Chemical Weathering of Smectitic Sulphide-Mineral-Bearing Unconsolidated Surficial Sediments in South-Central Alberta,Canada

This study used a mass-balance simulation approach in conjunction with geochemical, mineralogical, thermodynamic and isotopic constraints, to assess the origins of NaSO₄(±HCO₃) type groundwater and springwater associated with smectitic sulphide-mineral-bearing unconsolidated surficial sediments and the underlying Paskapoo Formation in south-central Alberta. Results indicate that alteration of albite to kaolinite and alteration of kaolinite to Na-smectite are the primary controls on dissolved Na and SiO₂ concentrations in groundwater and springwater. Concentrations of dissolved Ca and Mg are controlled by reactions involving carbonate minerals and possibly cation exchange. Dissolved SO₄ is generated primarily through oxidation of pyrite. Most H⁺ generated by oxidation of pyrite is consumed in aluminosilicate alteration reactions. The carbon isotopic composition of CO₂ gas required in mass-balance simulations suggests the presence of an isotopically heterogeneous environment with respect to ¹³C. This apparent isotopic heterogeneity may result from the presence of varying fractions of atmospheric and microbially respired CO₂.     

An approach to estimate Lower Jurassic seawater oxygen‐isotope composition using δ18O and Mg/Ca ratios of belemnite calcites (Early Pliensbachian,northern Spain)

Palaeotemperature estimates from the oxygen‐isotope compositions of belemnites have been hampered by not knowing ancient seawater isotope compositions well enough. We have tackled this problem using Mg/Ca as a proxy for temperature and here, we present a ~2 Ma record of paired Mg/Ca and δ¹⁸O measurements of Jurassic (Early Pliensbachian) belemnites from the Asturian basin as a palaeo‐proxy of seawater oxygen‐isotope composition. From the combined use of the two approaches, we suggest a δ¹⁸O_w composition of about ?0.1‰ for the Jamesoni–Ibex zones. This value may have been increased by about 0.6‰ during the Davoei Zone due to the effect of waters with a different δ¹⁸O_w composition. These findings illustrate the inaccuracy of using a globally homogeneous ice‐free value of δ¹⁸O_w = ?1‰ for δ¹⁸O_carb‐based palaeotemperature reconstructions. Our data suggest that previous palaeotemperatures calculated in the region from δ¹⁸O values of belemnites may have been underestimated as the seawater oxygen isotopic composition could have been higher.     

The impact of water-rock interaction and vegetation on calcium isotope fractionation in soil- and stream waters of a small, forested catchment (the Strengbach case)

This study aims to constrain the factors controlling the calcium isotopic compositions in surface waters, especially the respective role of vegetation and water-rock interactions on Ca isotope fractionation in a continental forested ecosystem. The approach is to follow changes in space and time of the isotopic composition and concentration of Ca along its pathway through the hydro-geochemical reservoirs from atmospheric deposits to the outlet of the watershed via throughfalls, percolating soil solutions and springs. The study is focused on the Strengbach catchment, a small forested watershed located in the northeast of France in the Vosges mountains. The δ^44/40Ca values of springs, brooks and stream waters from the catchment are comparable to those of continental rivers and fluctuate between 0.17 and 0.87‰. Soil solutions, however, are significantly depleted in lighter isotopes (δ^44/40Ca: 1.00-1.47‰), whereas vegetation is strongly enriched (δ^44/40Ca: −0.48‰ to +0.19‰). These results highlight that vegetation is a major factor controlling the calcium isotopic composition of soil solutions, with depletion in “light” calcium in the soil solutions from deeper parts of the soil compartments due to preferential ⁴⁰Ca uptake by the plants rootsystem. However, mass balance calculations require the contribution of an additional Ca flux into the soil solutions most probably associated with water-rock interactions. The stream waters are marked by a seasonal variation of their δ^44/40Ca, with low δ^44/40Ca in winter and high δ^44/40Ca in spring, summer and autumn. For some springs, nourishing the streamlet, a decrease of the δ^44/40Ca value is observed when the discharge of the spring increases, with, in addition, a clear covariation between the δ^44/40Ca and corresponding H₄SiO₄ concentrations: high δ^44/40Ca values and low H₄SiO₄ concentrations at high discharge; low δ^44/40Ca values and high H₄SiO₄ concentrations at low discharge. These data imply that during dry periods and low water flow rate the source waters carry a Ca isotopic signature from alteration of soil minerals, whereas during wet periods and high flow rates admixture of significant quantities of ⁴⁰Ca depleted waters (vegetation induced signal) from uppermost soil horizons controls the isotopic composition of the source waters. This study clearly emphasizes the potential of Ca isotopes as tracers of biogeochemical processes at the water-rock-vegetation interface in a small forested catchment.     

Reconciling the elemental and Sr isotope composition of Himalayan weathering fluxes: insights from the carbonate geochemistry of stream waters

