Basement Brines Research Articles

Ferrous Iron (Fe+2) Released From Iron‐Rich Chlorite as a Reductant for Unconformity‐Related Uranium Mineralization: Insights From Reactive Fluid Flow Modeling

AbstractDebate continues over the reducing mechanisms for the formation of unconformity‐related uranium (URU) deposits. This paper evaluates, for the first time, the potential of iron‐rich chlorite as a reductant for uranium mineralization using reactive fluid flow modeling method. Our results confirm that Fe2+, released from the breakdown of iron‐rich chlorite, can reduce aqueous hexavalent uranium to precipitate economically significant URU deposits similar in size and grade to those formed with CH4 as the reducing agent. The resulting uranium mineralization tends to occur in the basement and below the downwelling parts of overlying basinal fluid circulation cells, where oxidizing basinal fluid percolates across the unconformity and reacts with upward flowing reducing basement brine. Therefore, the basinal fluid circulation pattern controlled by the permeability of the sandstone aquifer is critical in determining the formation and distribution of URU deposits. When the sandstone layer is more permeable, the simulated uranium deposits become larger in size, and vice versa. If the sandstone permeability is <5 × 10−14 m2, no obvious uranium deposits can be formed. In contrast, the permeability of fault zones does not have a significant effect on uranium mineralization, although it does affect fluid flow behaviors within the fault zone itself. We also demonstrate that fault zones do not appear to be a prerequisite for the formation of URU deposits when Fe+2 serves as a reductant, which highlights important exploration implications. Uranium exploration should, in addition to continuing to target graphitic fault zones, also consider areas where faults and/or graphite units do not exist.

Diatreme-hosted fluorite mineralization in S-Namibia – A tale of cryogenic brine formation and fluid mixing below an unconformity in the context of Pangea rifting

The Garub fluorite deposit in south Namibia is hosted by a Neoproterozoic tuffisite diatreme which is cut by a hydrothermal vein with base metal mineralization. Petrographic observations indicate a single hydrothermal event producing a paragenesis of fluorite-baryte with base metal sulfides, quartz and carbonates. Microthermometry data from fluid inclusions show that hydrothermal fluorite and baryte were precipitated from a high-salinity (16.9–22.7 wt% NaCl + CaCl2), moderate-temperature brine (180–210 °C). This brine formed by mixing between a warmer, Ba- and F-rich endmember likely representing a deep-seated basement brine (chemically equilibrated with Namaqua-Natal-Metamorphic Complex basement rocks) and a cooler, SO4- and Ca-rich endmember that likely equilibrated with Nama Group limestone. Chlorine/Br mass ratios between 152 and 612 indicate the mixing of a fluid with a halite dissolution brine signature (endmember 1) and an equally saline brine derived from Nama Group limestone (endmember 2). Rubidium/Cesium (Rb/Cs) ratios between 2.2 and 20.5 provide evidence for significant fluid interaction with clay minerals. Since clay minerals are abundant in the tuffisite of the Garub diatreme, these Rb/Cs ratios indicate that fluids migrated along the diatreme-gneiss contact along a zone of weakness. Late-stage quartz and calcite likely reflect cooling and induced a shutdown of the hydrothermal system. The sulfide phases in this hydrothermal vein are strongly depleted in trace elements compared to other hydrothermal vein districts, which is interpreted as an inherited signature of the fluid source.There is no record of evaporites in the sedimentary rocks of the Nama Group. Based on the fluid chemistry of the mixed fluid, which clearly indicates halite dissolution and water-rock interaction with basement rocks, it is concluded that the basement brine fluid endmember is likely generated through cryogenic brine formation during the large scale Dwyka glaciation event. As a farfield consequence of Pangea breakup fluid pathways were established that acted as host structures for the Garub fluorite deposit. This could be the first evidence for unconformity-related hydrothermal fluorite deposit formation in the context of Dwyka cryogenic brine formation in southern Africa.

A tale of three fluids: Fluid-inclusion and carbonate clumped-isotope paleothermometry reveals complex dolomitization and dedolomitization history of the Latemar platform

