Gold partitioning in melt-vapor-brine systems

We used laser-ablation inductively coupled plasma mass spectrometry to measure the solubility of gold in synthetic sulfur-free vapor and brine fluid inclusions in a vapor + brine + haplogranite + magnetite + gold metal assemblage. Experiments were conducted at 800°C, oxygen fugacity buffered at Ni-NiO (NNO), and pressures ranging from 110 to 145 MPa. The wt% NaCl eq. of vapor increases from 2.3 to 19 and that of brine decreases from 57 to 35 with increasing pressure. The composition of the vapors and brines are dominated by NaCl + KCl + FeCl₂ + H₂O. Gold concentrations in vapor and brine decrease from 36 to 5 and 50 to 28 μg/g, respectively, and the calculated vapor:brine partition coefficients for gold decrease from 0.72 to 0.17 as pressure decreases from 145 to 110 MPa. These data are consistent with the thermodynamic boundary condition that the concentration of gold in the vapor and brine must approach a common value as the critical pressure is approached along the 800°C isotherm in the NaCl-KCl-FeCl₂-HCl-H₂O system.We use the equilibrium constant for gold dissolution as AuOH⁰, extrapolated from lower temperature and overlapping pressure range, to calculate expected concentrations of AuOH⁰ in our experimental vapors. These calculations suggest that a significant quantity of gold in our experimental vapors is present as a non-hydroxide species. Possible chloridogold(I) species are hypothesized based on the positively correlated gold and chloride concentrations in our experimental vapors. The absolute concentration of gold in our synthetic vapor, brine, and melt and calculated mass partition coefficients for gold between these physicochemically distinct magmatic phases suggests that gold solubility in aqueous fluids is a function of aqueous phase salinity, specifically total chloride concentration, at magmatic conditions. However, though we highlight here the effect of salinity, the combination of our data with data sets from lower temperatures evinces a significant decrease in gold solubility as temperature drops from 800°C to 600°C. This decrease in solubility has implications for gold deposition from ascending magmatic fluids.     

Holocene environments and climate in the Mongolian Altai reconstructed from the Hoton-Nur pollen and diatom records: a step towards better understanding climate dynamics in Central Asia

This study presents the results of the palynological and diatom analyses of the sediment core recovered in Hoton-Nur Lake (48°37′18″N, 88°20′45″E, 2083 m) in 2004. Quantitative reconstruction of the Holocene vegetation and climate dynamics in the semiarid Mongolian Altai suggests that boreal woodland replaced the primarily open landscape of northwestern Mongolia at about 10 kyr BP (1 kyr = 1000 cal yr) in response to a noticeable increase in precipitation from 200–250 mm/yr to 450–550 mm/yr. A decline of the forest vegetation and a return to a predominance of open vegetation types occurred after 5 kyr BP when precipitation sums decreased to 250–300 mm/yr. Prior to 11.5 kyr BP diatom concentrations are relatively low and the lake is dominated by planktonic Cyclotella and small Fragilariaceae, suggesting the existence of a relatively deep and oligotrophic/mesotrophic lake. The great abundance of Staurosirella pinnata from the beginning of the record until 10.7 kyr BP might imply intensified erosion processes in the catchment and this is fully consistent with the presence of scarce and dry vegetation and the generally arid climate during this period. From about 10.7 kyr BP, more planktonic diatom taxa appeared and increased in abundance, indicating that the lake became more productive as diatom concentration increased. This change correlates well with the development of boreal woodland in the catchment. Decrease in precipitation and changes in the vegetation towards steppe are reflected by the rapid increase in Aulacoseira distans from about 5 kyr BP. The Holocene pollen and diatom records do not indicate soil and vegetation cover disturbances by the anthropogenic activities, implying that the main transformations of the regional vegetation occurred as a result of the natural climate change. Our reconstruction is in agreement with the paleomonsoon records from China, demonstrating an abrupt strengthening of the summer monsoon at 12 kyr BP and an associated increase in precipitation and in lake levels between 11 and 8 kyr BP, followed by the stepwise attenuation of the monsoon circulation and climate aridization towards the modern level. The records from the neighboring areas of Kazakhstan and Russia, situated west and north of Hoton-Nur, demonstrate spatially and temporally different Holocene vegetation and climate histories, indicating that the Altai Mountains as a climate boundary are of pivotal importance for the Holocene environmental and, possibly, habitation history of Central Asia.     

