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The crush-leach technique is a frequently used method to determine the bulk composition of fluid inclusions trapped in a range of geological samples. We present a modified crush-leach technique combining ion chromatography (IC) and total reflection X-ray fluorescence spectroscopy (TXRF) which allows to determine a range of major, minor and trace elements out of one leachate. To date, trace element detection by means of TXRF is barely used in geosciences, although it combines the advantages of low to very low detection limits (µg/L to ng/L range), small sample amount needed (µL-range) and a fast and inexpensive analytical procedure. Previously described problems of adsorption of polyvalent cations at sample surfaces have been overcome by using acidified water as a leachate. Instead, it has been demonstrated that, for example, the syringe filter type used for IC measurements influences contamination and/or adsorption for a number of elements. The proposed method combination was evaluated for accuracy, reproducibility and system blanks and subsequently applied to quartz samples from hydrothermal vein deposits of the Schwarzwald ore district, SW Germany. [ABSTRACT FROM AUTHOR]

• Fluid inclusion data from carbonatite. • A new approach for quantification. • Exsolution of (Na,K)Cl + (Na,K) 2 CO 3 + (Na,K) 2 SO 4 fluids with salinities up ∼80 wt.% • Fluid boiling as trigger for apatite crystalization. Studies of fluid inclusions in carbonatitic rocks are essential for understanding physicochemical processes involved in carbonatite-related hydrothermal ore mineralization and fenitization. However, the composition of many carbonatite-derived fluids is challenging to quantify, which hampers their detailed interpretation. Here, we present a systematic study of microthermometry of fluid inclusions found in carbonatites from the Kaiserstuhl (SW Germany), and a simple numerical model to estimate the compositions of such fluids, which are typical of numerous carbonatites worldwide. Four types of fluid inclusions have been identified in the Kaiserstuhl carbonatites: (I) vapor-poor H 2 O-NaCl fluids with <50 wt.% salinity; (II) vapor-rich H 2 O-NaCl-CO 2 fluids with <5 wt.% salinity; (III) multi-component fluids with high salinity and high CO 2 contents; and (IV) multi-component fluids with high salinity but little to no CO 2. At present, it is only possible to quantify fluid compositions for types I and II. For the complex types III and IV, we conducted predictive modeling of the liquidus surface based on the Margules equations. The results suggest that carbonatite melts predominantly exsolve Na-K-sulfate-carbonate/bicarbonate-chloride brines (types III or IV). Such fluid inclusions may represent immiscible fluids that were trapped after segregation by boiling from a parental highly saline brine (type I). Fluid boiling, in turn, was probably triggered by a rapid pressure release during melt ascent. The present model enables quantification of fluid compositions associated with carbonatitic magmatism. [ABSTRACT FROM AUTHOR]

Native arsenic is an occasional ore mineral in some hydrothermal base metal deposits. Its rarity (compared to pyrite, arsenopyrite, galena, sphalerite, or chalcopyrite, for example) is surprising, as arsenic is a common constituent of upper crustal fluids. Hence, the conditions of formation must be quite special to precipitate native arsenic. An ideal location to investigate the formation of native As and to explore the parameters constraining its crystallization is the Michael vein near Lahr, Schwarzwald, southwest (SW) Germany. Here, galena, sphalerite, and native arsenic are the most abundant ore minerals. The two important ore stages comprise (1) galena-barite and (2) sphalerite-native arsenicquartz, the latter with a general mineral succession of pyrite → sphalerite ± jordanite-gratonite solid solution → galena → native As. The native arsenic-bearing mineralization formed by cooling of an at least 130 °C hot saline fluid accompanied by a reduction due to the admixing of a sulfide-bearing fluid. Thermodynamic calculations reveal that for the formation of native arsenic, reduced conditions in combination with very low concentrations of the transition metals Fe, Co, and Ni, as well as low sulfide concentrations, are essential. "Typical" hydrothermal fluids do not fulfill these criteria, as they typically can contain significant amounts of Fe and sulfide. This results in the formation of arsenides, sulfarsenides, or As-bearing sulfides instead of native arsenic. Very minor amounts of pyrite, sulfarsenides, and arsenides record the very low concentrations of Fe, Co, and Ni present in the oreforming fluid. High concentrations of aqueous Zn and Pb lead to early saturation of sphalerite and galena that promoted native arsenic precipitation by decreasing the availability of sulfide and hence suppressing realgar formation. Interestingly, native arsenic in the Michael vein acted as a trap for uranium during supergene weathering processes. Infiltrating oxidizing, U+VI-bearing fluids from the host lithologies reacted under ambient conditions with galena and native arsenic, forming a variety of U+VI (±Pb)-bearing arsenates such as hügelite, hallimondite, zeunerite, heinrichite, or novacekite together with U-free minerals like mimetite or anglesite. Some parts of the vein were enriched to U concentrations of up to 1 wt% by this supergene process. Reduced (hypogene) uranium phases like uraninite were never observed. [ABSTRACT FROM AUTHOR]