Abstract This work focuses on an exceptionally complex natural laboratory, the Triassic Latemar isolated platform in the Dolomite Mountains of northern Italy. It explores spatial and temporal gradients in processes and products related to contact metamorphism, dolomitization, and the dedolomitization of marine limestones. Rock samples were studied using dual fluid-inclusion thermometry and clumped-isotope thermometry. Independent of the spatial position at Latemar, Δ47 clumped-isotope and fluid-inclusion data provide contrasting paleotemperature estimates. An apparent lack of systematic patterns in fluid-inclusion data (homogenization temperature, salinity, density) results from analyses of micrometer-sized growth zones within a single crystal. The composition of the individual fluid inclusions represents a “snapshot” of fluid mixing with variable endmember elemental ratios. The bulk crush-leach data and slopes in Caexcessversus Nadeficit diagrams indicate different water–rock interactions and fluid signatures with evaporation sequences and crystalline rocks. The presence of three fluid types (crystalline basement brine, halite-dissolution brine, seawater) in all carbonates suggests that all fluids coexisted during contact metamorphism and dolomitization of Latemar carbonates. Non-equilibrium processes overruled thermodynamic controls on the precipitation of diagenetic phases. Fluid mixing resulted in the precipitation of two complex carbonate successions. The Δ47 data represent bulk temperatures, averaging the mixing ratio of fluids with different temperatures and their respective volume. Fluid-inclusions record patterns of remarkable complexity and shed light on the complexity of a multi-fluid system. Data shown here provide answers to the controversial interpretation of dolomitizing fluid temperature in the Latemar and exemplify the strengths of multi-proxy paleotemperature studies.

Effect of Fault Extension Relevant to Unconformity on Hydrothermal Fluid Flow, Mass Transport, and Uranium Deposition

In this study, a conceptual model is developed based on common features of typical unconformity-related uranium deposits in the Athabasca Basin, Canada. Three reactive flow modeling scenarios are designed to address the effect of fault extension on the formation of uranium deposits. Our results indicate that the location of the fault zone relevant to the unconformity is crucial to the fluid circulation in both the sandstone layer and the basement unit, the temperature distribution, the transport of aqueous components, and the uranium deposition. In particular, this research reveals that the circulating pattern of the basement brine is critical for the ore genesis. The reducing basal brine is capable of carrying aqueous uranium from depth to react with the shallow oxidizing fluid, being percolated to the basement from the overlain sandstone layer, for uranium precipitation. Scenarios 1 and 2, in which the fault zone is mainly in the basement, are in favor of focusing ore-forming hydrothermal fluids into the footwall area in the basement, leading to the formation of uranium deposits therein. Scenario 3, in which the fault zone is mainly in the sandstone layer with a limited extension below the unconformity, is unfavorable for the focusing of fluids, and hence no significant deposits can be formed, except for some minor uranium mineralization occurring in the footwall and other areas in the basement that are spatially associated with the upwelling flow zones in the sandstone layer.

Basement aquifer evolution and the formation of unconformity-related hydrothermal vein deposits: LA-ICP-MS analyses of single fluid inclusions in fluorite from SW Germany

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 CaCl2- 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 CaCl2 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 CaCl2-dominated, KCl-poor, deeper seated brine with a salinity of ~25 wt% CaCl2 + 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+CaCl2. Based on the Na-Ca-K and NaK 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.

Quantitative evaluation of hydrothermal fluids and their impact on diagenesis of deep carbonate reservoirs: Insights from geochemical modeling

Hydrothermal dolomitization is an important diagenetic process that affects the quality of carbonate reservoirs. While geochemical modeling is a useful tool to improve our understanding of this process, comparatively little research has been focused on producing reservoir intervals. This study examines deeply buried (over 4500 m deep), Lower Ordovician dolomitized limestones (more than 50 m revealed by the borehole) in an exploration well in the Tazhong Uplift, Tarim Basin. The well penetrated a fault zone that was affected by extensive hydrothermal activity during the Permian. Batch geochemical modeling and reactive transport modeling (RTM) were used to evaluate the potential sources of hydrothermal fluid and the associated mechanisms that resulted in a relatively restricted distribution of dolomitization in the study area. Simulation results show that the RTM, which can include geological heterogeneity, provides more reliable constraints for the volume of hydrothermal fluids required for the observed scale of dolomitization, compared to batch geochemical modeling. According to the simulation results, the interstitial fluids released from underlying Cambrian formations due to high pressure and high temperature are not the only source of hydrothermal dolomitization. Other mechanism like long-lasting recharge of seawater-derived basement brines may be took place. Scenario simulations also indicate that the patterns of hydrothermal dolomitization and porosity distributions are strongly related to permeability heterogeneity in the formation. This study shows the ability and feasibility of geochemical modeling as a tool to quantitatively evaluate and further understand hydrothermal dolomitization processes, which are also helpful for other similar geological process research. However, reliable and detailed geological information, geological constrains, especially geological heterogeneity distributions, are crucial to achieve beneficial conclusions.

