Magmatic-to-hydrothermal crystallization in the W–Sn mineralized Mole Granite (NSW, Australia): Part I: Crystallization of zircon and REE-phosphates over three million years—a geochemical and U–Pb geochronological study

Zircon, monazite and xenotime crystallized over a temperature interval of several hundred degrees at the magmatic to hydrothermal transition of the Sn and W mineralized Mole Granite. Magmatic zircon and monazite, thought to have crystallized from hydrous silicate melt, were dated by conventional U–Pb techniques at an age of 247.6 ± 0.4 and 247.7 ± 0.5 Ma, respectively. Xenotime occurring in hydrothermal quartz is found to be significantly younger at 246.2 ± 0.5 Ma and is interpreted to represent hydrothermal growth. From associated fluid inclusions it is concluded that it precipitated from a hydrothermal brine ≤ 600 °C, which is below the accepted closure temperature for U–Pb in this mineral. These data are compatible with a two-stage crystallization process: precipitation of zircon and monazite as magmatic liquidus phases in deep crustal magma followed by complete crystallization and intimately associated Sn–W mineralization after intrusion of the shallow, sill-like body of the Mole Granite. Later hydrothermal formation of monazite in a biotite–fluorite–topaz reaction rim around a mineralized vein was dated at 244.4 ± 1.4 Ma, which distinctly postdates the Mole Granite and is possibly related to a younger hidden intrusion and its hydrothermal fluid system.

Obtaining precise age data for magmatic and hydrothermal minerals of the Mole Granite is hampered by uncertainties introduced by different corrections required for multiple highly radiogenic minerals crystallising from evolved hydrous granites, including ²³⁰Th disequilibrium due to Th/U fractionation during monazite and possibly xenotime crystallization, variable Th/U ratios of the fluids from which xenotime was precipitating, elevated contents of common lead, and post-crystallization lead loss in zircon, enhanced by the fluid-saturated environment. The data imply that monazite can also survive as a liquidus phase in protracted magmatic systems over periods of 10⁶ years. The outlined model is in agreement with prominent chemical core-rim variation of the zircon.     

Magmatic zircon oxygen isotopes of 1.88–1.87 Ga orogenic and 1.65–1.54 Ga anorogenic magmatism in Finland

Summary Oxygen isotope ratios of igneous zircon from magmatic rocks in Finland provide insights into the evolution and growth of the Precambrian crust during the Svecofennian orogeny. These data preserve magmatic δ¹⁸O values and correlate with major discontinuities in the lower crust. Oxygen isotope ratios of zircon across the 1.88–1.87 Ga Central Finland granitoid complex (CFGC) range from 5.50‰ to 6.84‰, except for three plutons in contact with the adjacent greenstone and metasedimentary belts (δ¹⁸O(Zrc) = 7.60‰–7.78‰). There is a systematic variation in δ¹⁸O(Zrc) with respect to geographic location in the CFGC, ranging from 6.60±0.23‰ (σ) in the northeast to 5.90±0.40‰ in the west-southwest. These values correlate with a change in crustal thickness and shift in geochemical composition. The oxygen isotope composition of the 1.65–1.54 Ga rapakivi granites and related rocks in southern Finland show a decreasing trend from north to south, independent of their emplacement age. The southern anorogenic granite group has an average δ¹⁸O in zircon of 6.14±0.07‰ and the northern anorogenic group has an average δ¹⁸O in zircon of 8.14±0.59‰. This difference reflects the boundary between island arc terrains accreted during the Paleoproterozoic. Deceased     

