral precipitates, are envisaged to markedly change the flow paths, flow rates and interaction of migrating geofluids (water, petroleum, ore-forming solutions) with minerals and rocks.

Intracratonic crustal seawater circulation and the genesis of subseafloor zinc-lead mineralization in the Irish orefield

We have determined the chemical composition of ∼350-m.y.-old solutions extracted from fluid inclusions, and strontium isotopic compositions of hydrothermal minerals from the Irish zinc-lead orefield. These data show that ore-forming fluids were derived from evaporated seawater and acquired metals by deep circulation within fractures in continental crust. Mineralization occurred in the near-seafloor environment when these solutions returned to the surface via thermohaline convection and mixed with brines rich in H 2 S produced by bacterial reduction of seawater sulfate. The results indicate that deep penetration of seawater or evaporated seawater into the continental crust can occur in rift zones or extending passive margins and that this process can generate large volumes of base metal ore-forming solutions. Our results are inconsistent with topographic flow models for mineralization in the district, and support deep convection models for ore formation. The widespread development of evaporitic brines on the Laurussian continental margin under late Paleozoic greenhouse conditions is likely to have been critical for generating numerous accumulations of base metals in sedimentary basins at this time.

Geochemical characteristics of gold polymetallic deposits as exemplified by the Laozuoshan deposit, Heilongjiang, China

From the studies of ore deposit geologic settings, sulfur isotopes, lead isotopes, carbon isotopes and oxygen isotopes, fluid inclusions and petrochemistry in this paper, the authors have drawn a conclusion that the ore-forming hydrothermal solutions are the high-temperature magmatic hydrothermal solutions for the gold ore deposit, and at the same time, the involvement of crustal materials can not be ruled out. It is the first time that the authors have proposed that the Laozuoshan gold-polymetallic ore deposit in Heilongjiang Province was formed in the calc-alkaline series environment at the margin of an active continent.

Study of tectonic layering motion and layering mineralization in the Tongling metallogenic cluster

Analysis of the deep tectonics and cover tectonic deformations shows that tectonic layering motion is a typical lithospheric characteristic in the Tongling area and the metallogenic belt of the middle-lower Yangtze. Controlling of the deep tectonosphere over the shallow-seated tectonosphere involves various grades of tectonic layering motions. Multi-layer, multi-grade, and multi-directional gliding tectonics are the specific modes of tectonic layering motions in the cover of the Tongling metallogenic cluster. The gliding tectonics developed based on S-shaped folds of the Indosinian, and was continuously active in the Yanshanian. They correspond to the deformation systems of the EW and NNE extensions. The control of tectonic layering motion acts against ore-forming processes, the different interlayer gliding belts can easily form different genetic-type deposits, and the ore-forming features of different parts of the same gliding layer are different. All of these characters are closely related to tectonic gliding mechanisms, tectonic compounding characteristics, features of metallogenic wall rocks, and types of ore-forming hydrothermal solutions.

Stable isotope (S, O, H and C) studies of the phyllic and potassic–phyllic alteration zones of the porphyry copper deposit at Sungun, East Azarbaidjan, Iran

The porphyry copper deposit (PCD) at Sungun is located in East Azarbaidjan, NW of Iran. The magmatic suites in the Sungun area are a part of the NW–SE trending Cenozoic magmatic belt of Iran. The Sungun porphyries occur as stocks and dikes. The stocks are divided into two groups, I and II. Porphyry Stock II, ranging in composition from quartz monzonite through granodiorite to granite, hosts the Sungun PCD. Four distinct types of hypogene alterations were recognized at Sungun: (1) potassic; (2) potassic–phyllic; (3) phyllic; and (4) propylitic. Stable isotope (S, O, H, and C) studies were restricted to within the phyllic and potassic–phyllic alteration zones, where numerous cross-cutting quartz, sulfides, carbonates, and sulfate veinlets are present. The objective of these studies was to determine the origin of the ore-forming solutions, and their important components (e.g. sulfur and carbon). Twenty sulfide and four sulfate samples were taken from sulfide and gypsum veinlets within Porphyry Stock II and the associated skarn zone for sulfur isotopic analyses. The δ 34S values of sulfides (pyrite, chalcopyrite, molybdenite, galena, sphalerite) and sulfate (gypsum) range from −4.6 to −0.2‰ (mean of −1.5‰) and from 10.9 to 14.4‰ (mean of 12.9‰), respectively. These values are almost analogous to those from El Salvador (Chile) and Ajo (Arizona), and Twin Buttes (Arizona), and strongly suggest a magmatic source for the sulfur at Sungun. Twenty-eight fluid inclusion-rich quartz samples from quartz veinlets beneath the supergene zones of the Porphyry Stock II were chosen for O and H isotopic analyses. The δ 18O (of quartz) and δD (of fluid inclusions in quartz) values range from 8.3 to 10.2‰ (mean of 9.2‰) and −58 to −75‰ (mean of −66‰) relative to Standard Mean Ocean Water (SMOW), respectively. The calculated δ 18O values of the fluids range from 4.4‰ (T=375 ° C) to 7.6‰ (T=570 ° C) with a mean of 6.4‰. The δ 18O and δD values of the fluids lie within the typical range of magmatic waters. Based upon the lowest obtained δD values, the calculated maximum exchangeable meteoric water that might be involved in the phyllic and potassic–phyllic alteration processes was ∼20%. Fourteen calcite samples from carbonate veinlets in the Porphyry Stock II and two samples from associated marble aureole were collected for carbon and oxygen isotopic analyses. The δ 13C (calcite) from Porphyry Stock II and associated marble aureole varies from −0.4 to 2.9‰ and 0.06 to 2‰ relative to the PDB Standard of the University of Chicago, respectively. The corresponding δ 18O (calcite) values range from 6 to 13.2‰ relative to SMOW. The δ 13C values lie within the sedimentary range, suggesting that there was little or almost no magmatic carbon in the hydrothermal system. In contrast, The δ 18O (calcite) values are far lower than that of Cretaceous sedimentary carbonates which suggest that the values were influenced by those of magmatic fluids through isotopic re-equilibration. These isotopic investigations demonstrated that: (1) in contrast to some well-known PCDs, about 80% of the fluids involved in the phyllic and potassic–phyllic alterations at Sungun had a magmatic O and H isotopic signature; (2) the Upper Cretaceous limestone was the potential source of C; and (3) the sulfur had a magmatic origin.