Fluorite as indicator mineral in iron oxide-copper-gold systems: explaining the IOCG deposit diversity

Hydrothermal iron oxide-copper-gold (IOCG) ore deposits are globally important sources of Cu and Au. IOCG systems show many common features, but also considerable diversity in terms of geological setting, mineralization style and ore fluid characteristics. The key factors that control ore formation are controversially debated and no general ore deposit model has been able to explain the diversity of IOCG deposits on the global scale. Building on previous work that characterized four distinct fluid types at the Prominent Hill IOCG deposit, South Australia, we have analyzed the rare earth element (REE) composition of fluorite from the Prominent Hill, Olympic Dam and Ernest Henry IOCG deposits and from two prospects close to Prominent Hill. The REE data of fluorite from Prominent Hill show four distinct chondrite-normalized patterns, which reflect the four fluid types identified as metalliferous volcanic lake water derived fluid, magmatic-hydrothermal fluid, sedimentary basin brine, and wall rock-buffered basement brine. Two strikingly similar REE pattern types were found in fluorite from the Olympic Dam deposit and one in an exploratory data from the Ernest Henry deposit, demonstrating the involvement of the same principal fluid types. We therefore conclude that world-class IOCG deposits can form by interaction of host rocks with different characteristic types of ore fluids and their combinations, thus IOCG deposits do not necessarily form by a single sequence of processes.

Formation of hydrothermal fluorite-hematite veins by mixing of continental basement brine and redbed-derived fluid: Schwarzwald mining district, SW-Germany

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+CaCl2) 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.

Evidence of upgrading of gold tenor in an orogenic quartz-carbonate vein system by late magmatic-hydrothermal fluids at the Madrid Deposit, Hope Bay Greenstone Belt, Nunavut, Canada

Evidence of secondary gold enrichment due to the addition of new gold into an earlier orogenic quartz-carbonate vein deposit by magmatic-hydrothermal fluids is strongly suggested for the Madrid Deposit, hosted in the Hope Bay Greenstone Belt in Nunavut, Canada. The conclusion is based on an extensive in situ microanalytical protocol (SEM, confocal Raman microspectroscopy, microthermometry, decrepitate mound analysis, LA-ICP-MS, cathodoluminescence, SIMS) not previously applied to gold systems. This approach was used to characterize the mineralogy and fluid inclusion systematics associated with the upgrading event.Mineralization comprised of only Ag-bearing gold (“electrum”; 89.8 at. % Au avg.; n = 8) is present throughout all investigated laminated and brecciated orogenic quartz veins. However, in high-grade vein intersections where gold grades are locally elevated (up to 122 g/t), assemblages containing tennantite-tetrahedrite + chalcopyrite + electrum (80.7 at. % Au avg.; n = 15) ± AgPbAu tellurides occur that are texturally late-stage relative to electrum-only mineralization. Subdomains of quartz coeval with this later assemblage are optically- and texturally-distinct from earlier orogenic quartz. This late mineral assemblage is absent in all low-grade vein intersections (∼1 g/t Au avg.) examined where only electrum is identified. Quartz-hosted fluid inclusions (H2ONaCl ± CO2) of intermediate salinity (16.7 ± 1.2 wt.% NaCl equiv.; n = 93) were identified only in the high-grade vein samples and are present along healed planes associated with tennantite-tetrahedrite + chalcopyrite + electrum ± AgPbAu telluride assemblages. In situ SIMS δ18O analyses of quartz, combined with temperature constraints from mineral equilibria, show that early orogenic vein quartz and late quartz subdomains associated with gold upgrading precipitated from fluids with similar δ18OH2O values of 4.5–12.4‰ (n = 10) and −5.5 to 11.8‰ (n = 13), respectively. Isotopic data suggests that meteoric water was a negligible component in fluids responsible for gold precipitation. Microthermometry and Raman spectroscopy show that upgrading fluids were distinct in composition compared to the earlier metamorphic fluids (H2ONaClCO2 ± CH4 ± N2; 4.6 ± 1.6 wt.% NaCl equiv., n = 33) and later Canadian Shield basement brines (H2ONaCl; 22.4 ± 1.2 wt.% NaCl equiv., n = 12) which have also been identified in the fluid inclusion record at Madrid. Laser ablation ICP-MS analyses indicate the gold upgrading fluids are enriched in AsSbZnPb and LILE (CsBaRbSr); these data are consistent with late fluids derived from an evolved magmatic-hydrothermal system. Trace element mapping of pyrite, coupled with principle component analysis of the data, confirms a strong correlation between Au and AgTeSbBiW(As) in upgraded veins, whereas only Au and As strongly correlate in low-grade veins.The study suggests that gold upgrading, either involving newly introduced gold or remobilization of existing gold, can be linked to the incursion of a late magmatic-hydrothermal fluid that post-dated formation of the main orogenic-type auriferous quartz vein system. The geological setting and mineral-chemical features suggest an intrusion-related (i.e., porphyry), or intermediate-sulfidation epithermal mineralization style for the later event. This work provides another example of the importance of compositionally distinct cumulative hydrothermal events in the development of high-grade gold deposits in orogenic settings.