Elemental and isotopic fractionation of Type B calcium-, aluminum-rich inclusions: experiments, theoretical considerations, and constraints on their thermal evolution

Experiments exposing Type B calcium-, aluminum-rich inclusion (CAI)-like melts at high temperatures to high vacuum or reducing hydrogen-rich gas mixtures were used to determine the rates and consequences of elemental and isotopic fractionation by evaporation. Silicon and magnesium were found to evaporate much faster than calcium and aluminum, and the resulting residual liquid trajectories in composition space are reproduced via a thermodynamic model for the saturation vapor pressure of the evaporating species. Isotopic fractionations associated with evaporation were measured for magnesium. The resulting relationship between fraction of magnesium lost and enrichment of the residue in the heavy isotopes of magnesium follows a Rayleigh fractionation curve with a fractionation factor that is close to, but not exactly, the theoretically expected value. The rate of evaporation is found to be a strong function of temperature, oxygen fugacity, and melt composition, which can be understood and modeled in terms of the dependence of the saturation vapor pressures on these variables. The relationship between evaporation rate, which we measure, and calculated saturation vapor involves empirical evaporation coefficients that we find to be significantly less than one (∼0.1). Analytical and numerical models are used to characterize how diffusion in both the melt and in the surrounding gas affects evaporation rates and the degree of chemical and isotopic fractionation. The experimental data and theoretical considerations are combined to give a parameterization of the rates and consequences of evaporation of Type B CAI-like liquids, which is then used to translate the measured isotopic fractionation of Type B CAIs into constraints on their thermal history. Cooling rates of the order of 10°C per hour are indicated.     

Natural geobatteries associated with sulphide ore deposits, II. Field studies at the viburnum trend, southeast Missouri, U.S.A.

Any conductive sulphide ore body can generate electrical ore potentials and this can be regarded as a geobattery, with an upper positive cathode and a lower negative anode. Two mechanisms which can occur simultaneously and which appear to explain these potentials are the oxygen concentration cell (OCC) and the sulphide galvanic cell (SGC). When there is a difference of O₂ concentration between the cathode and anode, the OCC operates by contributing oxygen to the anode, and ceases when the difference is diminished. However, gradients of pH, temperature or pressure can keep the cell operating. In the SGC the sulphides dissolve at the anode (producing metal ions, sulphur and electrons), while at the cathode, either sulphides dissolve producing metal and sulphur ions, or reaction is as in the OCC. The ore potential measured in the field is the sum of the oxygen concentration cell and at times locally dominant sulphide galvanic cells.     

Scattered Data Approximation on the Bisphere and Application to Texture Analysis

The paper deals with the approximation and optimal interpolation of functions defined on the bisphere \mathbb S²×\mathbb S²\mathbb {S}^{2}\times \mathbb {S}^{2} from scattered data. We demonstrate how the least square approximation to the function can be computed in a stable and efficient manner. The analysis of this problem is based on Marcinkiewicz–Zygmund inequalities for scattered data which we present here for the bisphere. The complementary problem of optimal interpolation is also solved by using well-localized kernels for our setting. Finally, we discuss the application of the developed methods to problems of texture analysis in material science.     