9: Processes of tectonism, magmatism and mineralization: Lessons from Europe

Metallogenic provinces in Europe range in age from the Archaean to the Neogene. Deposit types include porphyry copper and epithermal Cu–Au, volcanic-hosted massive sulphide (VMS), orogenic gold, Fe-oxide–Cu–Au, anorthosite Fe–Ti-oxide and sediment-hosted base-metal deposits. Most of them formed during short-lived magmatic events in a wide range of tectonic settings; many can be related to specific tectonic processes such as subduction, hinge retreat, accretion of island arcs, continental collision, lithosphere delamination or slab tear. In contrast, most sediment-hosted deposits in Europe evolved in extensional, continental settings over significant periods of time. In Europe, as elsewhere, ore formation is an integral part of the geodynamic evolution of the Earth's crust and mantle. Many tectonic settings create conditions conducive to the generation of water-rich magma, but the generation of ore deposits appears to be restricted to locations and short periods of change in temperature and stress, imposed by transitory plate motions. Crustal influence is evident in the strong structural controls on the location and morphology of many ore deposits in Europe. Crustal-scale fault–fracture systems, many involving strike-slip elements, have provided the fabric for major plumbing systems. Rapid uplift, as in metamorphic core complexes, and hydraulic fracturing can generate or focus magmatic–hydrothermal fluid flow that may be active for time spans significantly less than a million years. Once a hydrologically stable flow is established, ore formation is strongly dependent on the steep temperature and pressure gradients experienced by the fluid, particularly within the upper crust. In Europe, significant fracture porosity deep in the crystalline basement (1%) is not only important for magmatic–hydrothermal systems, but allows brines to circulate down through sedimentary basins and then episodically upward, expelled seismically to produce sediment-hosted base-metal deposits and Kupferschiefer copper deposits. Emerging research, stimulated by GEODE, can improve the predicting power of numerical simulations of ore-forming processes and help discover the presence of orebodies beneath barren overburden.     

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     

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.     

Luminescence dating of ice‐marginal deposits in northern Germany: evidence for repeated glaciations during the Middle Pleistocene (MIS 12 to MIS 6)

The exact number, extent and chronology of the Middle Pleistocene Elsterian and Saalian glaciations in northern Central Europe are still controversial. This study presents new luminescence data from Middle Pleistocene ice‐marginal deposits in northern Germany, giving evidence for repeated glaciations during the Middle Pleistocene (MIS 12 to MIS 6). The study area is located in the Leine valley south of the North German Lowlands. The data set includes digital elevation models, high‐resolution shear wave seismic profiles, outcrop and borehole data integrated into a 3D subsurface model to reconstruct the bedrock relief surface. For numerical age determination, we performed luminescence dating on 12 ice‐marginal and two fluvial samples. Luminescence ages of ice‐marginal deposits point to at least two ice advances during MIS 12 and MIS 10 with ages ranging from 461±34 to 421±25 ka and from 376±27 to 337±21 ka. The bedrock relief model and different generations of striations indicate that the older ice advance came from the north and the younger one from the northeast. During rapid ice‐margin retreat, subglacial overdeepenings were filled with glaciolacustrine deposits, partly rich in re‐worked Tertiary lignite and amber. During MIS 8 and MIS 6, the study area may have been affected by two ice advances. Luminescence ages of glaciolacustrine delta deposits point to a deposition during MIS 8 or early MIS 6, and late MIS 6 (250±20 to 161±10 ka). The maximum extent of both the Elsterian (MIS 12 and MIS 10) and Saalian glaciations (MIS 8? and MIS 6) approximately reached the same position in the Leine valley and was probably controlled by the formation of deep proglacial lakes in front of the ice sheets, preventing a further southward advance.     

A methodology for regionalizing 3‐D effective porosity at watershed scale in crystalline aquifers

An innovative approach for regionalizing the 3‐D effective porosity field is presented and applied to two large, overexploited, and deeply weathered crystalline aquifers located in southern India. The method derives from earlier work on regionalizing a 2‐D effective porosity field in that part of an aquifer where the water table fluctuates, which is now extended over the entire aquifer using a 3‐D approach. A method based on geological and geophysical surveys has also been developed for mapping the weathering profile layers (saprolite and fractured layers). The method for regionalizing 3‐D effective porosity combines water table fluctuation and groundwater budget techniques at various cell sizes with the use of satellite‐based data (for groundwater abstraction), the structure of the weathering profile, and geostatistical techniques. The approach is presented in detail for the Kudaliar watershed (983 km²) and tested on the 730 km² Anantapur watershed. At watershed scale, the effective porosity of the aquifer ranges from 0.5% to 2% in Kudaliar and between 0.3% and 1% in Anantapur, which agrees with earlier works. Results show that (a) depending on the geology and on the structure of the weathering profile, the vertical distribution of effective porosity can be very different and that the fractured layers in crystalline aquifers are not necessarily characterized by a rapid decrease in effective porosity and (b) that the lateral variations in effective porosity can be larger than the vertical ones. These variations suggest that within a same weathering profile, the density of open fractures and/or degree of weathering in the fractured zone may significantly vary from a place to another. The proposed method provides information on the spatial distribution of effective porosity that is of prime interest in terms of flux and contaminant transport in crystalline aquifers. Implications for mapping groundwater storage and scarcity are also discussed, which should help in improving groundwater resource management strategies.     