The connection between hydrothermal fluids, mineralization, tectonics and magmatism in a continental rift setting: Fluorite Sm-Nd and hematite and carbonates U-Pb geochronology from the Rhinegraben in SW Germany

Understanding the physical basics of tectonic events, related fluid flow and ore deposition represents one of the great challenges in modern geosciences. In this contribution, Sm-Nd ages of hydrothermal fluorites and U-Pb ages of carbonates and iron oxides from unconformity-related vein type deposits in the Schwarzwald next to the Upper Rhinegraben rift in SW Germany are used to distinguish different pulses of hydrothermal fluid activity and to understand their relation to large-scale tectonics and magmatism. While the fluorites are of Early Jurassic to Oligocene age, carbonate (calcite, dolomite, siderite) and hematite dated by U-Pb small-scale isochrons records formation from Permian to Quaternary with a clear culmination in the Neogene.These new age-data in combination with microthermometry data of primary fluid inclusions from growth zones in the fluorites and carbonates are used to constrain the timing of fluid signatures. This contribution shows that the ages are correlated with changes in fluid properties and/or tectonic events in the evolving continental crust. Comparison with published thermochronological data, apparent ages of URG-related volcanic rocks and the tectono-sedimentary evolution of the Upper Rhinegraben rift show clear correlations between the intensity of hydrothermal mineralization (and, hence, the intensity of fracture-bound fluid flow) with the U-Pb carbonate ages. This method accordingly provides an excellent tool to date rift-related processes like fluid flow, ore deposition and tectonic activation or reactivation of fractures.Fluid properties changed after the deposition of Middle Triassic Muschelkalk evaporites from low salinity, high temperature (1–6 wt.% NaCleq, 200–270 °C, cooling late-metamorphic basement fluids) to high salinity, moderate temperature (20–26 wt.% (NaCl + CaCl2), 50–170 °C, mixture of a modified bittern brine (“basement brine”) with halite dissolution brine). This change led to large scale ore deposition (fluorite-barite-quartz with Pb-Zn-Cu, Bi-Co-Ni-Ag-U, Fe-Mn ores). During the Paleogene and Neogene, previously separated aquifers from various sedimentary units were connected by juxtaposition of the fluid source rocks during Rhinegraben rifting, which resulted in variable salinity and temperature fluids (1–26 wt. % (NaCl + CaCl2), 50–350 °C) by a multi-component fluid mixing process. Typical mineralization related to this shows barren or Pb-Zn-Cu veins with large amounts of barite.

Multi-reservoir fluid mixing processes in rift-related hydrothermal veins, Schwarzwald, SW-Germany

Fluid mixing is an important process in the formation of many hydrothermal vein-type deposits. Here, we present evidence from hydrothermal fluorite-barite-quartz veins with Pb-Zn-Cu-(Ag)-sulfides and associated mineralization, indicating that mineral precipitation was initiated by mixing of fluids derived from multiple sources, including mixing between more than two end-member fluid compositions. Based on our observations, we relate the diversity of the hydrothermal veins of the Schwarzwald mining district in terms of mineral assemblage and fluid inclusion chemistry to the disturbed and transient geological environment during ongoing rifting. Literature data on the regional geology, current groundwater reservoirs, formation processes and hydraulic features are augmented by new fluid inclusion analyses from post-Cretaceous, hydrothermal vein minerals including microthermometry, crush leach, Microraman and LA-ICP-MS analyses of individual fluid inclusions.Petrography and microthermometry of fluid inclusions show complex sequences of alternating fluid signatures within different growth zones of one crystal. High (20–26wt% NaCl+CaCl2), moderate (5–20wt% NaCl+CaCl2) and low salinity (<5wt% NaCl+CaCl2), sulfate- and/or CO2-bearing primary fluids were trapped during crystal growth. Such variations are commonly observed in minerals from different localities. Bulk crush leach analyses show significant variations in major element composition of the trapped fluids, within the overall Na-Ca-Cl-SO4-HCO3-system. These variations are caused by mixing of fluids from different aquifers and in various proportions. Ancient fluids show chemical similarities to modern groundwater aquifers that are available for direct sampling, such as granitic basement, Lower Triassic sandstones or Middle Triassic limestones and evaporites. Analyses of individual fluid inclusions by LA-ICP-MS support this interpretation and document the multi-component fluid mixing processes at individual localities recorded on the scale of single crystal growth zones. The latter data are used in a diffusion model to obtain the duration of mineral growth (before the fluid is homogenized), which implies very short-lived fluid events on the order of seconds to hours.By defining end member fluids and their proportions, we show that nearly all fluid mixtures are saturated with respect to barite. By contrast, fluorite-saturated fluids can only be modelled by mixing of a basement brine with fluids from Triassic sandstones. All fluid mixtures are strongly undersaturated with respect to galena, chalcopyrite and sphalerite, the most commonly observed ore minerals in the hydrothermal veins. As the calculated fluid mixtures are typically relatively oxidized and contain high sulfate/sulfide ratios, precipitation of sulfides was probably related to short-lived reduction events caused by an influx of hydrocarbons, by reactions with graphitic wall rocks in fractures by sulfidation related to fluid-rock reaction with the surrounding host rocks or an external influx of hydrocarbon-bearing fluids. The multi-aquifer fluid mixing processes involving aquifers of different chemical and physical constitution were triggered by brittle deformation related to rifting of the Rhine graben. This appears to be essential for the formation of a large number of mineralogically diverse hydrothermal ore deposits.

