On the origin of saline fluids in the KTB (continental deep drilling project of Germany)

Highly saline fluids were encountered during the German Continental Deep Drilling Project (KTB) from depths ranging between 2 and 3 km to about 9 km. The most reliable data were obtained from samples extracted during a long-term pumping test in the 4000-m deep KTB pilot hole. Some 460 m³ CaNaCl brines with about 68 g l⁻¹ total dissolved solids (TDS) and some 270 m³ associated gases, mainly N₂ and CH₄ were pumped to the surface from the main fracture system situated near the bottom of the pilot hole. Geochemical and isotopic data support the hydraulic tests which suggest the presence of an open and large fluid reservoir at depth. The pumped fluids from this main fracture system were released from a deep reservoir situated at more than 5500 m depth which is hydraulically connected with the 9101 m deep KTB main hole, drilled some 250 m to the northeast of the pilot hole.While Ca and Sr contents of the extracted brines may be the result of water-rock interaction, Cl is most likely of external origin. The Cl is hypothesized to derive from geotectonic processes rather than to descending infiltration of paleo-seawater (evaporitic brines). The sampled fluids have probably migrated from a deeper reservoir to their present position since the Cretaceous-Tertiary period due to tectonic activity. However, several isotopic studies have identified an admixture of descending paleowaters down to more than 4000 m depth. The high ³⁶ClCl ratio of the fluids sampled during the long-term pumping test point to a host rock highly enriched in UTh, unlike the sampled KTB country rocks. The fluid reservoir is believed to be in contact with the Falkenberg granite massif situated about 2 km to the E of the KTB holes capable of supplying sufficient neutron flux for considerable subsurface production of 36C1. The NaCl(K, SO₄) precursor fluids of the CaNaCI brines were produced in the course of extensive tectonic processes since the Late Caledonian within the Bohemian Massif.     

The role of evaporites in the formation of magnetite–apatite deposits along the Middle and Lower Yangtze River,China: Evidence from LA-ICP-MS analysis of fluid inclusions

Numerous magnetite–apatite deposits occur in the Ningwu and Luzong sedimentary basins along the Middle and Lower Yangtze River, China. These deposits are located in the contact zone of (gabbro)-dioritic porphyries with surrounding volcanic or sedimentary rocks and are characterized by massive, vein and disseminated magnetite–apatite ± anhydrite mineralization associated with voluminous sodic–calcic alteration. Petrologic and microthermometric studies on multiphase inclusions in pre- to syn-mineralization pyroxene and garnet from the deposits at Meishan (Ningwu basin), Luohe and Nihe (both in Luzong basin) demonstrate that they represent extremely saline brines (~ 90 wt.% NaCl_equiv) that were trapped at temperatures of about 780 °C. Laser ablation ICP-MS analyses and Raman spectroscopic studies on the natural fluid inclusions and synthetic fluid inclusions manufactured at similar P–T conditions reveal that the brines are composed mainly of Na (13–24 wt.%), K (7–11 wt.%), Ca (~ 7 wt.%), Fe (~ 2 wt.%), Cl (19–47 wt.%) and variable amounts of SO₄ (3–39 wt.%). Their Cl/Br, Na/K and Na/B ratios are markedly different from those of seawater evaporation brines and lie between those of magmatic fluids and sedimentary halite, suggesting a significant contribution from halite-bearing evaporites. High S/B and Ca/Na ratios in the fluid inclusions and heavy sulfur isotopic signatures of syn- to post-mineralization anhydrite (δ³⁴S_Anh = + 15.2 to + 16.9‰) and pyrite (δ³⁴S_Py = + 4.6‰ to + 12.1‰) further suggest a significant contribution from sedimentary anhydrite. These interpretations are in line with the presence of evaporite sequences in the lower parts of the sedimentary basins.The combined evidence thus suggests that the magnetite–apatite deposits along the Middle and Lower Yangtze River formed by fluids that exsolved from magmas that assimilated substantial amounts of Triassic evaporites during their ascent. Due to their Fe-oxide dominated mineralogy, their association with large-scale sodic–calcic alteration and their spatial and temporal associations with subvolcanic intrusions we interpret them as a special type of IOCG deposits that is characterized by unusually high contents of Na, Ca, Cl and SO₄ in the ore-forming fluids. Evaporite assimilation apparently led to the production of large amounts of high-salinity brine and thus to an enhanced capacity to extract iron from the (gabbro)-dioritic intrusions and to concentrate it in the form of ore bodies. Hence, we believe that evaporite-bearing sedimentary basins are more prospective for magnetite–apatite deposits than evaporite-free basins.     

Penetration of surface-evaporated brines into the Proterozoic basement and deposition of Co and Ag at Bou Azzer (Morocco): Evidence from fluid inclusions

Ag-ores occur in a specific zone of the Bou Azzer Co–As deposit in the Precambrian basement of the Anti-Atlas belt (Morocco), especially in highly microfractured quartz-depleted diorite. They formed after the main Co–As stage of mineralization, but both ore stages (Co–As and Ag-ore) appear linked to similar immiscible fluids: an hyper-saline Na–Ca brine (5.5–22 wt.%. eq. NaCl and 13.5–18.5 wt.% eq. CaCl₂, with Na/Ca ranging from 0.4 to 1.2 during Ag-mineralization) occurring as L + V ± halite fluid inclusions and CH₄–(N₂) gas dominated fluids. Pressure–temperature estimates for the Ag-stage range from 40 to 80 MPa and 150 to 200 °C e.g. at a temperature slightly lower than that of the preceding Co–As stage (200–220 °C).Chlorinity, cation (Na/Ca ca. 2.2) and halogen ratios (Cl/Br from 300 to 360) are typical of deep basinal brines, especially of surface-evaporated brines that have exceeded halite saturation. The primary brines were modified by fluid–rock interaction during burial and migration through the basement. Ag-deposition was probably favoured by dilution and cooling due to the mixing of brines with less saline fluids. Similarities between the Ag-brines from Bou Azzer, Zgounder and Imiter suggest a regional scale circulation of basinal brines during extension probably later than the Triassic, during the early stages of rifting of the Atlantic.     