A GLUE‐based uncertainty assessment framework for tritium‐inferred transit time estimations under baseflow conditions

The last decade has seen major technical and scientific improvements in the study of water transfer time through catchments. Nevertheless, it has been argued that most of these developments used conservative tracers that may disregard the oldest component of water transfer, which often has transit times greater than 5 years. Indeed, although the analytical reproducibility of tracers limits the detection of the older flow components associated with the most dampened seasonal fluctuations, this is very rarely taken into account in modelling applications. Tritium is the only environmental tracer at hand to investigate transfer times in the 5‐ to 50‐year range in surface waters, as dissolved gases are not suitable due to the degassing process. Water dating with tritium has often been difficult because of the complex history of its atmospheric concentration, but its current stabilization together with recent analytical improvements open promising perspectives. In this context, the innovative contribution of this study lies in the development of a generalized likelihood uncertainty estimation‐based approach for analysing the uncertainties associated with the modelling of transit time due to both parameter identification and tracer analytical precision issues. A coupled resampling procedure allows assessment of the statistical significance of the transfer time differences found in diverse waters. This approach was developed for tritium and the exponential‐piston model but can be implemented for virtually any tracer and model. Stream baseflow, spring and shallow aquifer waters from the Vallcebre research catchments, analysed for tritium in different years with different analytical precisions, were investigated by using this approach and taking into account other sources of uncertainty. The results showed three groups of waters of different mean transit times, with all the stream baseflow and spring waters older than the 5‐year threshold needing tritium. Low sensitivity of the results to the model structure was also demonstrated. Dual solutions were found for the waters sampled in 2013, but these results may be disambiguated when additional analyses will be made in a few years. Copyright © 2016 John Wiley & Sons, Ltd.     

Towards more systematic perceptual model development: a case study using 3 Luxembourgish catchments

The synthesis of experimental understanding of catchment behaviour and its translation into qualitative perceptual models is an important objective of hydrological sciences. We explore this challenge by examining the cumulative understanding of the hydrology of three experimental catchments and how it evolves through the application of different investigation techniques. The case study considers the Huewelerbach, Weierbach and Wollefsbach headwater catchments of the Attert basin in Luxembourg. Subsurface investigations including bore holes and pits, analysis of soil samples and Electrical Resistivity Tomography measurements are presented and discussed. Streamflow and tracer data are used to gain further insights into the streamflow dynamics of the catchments, using end‐member mixing analysis and hydrograph separation based on dissolved silica and electrical conductivity. We show that the streamflow generating processes in all three catchments are controlled primarily by the subsolum and underlying bedrock. In the Huewelerbach, the permeable sandstone formation supports a stable groundwater component with little seasonality, which reaches the stream through a series of sources at the contact zone with the impermeable marls formation. In the Weierbach, the schist formation is relatively impermeable and supports a ‘fill and spill’‐type of flow mechanism; during wet conditions, it produces a delayed response dominated by pre‐event water. In the Wollefsbach, the impermeable marls formation is responsible for a saturation‐excess runoff generating process, producing a fast and highly seasonal response dominated by event water. The distinct streamflow generating processes of the three catchments are represented qualitatively using perceptual models. The perceptual models are in turn translated into quantitative conceptual models, which simulate the hydrological processes using networks of connected reservoirs and transfer functions. More generally, the paper illustrates the evolution of perceptual models based on experimental fieldwork data, the translation of perceptual models into conceptual models and the value of different types of data for processes understanding and model representation. Copyright © 2014 John Wiley & Sons, Ltd.