Sulfate is among the most abundant ions in seawater and sulfate-bearing brines are common in sedimentary basins, among other environments. However, the properties of sulfate-bearing fluid inclusions during microthermometry are as yet poorly constrained, restricting the interpretation of fluid-inclusion compositions where sulfate is a major ion. The Schwarzwald mining district on the eastern shoulder of the Upper Rhinegraben rift is an example of a geologic system characterized by sulfate-bearing brines, and constraints on the anion abundances (chloride versus sulfate) would be desirable as a potential means to differentiate fluid sources in hydrothermal veins in these regions. Here, we use the Pitzer-type formalism to calculate equilibrium conditions along the vapor-saturated liquidus of the system H 2 O-Na-Ca-Cl-SO 4 , and construct phase diagrams displaying the predicted phase equilibria. We combine these predicted phase relations with microthermometric and crush-leach analyses of fluid inclusions from veins in the Schwarzwald and Upper Rhinegraben, to estimate the compositions of these brines in terms of bulk salinity as well as cation and anion loads (sodium versus calcium, and chloride versus sulfate). These data indicate systematic differences in fluid compositions recorded by fluid inclusions, and demonstrate the application of detailed low-temperature microthermometry to determine compositions of sulfate-bearing brines. Thus, these data provide new constraints on fluid sources and paleo-hydrology of these classic basin-hosted ore-forming systems. Moreover, the phase diagrams presented herein can be applied directly to compositional determinations in other systems. [ABSTRACT FROM AUTHOR]

The significance of magnesium isotope (δ 26 Mg) fractionation in the continental hydrothermal domain is poorly explored. Here, a detailed Mg isotope dataset from various aquifer host rocks and corresponding hydrothermal carbonate precipitates from the Schwarzwald mining area in SW Germany is documented and discussed. This study is motivated by the very considerable existing data set on hydrothermal mineralizations in the study area and the excellent regional control of sampling points. Based on structural, mineralogical and microthermometrical arguments, we here subdivide three clusters of veins: (i) Permian, (ii) Jurassic–Cretaceous and (iii) post-Cretaceous (Cenozoic). The focus is on clusters ii and iii and their corresponding, texturally older hydrothermal fluid inclusion-rich, coarse-grained, low-Mg calcite and dolomite–ankerite solid solutions and younger, oscillatory zoned low-Mg calcite and dolomite–ankerite solid solution crystals precipitated from fluids with temperatures between 50 and 350 °C. In terms of their δ 26 Mg ratios, three characteristic groups of hydrothermal carbonates can be distinguished: (i) Jurassic–Cretaceous veins (δ 26 Mg = − 3.38 to − 0.82‰) in the central Schwarzwald precipitated from fluids containing a significant proportion of sedimentary cover-derived waters. They yield 26 Mg-depleted Mg isotope signatures typical of sedimentary carbonate lithologies. (ii) Jurassic–Cretaceous vein carbonates in the southern Schwarzwald precipitated from mainly basement-derived fluids with 26 Mg-enriched signatures (δ 26 Mg = − 1.22 to + 0.05‰). Supporting evidence for the origin of these fluids comes from Sr–C–Pb isotope systematics and trace element compositional variations of fahlore and sphalerite. The Mg isotope variations are controlled by differences in fluid source characteristics dominate over variations exerted by mineralogical differences (where low-Mg calcites are generally, but not in all cases, more depleted in 26 Mg compared to dolomite–ankerite solid solutions). (iii) Post-Cretaceous (Cenozoic), Rhinegraben-related veins represent a complex tectonic juxtaposition of different aquifer lithologies. As expected, this phase spans the full range from silicate to carbonate Mg isotope signatures (+ 0.45 to − 3.4‰). Magnesium isotope data are supported by textural analyses (optical and cathodoluminescence microscopy), electron microprobe, microthermometry and published radiogenic 87 Sr/ 86 Sr isotope systematics. Our data are not in agreement with a significant temperature-controlled Δ 26 Mg fluid-calcite and no obvious relation between fluid salinity and hydrothermal carbonate δ 26 Mg is found. The results of this study suggest that hydrothermal carbonate magnesium isotope ratios have a significant potential as tracer of hydrothermal fluid sources and corresponding aquifer lithologies. [ABSTRACT FROM AUTHOR]