Solubility of Fe2(OH)3Cl (pure-iron end-member of hibbingite) in NaCl and Na2SO4 brines

Pure-iron end-member hibbingite, Fe₂(OH)₃Cl(s), may be important to geological repositories in salt formations, as it may be a dominant corrosion product of steel waste canisters in an anoxic environment in Na–Cl- and Na–Mg–Cl-dominated brines. In this study, the solubility of Fe₂(OH)₃Cl(s), the pure-iron end-member of hibbingite (Fe^II, Mg)₂(OH)₃Cl(s), and Fe(OH)₂(s) in 0.04 m to 6 m NaCl brines has been determined. For the reactionFe₂(OH)₃Cl(s) + 3H⁺ ? 3 H₂O + 2 Fe²⁺ + Cl^?,the solubility constant of Fe₂(OH)₃Cl(s) at infinite dilution and 25 °C has been found to be log₁₀ K = 17.12 ± 0.15 (95% confidence interval using F statistics for 36 data points and 3 parameters). For the reactionFe(OH)₂(s) + 2H⁺ ? 2 H₂O + Fe²⁺,the solubility constant of Fe(OH)₂ at infinite dilution and 25 °C has been found to be log₁₀ K = 12.95 ± 0.13 (95 % confidence interval using F statistics for 36 data points and 3 parameters). For the combined set of solubility data for Fe₂(OH)₃Cl(s) and Fe(OH)₂(s), the Na⁺–Fe²⁺ pair Pitzer interaction parameter θ_{Na⁺/Fe²⁺} has been found to be 0.08 ± 0.03 (95% confidence interval using F statistics for 36 data points and 3 parameters). In nearly saturated NaCl brine we observed evidence for the conversion of Fe(OH)₂(s) to Fe₂(OH)₃Cl(s). Additionally, when Fe₂(OH)₃Cl(s) was added to sodium sulfate brines, the formation of green rust(II) sulfate was observed, along with the generation of hydrogen gas. The results presented here provide insight into understanding and modeling the geochemistry and performance assessment of nuclear waste repositories in salt formations.     

Fluid types and their genetic meaning for the BIF-hosted iron ores,Krivoy Rog,Ukraine

This paper contributes to the understanding of the genesis of epigenetic, hypogene BIF-hosted iron deposits situated in the eastern part of Ukrainian Shield. It presents new data from the Krivoy Rog iron mining district (Skelevatske–Magnetitove deposit, Frunze underground mine and Balka Severnaya Krasnaya outcrop) and focuses on the investigation of ore genesis through application of fluid inclusion petrography, microthermometry, Raman spectroscopy and baro-acoustic decrepitation of fluid inclusions. The study investigates inclusions preserved in quartz and magnetite associated with the low-grade iron ores (31–37% Fe) and iron-rich quartzites (38–45% Fe) of the Saksaganskaya Suite, as well as magnetite from the locally named high-grade iron ores (52–56% Fe). These high-grade ores resulted from alteration of iron quartzites in the Saksaganskiy thrust footwall (Saksaganskiy tectonic block) and were a precursor to supergene martite, high-grade ores (60–70% Fe). Based on the new data two stages of iron ore formation (metamorphic and metasomatic) are proposed.The metamorphic stage, resulting in formation of quartz veins within the low-grade iron ore and iron-rich quartzites, involved fluids of four different compositions: CO₂-rich, H₂O, H₂O–CO₂(± N₂–CH₄)–NaCl(± NaHCO₃) and H₂O–CO₂(± N₂–CH₄)–NaCl. The salinities of these fluids were relatively low (up to 7 mass% NaCl equiv.) as these fluids were derived from dehydration and decarbonation of the BIF rocks, however the origin of the nahcolite (NaHCO₃) remains unresolved. The minimum P–T conditions for the formation of these veins, inferred from microthermometry are T_min = 219–246 °C and P_min = 130–158 MPa. The baro-acoustic decrepitation analyses of magnetite bands indicated that the low-grade iron ore from the Skelevatske–Magnetitove deposit was metamorphosed at T = ~ 530 °C.The metasomatic stage post-dated and partially overlapped the metamorphic stage and led to the upgrade of iron quartzites to the high-grade iron ores. The genesis of these ores, which are located in the Saksaganskiy tectonic block (Saksaganskiy ore field), and the factors controlling iron ore-forming processes are highly controversial. According to the study of quartz-hosted fluid inclusions from the thrust zone the metasomatic stage involved at least three different episodes of the fluid flow, simultaneous with thrusting and deformation. During the 1^st episode three types of fluids were introduced: CO₂–CH₄–N₂(± C), CO₂(± N₂–CH₄) and low salinity H₂O–N₂–CH₄–NaCl (6.38–7.1 mass% NaCl equiv.). The 2^nd episode included expulsion of the aqueous fluids H₂O–N₂–CH₄–NaCl(± CO₂, ± C) of moderate salinities (15.22–16.76 mass% NaCl equiv.), whereas the 3^rd event involved high salinity fluids H₂O–NaCl(± C) (20–35 mass% NaCl equiv.). The fluids most probably interacted with country rocks (e.g. schists) supplying them with CH₄ and N₂. The high salinity fluids were most likely either magmatic–hydrothermal fluids derived from the Saksaganskiy igneous body or heated basinal brines, and they may have caused pervasive leaching of Fe from metavolcanic and/or the BIF rocks. The baro-acoustic decrepitation analyses of magnetite comprising the high-grade iron ore showed formation T = ~ 430–500 °C. The fluid inclusion data suggest that the upgrade to high-grade Fe ores might be a result of the Krivoy Rog BIF alteration by multiple flows of structurally controlled, metamorphic and magmatic–hydrothermal fluids or heated basinal brines.     