The Gibbs method and Duhem's theorem: The quantitative relationships among P,T, chemical potential,phase composition and reaction progress in igneous and metamorphic systems

The Gibbs method permits simultaneous evaluation of the relationships among all intensive thermodynamic variables of a heterogeneous system in equilibrium. Addition of mass balance constraints permits simultaneous evaluation of both intensive and extensive variables so that changes in phase chemistry and modes may be monitored. Assumption of closed system behavior results in a system of equations with two degrees of freedom, regardless of the thermodynamic variance, as specified by Duhem's theorem. Open system behavior increases the number of degrees of freedom by the number of components to which the system is open. The methodology presented is therefore a formal statement of the constraints among the differential of all of the intensive and extensive variables of a heterogeneous system.Examples of the application of this formalism include contouring pressure-temperature space for mineral composition, modal changes and reaction progress; contouring reaction space with pressure, temperature and mineral composition; and calculation of compositional and modal changes of phases for prescribed changes in pressure and temperature, as, for example, in the calculation of synthetic garnet zoning profiles or liquid lines of descent in crystallizing magmas.     

Geology and Metallogenesis of the Sawayaerdun Gold Deposit in the Southwestern Tianshan Mountains, Xinjiang, China

The Sawayaerdun gold deposit, located in Wuqia County, Southwest Tianshan, China, occurs in Upper Silurian and Lower Devonian low‐grade metamorphic carbonaceous turbidites. The orebodies are controlled by a series of NE‐NNE‐trending, brittle–ductile shear zones. Twenty‐four gold mineralized zones have been recognized in the Sawayaerdun ore deposit. Among these, the up to 4‐km‐long and 200‐m wide No. IV mineralized zone is economically the most important. The average gold grade is 1–6 g/t. Gold reserves of the Sawayaerdun deposit have been identified at approximately 37 tonnes and an inferred resource of 123 tonnes. Hydrothermal alteration is characterized by silicification, pyritization, arsenopyritization, sericitization, carbonatization and chloritization. On the basis of field evidence and petrographic analysis, five stages of vein emplacement and hydrothermal mineralization can be distinguished: stage 1, early quartz stage, characterized by the occurrence of quartz veins; stage 2, arsenopyrite–pyrite–quartz stage, characterized by the formation of auriferous quartz veinlets and stockworks; stage 3, polymetallic sulfide quartz stage, characterized by the presence of auriferous polymetallic sulfide quartz veinlets and stockworks; stage 4, antimony–quartz stage, characterized by the formation of stibnite–jamesonite quartz veins; and stage 5, quartz–carbonate vein stage. Stages 2 and 3 represent the main gold mineralization, with stage 4 representing a major antimony mineralization episode in the Sawayaerdun deposit. Two types of fluid inclusion, namely H₂O–NaCl and H₂O–CO₂–NaCl types, have been recognized in quartz and calcite. Aqueous inclusions show a wide range of homogenization temperatures from 125 to 340°C, and can be correlated with the mineralization stage during which the inclusions formed. Similarly, salinities and densities of these fluids range for each stage of mineralization from 2.57 to 22 equivalent wt% NaCl and 0.76 to 1.05 g/cm³, respectively. The ore‐forming fluids thus are representative of a medium‐ to low‐temperature, low‐ to medium‐salinity H₂O–NaCl–CO₂–CH₄–N₂ system. The δ³⁴S_CDT values of sulfides associated with mineralization fall into a narrow range of ?3.0 to +2.6‰ with a mean of +0.1‰. The δ¹³C_PDB values of dolomite and siderite from the Sawayaerdun gold deposit range from ?5.4 to ?0.6‰, possibly reflecting derivation of the carbonate carbon from a mixed magmatic/sedimentary source. Changes in physico‐chemical conditions and composition of the hydrothermal fluids, water–rock exchange and immiscibility of hydrothermal fluids are inferred to have played important roles in the ore‐forming process of the Sawayaerdun gold–antimony deposit.     

