Organic matters and acid‐sulfate alteration in Itomuka mercury mine,Hokkaido, Japan: Implications for the transportation and deposition mechanisms of Hg

In order to examine the transportation and deposition mechanisms of Hg, we investigated the ore and hydrothermal alteration minerals and solid organic matters from Itomuka mercury mine located in the eastern part of central Hokkaido. In addition to the ore minerals, native mercury and cinnabar, quartz, marcasite, alunite, kaolinite, and minor amounts of pyrite and smectite were identified in the Hg ore by powder X‐ray diffraction (XRD) analysis. This mineral assemblage of acid sulfate alteration was likely developed under the conditions of low temperature (≤100°C) and low pH (≤2) in the steam‐heated environment. The H₂SO₄ was produced above the water table by the oxidation of H₂S separated from deep, near‐neutral fluids by boiling. The dominance of native mercury over cinnabar in Hg ore indicates that the greater part of mineralized Hg was transported as Hg⁰ in aqueous solution and vapor with low sulfur fugacity. The solid organic matters found in the Hg ore were analyzed with SEM‐EDS, micro‐XRD, and micro‐Fourier transform infrared (FTIR) spectroscopy, and these results suggest that the organic matters contributed to keeping the low fO₂ of the Hg‐bearing fluid and transportation of Hg as Hg⁰ in S‐poor condition. Because the solubility of Hg in acidic fluid is low, neutral to alkaline fluid seems to have leached Hg from the basement sedimentary rocks of Hidaka Group which also supplied the organic matters to the fluid. The oxidation and cooling of Hg‐bearing solution and vapor triggered the deposition of liquid Hg as a primary phase.     

Hg<Superscript>0</Superscript>(liq)-Hg<Superscript>0</Superscript>(solution) equilibrium and solubility of elementary mercury in water

The solubility metallic mercury in water and its dominating forms were studied. The prevalence of the Hg_aq⁰ form in the high-temperature range was confirmed and the reaction constant Hg_liq⁰ ai Hg_aq⁰ (logK = logm = −8.01) at 25°C with the predominance of oxidized forms of mercury for the 20–80°C area of low temperatures was found.     

Mercury speciation in tailings of the Idrija mercury mine

Five hundred years of mercury (Hg) mining activity in Idrija, Slovenia caused widespread Hg contamination. Besides Hg emissions from the ore smelter, tailings have been found to be the major source of river sediment contamination. In the present study, solid phase binding forms and the aqueous mobility of Hg have been investigated in tailings of the Idrija Hg mine by means of a pyrolysis technique and aqueous Hg speciation. Results show that Hg binding forms differ with the age of the tailings due to the processing of different ores with different roasting techniques. In older tailings, the predominant Hg species is cinnabar (HgS), due to incomplete roasting, whereas in tailings of the 20th century the amount of cinnabar in the material decreased due to a higher efficiency of the roasting process and the increasing use of ores bearing native Hg. In younger tailings, metallic Hg (Hg⁰) sorbed to mineral matrix components such as dolomite and Fe-oxyhydroxides became the predominant Hg binding form in addition to unbound Hg⁰ and traces of HgO. Leaching tests show that in younger tailings high amounts of soluble Hg exist in reactive form. In older tailings most of the soluble Hg occurs bound to soluble complexes. It might be assumed that in the long term, matrix-bound Hg⁰ could be bound to humic acids derived from soils covering the tailings. This means that, despite the lower total Hg concentrations found in the younger tailings, the long-term risk potential of its mobile matrix-bound Hg⁰ is higher than that of older tailings bearing mostly immobile cinnabar.     

