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.     

Adsorption and Desorption of Phosphate on Calcite and Aragonite in Seawater

The adsorption and desorption of phosphate on calcite and aragonite were investigated as a function of temperature (5–45 °C)and salinity (0–40) in seawater pre-equilibrated with CaCO₃. An increase in temperature increased the equilibrium adsorption; whereas an increase in salinity decreased the adsorption. Adsorption measurements made in NaCl were lower than the results in seawater. The higher values in seawater were due to the presence of Mg²⁺ and Ca²⁺ ions. The increase was 5 times greater for Ca²⁺ than Mg²⁺. The effects ofCa²⁺ and Mg²⁺ are diminished with the addition of SO₄ ^2- apparently due to the formation of MgSO₄ and CaSO₄ complexes in solution and/or SO₄ ^2- adsorption on the surface of CaCO₃. The adsorbed Ca²⁺ and Mg²⁺ on CaCO₃ (at carbonate sites) may act as bridges to PO₄ ^3- ions. The bridging effect of Ca²⁺is greater than Mg²⁺ apparently due to the stronger interactions of Ca²⁺ with PO₄ ^3-.The apparent effect of salinity on the adsorption of PO₄ was largely due to changes in the concentration of HCO₃ ^- in the solutions. An increase in the concentration of HCO₃ ^- caused the adsorption of phosphate to decrease, especially at low salinities. The adsorption at the same level of HCO₃ ^- (2 mM) was nearly independent of salinity. All of the adsorption measurements were modeled empirically using a Langmuir-type adsorption isotherm[ [PO₄]_ad = K_mC_m[PO₄]_T/(1 +K_m [PO₄]_T) , ]where [PO₄]_ad and [PO₄]_T are the adsorbed and total dissolved phosphate concentrations, respectively. The values of C_m (the maximum monolayer adsorption capacity, (mol/g) and K_m (the adsorption equilibrium constant, g/(mol) over the entire temperature (t, °C) and salinity (S) range were fitted to[ C_m = 17.067 + 0.1707t - 0.4693S + 0.0082S² ( = 0.7) ][ ln K_m = - 2.412 + 0.0165t - 0.0004St - 0.0008S² ( = 0.1) ]These empirical equations reproduce all of our measurements of[PO₄]_ad up to 14 mol/g and within ±0.7 mol/g.The kinetic data showed that the phosphate uptake on carbonate minerals appears to be a multi-step process. Both the adsorption and desorption were quite fast in the first stage (less than 30 min) followed by a much slower process (lasting more than 1 week). Our results indicate that within 24 hours aragonite has a higher sorption capacity than calcite. The differences between calcite and aragonite become smaller with time. Consequently, the mineral composition of the sediments may affect the short-term phosphate adsorption and desorption on calcium carbonate. Up to 80 % of the adsorbed phosphate is released from calcium carbonate over one day. The amount of PO₄ left on the CaCO₃ is close to the equilibrium adsorption. The release of PO₄ from calcite is faster than from aragonite. Measurements with Florida Bay sediments produced results between those for calcite and aragonite. Our results indicate that the calcium carbonate can be both a sink and source of phosphate in natural waters.     

Pre-Cenozoic intra-plate magmatism along the Central Andes (17–34°S): Composition of the mantle at an active margin

Sr–Nd–Pb isotope ratios of alkaline mafic intra-plate magmatism constrain the isotopic compositions of the lithospheric mantle along what is now the eastern foreland or back arc of the Cenozoic Central Andes (17–34°S). Most small-volume basanite volcanic rocks and alkaline intrusive rocks of Cretaceous (and rare Miocene) age were derived from a depleted lithospheric mantle source with rather uniform initial ¹⁴³Nd/¹⁴⁴Nd ( 0.5127–0.5128) and ⁸⁷Sr/⁸⁶Sr ( 0.7032–0.7040). The initial ²⁰⁶Pb/²⁰⁴Pb ratios are variable (18.5–19.7) at uniform ²⁰⁷Pb/²⁰⁴Pb ratios (15.60 ± 0.05). A variety of the Cretaceous depleted mantle source of the magmatic rocks shows elevated Sr isotope ratios up to 0.707 at constant high Nd isotope ratios. The variable Sr and Pb isotope ratios are probably due to radiogenic growth in a metasomatized lithospheric mantle, which represents the former sub-arc mantle beneath the early Palaeozoic active continental margin. Sr–Nd–Pb isotope signatures of a second mantle type reflected in the composition of Cretaceous (one late Palaeozoic age) intra-plate magmatic rocks (¹⁴³Nd/¹⁴⁴Nd  0.5123, ⁸⁷Sr/⁸⁶Sr  0.704, ²⁰⁶Pb/²⁰⁴Pb  17.5–18.5, and ²⁰⁷Pb/²⁰⁴Pb  15.45–15.50) are similar to the isotopic composition of old sub-continental lithospheric mantle of the Brazilian Shield.

Published Nd and Sr isotopic compositions of Mesozoic to Cenozoic arc-related magmatic rocks (18–40°S) represent the composition of the convective sub-arc mantle in the Central Andes and are similar to those of the Cretaceous (and rare Miocene) intra-plate magmatic rocks. The dominant convective and lithospheric mantle type beneath this old continental margin is depleted mantle, which is compositionally different from average MORB-type depleted mantle. The old sub-continental lithospheric mantle did not contribute to Mesozoic to Cenozoic arc magmatism.     