Methane and the origin of five-element veins: Mineralogy, age, fluid inclusion chemistry and ore forming processes in the Odenwald, SW Germany

Five-element veins (Ag, Bi, Co, Ni, As) have been valuable mineral deposits since medieval times. The characteristic occurrence of large aggregates of native metals (up to several dm) surrounded by a succession of arsenides makes this vein-type attractive for mining industry, natural history museums and private mineral collectors. Nevertheless, the exact formation process of these specific vein types has not been fully understood. This is the first case study applying a new model, which includes methane as a reducing agent to two typical examples of such mineralisations from the Odenwald, SW Germany. We analysed all mineralogical varieties (Ag-, As- and Bi-dominated) of the five-element veins in the Odenwald (SW Germany) in terms of ore textures, mineral chemistry, fluid inclusion compositions (microthermometry and Raman spectroscopy), stable isotopes (C, O and S) and in-situ U-Pb age dating of calcite and prehnite.A variety of Ag-, Bi- and As-dominated native metal-arsenide-calcite veins, sulphide-calcite veins and arsenide-free Ag-Hg-barite veins occurs in the Odenwald and has been examined in this study. All arsenide veins have in common that up to dm-sized, often dendritic native metals are overgrown by a succession of arsenides, followed by carbonate and finally sulphides. The succession of arsenides shows a distinct spatial and temporal chemical trend in their composition. This trend evolves from Ni- to Co and finally Fe-dominated compositions from the core to the rim. In contrast, spatially closely related Ag-Hg-barite veins consist of almost mono-mineralic amalgam inter-grown with barite.In-situ U-Pb age dating of low-U calcite and prehnite was applied to constrain the age of hydrothermal mineralisation. The results imply that the five-element veins formed at 170–180Ma from Na-Ca-Cl fluids at 290°C, salinities of ~27wt.% and Ca/(Ca+Na) of 0.30 to 0.35 in the presence of methane. The age data clearly relate the relevant fluid migration to extension and crustal thinning caused by the opening of the North Atlantic. Ternary mixing of a deep-seated metal-rich basement brine (fluid A), a sulphide-bearing (H2S and HS−) basinal/sedimentary brine (fluid B) and methane-dominated fluid/gas (fluid C) induce ore formation. Mixing of such chemically contrasting fluids results in a strong chemical disequilibrium of the mixed fluid, which potentially leads to rapid precipitation of native metals and arsenides with these specific ore textures. In contrast, sulphide-bearing calcite veins formed under similar P-T-conditions due to mixing of fluid A and B, while fluid C was absent. Additionally, U-Pb analyses of post-ore calcite yields ages of ~60Ma, which indicates that a second calcite formation event is associated with the onset of the Upper Rhine Graben rifting.Veins with amalgam and barite form as a consequence of post-ore oxidation of Ag2S at ~135°C. Conspicuously, this secondary silver II has Hg contents of up to ~30wt.%, in contrast to Hg contents below 1wt.% of primary silver I and Ag2S. The formation of amalgam was most likely related to decrease of the S2−/SO42− ratio due to cooling of the late hydrothermal fluid resulting in the destabilisation of Hg-bisulphide complexes in this fluid.

A sulfate conundrum: Dissolved sulfates of deep-saline brines and carbonate-associated sulfates

Sulfates in deeply circulating brines and carbonate-associated sulfates (CAS) within sedimentary units of the Cambrian strata in the Illinois Basin record a complex history. Dissolved sulfate within the Mt. Simon Sandstone brines exhibits average δ34SSO4 values of 35.4‰ and δ18OSO4 values of 14.6‰ and appears to be related to Cambrian seawater sulfate, either original seawater or sourced from evaporite deposits such as those in the Michigan Basin. Theoretical and empirical relationships based on stable oxygen isotope fractionation suggest that sulfate within the lower depths of the Mt. Simon brines has experienced a long period of isolation, possibly several tens of millions of years. Comparison with brines from other stratigraphic units shows the Mt. Simon brines are geochemically unique. Dissolved sulfate from brines within the Ironton-Galesville Sandstone averages 22.7‰ for δ34SSO4 values and 13.0‰ for δ18OSO4 values. The Ironton-Galesville brine has mixed with younger groundwater, possibly of Ordovician to Devonian age and younger. The Eau Claire Formation lies between the Mt. Simon and Ironton-Galesville Sandstones. The carbonate units of the Eau Claire and stratigraphically equivalent Bonneterre Formation contain CAS that appears isotopically related to the Late Pennsylvanian-Early Permian Mississippi Valley-type ore pulses that deposited large sulfide minerals in the Viburnum Trend/Old Lead Belt ore districts. The δ34SCAS values range from 21.3‰ to 9.3‰, and δ18OCAS values range from +1.4‰ to −2.6‰ and show a strong covariance (R2=0.94). The largely wholesale replacement of Cambrian seawater sulfate signatures in these dolomites does not appear to have affected the sulfate signatures in the Mt. Simon brines even though these sulfide deposits are found in the stratigraphically equivalent Lamotte Sandstone to the southwest. On the basis of this and previous studies, greater fluid densities of the Mt. Simon brines may have prevented the less dense Mississippi Valley-type fluids from interacting with these deeply circulating brines. Progressive in situ quartz cementation that occurred in the Mt. Simon Sandstone contemporaneous to the ore pulses may also have precluded fluid migration. The Mt. Simon brines appear to be a mixture of evaporated connate Cambrian seawater, recirculating deep-seated crystalline basement brines, and meteoric water.