Mercury mobilization by oxidative dissolution of cinnabar (α-HgS) and metacinnabar (β-HgS)

Cinnabar (α-HgS) and metacinnabar (β-HgS) dissolved at environmentally significant rates in oxygenated slurry experiments simulating a low-flow fluvial system. Based on SO₄²⁻ production, cinnabar dissolution rates were 2.64 to 6.16 μmol (SO₄²⁻) m^− 2 day^− 1, and metacinnabar dissolution rates were 1.20 to 1.90 μmol (SO₄²⁻) m^− 2 day^− 1. Monodentate-bound thiosulfate (S₂O₃²⁻) was identified as an oxidation product on the HgS surface by ATR-IR spectroscopy based on strong infrared absorption bands in the 1140–1145 cm^− 1 and 1006–1014 cm^− 1 regions. The presence of sulfide oxidation intermediates on the HgS surface indicates that SO₄²⁻ concentration underestimates α-HgS and β-HgS dissolution in this setting. Mercury release rates during dissolution were more than two orders of magnitude less than SO₄²⁻ production, but were significant: 0.47 mg (Hg) m^− 2 y^− 1 from cinnabar [6.45 nmol (Hg) m^− 2 day^− 1], and 0.17 mg (Hg) m^− 2 y^− 1 from metacinnabar [2.29 nmol (Hg) m^− 2 day^− 1]. The Hg mobilized during α-HgS and β-HgS dissolution is sufficient to form natural Au–Hg amalgam in downstream placer settings. The proportion of mercury that is not remobilized during α-HgS and β-HgS dissolution likely adsorbs to the dissolving mercuric sulfide. Adsorption of Hg²⁺ to cinnabar was detected in situ by anodic stripping voltammetry using a cinnabar-modified carbon paste electrode following accumulation of Hg²⁺ on the electrode at open circuit potential.     

Mercury mobility in mine waste from Hg-mining areas in Almería,Andalusia (Se Spain)

Mining wastes and calcines from two abandoned mining areas (Valle del Azogue and Bayarque in Almería) have been characterized. In the mining wastes, the dominant mercury phases are cinnabar and elemental mercury in the matrix. In the calcines, however, the dominant mercury phase is elemental mercury bounded to the matrix. Water-leaching experiments were conducted on low-grade stockpiles and calcines in order to simulate the mobilization of mercury by runoff under environmental conditions. The laboratory column-leaching experiments show a possible mobilization of mercury from Hg⁰ dissolution, colloid transport and a possible dissolution of calomel and other soluble phases in the mine wastes from the Valle del Azogue and Bayarque mines. Equilibrium speciation modeling of Hg, conducted using the numerical code MINTEQ, showed that the theoretical dominant mercury species in the calcine and mining wastes samples are Hg(OH)₂, HgCl₂, HgClOH and Hg⁰. In some leachates obtained from the Valle del Azogue mining wastes (sample A06), the high Hg concentrations may indicate the possible dissolution of mineral phases such as calomel and other soluble phases, which are subsaturated. The environmental results indicate a great environmental mobility of mercury, especially during wet episodes associated with intense precipitation events, when there are significative amounts of secondary soluble minerals.     

Geological and anthropogenic factors influencing mercury speciation in mine wastes: an EXAFS spectroscopy study

The speciation of Hg is a critical determinant of its mobility, reactivity, and potential bioavailability in mine-impacted regions. Furthermore, Hg speciation in these complex natural systems is influenced by a number of physical, geological, and anthropogenic variables. In order to investigate the degree to which several of these variables may affect Hg speciation, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the Hg phases and relative proportions of these phases present in Hg-bearing wastes from selected mine-impacted regions in California and Nevada. The geological origin of Hg ore has a significant effect on Hg speciation in mine wastes. Specifically, samples collected from hot-spring Hg deposits were found to contain soluble Hg-chloride phases, while such phases were largely absent in samples from silica-carbonate Hg deposits; in both deposit types, however, Hg-sulfides in the form of cinnabar (HgS, hex.) and metacinnabar (HgS, cub.) dominate. Calcined wastes in which Hg ore was crushed and roasted in excess of 600 °C, contain high proportions of metacinnabar while the main Hg-containing phase in unroasted waste rock samples from the same mines is cinnabar. The calcining process is thought to promote the reconstructive phase transformation of cinnabar to metacinnabar, which typically occurs at 345 °C. The total Hg concentration in calcines is strongly correlated with particle size, with increases of nearly an order of magnitude in total Hg concentration between the 500–2000 μm and <45 μm size fractions (e.g., from 97–810 mg/kg Hg in calcines from the Sulphur Bank Mine, CA). The proportion of Hg-sulfides present also increased by 8–18% as particle size decreased over the same size range. This finding suggests that insoluble yet soft Hg-sulfides are subject to preferential mechanical weathering and become enriched in the fine-grained fraction, while soluble Hg phases are leached out more readily as particle size decreases. The speciation of Hg in mine wastes is similar to that in distributed sediments located downstream from the same waste piles, indicating that the transport of Hg from mine waste piles does not significantly impact Hg speciation. Hg L_III-EXAFS analysis of samples from Au mining regions, where elemental Hg(0) was introduced to aid in the Au recovery process, identified the presence of Hg-sulfides and schuetteite (Hg₃O₂SO₄), which may have formed as a result of long-term Hg(0) burial in reducing high-sulfide sediments.     