Characterisation and isotopic evolution of saline waters of the Outokumpu Deep Drill Hole,Finland – Implications for water origin and deep terrestrial biosphere

The isotopic composition of water and dissolved Sr as well as other geochemical parameters at the 2516 m deep Outokumpu Deep Drill Hole, Finland were determined. The drill hole is hosted by Palaeoproterozoic turbiditic metasediments, ophiolite-derived altered ultramafic rocks and pegmatitic granitoids. Sodium–Ca–Cl and Ca–Na–Cl-rich waters (total dissolved solids up to ca. 70 g L⁻¹) containing significant amounts of gas, mainly CH₄ (up to 32 mmol L⁻¹), N₂ (up to 10 mmol L⁻¹), H₂ (up to 3.1 mmol L⁻¹) and He (up to 1.1 mmol L⁻¹) discharge from fracture zones into the drill hole. This water is distinct from the shallow fresh groundwater of the area, and has an isotopic composition typical of shield brines that have been modified during long-term water–rock interaction. Based on water stable isotopes and geochemistry, the drill hole water profile can be divided into five water types, each discharging from separate fracture systems and affected by the surrounding rocks. The δ²H varies from −90‰ to −56‰ (VSMOW) and δ¹⁸O from −13.5‰ to −10.4‰ (VSMOW), plotting clearly above the Global and Local Meteoric Water Lines on a δ²H vs. δ¹⁸O diagram. The ⁸⁷Sr/⁸⁶Sr ratios range between 0.72423 and 0.73668. Simple two-component mixing between ²H and ¹⁸O rich end-member brine and meteoric water cannot explain the water stable isotopic composition and trends observed. Instead, hydration of silicates by ancient groundwaters recharged under different climatic conditions, warmer than at present, is the most likely mechanism to have caused the variation of the δ²H and δ¹⁸O values. Water types correlate with changes in microbial communities implying that different ecosystems occur at different depths. The different water types and microbial populations have remained isolated from each other and from the surface for long periods of time, probably tens of millions of years.     

Fluid origin of fluorite-rich carbonate-hosted Pb–Zn mineralization of the Himalayan–Zagros collisional orogenic system: A case study of the Mohailaheng deposit,Tibetan Plateau,China

A significant belt of carbonate-hosted Pb–Zn mineralization occurs in the Himalayan–Zagros collisional orogenic system. Three differing types of these Pb–Zn deposits within this belt have been identified based on variations in gangue mineral assemblages, leading to the classification of carbonate-, quartz- and fluorite-rich classes of Pb–Zn deposits. The third Pb–Zn mineralization (fluorite-rich) type is common in this orogenic system, but little research has been undertaken on it. Here, we focus on the Mohailaheng deposit, a large-sized fluorite-rich carbonate-hosted Pb–Zn deposit (> 100 Mt Pb + Zn ores with average grade of 2.18%–4.23%); the deposit is located in the Sanjiang Cenozoic thrust-fold belt, an important part of the Himalayan–Zagros collisional orogenic system and an area that formed during the early Tertiary India–Eurasia collision. The main orebodies in this deposit are stratabound and are hosted by Carboniferous limestones that are located along secondary faults associated with a regional thrust fault. The main assemblage is a sphalerite + galena + pyrite sulfide assemblage associated with a calcite + fluorite + barite + quartz + dolomite gangue assemblage. Detailed field and experimental work indicates that the deposit formed during three distinct phases of hydrothermal activity. Studies on fluid inclusion and stable isotopes of gangue minerals indicate that two dominant distinct fluids involving the deposit formation. They include (1) a low-temperature (130–140 °C), high-salinity (23–24 wt.% NaCl equivalent) basinal brine containing Na⁺–K⁺–Mg^2 +–Ca^2 +–Cl⁻ ions and abnormally high SO₄^2 − concentrations, which probably derived from Tertiary basins in the regional district, and (2) a low- to moderate-temperature (170–180 °C) and moderate- to high-salinity (19–20 wt.% NaCl equivalent) metamorphic fluid containing Na⁺–K⁺–Mg^2 +–Cl^––SO₄^2 − ions and abnormally high F⁻ and organic matter concentrations, that probably formed during regional metamorphism. Some evaporated seawaters and meteoric fluids were also identified in mixtures with these two dominant fluids. The Pb–Zn mineralization at Mohailaheng formed during three distinct stages, consistent with the regional tectonic history. The first stage involved the formation of favorable lithological and structural traps at Mohailaheng during regional thrusting, leading to the migration of compressed metamorphic waters at depth along a detachment zone, sequestering metals from sediments within the region. Basinal brines at the surface also began to infiltrate down along the secondary faults, dissolving gypsum from the underlying sediments. The second stage was associated with the cessation of thrusting and the onset of strike-slip movements along these thrust faults. Metamorphic fluids containing high concentrations of halogen ions, organic gases, and metals ascended into the structural traps at Mohailaheng along the reactivated thrust faults, causing fluorite, calcite, and some sulfide precipitation. Then, basinal brines rich in SO₄^2 − quickly descended into the structural traps along the reactivated faults, causing reduction of SO₄^2 − by organic matter, and producing significant amounts of H₂S. The reduced sulfur then reacted with the metals in the fluids, causing significant sulfide precipitation. The third stage was associated with metal-depleted fluids, which only resulted in the precipitation of calcite from the diluted basinal brines. Combining these findings with research results on other fluorite-rich carbonate-hosted Pb–Zn deposits in the Himalayan–Zagros orogenic system suggests that this type of carbonate-hosted Pb–Zn deposits can also be classified as Mississippi Valley-type (MVT) deposits, and that the origin of the fluorite in these deposits may be related to multiple hydrothermal fluids involved in the mineralization evolution.     