The effect of temperature and cataclastic deformation on the composition of upper crustal fluids — An experimental approach

We investigated the potential of common crystalline rocks to facilitate the geochemical evolution of continental basement brines and to serve as a metal source for hydrothermal ore deposits. We performed leaching experiments on typical crystalline basement rocks (granite and gneiss), a redbed sandstone and their mineral separates (feldspar, quartz and biotite) at variable T (25, 180, 275 and 350°C), P (ambient pressure, 0.9, 1.4 and 1.9kbar), grain-size fractions (<0.01mm, 0.063–0.125 and 2–4mm) and variable fluid/rock ratios (10 to 1.1) with ultrapure water and 25wt.% NaCl solution as solvents.The modification of the fluid chemistry during water–rock interaction strongly depends on grain-size: leachates (using pure H2O) of fine-grained rock powders have lower Na/Cl and Cl/Br ratios but much higher chlorinities (by a factor of up to 40) compared to leachates from coarse-grained rock powders. The Cl/Br ratios of all leachates are lower than that of their respective whole-rocks. Smaller grain-sizes of the starting materials yield element ratios (Cl/Br and Na/Cl) similar to those found in natural fluids, emphasizing the influence of cataclastic deformation on the fluid chemistry of crustal fluids. During our leaching experiments, Pb, Zn, Cu and W are released by felsic minerals, while biotite alteration releases Ni, As and additional Zn and Cu.Our experiments confirm that crystalline rocks may serve as metal source for hydrothermal ore deposits. Short-term water–rock interactions along cataclastic fault zones in the brittle crust may influence the geochemical evolution of upper crustal fluids. This is further suggested by low F/Cl and Cl/Br ratios in some of the leachates being very similar to halogen systematics in natural fluid samples.

Long‐term chemical evolution and modification of continental basement brines – a field study from the Schwarzwald, SW Germany

AbstractHighly saline, deep‐seated basement brines are of major importance for ore‐forming processes, but their genesis is controversial. Based on studies of fluid inclusions from hydrothermal veins of various ages, we reconstruct the temporal evolution of continental basement fluids from the Variscan Schwarzwald (Germany). During the Carboniferous (vein type i), quartz–tourmaline veins precipitated from low‐salinity (&lt;4.5wt% NaCl + CaCl2), high‐temperature (≤390°C) H2O‐NaCl‐(CO2‐CH4) fluids with Cl/Br mass ratios = 50–146. In the Permian (vein type ii), cooling of H2O‐NaCl‐(KCl‐CaCl2) metamorphic fluids (T ≤ 310°C, 2–4.5wt% NaCl + CaCl2, Cl/Br mass ratios = 90) leads to the precipitation of quartz‐Sb‐Au veins. Around the Triassic–Jurassic boundary (vein type iii), quartz–haematite veins formed from two distinct fluids: a low‐salinity fluid (similar to (ii)) and a high‐salinity fluid (T = 100–320°C, &gt;20wt% NaCl + CaCl2, Cl/Br mass ratios = 60–110). Both fluids types were present during vein formation but did not mix with each other (because of hydrogeological reasons). Jurassic–Cretaceous veins (vein type iv) record fluid mixing between an older bittern brine (Cl/Br mass ratios ~80) and a younger halite dissolution brine (Cl/Br mass ratios &gt;1000) of similar salinity, resulting in a mixed H2O‐NaCl‐CaCl2 brine (50–140°C, 23–26wt% NaCl + CaCl2, Cl/Br mass ratios = 80–520). During post‐Cretaceous times (vein type v), the opening of the Upper Rhine Graben and the concomitant juxtaposition of various aquifers, which enabled mixing of high‐ and low‐salinity fluids and resulted in vein formation (multicomponent fluid H2O‐NaCl‐CaCl2‐(SO4‐HCO3), 70–190°C, 5–25wt% NaCl‐CaCl2 and Cl/Br mass ratios = 2–140). The first occurrence of highly saline brines is recorded in veins that formed shortly after deposition of halite in the Muschelkalk Ocean above the basement, suggesting an external source of the brine's salinity. Hence, today's brines in the European basement probably developed from inherited evaporitic bittern brines. These were afterwards extensively modified by fluid–rock interaction on their migration paths through the crystalline basement and later by mixing with younger meteoric fluids and halite dissolution brines.