Overstepping the garnet isograd: a comparison of QuiG barometry and thermodynamic modeling

The consequences of overstepping the garnet isograd reaction have been investigated by comparing the composition of garnet formed at overstepped P–T conditions (the overstep or “OS” model) with the P–T conditions that would be inferred by assuming garnet nucleated in equilibrium with the matrix assemblage at the isograd (the equilibrium or “EQ” model). The garnet nucleus composition formed at overstepped conditions is calculated as the composition that produces the maximum decrease in Gibbs free energy from the equilibrated, garnet-absent, matrix assemblage for the bulk composition under study. Isopleths were then calculated for this garnet nucleus composition assuming equilibrium with the matrix assemblage (the EQ model). Comparison of the actual P–T conditions of nucleation (the OS model) with those inferred from the EQ model reveals considerable discrepancy between the two. In general, the inferred garnet nucleation P–T conditions (the EQ model) are at a lower temperature and higher or lower pressure (depending on the coexisting calcic phase(s)) than the actual (OS model) nucleation conditions. Moreover, the degree of discrepancy increases with the degree of overstepping. Independent estimates of the pressure of nucleation of garnet were made using the Raman shift of quartz inclusions in garnet (quartz-in-garnet or QuiG barometry). To test the validity of this method, an experimental synthesis of garnet containing quartz inclusions was made at 800 °C, 20 kbar, and the measured Raman shift reproduced the synthesis conditions to within 120 bars. Raman band shifts from three natural samples were then used to calculate an isochore along which garnet was presumed to have nucleated. Model calculations were made at several temperatures along this isochore (the OS model), and these P–T conditions were compared to those computed assuming equilibrium nucleation (the EQ model) to estimate the degree of overstepping displayed by these samples. A sample from the garnet isograd in eastern Vermont is consistent with overstepping of around 10 degrees and 0.6 kbar (affinities of around 2 kJ/mole garnet). A sample from the staurolite–kyanite zone in the same terrane requires overstepping of around 50 °C and 2–5 kbar (affinities of around 10–18 kJ/mole garnet). A similar amount of overstepping was inferred for a blueschist sample from Sifnos, Greece. These results indicate that overstepping of garnet nucleation reactions may be common and pronounced in regionally metamorphosed terranes, and that the P–T conditions and paths inferred from garnet zoning studies may be egregiously in error.     

Responses to the 2011 floods in Central Thailand: Perpetuating the vulnerability of small and medium enterprises?

Natural Hazards - The 2011 flood was the worst in Thailand in decades. Many of the impacts occurred in the Bangkok Metropolitan Region. The floods negatively affected small and medium enterprises...     

Satellite altimetry for measuring river stages in remote regions

The advent in satellite altimetry with the most accurate satellite radar altimeter since 1992 and its successive missions have enabled the routine global monitoring of water-level (or stage) for surface waters and changes in the quantities of dammed water reservoirs. However, satellite altimeter measurements typically have spatial resolution capable of observing only large water bodies, such as major lakes and rivers. This paper addresses the challenges of how to investigate water levels in medium (~?1 km in width) to small (~?100 m and narrower) rivers. Comparisons between the ENVISAT altimetry ICE-1 waveform retracking height and standard water-level measurements for multiple sections of Ohio River, Columbia River, and Red River of the North in the United States (US) reveals that the satellite altimetry measured water levels agree well with those observed at nearby US Geological Survey gaging stations over the 10-year period starting from 2002. The significant results include those obtained at Thompson, North Dakota (ND, correlation coefficient or R value of 0.76 between satellite and in situ water-level measurements) and Fargo, ND (R?=?0.74), where the stream channels of Red River are merely?~?50 m and ~?40 m wide, respectively, under normal climatic conditions. In addition, demonstrations of the approach over largely inaccessible portions of Tigris–Euphrates Rivers and Helmand River in the Middle East aided in understanding hydrology in these systems. This study demonstrates the ability of satellite radar altimetry to characterize rivers in these study regions which are much narrower than 100 m in width.