An experimental study of lake water-sediment interaction rates

Dissolution rates of sediments obtained from the Oued Cherf reservoir were measured in closed-system batch reactors at 25 °C in fluids sampled concurrently from the same locations as the sediments. The BET surface areas of the sediments ranged from 16 to 45 m²/g and consisted primarily of quartz, calcite, and clay minerals. After a brief initial period, release rates of Si, Mg, Ca, Cl, SO₄, and NO₃ from these sediments are approximately linear with time over the course of the experiments, which lasted from 3 to 5 months. BET surface area normalized Si release rates ranged from 10^–17.4 to 10^–18.4 mol/cm²/s. These release rates match closely Si release rates from quartz and clay minerals determined from laboratory dissolution rates reported in the literature. This coherence suggests that laboratory measured silicate dissolution rates can be used with confidence to predict the dissolution behavior of sediments in natural surface waters.     

Dissolution kinetics of Devonian carbonates at circum-neutral pH, 50 bar pCO2, 105 °C,and 0.4 M: The importance of complex brine chemistry on reaction rates

The dissolution kinetics of carbonate rocks sampled from the Keg River Formation in Northeast British Columbia were measured at 50 bar pCO₂ and 105 °C, in both natural and synthetic brines of 0.4 M ionic strength. Natural brines yielded reaction rates of −12.16 ± 0.11 mol cm⁻² s⁻¹ for Log R_Ca, and −12.64 ± 0.05 for Log R_Mg. Synthetic brine yielded faster rates of reaction than natural brines. Experiments performed on synthetic brines, spiked with 10 mmol of either Sr or Zn, suggest that enhanced reaction rates observed in synthetic brines are due to a lack of trace ion interaction with mineral surfaces. Results were interpreted within the surface complexation model framework, allowing for the discrimination of reactive surface sites, most importantly the hydration of the >MgOH surface site. Dissolution rates extrapolated from experiments predict that CO₂ injected into the Keg River Formation will dissolve a very minor portion of rock in contact with affected formation waters.     

Segregation of magmatic fluids and their potential in the mobilization of platinum-group elements in the South Kawishiwi Intrusion,Duluth Complex,Minnesota — Evidence from petrography,apatite geochemistry and coexisting fluid and melt inclusions

Pegmatitic and other felsic rock pockets and dike-like intrusions are abundant in the South Kawishiwi Intrusion of the Duluth Complex, including the basal, Cu–Ni–PGE mineralized units. These occurrences are found as pockets, pods or as veins and contain abundant accessory apatite and quartz. Quartz hosts primary fluid inclusions as well as silicate melt inclusions. Combined microthermometry and Raman spectroscopy helped to determine the bulk composition of primary fluid inclusions that are CO₂-rich (95 mol%) and contain small amounts of H₂O (4.5 mol%), CH₄ (0.4 mol%) and trace N₂, respectively. This combined technique also made it possible to measure total homogenization temperatures of the inclusions (Th_tot = ~ 225 ± 10 °C), otherwise not detectable during microthermometry. Silicate melt inclusions have been quenched to produce homogeneous glasses corresponding to the original melt. Composition of the entrapped melt is granitoid, peraluminous and is very poor in mafic components. We interpret the melt as a product of partial melting of the footwall rocks due to the contact effect of the South Kawishiwi Intrusion. The presence of CO₂ in the vapor bubbles of the quenched melt inclusions and petrographic evidence suggest that the fluid and melt inclusion assemblages are coeval. The composition of the fluid and melt phase implies that the fluid originates from the mafic magma of the South Kawishiwi Intrusion and the fluid and melt phases coexisted as a heterogeneous melt–fluid system until entrapment of the inclusions.Coexistence of primary fluid and melt inclusions makes it possible to calculate a minimum entrapment pressure (~ 1.7 kbar) and thus estimate formation depth (~ 5.8 km) for the inclusions. Chlorine is suggested to behave compatibly in the silicate melt phase in the fluid–melt system represented by the inclusions, indicated by the high (up to 0.3%) Cl-concentrations of the silicate melt and CO₂-rich nature of the fluid.Apatite halogen-contents provide further details on the behavior of Cl. Apatite in pegmatitic pockets often has elevated Cl-concentrations compared to troctolitic rocks, suggesting enrichment of Cl with progressive crystallization. Systematic trends of Cl-loss at some differentiated melt pockets suggest that in some places Cl exsolved into a fluid phase and migrated away from its source. The segregation of Cl from the melt is probably inhibited by the presence of CO₂-rich fluids until the last stages of crystallization, increasing the potential for the development of late-stage saline brines.Platinum-group minerals are often present in microcracks in silicate minerals, in late-stage differentiated sulfide veinlets and in association with chlorapatite, indicating the potential role of Cl-bearing fluids in the final distribution of PGEs.     