Isotopic and geochemical characterization of fossil brines of the Cambrian Mt. Simon Sandstone and Ironton–Galesville Formation from the Illinois Basin, USA

Geochemical and isotopic characteristics of deep-seated saline groundwater provide valuable insight into the origin and evolving composition, water–rock interaction, and mixing potential of fossil brines. Such information may yield insight into intra- and interbasinal brine movement and relationships between brine evolution and regional groundwater flow systems. This investigation reports on the δ18O and δD composition and activity values, 87Sr/86Sr ratios and Sr concentrations, and major ion concentrations of the Cambrian-hosted brines of the Mt. Simon Sandstone and Ironton–Galesville Formation and discusses the evolution of these brines as they relate to other intracontinental brines. Brines in the Illinois Basin are dominated by Na–Ca–Cl-type chemistry. The Mt. Simon and overlying Ironton–Galesville brines exhibit total dissolved solids concentrations of ∼195,000mg/L and ∼66,270mg/L, respectively. The δD of brine composition of the Mt. Simon ranges from −34‰ to −22‰ (V-SMOW), and the Ironton–Galesville is ∼−53.2‰ (V-SMOW). The δ18O composition of the Mt. Simon brine ranges from −5.0‰ to −2.8‰ (V-SMOW), and the Ironton–Galesville brine is ∼−6.9‰ (V-SMOW). The 87Sr/86Sr values in the Mt. Simon brine range from 0.7110 to 0.7116. The less radiogenic Ironton–Galesville brine has an average 87Sr/86Sr value of 0.7107. Evaluation of δ18O and δD composition and activities and 87Sr/86Sr ratios suggests that the Mt. Simon brine is likely connate seawater and recirculating deep-seated brines that have been diluted with meteoric water and influenced by the dissolution of evaporites with a minimal halite contribution based on Cl/Br ratios. The Ironton–Galesville brine is also likely originally connate seawater that mixed with other brines and meteoric waters, including possibly Pleistocene glacial recharge. The Ca-excess vs. Na-deficiency comparison with the Basinal Fluid Line suggests the Mt. Simon and Ironton–Galesville brines have been influenced by the effects of albitization and plot very close to the Basinal Fluid Line. These Cambrian-hosted brines appear to have a different albitization history than other regional basin brines and a strong component of seawater. The Ironton–Galesville brine appears more geochemically associated with other Illinois Basin brines than the Mt. Simon brine which appears more geochemically conservative. Comparisons with other extrabasinal North American brines suggest that the Michigan basin brines are geochemically most similar to the Mt. Simon brines with the exception of the influence from carbonates in the Michigan Basin. Analyses of 87Sr/86Sr values in the Mt. Simon brine suggest that brine Sr has isotopically equilibrated with clay minerals in the Lower Mt. Simon and underlying bedrock formations and not with whole rock suggesting the influence of recirculating brines from the crystalline basement. Overall, the geochemistry of these Cambrian-hosted brines suggests an evolution from original seawater-like compositions. This investigation shows that intracratonic basins do not behave as closed systems but can be strongly affected by water–rock interaction and regional groundwater flow systems that circulate deep crystalline basement brines and brines from nearby basins.

Fluid mixing from below in unconformity-related hydrothermal ore deposits

Unconformity-related hydrothermal ore deposits typically form by mixing of hot, deep, rock-buffered basement brines and cooler fluids derived from the surface or overlying sediments. Current models invoking simultaneous downward and upward flow of the mixing fluids are inconsistent with fluid overpressure indicated by fracturing and brecciation, fast fluid flow suggested by thermal disequilibrium, and small-scale fluid composition variations indicated by fluid inclusion analyses. We propose a new model where fluids first descend, then evolve while residing in pores and later ascend. We use the hydrothermal ore deposits of the Schwarzwald district in southwest Germany as an example. Oldest fluids reach the greatest depths, where long residence times and elevated temperatures allow them to equilibrate with their host rock, to reach high salinity, and to scavenge metals. Youngest fluids can only penetrate to shallower depths and can (partially) retain their original signatures. When fluids are released from different levels of the crustal column, these fluids mix during rapid ascent in hydrofractures to form hydrothermal ore deposits. Mixing from below during ascent provides a viable hydromechanical mechanism to explain the common phenomenon of mixed shallow and deep fluids in the formation of hydrothermal ore deposits.