Mercury methylation influenced by areas of past mercury mining in the Terlingua district,Southwest Texas,USA

Speciation and microbial transformation of Hg was studied in mine waste from abandoned Hg mines in SW Texas to evaluate the potential for methyl-Hg production and degradation in mine wastes. In mine waste samples, total Hg, ionic Hg²⁺, Hg⁰, methyl-Hg, organic C, and total S concentrations were measured, various Hg compounds were identified using thermal desorption pyrolysis, and potential rates of Hg methylation and methyl-Hg demethylation were determined using isotopic-tracer methods. These data are the first reported for Hg mines in this region. Total Hg and methyl-Hg concentrations were also determined in stream sediment collected downstream from two of the mines to evaluate transport of Hg and methylation in surrounding ecosystems. Mine waste contains total Hg and methyl-Hg concentrations as high as 19,000 μg/g and 1500 ng/g, respectively, which are among the highest concentrations reported at Hg mines worldwide. Pyrolysis analyses show that mine waste contains variable amounts of cinnabar, metacinnabar, Hg⁰, and Hg sorbed onto particles. Methyl-Hg concentrations in mine waste correlate positively with ionic Hg²⁺, organic C, and total S, which are geochemical parameters that influence processes of Hg cycling and methylation. Net methylation rates were as high as 11,000 ng/g/day, indicating significant microbial Hg methylation at some sites, especially in samples collected inside retorts. Microbially-mediated methyl-Hg demethylation was also observed in many samples, but where both methylation and demethylation were found, the potential rate of methylation was faster. Total Hg concentrations in stream sediment samples were generally below the probable effect concentration of 1.06 μg/g, the Hg concentration above which harmful effects are likely to be observed in sediment dwelling organisms; whereas total Hg concentrations in mine waste samples were found to exceed this concentration, although this is a sediment quality guideline and is not directly applicable to mine waste. Although total Hg and methyl-Hg concentrations are locally high in some mine waste samples, little Hg appears to be exported from these Hg mines in stream sediment primarily due to the arid climate and lack of precipitation and mine runoff in this region.     

Characteristics of the geothermal water in Changbai Mountain volcanic region,northeast of China

Geothermal water is plentiful in Changbai Mountain region, northeastern China, due to the volcanic activities and widespread faults. For the exploration of geothermal resources, this study uses quartz and cation geothermometer to estimate the temperatures of the geothermal reservoir and uses the tubular models to evaluate the thermal gradient. The hydrogeochemical characteristics of the geothermal resources were also evaluated by hydrogeochemical analysis. The results showed that the geothermal reservoir temperatures of the four major thermal springs in Changbai Mountain region range from 72 to 169 °C. The average geothermal reservoir temperatures of Jinjiang hot springs, Changbai hot springs I, Xianrenqiao hot springs, and Changbai hot springs II are 129.25, 169, 89, and 73.67 °C, respectively. The geothermal gradient values of the four major thermal springs have different characteristics. The geothermal gradient values of Jinjiang hot springs and Changbai hot springs I are 4.6 and 3.1 °C/100 m, respectively. The geothermal gradient values of Xianrenqiao thermal springs and Changbai thermal springs II are both lower than 1.5 °C/100 m, with the values of 1.1 and 1.4 °C/100 m. And the geothermal gradients are influenced by Changbai Mountain Tianchi volcano. In addition, the water chemical analyses showed that the geothermal water types are HCO₃-Na with higher concentrations of Na⁺, Cl^?, SO₄ ^2?, TDS, and HCO₃ ^? than the non-thermal waters, which suggested a deep and long water cycle of the thermal water, and therefore a sufficient water-rock interaction.     