Geochemical constraint on origin and evolution of solutes in geothermal springs in western Yunnan,China

Geothermal resources are very rich in Yunnan, China. However, source of dissolved solutes in geothermal water and chemical evolution processes remain unclear. Geochemical and isotopic studies on geothermal springs and river waters were conducted in different petrological-tectonic units of western Yunnan, China. Geothermal waters contain Ca–HCO₃, Na–HCO₃, and Na (Ca)–SO₄ type, and demonstrate strong rock-related trace elemental distributions. Enhanced water–rock interaction increases the concentration of major and trace elements of geothermal waters. The chemical compositions of geothermal waters in the Rehai geothermal field are very complicated and different because of the magma chamber developed at the shallow depth in this area. In this geothermal field, neutral-alkaline geothermal waters with high Cl, B, Li, Rb Cs, As, Sb, and Tl contents and acid–sulfate waters with high Al, Mn, Fe, and Pb contents are both controlled by magma degassing and water–rock interaction. Geothermal waters from metamorphic, granite, and sedimentary regions (except in the Rehai area) exhibit varying B contents ranging from 3.31 mg/L to 4.49 mg/L, 0.23 mg/L to 1.24 mg/L, and <0.07 mg/L, respectively, and their corresponding δ¹¹B values range from −4.95‰ to −9.45‰, −2.57‰ to −8.85‰, and −4.02‰ to +0.06‰. The B contents of these geothermal waters are mainly controlled by leaching host rocks in the reservoir, and their δ¹¹B values usually decrease and achieve further equilibrium with its surrounding rocks, which can also be proven by the positive δ¹⁸O-shift. In addition to fluid–rock reactions, the geothermal waters from Rehai hot springs exhibit higher δ¹¹B values (−3.43‰ to +1.54‰) than those yielded from other areas because mixing with the magmatic fluids from the shallow magma. The highest δ¹¹B of steam–heated waters (pH 3.25) from the Zhenzhu spring in Rehai is caused by the fractionation induced by pH and the phase separation of coexisting steam and fluids. Given the strong water–rock interaction, some geothermal springs in western Yunnan show reservoir temperatures higher than 180 °C, which demonstrate potential for electricity generation and direct-use applications. The most potential geothermal field in western Yunnan is located in the Rehai area because of the heat transfer from the shallow magma chamber.     

Halogens and noble gases in sedimentary formation waters and Zn–Pb deposits: A case study from the Lennard Shelf,Australia

Halogen ratios (Br/Cl and I/Cl) and concentrations provide important information about how sedimentary formation waters acquire their salinity, but the possible influence of organic Br derived from sedimentary wall-rocks is rarely quantified. Here, it is demonstrated that Br/Cl versus I/Cl mixing diagrams can be used to deconvolve organic Br contributions; that organic matter has a limited range of Br/I ratios; and that organic Br is a more significant component in Zn–Pb deposit ore fluids than previously recognised. The significance of these findings is illustrated for the Lennard Shelf Zn–Pb deposits of Western Australia.Fluid inclusions related to Lennard Shelf Zn–Pb mineralisation have variable salinity and hydrocarbon contents. The halogen data from these fluid inclusions require mixing of three fluid end-members: (1) an evaporated seawater bittern brine (30 wt.% NaCl equiv.) with greater than seawater Br/Cl ratio; (2) a lower salinity pore fluid (?5 wt.% NaCl equiv.) with moderately elevated Br/Cl and I/Cl; and (3) fluids with Br/Cl ratios of ～5 times seawater and extremely elevated I/Cl ratios of ～11,500 times seawater. The first two fluids have ⁴⁰Ar/³⁶Ar of 300–400 and greater than air saturated water ³⁶Ar concentrations that are typical of fluid inclusions related to Zn–Pb mineralisation. The third ‘organic-rich’ fluid has the highest ⁴⁰Ar/³⁶Ar ratio of up to 1500 and a depleted ³⁶Ar concentration.Mineralisation is interpreted to have resulted from mixing of Zn-rich evaporitic brines and H₂S present in hydrocarbons. It is suggested that aqueous fluids acquired organic Br and I from hydrocarbons, and that hydrocarbons exsolving from the aqueous fluid removed noble gases from solution. Interaction of variably saline brines and hydrocarbons could account for the variable Br/Cl and I/Cl composition, and ³⁶Ar concentrations, recorded by Lennard Shelf fluid inclusions. The distinct ⁴⁰Ar/³⁶Ar signature of the fluid with the highest I/Cl ratio suggests the hydrocarbons and brines were sourced independently from different parts of the sedimentary basin. These data indicate the complementary nature of halogen and noble gas analysis and provide new constraints on important mixing processes during sediment-hosted Zn–Pb mineralisation.     