Hydrothermal fluorite-hematite veins represent a relatively rare vein type, which is sometimes associated with more common, fluorite-barite-quartz‑carbonate veins containing base metal mineralization. The origin and significance of the fluorite-hematite veins, and how they relate to the more common expression of mineralization, is essentially unknown. Here, we present new data illuminating the formation conditions of these "sulfide-barren" fluorite-hematite veins in a mining district known for hydrothermal Pb + Zn + Ag ores for which formation conditions are well understood: the Schwarzwald district in SW Germany. The exemplary Ödsbach-Hesselbach vein was chosen to study the fluids involved in fluorite-hematite precipitation through the first, direct investigation of fluid inclusions hosted in hydrothermal hematite using combined infra-red light microscopy, microthermometry and LA-ICPMS. The results indicate that the hematite-precipitating fluids are nearly identical to those observed in the associated fluorite, showing consistent salinities of 24.6–25.0 wt% (NaCl+CaCl 2) and homogenization temperatures of 150 to 155 °C. Moreover, the trace element abundances determined by the LA-ICPMS analyses show a composition similar to other inclusions observed in the common mineralization in the mining district, including elevated Pb (>5000 μg/g) and Zn (>2000 μg/g) concentrations at low Cl/Br mass ratios, and sulfur contents mostly below the limits of detection. The results suggest fluid mixing between a continental basement brine and a redbed-derived fluid from the Triassic Buntsandstein. Therefore, the formation of the rare fluorite-hematite veins was probably triggered by a change of the sedimentary fluid endmember representing a shift from the Middle Triassic Muschelkalk fluid, which drove the more common Pb + Zn + Ag mineralization, towards fluids derived from the Buntsandstein. Furthermore, the absence of sulfur is interpreted to have precluded base metal sulfide precipitation, and the formation of hematite points to unusually oxidized conditions and hence towards a lack of a reducing agent, which would also have been required to generate a mineralization of base metal sulfides. • First LA-ICPMS data from hematite-hosted fluid inclusions • How a missing redox agent influence vein mineralogy. • Low S systems are needed to precipitate fluorite-hematite veins. [ABSTRACT FROM AUTHOR]

Mixing of compositionally contrasting fluids is widely accepted as the major ore-forming process in unconformity-related hydrothermal Pb-Zn-fluorite-barite veins. Although the general process is relatively well understood, the temporal evolution of such fluid systems which may result in distinct mineralogical changes of the ore and gangue minerals precipitating are insufficiently constrained. One specific example is the occurrence of late-stage siderite-chalcopyrite-gersdorffite mineralization in 28 hydrothermal veins of the Schwarzwald, SW Germany post-dating the major fluorite-barite-galena-sphalerite phase which is very common in the whole area. To investigate the underlying process for this late-stage Cu-Ni-stage, published fluid inclusion data have been complemented by detailed confocal Raman micro-spectroscopy of fluid inclusions, petrographic observations and electron microprobe analyses. Petrography as well as mineral compositions of sphalerite, gersdorffite, pyrite, arsenopyrite, fahlore and galena record a gradual, but significant influx of Cu and Ni into a prevailing Pb-Zn hydrothermal system. This influx caused a distinct shift towards lower fO 2 and Pb + Zn + Sb + Ag (+ S) in the hydrothermal system at the transition from the Pb-Zn to the Cu-Ni mineralization stage. This transition in mineralogy and the related gradual change of the hydrothermal fluid can be explained by changes in the relative proportion of involved fluid components. However, the transition to the Cu-Ni mineralization stage by fluid influx is significantly different compared to the common rapid fluid mixing from below (which is thought to be responsible for the typical Pb-Zn veins) and probably records the gradual transition from long-term stable deep fluid reservoirs with constant chemical compositions towards more shallow and perturbed fluid reservoirs during rifting and exhumation. [ABSTRACT FROM AUTHOR]