The use of geochemical indicator elements in the exploration for hot water sources within geothermal fields

Soils, rocks, altered rocks, hot and cold waters, and hot spring precipitates were sampled within and on the outskirts of geothermal fields in China. The contents of thirty trace elements in soils and rocks show that Hg, As, Sb, Bi, Li, Rb, Cs, Au, Ag, B, W, Sn, Pb, Zn, Mn, Ni and Co can serve as direct and indirect indicators for geothermal field exploration. Large amounts of data indicate that Hg, As and Sb are the best indicators of hot water sources. Altered rocks contain higher Hg, As, Sb, Bi and Be than unaltered rocks. Based on their abundances in hot waters, it is suggested that the following elements may be used as hydrochemical indicators of high-temperature hot-water geothermal systems: K⁺, Na⁺, Ca²⁺, Mg²⁺, SO²⁻₄, HCO⁻₃, F⁻, Cl⁻, SiO₂, HBO₂, CO₂, pH, total dissolved solids and hydrochemical types, as well as Hg, As, Sb, Be, Li, Rb and Cs. Modern precipitates associated with hot springs have high contents of Ba, Be, Fe, Ti, Hg, As, Sb and Bi. Using these geochemical data, the authors have had much success in locating hot water drill sites within geothermal fields. Case histories are described for five geothermal areas.     

Le système hydrothermal actuel de Los Humeros (Mexique): Etat du système SO −− 4 —SH2 à 300°C,origine du soufre et phénomènes d'oxydation associés à l'ébullition du fluide ascendant

In the geothermal system of Los Humeros, hydrothermal fluids are low in sulfur (7.7 mM/kg) and are slightly alkaline (pH of ca. 8.5) at depth. Nevertheless, the aqueous sulfate-sulfide species are in isotopic and chemical equilibrium. The “freezing” of these equilibria at 290 °C is tentatively related to boiling of water at this temperature. In the LH1 borehole δ³⁴S values for pyrite (ca. 0‰) and present aqueous SH₂ (ca. ?12‰) are very different. Measured δ³⁴S value of the bulk aqueous sulfur is close to ?11‰ These data suggest a possible magmatic origin of pyrite (ca. 0‰) and, in contrast, a sedimentary source for the present hydrothermal sulfur. The CO₂/CH₄ molar ratio of 58 determined in the fluid from this well is much lower than the ratio calculated for 300° and 350 °C. This divergence is eliminated when the equilibrium constant is reestimated (log K_G=?7.9 at 300 °C). Based on fluid inclusion study the boiling of hydrothermal fluid before the geothermal area was opened by drilling is proven in neoformed minerals sampled at different levels of the volcanic sequence. In this way, the pervasive oxidation of the primary reduced paragenesis (pyrite + pyrrhotite + magnetite) can be explained. The boiling of the ascending water does induce a H₂ loss from the liquid and creates more oxidizing conditions in the ascending liquid. Moreover, the continuous vaporization of liquid water induces its gradual cooling and increases the ascension speed. Furthermore, a persistence of chemical equilibrium between primary paragenesis and the hydrothermal fluid at different levels would require a very fast and unrealistic adjustment of the fO₂-fH₂ parameters to the local equilibrium conditions. This expected disequilibrium induces the afore mentioned oxidation processes under steady-state conditions.     