Migration of brines in the basement rocks of the Athabasca Basin through microfracture networks (P-Patch U deposit,Canada)

The unconformity-type uranium deposits of the Athabasca Basin (Saskatchewan, Canada) are hosted near the unconformity between a middle Proterozoic intracratonic sedimentary basin and an Archean to Paleo-Proterozoic metamorphic and plutonic basement. These deposits, which are considered to be the richest U deposits in the world, are the result of massive basinal fluid migrations in the basement rocks.This study shows that basinal brines have strongly penetrated into the basement not only through faults and major pathways but also by way of dense networks of microfractures which favoured the percolation of fluids down to considerable depths (hundred metres below the unconformity) and their chemical modification (salinity increase) by interaction with basement lithologies. These processes are one of the major causes of uranium mobility within the basement rocks and the formation of unconformity-type mineralization.Microfracture networks, which opened during the basinal brine stage (ca. 1600–1400 Ma) are interpreted as sets of mode I cracks corresponding to a specific stage of deformation and occur as fluid inclusion planes after healing. The stress field at that stage (σ₁ = N130–150 °E, subvertical) partly reopened the earlier microcrack networks (σ₁ = N80–110 °E and N130–150 °E, subvertical) issued from the Trans-Hudson Orogeny late retrograde metamorphic stage (ca. 1795–1720 Ma). The circulation of the two types of fluids (carbonic and brines) occurs thus at two distinct events (Trans-Hudson Orogeny late retrograde metamorphism for carbonic fluids and maximal burial diagenesis for brines) but the same main microfissure geometry was used by the fluids. This demonstrates the existence of a similar stress field direction acting before and after the basin formation. Moreover, the brine circulations in the basement acted in a wider volume than the clay-rich alteration halo surrounding the U-ores, generally considered as the main envelope of fluid percolation outside the fault systems. The data on the chemistry of the fluids and on the geometry of their migration at various scales emphasise the fundamental role of the basement in the chemical evolution of highly saline brines linked to unconformity-related uranium mineralization in the Athabasca Basin.     

Carbonate dissolution in Mesozoic sand- and claystones as a response to CO2 exposure at 70 °C and 20 MPa

The response to CO₂ exposure of a variety of carbonate cemented rocks has been investigated using pressurised batch experiments conducted under simulated reservoir conditions, 70 °C and 20 MPa, and with a durations of up to14 months. Calcite, dolomite, ankerite and siderite cement were present in the unreacted reservoir rocks and caprocks. Core plugs of the reservoir rocks were used in order to investigate the alterations in situ. Crushing of the caprock samples was necessary to maximise reactions within the relatively short duration of the laboratory experiments. Synthetic brines were constructed for each batch experiment to match the specific formation water composition known from the reservoir and caprock formations in each well. Chemical matched synthetic brines proved crucial in order to avoid reactions due to non-equilibra of the fluids with the rock samples, for example observations of the dissolution of anhydrite, which were not associated with the CO₂ injection, but rather caused by mismatched brines.Carbonate dissolution as a response to CO₂ injection was confirmed in all batch experiments by both petrographical observations and geochemical changes in the brines. Increased Ca and Mg concentrations after 1 month reaction with CO₂ and crushed caprocks are ascribed to calcite and dolomite dissolution, respectively, though not verified petrographically. Ankerite and possible siderite dissolution in the sandstone plugs are observed petrographically after 7 months reaction with CO₂; and are accompanied by increased Fe and Mn contents in the reacted fluids. Clear evidence for calcite dissolution in sandstone plugs is observed petrographically after 14 months of reaction with CO₂, and is associated with increased amounts of Ca (and Mg) in the reacted fluid. Dolomite in sandstones shows only minor dissolution features, which are not clearly supported by increased Mg content in the reacted fluid.Silicate dissolution cannot be demonstrated, either by chemical changes in the fluids, as Si and Al concentrations remain below the analytical detection limits, nor by petrographical changes, as partly dissolved feldspar grains and authigenic analcime are present in the sediments prior to the experiments. It is noteworthy, that authigenic K-feldspar and authigenic albite in sandstones show no signs of dissolution and consequently seem to be stable under the experimental conditions.     

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development,north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH₄ gas content and its C isotopes (δ¹³C_CH4), and select isotope tracers (δ¹¹B, ⁸⁷Sr/⁸⁶Sr, δ²H, δ¹⁸O, δ¹³C_DIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH₄ was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH₄/L. The δ¹³C_CH4 of dissolved CH₄ ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH₄ concentrations, with a possible minor contribution of trace amounts of thermogenic CH₄. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ¹³C_CH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO₃ dominated, (3) TDS > 100 mg/L and Na–HCO₃ dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (⁸⁷Sr/⁸⁶Sr = 0.7097–0.7166), C (δ¹³C_DIC = −21.3‰ to −4.7‰), and B (δ¹¹B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO₃, and higher-mineralized Na–HCO₃ composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH₄ and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.     

