Magma evolution and the formation of porphyry Cu–Au ore fluids: evidence from silicate and sulfide melt inclusions

Silicate and sulfide melt inclusions from the andesitic Farallón Negro Volcanic Complex in NW Argentina were analyzed by laser ablation ICPMS to track the behavior of Cu and Au during magma evolution, and to identify the processes in the source of fluids responsible for porphyry-Cu-Au mineralization at the 600 Mt Bajo de la Alumbrera deposit. The combination of silicate and sulfide melt inclusion data with previously published geological and geochemical information indicates that the source of ore metals and water was a mantle-derived mafic magma that contained approximately 6 wt.% H₂O and 200 ppm Cu. This magma and a rhyodacitic magma mixed in an upper-crustal magma chamber, feeding the volcanic systems and associated subvolcanic intrusions over 2.6 million years. Generation of the ore fluid from this magma occurred towards the end of this protracted evolution and probably involved six important steps: (1) Generation of a sulfide melt upon magma mixing in some parts of the magma chamber. (2) Partitioning of Cu and Au into the sulfide melt (enrichment factor of 10,000 for Cu) leading to Cu and Au concentrations of several wt.% or ppm, respectively. (3) A change in the tectonic regime from local extension to compression at the end of protracted volcanism. (4) Intrusion of a dacitic magma stock from the upper part of the layered magma chamber. (5) Volatile exsolution and resorption of the sulfide melt from the lower and more mafic parts of the magma chamber, generating a fluid with a Cu/Au ratio equal to that of the precursor sulfide. (6) Focused fluid transport and precipitation of the two metals in the porphyry, yielding an ore body containing Au and Cu in the proportions dictated by the magmatic fluid source. The Cu/S ratio in the sulfide melt inclusions requires that approximately 4,000 ppm sulfur is extracted from the andesitic magma upon mixing. This exceeds the solubility of sulfide or sulfate in either of the silicate melts and implies an additional source for S. The extra sulfur could be added in the form of anhydrite phenocrysts present in the rhyodacitic magma. It appears, thus, that unusually sulfur-rich, not Cu-rich magmas are the key to the formation of porphyry-type ore deposits. Our observations imply that dacitic intrusions hosting the porphyry–Cu–Au mineralization are not representative of the magma from which the ore-fluid exsolved. The source of the ore fluid is the underlying more mafic magma, and unaltered andesitic dikes emplaced immediately after ore formation are more likely to represent the magma from which the fluids were generated. At Alumbrera, these andesitic dikes carry relicts of the sulfide melt as inclusions in amphibole. Sulfide inclusions in similar dykes of other, less explored magmatic complexes may be used to predict the Au/Cu ratio of potential ore-forming fluids and the expected metal ratio in any undiscovered porphyry deposit.Editorial handling: B. Lehmann     

Uncertainties of geochemical modeling during CO<Subscript>2</Subscript> sequestration applying batch equilibrium calculations

One of the uncertainties in the field of carbon dioxide capture and storage (CCS) is caused by the parameterization of geochemical models. The application of geochemical models contributes significantly to calculate the fate of the CO₂ after its injection. The choice of the thermodynamic database used, the selection of the secondary mineral assemblage as well as the option to calculate pressure dependent equilibrium constants influence the CO₂ trapping potential and trapping mechanism. Scenario analyses were conducted applying a geochemical batch equilibrium model for a virtual CO₂ injection into a saline Keuper aquifer. The amount of CO₂ which could be trapped in the formation water and in the form of carbonates was calculated using the model code PHREEQC. Thereby, four thermodynamic datasets were used to calculate the thermodynamic equilibria. Furthermore, the equilibrium constants were re-calculated with the code SUPCRT92, which also applied a pressure correction to the equilibrium constants. Varying the thermodynamic database caused a range of 61% in the amount of trapped CO₂ calculated. Simultaneously, the assemblage of secondary minerals was varied, and the potential secondary minerals dawsonite and K-mica were included in several scenarios. The selection of the secondary mineral assemblage caused a range of 74% in the calculated amount of trapped CO₂. Correcting the equilibrium constants with respect to a pressure of 125 bars had an influence of 11% on the amount of trapped CO₂. This illustrates the need for incorporating sensitivity analyses into reaction pathway modeling.     