Mercury in the Southern Ocean

We present here the first mercury speciation study in the water column of the Southern Ocean, using a high-resolution south-to-north section (27 stations from 65.50°S to 44.00°S) with up to 15 depths (0-4440 m) between Antarctica and Tasmania (Australia) along the 140°E meridian. In addition, in order to explore the role of sea ice in Hg cycling, a study of mercury speciation in the “snow-sea ice-seawater” continuum was conducted at a coastal site, near the Australian Casey station (66.40°S; 101.14°E). In the open ocean waters, total Hg (Hg_T) concentrations varied from 0.63 to 2.76 pmol L⁻¹ with “transient-type” vertical profiles and a latitudinal distribution suggesting an atmospheric mercury source south of the Southern Polar Front (SPF) and a surface removal north of the Subantartic Front (SAF). Slightly higher mean Hg_T concentrations (1.35 ± 0.39 pmol L⁻¹) were measured in Antarctic Bottom Water (AABW) compared to Antarctic Intermediate water (AAIW) (1.15 ± 0.22 pmol L⁻¹). Labile Hg (Hg_R) concentrations varied from 0.01 to 2.28 pmol L⁻¹, with a distribution showing that the Hg_T enrichment south of the SPF consisted mainly of Hg_R (67 ± 23%), whereas, in contrast, the percentage was half that in surface waters north of PFZ (33 ± 23%). Methylated mercury species (MeHg_T) concentrations ranged from 0.02 to 0.86 pmol L⁻¹. All vertical MeHg_T profiles exhibited roughly the same pattern, with low concentrations observed in the surface layer and increasing concentrations with depth up to an intermediate depth maximum. As for Hg_T, low mean MeHg_T concentrations were associated with AAIW, and higher ones with AABW. The maximum of MeHg_T concentration at each station was systematically observed within the oxygen minimum zone, with a statistically significant MeHg_Tvs Apparent Oxygen Utilization (AOU) relationship (p < 0.001). The proportion of Hg_T as methylated species was lower than 5% in the surface waters, around 50% in deep waters below 1000 m, reaching a maximum of 78% south of the SPF. At Casey coastal station Hg_T and Hg_R concentrations found in the “snow-sea ice-seawater” continuum were one order of magnitude higher than those measured in open ocean waters. The distribution of Hg_T there suggests an atmospheric Hg deposition with snow and a fractionation process during sea ice formation, which excludes Hg from the ice with a parallel Hg enrichment of brine, probably concurring with the Hg enrichment of AABW observed in the open ocean waters. Contrastingly, MeHg_T concentrations in the sea ice environment were in the same range as in the open ocean waters, remaining below 0.45 pmol L⁻¹. The MeHg_T vertical profile through the continuum suggests different sources, including atmosphere, seawater and methylation in basal ice. Whereas Hg_T concentrations in the water samples collected between the Antarctic continent and Tasmania are comparable to recent measurements made in the other parts of the World Ocean (e.g., Soerensen et al., 2010), the Hg species distribution suggests distinct features in the Southern Ocean Hg cycle: (i) a net atmospheric Hg deposition on surface water near the ice edge, (ii) the Hg enrichment in brine during sea ice formation, and (iii) a net methylation of Hg south of the SPF.     

Metal contents of recent thermal waters, mineral precipitates and hydrothermal alteration in active geothermal fields, Kamchatka

All the Kamchatkan recent hydrothermal systems are restricted to two volcanic zones, Central Kamchatka of Late Miocene-Pliocene age and East Kamchatka, where several active volcanoes are located. Solutions from active hydrothermal systems commonly contain elements, including As, Sb, Hg, Li, Rb, Cs, B, Cu, Pb, Zn, Ag, Au,Sr and Ba, with the first seven predominating. Higher abundances of ore elements occur in active hydrothermal systems with solutions of sodium chloride composition. Those are the Kireunskaya, Dvukhyurtochnaya and Apapelskaya systems in the Central Kamchatka volcanic zone and the Uzon hydrothermal system in the East Kamchatka volcanic zone. The hydrothermal systems are restricted to structures having very long histories of evolution and which are characterized by contrasting types of magmatism. At present chemical precipitates and altered rocks with higher abundances of As, Sb and trace amounts of Au, Ag, Cu, Ph and Zn are forming in the discharge zones of these hydrothermal systems. Large zones of alterations (alunitic quartzites^* and argillites) with high abundances of As, Sb, Hg, Cu, Pb, Ga and Zr occur in the Central Kamchatka volcanic zone. Here zones of mineralization (cinnabar, realgar, stibnite, orpiment, pyrite, chalcopyrite, sphalerite, galena) occur also; native gold, native silver and gudmundite occur rarely.In the recent Uzon caldera hydrothermal system, As-Sb-Hg mineralization with bitumen and oils is now forming. The ore deposit is zoned, with the most abundant ore minerals being realgar, uzonite, alacranite, stibnite and pyrite. Cinnabar, orpiment, marcasite and native mercury occur occasionally, and single grains of native gold, native silver and native copper are present. At present a total of 7000 t As, 350 t Sb and 200 t Hg have been deposited in the mineralization zone at geochemical boundaries. The general geological and geochemical data suggest that at depth the As-Sb-Hg mineralization may change to gold-silver mineralization.     