Geology,fluid inclusion and isotope constraints on ore genesis of the post-collisional Dabu porphyry Cu–Mo deposit,southern Tibet

The Dabu Cu-Mo porphyry deposit is situated in the southern part of the Lhasa terrane within the post-collisional Gangdese porphyry copper belt (GPCB). It is one of several deposits that include the Qulong and Zhunuo porphyry deposits. The processes responsible for ore formation in the Dabu deposit can be divided into three stages of veining: stage I, quartz–K-feldspar (biotite) ± chalcopyrite ± pyrite, stage II, quartz–molybdenite ± pyrite ± chalcopyrite, and stage III, quartz–pyrite ± molybdenite. Three types of fluid inclusions (FIs) are present: liquid-rich two-phase (L-type), vapor-rich two-phase (V-type), and solid bearing multi-phase (S-type) inclusions. The homogenization temperatures for the FIs from stages I to III are in the ranges of 272–475 °C, 244–486 °C, and 299–399 °C, and their salinities vary from 2.1 to 49.1, 1.1 to 55.8, and 2.9 to 18.0 wt% NaCl equiv., respectively. The coexistence of S-type, V-type and L-type FIs in quartz of stage I and II with similar homogenization temperatures but contrasting salinities, indicate that fluid boiling is the major factor controlling metal precipitation in the Dabu deposit. The ore-forming fluids of this deposit are characterized by high temperature and high salinity, and they belong to a H₂O–NaCl magmatic–hydrothermal system. The H–O–S–Pb isotopic compositions indicate that the ore metals and fluids came primarily from a magmatic source linked to Miocene intrusions characterized by high Sr/Y ratios, similar to other porphyry deposits in the GPCB. The fluids forming the Dabu deposit were rich in Na and Cl, derived from metamorphic dehydration of subducted oceanic slab through which NaCl-brine or seawater had percolated. The inheritance of ancient subduction-associated arc chemistry, without shallow level crustal assimilation and/or input of the meteoric water, was responsible for the generation of fertile magma, as well as CO₂-poor and halite-bearing FIs associated with post-collisional porphyry deposits. The estimated mineralization depths of Qulong, Dabu and Zhunuo deposits are 1.6–4.3 km, 0.5–3.4 km and 0.2–3.0 km, respectively, displaying a gradual decrease from eastern to western Gangdese. Deep ore-forming processes accounted for the generation of giant-sized Qulong deposit, because the exsolution of aqueous fluids with large fraction of water and chlorine in deep or high pressure systems can extract more copper from melts than those formed in shallow systems. However, the formation of small-sized Dabu deposit can be explained by a single magmatic event without additional replenishment of S, metal, or thermal energy. In addition, the ore-forming conditions of porphyry Cu–Mo deposits in GPCB are comparable to those of porphyry Cu ± Au ± Mo deposits formed in oceanic subduction-related continental or island arcs, but differ from those of porphyry Mo deposit formed in the Dabie-Qinling collisional orogens. The depth of formation of the mineralization and features of primary magma source are two major controls on the metal types and ore-fluid compositions of these porphyry deposits.     

Geology,mineralization, stable isotope,and fluid inclusion characteristics of the Vostok-2 reduced W-Cu skarn and Au-W-Bi-As stockwork deposit,Sikhote-Alin,Russia

The large (>180 Kt WO₃ and at least 10–15 t Au) Vostok-2 deposit is situated in a metallogenic belt of W, Sn-W, Au, and Au-W deposits formed in late to post-collisional tectonic environment after cessation of active subduction. The deposit is related to an ilmenite-series high-K calc-alkaline plutonic suite that, by its petrologic signatures, is transitional between those at W-dominant and Au-dominant reduced intrusion-related deposits. Consistently, besides large W-Cu skarns of the reduced type, the deposit incorporates quartz stockworks with significant Au-W-Bi mineralization also formed in a reduced environment. The hydrothermal stages include prograde and retrograde, essentially pyroxene skarns, hydrosilicate (amphibole, chlorite, quartz) alteration, and phyllic (quartz, sericite, albite, apatite, and carbonate) alteration assemblages. These assemblages contain abundant scheelite associated with pyrrhotite, chalcopyrite and, at the phyllic stage, also with Bi minerals, As-Bi-Sb-Te-Pb-Zn sulfides and sulfosalts, as well as Au mineralization. The fluid evolution included hot, high-pressure (420–460 °C, 1.1–1.2 kbar), low-salinity (5.4–6.0 wt% NaCl-equiv.) aqueous fluids at the retrograde skarn stage, followed by lower temperature cyclic releases of high-carbonic, low salinity to non-carbonic moderate-salinity aqueous fluids. At the hydrosilicate stage, a high-carbonic, CH₄-dominated, hot (350–380 °C) low salinity fluid was followed by cooler (300–350 °C) non-carbonic moderate-salinity (5.7–14.9 wt% NaCl-equiv.) fluid. At the phyllic stage, a high-carbonic, CO₂-dominated, moderately-hot (330–355 °C, 0.9 kbar) low salinity fluid was followed by cooler (230–265 °C) non-carbonic moderate-salinity (6.6–12.0 wt% NaCl-equiv.) fluid. A homogenized magmatic source of water (δ¹⁸O_H2O = +8.3 to +8.7‰), and a sedimentary source of sulfur (δ³⁴S = −6.9 to −6.2‰) and carbon (δ¹³C_fluid = −20.1 to −14.9‰) at the hydrosilicate stage are suggested. A magmatic source of water (δ¹⁸O = +8.6 to +9.2‰) and a sedimentary source of sulfur (δ³⁴S = −9.3 to −4.1‰) but a magmatic (mantle- to crustal-derived) source of carbon (δ¹³C_fluid = −6.9 to −5.2‰) are envisaged for fluids that formed the early mineral assemblage of the phyllic stage. Then, the role of sedimentary carbon again increased toward the intermediate (δ¹³C_fluid = −16.4 to −14.5‰) and late (δ¹³C_fluid = −16.3 to −14.7‰) phyllic mineral assemblages. The magmatic differentiation was responsible for the fluid enrichment in W, whereas Au and Bi could also have been sourced from mafic magma. The decreasing temperatures, together with elevated Ca content in non-boiling fluids, promoted scheelite deposition at the early hydrothermal stages. The most intense scheelite deposition at the phyllic stage was caused by CO₂ removal due to boiling of CO₂-rich fluids; further cooling of non-boiling fluids favoured joint deposition of scheelite, Bi and Au.     