Security of supply of "hi-tech" raw materials (including the rare earth elements (REE) and some high-field-strength elements (HFSEs)) is a concern for the European Union. Exploration and research projects mostly focus on deposit- to outcrop-scale description of carbonatite- and alkaline igneous-associated REE-HFSE mineralization. The REE-HFSE mineral system concept and approach are at a nascent stage, so developed further here. However, before applying the mineral system approach to a chosen REE-HFSE metallogenic province its mineral system extent first needs defining and mapping. This shifts a mineral system project's foundation from the mineral system concept to a province's mineral system extent. The mapped extent is required to investigate systematically the pathways and potential trap locations along which the REE-HFSE mass may be distributed. A workflow is presented to standardize the 4-D definition of a REE-HFSE mineral system at province-scale: (a) Identify and hierarchically organize a mineral system's genetically related sub-divisions and deposits, (b) map its known and possible maximum extents, (c) name it, (d) discern its size (known mineral endowment), and (e) assess the favorability of the critical components to prioritize further investigations. The workflow is designed to generate process-based perspective and improve predictive targeting effectiveness along under-evaluated plays of any mineral system, for the future risking, comparing and ranking of REE-HFSE provinces and plays. [ABSTRACT FROM AUTHOR]

Peculiar bimodal volcanism in the Hegau region (SW Germany) comprises two contrasting SiO 2 -undersaturated rock suites. (I) Primitive olivine melilitites and melilite-bearing olivine nephelinites (12–9 Ma) are characterized by high MgO, CaO, Fe 2 O 3 , TiO 2 , Ni, V, F, moderate alkalis, Al 2 O 3 , P 2 O 5 , Ba, Nb, Zr, and low SiO 2 , Rb, Pb, and U concentrations. The rocks are composed of forsteritic olivine, diopsidic clinopyroxene, melilite, perovskite, Cr-bearing oxyspinel, F- and Ba-rich mica, and fluorapatite. In rare cases, they contain coeval coarse-grained ijolite patches generated by rapid in-situ fractionation in small melt pockets. (II) Evolved nosean phonolites (14–11 Ma) comprise high alkalis, Al 2 O 3 , SiO 2 , Rb, Nb, Zr, U, Pb, S, and low MgO, CaO, Fe 2 O 3 , TiO 2 , P 2 O 5 , Ba, Ni, and V concentrations, and contain abundant Ba-bearing alkali feldspar and nosean-haüyne-sodalite ss macrocrysts, aegirine-augitic clinopyroxene, as well as accessory apatite, titanite, zircon, and pyrochlore. The melilititic–nephelinitic rocks formed by low degrees of partial melting of a carbonated amphibole ± phlogopite-bearing garnet wehrlite in the uppermost asthenosphere or in the thermal boundary layer and occur also in neighbouring regions. However, their coexistence with evolved nosean phonolites is a unique and so far, unexplained feature in the southern Central European Volcanic Province. Thermodynamic modelling implies that removal of 11–19% oxyspinel, 4–10% olivine, 42–57% clinopyroxene, <3% mica, <9% feldspathoids, <8% feldspar from melilititic–nephelinitic parental melts at upper crustal conditions (∼200 MPa) results in significant amounts of phonolitic residues that are compositionally similar to the exposed nosean phonolites. Strongly negative P and Ti anomalies and a trough of MREE in primitive mantle-normalized trace element patterns of phonolites indicate additional fractionation of titanite and apatite, consistent with the mineralogy of coarse-grained (nepheline) syenitic cumulates, which are present as enclaves in both rock suites. The modelling results suggest crystallization of the (nepheline) syenite cumulates between 1050 and 800 °C and ascent and eruption of the phonolite residues at no less than ∼900 °C with complete solidification of the observed assemblage at >750 °C. Significant crustal assimilation during fractionation appears unnecessary to explain the mineralogical, mineral chemical, and geochemical characteristics of the phonolites. Prolonged upper crustal differentiation of the magmas in one case (nosean phonolites) and fast ascent of primitive melts in the other (olivine melilitites and melilite-bearing olivine nephelinites) can be explained by stress field changes from an extensional to a more compressive regime, the magma ascent becoming thereby increasingly structurally controlled and supported by brittle deformation. • Hegau phonolites derived from melilitites/nephelinites by fractional crystallization. • Their geochemistry and mineralogy are largely reproducible by MELTS modelling. • Nepheline syenite enclaves represent entrained cumulate rocks of upper crustal origin. • Ijolitic patches in melilites/nephelinites are generated by in-situ differentiation. • Ascent of both volcanic suites is controlled by faulting and basement unit competence. [ABSTRACT FROM AUTHOR]