Seawater sulfate reduction and sulfur isotope fractionation in basaltic systems: Interaction of seawater with fayalite and magnetite at 200–350°C

Sulfate reduction during seawater reaction with fayalite and with magnetite was rapid at 350°C, producing equilibrium assemblages of talc-pyrite-hematite-magnetite at low water/rock ratios and talc-pyrite-hematite-anhydrite at higher water/rock ratios. At 250°C, seawater reacting with fayalite produced detectable amounts of dissolved H₂S, but extent of reaction of solid phases was minor after 150 days. At 200°C, dissolved H₂S was not detected, even after 219 days, but mass balance calculations suggest a small amount of pyrite may have formed. Reaction stoichiometry indicates that sulfate reduction requires large amounts of H⁺, which, in subseafloor hydrothermal systems is provided by Mg metasomatism. Seawater contains sufficient Mg to supply all the H⁺ necessary for quantitative reduction of seawater sulfate.Systematics of sulfur isotopes in the 250 and 350°C experiments indicate that isotopic equilibrium is reached, and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H₂S in natural systems is strongly dependent upon the seawater/basalt ratio in the geothermal system, which controls the relative sulfide contributions from the two important sulfur sources, seawater sulfate and sulfide phases in basalt. Anhydrite precipitation during geothermal heating severely limits sulfate ingress into high temperature interaction zones. Quantitative sulfate reduction can thus be accomplished without producing strongly oxidized rocks and resultant sulfide sulfur isotope values represent a mixture of seawater and basaltic sulfur.     

Hydrochemical,isotopic, and reservoir characterization of the Pasinler (Erzurum) geothermal field,eastern Turkey

The reservoir temperature and conceptual model of the Pasinler geothermal area, which is one of the most important geothermal areas in Eastern Anatolia, are determined by considering its hydrogeochemical and isotope properties. The geothermal waters have a temperature of 51 °C in the geothermal wells and are of Na–Cl–HCO₃ type. The isotope contents of geothermal waters indicate that they are of meteoric origin and that they recharge on higher elevations than cold waters. The geothermal waters are of immature water class and their reservoir temperatures are calculated as 122–155 °C, and their cold water mixture rate is calculated as 32%. According to the δ¹³C_VPDB values, the carbon in the geothermal waters originated from the dissolved carbon in the groundwaters and mantle-based CO₂ gases. According to the δ³⁴S_CDT values, the sources of sulfur in the geothermal waters are volcanic sulfur, oil and coal, and limestones. The sources of the major ions (Na⁺, Ca²⁺, Mg²⁺, Cl^?, and HCO₃ ^?) in the geothermal waters are ion exchange and plagioclase and silicate weathering. It is determined that the volcanic rocks in the area have effects on the water chemistry and elements like Zn, Rb, Sr, and Ba originated from the rhyolite, rhyolitic tuff, and basalts. The rare earth element (REE) content of the geothermal waters is low, and according to the normalized REE diagrams, the light REE are getting depleted and heavy REE are getting enriched. The positive Eu and negative Ce anomalies of waters indicate oxygen-rich environments.     