中国南京与美国德克萨斯稻田甲烷排放的比较

Field measurements of methane emission from rice paddies were made in Nanjing, China and in Texas, USA, respectively. Soil temperature at approximately 10 cm depth of the flooded soils was automatically recorded. Aboveground biomass of rice crop was measured approximately every 10 days in Nanjing and every other week in Texas. Seasonal variation of soil temperature in Nanjing was quite wide with a magnitude of 15.3℃ and that in Texas was narrow with a magnitude of 2.9℃. Analysis of methane emission fluxes against soil temperature and rice biomass production demonstrated that the seasonal course of methane emission in Nanjing was mostly attributed to soil temperature changes, while that in Texas was mainly related to rice biomass production. We concluded that under the permanent flooding condition, the seasonal trend of methane emission would be determined by the soil temperature where there was a wide variation of soil temperature, and the seasonal trend would be mainly determined by rice biomass production if there are no additional organic matter inputs and the variation of soil temperature over the rice growing season is small.     

Anthropogenic changes of the thermal and zonal flow structure over Western Europe and Eastern North Atlantic in CMIP3 and CMIP5 models

The anthropogenic changes during boreal winter in the thermal and zonal flow structure over Eastern Atlantic and Western Europe (EAWE) have been investigated using an ensemble of CMIP3 and CMIP5 models. The ensemble mean change in the zonal wind at 500 hPa over this region is characterized by an eastward extension of the belt of zonal winds. Using the thermal wind relation these wind changes are found to be consistent with the changes in the tropospheric temperature profile. An enhanced warming is simulated in the subtropical upper troposphere and a relative surface cooling in the mid-latitudes. The subtropical upper tropospheric warming is related to the downward branch of the mean meridional circulation, whereas the mid-latitude lower tropospheric relative cooling is linked to the ocean processes that govern changes in its surface temperatures. Inter-model differences in the simulated change of the zonal wind over the EAWE by the CMIP3 and CMIP5 models relate well with differences in the upper tropospheric subtropical warming and the mid-latitude lower tropospheric relative cooling. The simulated change of the zonal wind over the EAWE region by the CMIP3 and CMIP5 models correlates well with changes in the meridional SST gradient. We conclude that uncertainties in the projected changes of the zonal flow over Europe are at least partly due to uncertainties in the response of the North Atlantic Ocean to increased levels of greenhouse gases.     

柴达木盆地北缘大柴旦地区古生代花岗岩锆石SHRIMP定年

大柴旦地区是柴北缘古生代超高压带的重要组成部分,与超高压岩石相伴的花岗岩十分发育。这些花岗岩具有两类不同的岩石地球化学特征,Ⅰ类以 Na_2O/K_2O 比值小于1、明显的负 Eu 异常和低 Sr、高 Y 为特征,具有 S-型花岗岩的属性,Ⅱ类以 Na_2O/K_2O 比值大于1、弱负 Eu 异常到正 Eu 异常和高 Sr、低 Y 为特征,具有Ⅰ-型花岗岩的属性,反映了它们的源岩及成因上的差异。锆石 SHRIMP U—Ph 定年结果表明,大柴旦地区花岗岩的年龄可分为三组,第一组年龄为446.3±3.9Ma,第二组年龄分别为408.6±4.4Ma、403.3±3.8Ma、401.8±3Ma,第三组年龄分别为374.5±1.6Ma、372±2.1Ma。结合区域地质特征,我们认为,第一组年龄可能反映了柴达木陆块与中南祁连板块碰撞的时代,第二组年龄可能反映了深俯冲地下的板块由于拆沉而折返的时代,第三组年龄可能反映了碰撞隆起后造山带上不同块体之间的伸展、滑塌的时代。     

Turbulent fluxes from Helipod flights above quasi-homogeneous patches within the LITFASS area

Turbulent fluxes of sensible and latent heat were measured with the helicopter-borne turbulence probe Helipod over a heterogeneous landscape around the Meteorological Observatory Lindenberg during the STINHO-2 and LITFASS-2003 field experiments. Besides the determination of area-averaged heat fluxes, the analysis focused on different aspects of the response of the turbulent structure of the convective boundary layer (CBL) on the surface heterogeneity. A special flight pattern was designed to study flux profiles both over quasi-homogeneous sub-areas of the study region (representing the major land use types—forest, farmland, water) and over a typical mixture of the different surfaces. Significant differences were found between the heat fluxes over the individual surfaces along flight legs at about 80 m above ground level, in agreement with large-aperture scintillometer measurements. This flux separation was still present during some flights at levels near the middle of the CBL. Different scales for the blending height and horizontal heterogeneity were calculated, but none of them could be identified as a reliable indicator of the mixing state of the lower CBL. With the exception of the flights over water, the latent heat flux measurements generally showed a larger statistical error when compared with the sensible heat flux. Correlation coefficients a nd integral length scales were used to characterise the interplay between the vertical transport of sensible and latent heat, which was found to vary between ‘fairly correlated’ and ‘decoupled’, also depending on the soil moisture conditions.