Petrogenesis of coexisting high-silica aluminous and peralkaline rhyolites from Yunshan (Yongtai), southeastern China

The Late Cretaceous bimodal Yunshan (Yongtai) volcanics in Fujian province contain peralkaline rhyolites, the only presence of such rhyolites in southeastern China. Whole-rock and mineral chemical compositions are analyzed for the coexisting aluminous (metaluminous to weakly peraluminous)-peralkaline high-silica rhyolites from the Yunshan volcanics. They are sparsely porphyritic, and contain K-feldspar, ferromagnesian minerals, quartz, magnetite, and titanomagnetite phenocrysts, as well as accessory minerals such as fayalite, chevkinite, apatite and zircon. The mineral assemblage indicates an oxidizing pre-eruption condition. These rhyolites exhibit diagnostic geochemical features of A-type granites, such as elevated 10⁴ * Ga/Al (mostly greater than 2.6) and FeO^T/(FeO^T + MgO) ratios, enrichment in high field strength elements (HFSE) such as Zr (>400 ppm) and Nb, and strong depletion in Al₂O₃ (<13 wt%), CaO, Ba and Sr. On the basis of their petrographic and geochemical characteristics, it is suggested that the rhyolite magmas are derived from partial melting of H₂O-poor (meta) granitic igneous rocks in the deep crust, and cannot be fractionated from the coeval Yunshan mafic magmas. Geochemical variations of major and trace elements indicate the possible fractionation of K-feldspar, calcium-rich pyroxene, Fe–Ti oxides and minor chevkinite during the magma evolution. In peralkaline rhyolites, we found that the pre-existing Fe–Ti oxide and hedenbergite phenocrysts had been transformed into aegirine + oxide and aegirine + oxide + fluorite assemblages, respectively. These mineral assemblages are the products of the subsolidus reaction of pre-existing phenocrysts and extraneous Na–F-rich fluids. Such Na–F-rich fluids may be derived from the degassing of the subvolcanic rocks. The reactions indicate that the Yunshan peralkaline rhyolites could be generated through the reaction of highly fractionated aluminous silica magmas and Na–F-rich fluids.     

The Gounkoto Au deposit,West Africa: Constraints on ore genesis and volatile sources from petrological,fluid inclusion and stable isotope data

The Loulo–Gounkoto complex in the Kédougou–Kéniéba Inlier hosts three multi-million ounce orogenic gold deposits, situated along the Senegal–Mali Shear Zone. This west Malian gold belt represents the largest West African orogenic gold district outside Ghana. The Gounkoto deposit is hosted to the south of the Gara and Yalea gold mines in the Kofi Series metasedimentary rocks. The ore body is structurally controlled and is characterised by sodic and phyllic alteration, As- and Fe-rich ore assemblages, with abundant magnetite, and overall enrichment in Fe–As–Cu–Au–Ag–W–Ni–Co–REE + minor Te–Pb–Se–Cd. Fluid inclusion analysis indicates that the deposit formed at P–T conditions of approximately 1.4 kbar and 340 °C and that two end member fluids were involved in mineralisation: (1) a moderate temperature (315–340 °C), low salinity (< 10 wt.% NaCl equiv.), low density (≤ 1 g·cm^− 3), H₂O–CO₂–NaCl–H₂S ± N₂–CH₄ fluid; (2) a high temperature (up to 445 °C), hypersaline (~ 40 wt.% NaCl equiv.), high density (~ 1.3 g·cm^− 3), H₂O–CO₂–NaCl ± FeCl₂ fluid. Partial mixing of these fluids within the Jog Zone at Gounkoto enhanced phase separation in the aqueo-carbonic fluid and acted as a precipitation mechanism for Au. These findings demonstrate the widespread, if heterogeneously distributed, nature of fluid mixing as an ore forming process in the Loulo–Gounkoto complex, operating over at least a 30 km strike length of the shear zone. Stable isotope analyses of ore components at Gounkoto indicate a dominant metamorphic source for H₂O, H₂S and CO₂, and by extension Au. It thus can be reasoned that both the aqueo-carbonic and the hypersaline fluid at Gounkoto are of metamorphic origin and that the high levels of salinity in the brine are likely derived from evaporite dissolution.     

Geochemical evolution of groundwater in the Cambrian–Vendian aquifer system of the Baltic Basin

The shallowly buried marginal part of the Cambrian–Vendian confined aquifer system of the Baltic Basin is characterised by fresh and low δ¹⁸O composition water, whereas the deeply settled parts of the aquifer are characterized by typical Na–Ca–Cl basinal brines. Spatial variation in water geochemistry and stable isotope composition suggests mixing origin of the diluted water of three end-members—glacial melt water of the Weichselian Ice Age (115 000–10 000 BP), Na–Ca–Cl composition basin brine and modern meteoric water. The mixing has occurred in two stages. First, the intrusion and mixing of isotopically depleted glacial waters with basinal brines occurred during the Pleistocene glacial periods when the subglacial melt-water with high hydraulic gradient penetrated into the aquifer. The second stage of mixing takes place nowadays by intrusion of meteoric waters. The freshened water at the northern margin of the basin has acquired a partial equilibrium with the weakly cemented rock matrix of the aquifer.