Sorption of inorganic mercury and monomethyl mercury in an iron–humus podzol soil of southern Norway studied by batch experiments

Considerable fractions of the Hg content of lake and river systems in Scandinavia are discharged from the soil of the catchments. An important soil type in Scandinavia is the iron–humus podzol. The sorption characteristics of this soil type for inorganic Hg(II) and monomethyl mercury were investigated by batch experiments. The solubility of Hg²⁺ and CH₃Hg⁺ in the soil horizons containing organic matter increases with increasing pH of the soil solution by favoring the formation of solute organic matter–mercury complexes. While the solubility of Hg²⁺ is strongly dependent on complexation to dissolved organic matter, the solubility of CH₃Hg⁺ is more dependent on ion exchange. The concentration of solute inorganic Hg(II) increased with increasing temperature probably because of an increase in the concentration of dissolved organic carbon. There was no effect of temperature on the concentration of solute CH₃Hg⁺. At pH values where inorganic mercury–hydroxo complexes are formed, inorganic Hg(II) is efficiently sorbed to the metal oxides of the mineral soil. The soil–water distributions of inorganic Hg(II) in the different soil horizons were described by Freundlich isotherms or linear isotherms for common and contaminated mercury contents in the soils.     

The formation of lead(II) chloride complexes to 300°C: A spectrophotometric study

The spectra of chlorolead(II) complexes in the ultraviolet region have been measured in acid chloride solutions from 0.0012 to 3.223 m and at temperatures from 25 to 300°C. The thermodynamic cumulative and stepwise formation constants as well as the spectra of the individual chlorolead(II) species have been calculated from the spectrophotometric data. At 25°C, the five species PbCl^2?n_n (0 ≤ n ≤ 4) occur, however, at 300°C the predominant species were PbCl⁺, PbCl⁰₂ and PbCl^?₃. Pb²⁺ occurs as a minor species in dilute solutions where total chloride is <0.003 m at 300°C and the presence of PbCl^2?₄ in concentrated solutions was not detected above 150°C. With increasing temperature, chlorolead(II) complex stability is characterised by large endothermic enthalpies and large positive entropies of formation. Lead(II) chloride complexes are important in the transport and deposition of lead by hydrothermal ore solutions of moderate to high salinity.     

Calcite Dissolution in Deionized Water from 50°C to 250°C at 10 MPa: Rate Equation and Reaction Order

Carbonate minerals and water （or geofluids） reactions are important for modeling of geochemical processes and have received considerable attention over the past decades. The calcite dissolution rates from 50℃ to 250℃ at 10 MPa in deionized water with a flow rate varying from 0.2 to 5 mL/min were experimentally measured in a continuous flow column pressure vessel reactor. The dissolution began near the equilibrium with c/ceq 〉 0.3 and finally reached the equilibrium at 100℃-250℃, so the corresponding solubility was also determined as 1.87, 2.02, 2.02 and 1.88×10^-4.mol/L at 100℃, 150℃, 200℃ and 250℃ respectively, which was first increasing and then switching to decreasing with temperature and the maximum value might occur between 150℃ and 200℃. The experimental dissolution rate not only increased with temperature, but also had a rapid increase between 150℃ and 200℃ at a constant flow rate of 4 mL/min. The measured dissolution rates can be described using rate equations of R = k（1-c/ceq）n or R = kc-n. In these equations the reaction order n changed with temperature, which indicates that n was a variable rather than a constant, and the activation energy was 13.4 kJ/mol calculated with R = k（1-c/ceq）n or 18.0 kJ/mol with R = kc^-n, which is a little lower than the surface controlled values. The varied reaction order and lower activation energy indicates that calcite dissolution in this study is a complex interplay of diffusion controlled and surface controlled processes.     

Tectono-sedimentary evolution of active extensional basins controlling the deposition of the Middle Miocene Kareem Formation,southwestern Gulf of Suez,Egypt