Formation waters from Cambrian-age strata, Illinois Basin, USA: Constraints on their origin and evolution

Recently, brine samples from the Cambrian-age Mount Simon Formation (the deepest, most inaccessible sedimentary rock formation of the Illinois Basin) and the overlying Ironton–Galesville Formation were collected as part of a major research effort evaluating the feasibility of sequestration of carbon dioxide in deep geologic formations. Halide and halide/cation ratios (especially Cl/Br and Na/Br ratios) from groundwater samples collected during this investigation suggest that the brines of the Cambrian-age strata formed by the evaporation of seawater well beyond the point of halite precipitation. The Cl/Br and Na/Br ratios, the presence of Mississippi-Valley-Type (MVT) ore mineralization in close proximity to the Illinois Basin, and the tectonic history of the region and the Illinois Basin suggest that components of ore-forming brines and perhaps crystalline basement brine are likely still present within the Mount Simon Formation. Halide and cation/halide ratio plots show that these brines have mixed with and have been diluted by subaerially evaporated seawater, seawater and dilute groundwater. Movement of brines out of the Mount Simon Formation and/or exchange with brines of other formations is constrained by the overlying, siltstone- and shale-rich Eau Claire Formation, a low-permeability layer.The most plausible interpretation of the halide and halide/cation ratio data is that the brines of the Cambrian-age strata were introduced to the Illinois Basin from outside of the basin, perhaps when the Illinois Basin was connected to the Arkoma (Oklahoma and Arkansas) and Black Warrior Basins (Alabama and Mississippi) via the Reelfoot Rift during Cambrian and early Ordovician time. In addition, the presence of some percentage of high NaCl, low Cl/Br brines from the crystalline basement is suggested given the geochemical relationships of the halide and cation/halide ratios and the tectonic history of the Illinois Basin. Finally, halide and cation/halide ratios determined by this investigation, and regional geochemical evidence and hydrogeologic modeling (by others) suggest that the brines of these strata probably were affected by regional hydrothermal activity during Permian time that was responsible for the MVT ore deposits of the Midwestern U.S. Thus, the brines of the deepest strata of the Illinois Basin constitute a different, more complex type of fluid than those found elsewhere in the basin. Halide and halide-cation ratios suggest that these deep brines are dominated by residual evaporitic brine (possibly originating as ore-forming brines) with dilution by seawater and dilute groundwater. Other components may include subaerially evaporated seawater and crystalline basement brines.

Fluid mixing forms basement-hosted Pb-Zn deposits: Insight from metal and halogen geochemistry of individual fluid inclusions

Fluid mixing across unconformities between crystalline basement and overlying sedimentary basins is commonly invoked as an efficient chemical mechanism for ore deposition, but the origin of basement brines and the process of ore formation have rarely been linked by direct evidence. Using laser ablation–inductively coupled plasma–mass spectrometry microanalysis of individual fluid inclusions with an improved detection approach for anion components, we determined simultaneously the ore metal concentrations and the Cl/Br ratio in texturally well constrained inclusion assemblages from a basement-hosted quartz-fluorite-barite-Pb-Zn vein system. An inverse correlation between the Pb + Zn concentrations and the Cl/Br mass ratios in the fluid inclusions provides clear evidence for mixing of a basement-derived metal-rich brine and a metal-poor formation water that acquired its salinity from halite dissolution in Triassic evaporites of the sedimentary cover. This mixing of two distinct brines with comparable salinity is recorded during the growth of individual quartz crystals containing small galena inclusions, demonstrating the transient and episodic nature of fluid mixing during mineral deposition.

Accurate and precise quantification of major and trace element compositions of calcic–sodic fluid inclusions by combined microthermometry and LA-ICPMS analysis

Determination of absolute trace-element concentrations in fluid inclusions using laser-ablation (LA) ICPMS requires an internal standard, i.e., the concentration of one element must be independently known from independent observation. Microthermometric determination of the last melting temperature of ice, hydrohalite or halite is routinely used to calculate apparent salinities in wt.% NaCl equivalent, using phase relations in the binary H2O–NaCl system to estimate Na concentration. Calculating the concentrations of all other elements requires an empirical correction, if additional salt concentrations are of similar magnitude as that of NaCl. If CaCl2 is the main additional salt component, as in many low-temperature basin and basement brines, absolute Na concentrations (wt.% NaCl abs.) can be obtained by observing two melting temperatures (hydrohalite and either ice or halite), uniquely defining the major element composition of the fluid in the ternary model system H2O–NaCl–CaCl2 and allowing Na to be used as internal standard for quantifying all minor and trace elements. Test results for a range of compositions show that calcium concentration can be determined more precisely by microthermometry than by LA-ICPMS analysis, but that both methods agree within error. The combined approach of microthermometry and LA-ICPMS analysis described here permits reliable quantification of major (Ca, Na) as well as trace element concentrations in sodic–calcic brine inclusions, even in Ca-rich host minerals such as fluorite or Ca-bearing carbonates.