Intercomparison of measurements of bulk snow density and water equivalent of snow cover with snow core samplers: Instrumental bias and variability induced by observers

Manually collected snow data are often considered as ground truth for many applications such as climatological or hydrological studies. However, there are many sources of uncertainty that are not quantified in detail. For the determination of water equivalent of snow cover (SWE), different snow core samplers and scales are used, but they are all based on the same measurement principle. We conducted two field campaigns with 9 samplers commonly used in observational measurements and research in Europe and northern America to better quantify uncertainties when measuring depth, density and SWE with core samplers. During the first campaign, as a first approach to distinguish snow variability measured at the plot and at the point scale, repeated measurements were taken along two 20 m long snow pits. The results revealed a much higher variability of SWE at the plot scale (resulting from both natural variability and instrumental bias) compared to repeated measurements at the same spot (resulting mostly from error induced by observers or very small scale variability of snow depth). The exceptionally homogeneous snowpack found in the second campaign permitted to almost neglect the natural variability of the snowpack properties and focus on the separation between instrumental bias and error induced by observers. Reported uncertainties refer to a shallow, homogeneous tundra-taiga snowpack less than 1 m deep (loose, mostly recrystallised snow and no wind impact). Under such measurement conditions, the uncertainty in bulk snow density estimation is about 5% for an individual instrument and is close to 10% among different instruments. Results confirmed that instrumental bias exceeded both the natural variability and the error induced by observers, even in the case when observers were not familiar with a given snow core sampler.     

Microstructural observations on natural syntectonic fibrous veins: implications for the growth process

Syntectonic antitaxial and ataxial fibrous veins were investigated using SEM, microprobe, cathodoluminescence (CL) and optical microscopy. In antitaxial calcite veins, fibres and surrounding selvage grew simultaneously, with similar growth rates of crystallographically differently oriented grains. New material precipitated at the vein margin in antitaxial and bi-mineralic ataxial microstructures. Bridges of country rock material formed during vein growth in an initial en-echelon vein system. In our antitaxial and bi-mineralic ataxial samples, the spacing of solid inclusions does not reflect individual crack-seal openings.     

Winter synoptic-scale variability over the Mediterranean Basin under future climate conditions as simulated by the ECHAM5

Changes of the winter climate in the Mediterranean Basin (MB) for future A2 conditions are investigated for the period 2071–2100 and compared with the control period 1961–1990. The analysis is based on time-slice simulations of the latest version of the ECHAM model. First, the control simulation is evaluated with reanalysis data. The emphasis is given to synoptic and large-scale features and their variability in the MB. The model is found to be capable of reproducing the main features of the MB and southern Europe in the winter season. Second, the A2 simulation is compared with the control simulation, revealing considerable changes of the synoptic variability. Focusing on the synoptic spatio-temporal scale aims to unfold the dynamic background of the climatic changes. The Mediterranean cyclones, which are individually detected and tracked, decrease by 10% in the Western Mediterranean (WM) whereas no significant change is found in the Eastern Mediterranean. The cyclone intensity is slightly reduced in the entire region. To understand these changes, the underlying dynamical background is analyzed. It is found that changes in baroclinicity, static stability, transformation from eddy kinetic energy to kinetic energy of the mean flow and stationary wave activity are significant in particular in the WM and the coastline of North Africa. The reduction of cyclonic activity severely impacts the precipitation mainly in the southern part of the WM.     

Amorphous silica mobilization by inter‐rill erosion: insights from rainfall experiments

Amorphous silica (ASi) carried in suspension by rivers is an important component in the global Si budget. Water erosion processes in cultivated catchments are likely to drive ASi delivery to the river system. However, no studies have investigated the controls on ASi mobilization by erosional processes in croplands. Rainfall experiments were performed on split fields (i.e. a part conventionally ploughed and a part under reduced tillage) to simulate ASi mobilization by inter‐rill erosion in croplands, and identify its dependency on soil, field and rainfall characteristics. The ASi content of the soil and the inter‐rill erosion rate were determined as the major controls on ASi mobilization. Variables such as tillage technique and crop type did not have a consistent direct or indirect effect. Inter‐rill erosion is clearly selective with respect to ASi, indicating association of ASi with the fine soil fraction and with soil organic carbon. Our experiments demonstrate that erosion increases due to human perturbation will increase the delivery of reactive Si to aquatic systems. We estimate that globally, c. 7% of all reactive Si that enters aquatic systems is derived from erosion of agricultural soils. Copyright © 2015 John Wiley & Sons, Ltd.     

The diurnal variation of polar mesospheric cloud frequency near 55°N observed by SHIMMER

We present the first measurement of polar mesospheric cloud (PMC) occurrence frequency over the diurnal cycle from a satellite. The observations are made during the 2007 northern hemisphere PMC season by the Spatial Heterodyne IMager for MEsospheric Radicals (SHIMMER), which views the limb near 309 nm typically between 34 and 98 km. The PMC diurnal variation is derived between 50 and 58°N, where local times at the tangent point precess by ～30 min/day allowing for observations between 0330 and 2130 local time during the PMC season. We find that the occurrence frequencies exhibit a strong semidiurnal behavior with peaks near 0600 and 1800 local time and a minimum between 0900 and 1600 during which they are on average an order of magnitude less. The semidiurnal dependence is strongly correlated with concurrent ground-based measurements of meridional winds and temperatures measured at the same latitude. Our results for PMC frequency over the diurnal cycle can be used to help reconcile observations from other satellites that only permit cloud measurements at discrete local times.