The Naozhi Au–Cu deposit is located on the continental margin of Northeast China, forming part of the West Pacific porphyry–epithermal gold–copper metallogenic belt. In this paper, we systematically analyzed the compositions, homogenization temperatures, and salinity of fluid inclusions as well as their noble gas isotopic and Pb isotopic compositions from the deposit. These new data show that (1) five types of fluid inclusions were identified as pure gas inclusions (V-type), pure liquid inclusions (L-type), gas–liquid two-phase inclusions (W-type, as the main fluid inclusions (FIs)), CO₂-bearing inclusions (C-type), and daughter-mineral-bearing polyphase inclusions (S-type); (2) W-type FIs in quartz crystals of early, main, and late stage are homogenized at temperatures of 324.7–406.7, 230–338.8, and 154.6–308 °C, with salinities of 2.40–7.01 wt% NaCl_eq, 1.73–9.47 wt% NaCl_eq, and 6.29 wt% NaCl_eq, respectively. S-type FIs in quartz crystals of early stage are homogenized at temperatures of 328.6–400 °C, with salinities of 39.96–46.00 wt% NaCl_eq; (3) Raman analysis results reveal that the vapor compositions of early ore-forming fluids consisted of CO₂ and H₂O, with H₂O gradually increasing and CO₂ being absent at the late mineralization stage; (4) fluid inclusions in pyrite and chalcopyrite have ³He/⁴He ratios of 0.03–0.104 Ra, ²⁰Ne/²²Ne ratios of 9.817–9.960, and ⁴⁰Ar/³⁶Ar ratios of 324–349. These results indicate that the percentage of radiogenic ⁴⁰Ar* in fluid inclusions varies from 8.8 to 15.5 %, containing 84.5–91.2 % atmospheric ⁴⁰Ar; (5) the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁶Pb/²⁰⁴Pb ratios of sulfides are 18.1822–18.3979, 15.5215–15.5998, and 38.1313–38.3786, respectively. These data combined with stable isotope data and the chronology of diagenesis and metallogenesis enable us suppose that the ore-forming fluids originated from the melting of the lower crust, caused by the subduction of an oceanic slab, whereas the mineralized fluids were exsolved from the late crystallization stage and subsequently contaminated by crustal materials/fluids during ascent, including meteoric water, and the mineral precipitation occurred at a shallow crustal level.

     

Metallogeny of the Shilu Fe–Co–Cu deposit,Hainan Island,South China: Constraints from fluid inclusions and stable isotopes

The Shilu deposit is a world-class Fe–Co–Cu orebody located in the Changjiang area of the western part of Hainan Island, South China. The distribution of Fe, Co, and Cu orebodies is controlled by strata of the No. 6 Formation in the Shilu Group and the Beiyi synclinorium. Based on a petrological study of the host rocks and their alteration assemblages, and textural and structural features of the ores, four mineralization stages have been identified: (1) the sedimentary ore-forming period; (2) the metamorphic ore-forming period; (3) the hydrothermal mineralization comprising the skarn and quartz–sulfide stage; and (4) the supergene period. The fluid inclusions in sedimentary quartz and/or chert indicate low temperatures (ca. 160 °C) and low salinities from 0.7 to 3.1 wt.% NaCl_eq, which corresponds to densities of 0.77 to 0.93 g/cm³. CO₂-bearing or carbonic inclusions have been interpreted to result from regional metamorphism. Homogenization temperatures of fluid inclusions for the skarn stage have a wide range from 148 °C to 497 °C and the salinities of the fluid inclusions range from 1.2 to 22.3 wt.% NaCl_eq, which corresponds to densities from 0.56 to 0.94 g/cm³. Fluid inclusions of the quartz–sulfide stage yield homogenization temperatures of 151–356 °C and salinities from 0.9 to 8.1 wt.% NaCl_eq, which equates to fluid densities from 0.63 to 0.96 g/cm³.Sulfur isotopic compositions indicate that sulfur of the sedimentary anhydrite and Co-bearing pyrite, and the quartz–sulfide stage, was derived from seawater sulfate and thermochemical sulfate reduction of dissolved anhydrite at temperatures of 200 °C and 300 °C, respectively. H and O isotopic compositions of the skarn and quartz–sulfide stage demonstrate that the ore-forming fluids were largely derived from magmatic water, with minor inputs from metamorphic or meteoric water. The Shilu iron ore deposit has an exhalative sedimentary origin, but has been overprinted by regional deformation and metamorphism. The Shilu Co–Cu deposit has a hydrothermal origin and is temporally and genetically associated with Indosinian granitoid rocks.     

Dissolution of cinnabar (HgS) in the presence of natural organic matter

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 × 10⁻¹³ to 7.16 × 10⁻¹² mol Hg (mg C)⁻¹ m⁻²s⁻¹. Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R² = 0.88), aromaticity (R² = 0.80), and molecular weight (R² = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface.