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.     

Trace element compositions of submicroscopic inclusions in coated diamond: A tool for understanding diamond petrogenesis

Trace element compositions of submicroscopic inclusions in both the core and the coat of five coated diamonds from the Democratic Republic of Congo (DRC, formerly Zaire) have been analyzed by Laser Ablation Inductively Coupled Mass Plasma Spectrometry (LA-ICP-MS). Both the diamond core and coat inclusions show a general 2-4-fold enrichment in incompatible elements relative to major elements. This level of enrichment is unlikely to be explained by the entrapment of silicate mantle minerals (olivine, garnet, clinopyroxene, phlogopite) alone and thus submicroscopic fluid or glass inclusions are inferred in both the diamond coat and in the gem quality diamond core. The diamond core fluids have elevated High Field Strength Element (Ti, Ta, Zr, Nb) concentrations and are enriched in U relative to inclusions in the diamond coats and relative to chondrite. The core fluids are also moderately enriched in LILE (Ba, Sr, K). Therefore, we suggest that the diamond cores contain inclusions of silicate melt. However, the Ni content and Ni/Fe ratio of the trapped fluid are very high for a silicate melt in equilibrium with mantle minerals; high Ni and Co concentrations in the diamond cores are attributed to the presence of a sulfide phase coexisting with silicate melt in the diamond core inclusions. Inclusions in the diamond coat are enriched in LILE (U, Ba, Sr, K) and La over the diamond core fluids and to chondrite. The coats have incompatible element ratios similar to natural carbonatite (coat fluid: Na/Ba ≈0.66, La/Ta≈130). The coat fluid is also moderately enriched in HFSE (Ta, Nb, Zr) when normalized to chondritic Al. LILE and La enrichment is related to the presence of a carbonatitic fluid in the diamond coat inclusions, which is mixed with a HFSE-rich hydrous silicate fluid similar to that in the core. The composition of the coat fluid is consistent with a genetic link to group 1 kimberlite.     

The use of the exponent K(q) function to delimit homogeneous regions in regional frequency analysis of extreme annual daily rainfall

The regional frequency analysis of extreme annual rainfall data is a useful methodology in hydrology to obtain certain quantile values when no long data series are available. The most crucial step in the analysis is the grouping of sites into homogeneous regions. This work presents a new grouping criterion based on some multifractal properties of rainfall data. For this purpose, a regional frequency analysis of extreme annual rainfall data from the Maule Region (Chile) has been performed. Daily rainfall data series of 53 available stations have been studied, and their empirical moments scaling exponent functions K(q) have been obtained. Two characteristics parameters of the K(q) functions (γ_max and K(0)) have been used to group the stations into three homogeneous regions. Only five sites have not been possible to include into any homogenous regions, being the local frequency analysis of extreme daily rainfall the most appropriate method to be used at these locations. Copyright © 2014 John Wiley & Sons, Ltd.     

Contrasting hydrological response of coastal and desert biocrusts

Biocrusts abound in southern Israel, covering the Hallamish dune field near Nizzana (NIZ) in the Negev (mean annual precipitation of 95 mm) and the coast of Nizzanim (NIM) near Ashdod (mean annual precipitation of 500 mm). While the hydrological response of the NIZ crust to natural rain events was thoroughly investigated, no data is available on the hydrological response of the NIM crust. Runoff was monitored in runoff plots during the years 2005–2008, and in addition, sprinkling experiments were carried out on NIM and NIZ crusts. For the evaluation of the possible factors that may control runoff initiation, fine content of the parent material, crust thickness, compressional strength, hydrophobicity, surface microrelief, organic matter, biomass (chlorophyll a and total carbohydrates) and the crust's species composition of NIM were studied and compared to that of NIZ. The data showed that in comparison to the NIZ crust that readily generated runoff, no runoff was produced by the NIM crust. This was so despite the fact that (1) Microculeus vaginatus predominated in both crusts, (2) the substantially higher rain intensities in NIM, (3) the greater thickness and higher chlorophyll content and (4) the lower microrelief at NIM in comparison to NIZ. The lack of runoff in NIM was explained by its low amounts of exopolysaccharides that did not suffice to affectively clog the surface and in turn to facilitate runoff initiation. The absence of runoff and its consequences on the NIM ecosystem are discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Groundwater – the disregarded component in lake water and nutrient budgets. Part 2: effects of groundwater on nutrients

Lacustrine groundwater discharge (LGD) transports nutrients from a catchment to a lake, which may fuel eutrophication, one of the major threats to our fresh waters. Unfortunately, LGD has often been disregarded in lake nutrient studies. Most measurement techniques are based on separate determinations of volume and nutrient concentration of LGD: Loads are calculated by multiplying seepage volumes by concentrations of exfiltrating water. Typically low phosphorus (P) concentrations of pristine groundwater often are increased due to anthropogenic sources such as fertilizer, manure or sewage. Mineralization of naturally present organic matter might also increase groundwater P. Reducing redox conditions favour P transport through the aquifer to the reactive aquifer‐lake interface. In some cases, large decreases of P concentrations may occur at the interface, for example, due to increased oxygen availability, while in other cases, there is nearly no decrease in P. The high reactivity of the interface complicates quantification of groundwater‐borne P loads to the lake, making difficult clear differentiation of internal and external P loads to surface water. Anthropogenic sources of nitrogen (N) in groundwater are similar to those of phosphate. However, the environmental fate of N differs fundamentally from P because N occurs in several different redox states, each with different mobility. While nitrate behaves essentially conservatively in most oxic aquifers, ammonium's mobility is similar to that of phosphate. Nitrate may be transformed to gaseous N₂ in reducing conditions and permanently removed from the system. Biogeochemical turnover of N is common at the reactive aquifer‐lake interface. Nutrient loads from LGD were compiled from the literature. Groundwater‐borne P loads vary from 0.74 to 2900 mg PO₄‐P m^?2 year^?1; for N, these loads vary from 0.001 to 640 g m^?2 year^?1. Even small amounts of seepage can carry large nutrient loads due to often high nutrient concentrations in groundwater. Large spatial heterogeneity, uncertain areal extent of the interface and difficult accessibility make every determination of LGD a challenge. However, determinations of LGD are essential to effective lake management. Copyright © 2014 John Wiley & Sons, Ltd.