The main ore stage of three similar unconformity-related vein systems in the Schwarzwald, SW Germany spanning a period of activity of ~150 Ma, was investigated to understand the details of fluid penetration from overlying sediments/marine environment into the basement, their evolution as well as the processes involved in vein formation. To investigate temporal and spatial variations of the hydrothermal fluids responsible for mineralization, over 1650 fluid inclusions were analyzed by microthermometry. Of these, a total of 108 fluid inclusions (mainly in fluorite) were successfully analyzed by LA-ICP-MS. The fluid inclusions reveal a binary mixing trend between a CaCl 2 - and a NaCl-rich endmember. Independent of major element composition, the fluids are metal-bearing (e.g., up to ~100 mg/kg Ba, Pb, Zn, Ni and up to 10 mg/kg Ag), show high As (up to 1000 mg/kg) and low S (below the detection limit in most analyses). Over time, the mixed fluid shows a gradual decrease in CaCl 2 and increase in NaCl with slightly decreasing total salinity. Based on earlier studies and geochemical arguments, the veins formed by anisothermal binary fluid mixing of two fluids, which both were originally derived from seawater and chemically modified through interaction with the basement and sedimentary rocks in different ways. This produced a gradual stratified basement fluid reservoir comprising a modified bittern/halite dissolution brine. The fluids involved in the vein formation are sourced from different depths of this modified bittern/halite dissolution basement brine reservoir: fluid A, a CaCl 2 -dominated, KCl-poor, deeper seated brine with a salinity of ~25 wt% CaCl 2 + NaCl, and fluid B, an NaCl-dominated and KCl-richer brine situated at shallower depths in the crystalline basement with salinities of ~22 wt% NaCl+CaCl 2. Based on the Na-Ca-K and Na K thermometers and on Rb/Cs systematics, fluid A records alteration of the Na-, K- and Ca-bearing feldspars of the host rocks; progressive alteration led to consumption of mainly Ca-rich plagioclase in contact with these basement brines. Accordingly, fluid B that subsequently entered the basement was only in equilibrium with alkali feldspars and clay minerals. This scenario produced a gradual change of fluid composition with depth that was pushed to greater depth over time. The source temperatures are estimated to ~250 °C while vein formation occurred at 100–170 °C, based on fluid inclusion homogenization temperatures. Thus, significant fluid cooling without abundant fluid mixing (and without major mineralization) must have occurred during fluid ascent (3–7 km, depending on the assumed geothermal gradient). Fluid mixing then resulted in the formation of the major gangue minerals fluorite, quartz, barite and calcite, while the locally confined sulfides must have formed due to an influx of sulfide into the binary mixed fluid. The process of fluid mixing is a rapid and turbulent process. This is recorded by a great diversity of fluid compositions (including ones close to the mixing endmembers) trapped within the same crystal. Compositional variations are even visible within individual fluid inclusion trails. [Display omitted] • Major and trace element analysis by LA-ICP-MS on fluid inclusions in fluorite. • ~150 Ma spanning evolution of a basement brine reservoir from CaCl 2 -rich to NaCl-dominated. • Basement fluid stratification of shallow NaCl-dominated and deeper CaCl 2 -rich fluids. • Spatial and temporal fluid evolution linked to aquifer, Ca-rich plagioclase, alteration. • Near endmember fluid composition constrained by variability in fluid mixing ratio. [ABSTRACT FROM AUTHOR]