Determining the relative proportions of silicate vs. carbonate weathering in the Himalaya is important for understanding atmospheric CO₂ consumption rates and the temporal evolution of seawater Sr. However, recent studies have shown that major element mass-balance equations attribute less CO₂ consumption to silicate weathering than methods utilizing Ca/Sr and ⁸⁷Sr/⁸⁶Sr mixing equations. To investigate this problem, we compiled literature data providing elemental and ⁸⁷Sr/⁸⁶Sr analyses for stream waters and bedrock from tributary watersheds throughout the Himalaya Mountains. In addition, carbonate system parameters (P_CO2, mineral saturation states) were evaluated for a selected suite of stream waters. The apparent discrepancy between the dominant weathering source of dissolved major elements vs. Sr can be reconciled in terms of carbonate mineral equilibria. Himalayan streams are predominantly Ca²⁺-Mg²⁺-HCO₃⁻ waters derived from calcite and dolomite dissolution, and mass-balance calculations demonstrate that carbonate weathering contributes ∼87% and ∼76% of the dissolved Ca²⁺ and Sr²⁺, respectively. However, calculated Ca/Sr ratios for the carbonate weathering flux are much lower than values observed in carbonate bedrock, suggesting that these divalent cations do not behave conservatively during stream mixing over large temperature and P_CO2 gradients in the Himalaya.The state of calcite and dolomite saturation was evaluated across these gradients, and the data show that upon descending through the Himalaya, ∼50% of the streams evaluated become highly supersaturated with respect to calcite as waters warm and degas CO₂. Stream water Ca/Mg and Ca/Sr ratios decrease as the degree of supersaturation with respect to calcite increases, and Mg²⁺, Ca²⁺, and HCO₃⁻ mass balances support interpretations of preferential Ca²⁺ removal by calcite precipitation. On the basis of patterns of saturation state and P_CO2 changes, calcite precipitation was estimated to remove up to ∼70% of the Ca²⁺ originally derived from carbonate weathering. Accounting for the nonconservative behavior of Ca²⁺ during riverine transport brings the Ca/Sr and ⁸⁷Sr/⁸⁶Sr composition of the carbonate weathering flux into agreement with the composition of carbonate bedrock, thereby permitting consistency between elemental and Sr isotope approaches to partitioning stream water solute sources. These results resolve the dissolved Sr²⁺ budget and suggest that the conventional application of two-component Ca/Sr and ⁸⁷Sr/⁸⁶Sr mixing equations has overestimated silicate-derived Sr²⁺ and HCO₃⁻ fluxes from the Himalaya. In addition, these findings demonstrate that integrating stream water carbonate mineral equilibria, divalent cation compositional trends, and Sr isotope inventories provides a powerful approach for examining weathering fluxes.     

Seawater sulfate reduction and sulfur isotope fractionation in basaltic systems: Interaction of seawater with fayalite and magnetite at 200–350°C

Sulfate reduction during seawater reaction with fayalite and with magnetite was rapid at 350°C, producing equilibrium assemblages of talc-pyrite-hematite-magnetite at low water/rock ratios and talc-pyrite-hematite-anhydrite at higher water/rock ratios. At 250°C, seawater reacting with fayalite produced detectable amounts of dissolved H₂S, but extent of reaction of solid phases was minor after 150 days. At 200°C, dissolved H₂S was not detected, even after 219 days, but mass balance calculations suggest a small amount of pyrite may have formed. Reaction stoichiometry indicates that sulfate reduction requires large amounts of H⁺, which, in subseafloor hydrothermal systems is provided by Mg metasomatism. Seawater contains sufficient Mg to supply all the H⁺ necessary for quantitative reduction of seawater sulfate.Systematics of sulfur isotopes in the 250 and 350°C experiments indicate that isotopic equilibrium is reached, and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H₂S in natural systems is strongly dependent upon the seawater/basalt ratio in the geothermal system, which controls the relative sulfide contributions from the two important sulfur sources, seawater sulfate and sulfide phases in basalt. Anhydrite precipitation during geothermal heating severely limits sulfate ingress into high temperature interaction zones. Quantitative sulfate reduction can thus be accomplished without producing strongly oxidized rocks and resultant sulfide sulfur isotope values represent a mixture of seawater and basaltic sulfur.     

The isotopic and chemical composition of CO2-rich thermal waters in the Mont-Dore region (Massif-Central,France)

Chemical and isotope compositions of fluid samples, collected between 1974 and 1986 from 52 springs or shallow boreholes located in the Mont-Dore region (Massif Central, France), were examined. Some springs and wells were sampled several times during this period. The fluids emerge from Quaternary volcanic rocks or Paleozoic granite at temperatures between 4 and 62°C, and the origin of the H₂O is meteoric. The waters can be classified into three groups: bicarbonate fluids, mixed bicarbonate-chloride fluids (with a mineralization up to 8 g/l), and acid-sulfate fluids. Only two fluids contain sufficient Cl⁻ to be considered as ‘mature’ waters. Previous work has demonstrated that they all contain partly mantle-derived CO₂ gas, and that the CO₂-rich gas phase and bicarbonate-chloride waters are separated at substantial depth.Mineralized fluids circulate at depth and undergo several processes, such as cooling or dilution with recent freshwater, during their ascent to the surface. Therefore, the CO₂-rich gas phase can be partly dissolved in the freshwater, or in deep fluids after their dilution. This process leads to the dissolution of surrounding rocks; such dissolution is discussed on the basis of major-element concentrations (Na, K, Ca, Mg), as well as the Sr 87/86 isotope ratio. Dissolution of S-bearing minerals has also been demonstrated. The presence of the CO₂-rich gas phase also leads to isotope exchange between CO₂ and H₂O. Some mineralized fluids are less affected by these processes than others, in which case they display the chemical and isotopic characteristics of the original deep fluids.It was shown that the applicability of geothermometer calculations for these waters is hampered by several processes that modify the chemical composition. However, some geothermometers can be used for estimating the temperature of the deep fluids using the chemical composition of the less modified fluids. They indicate that fluids emerging from volcanic rocks in the Dordogne valley reach temperatures of around 100–130°C at depth, while the temperature of the fluid that issues from the granite at Saint-Nectaire is 160–175°C at depth.     

Remobilization of arsenic from buried wastes at an industrial site: mineralogical and geochemical control

An industrial area contaminated by As was studied to determine the source of this element and its speciation in As-bearing solids and in run-off waters. Mineral precipitates and water samples were collected and analyzed to assess processes controlling As mobility at this site. The integrated study of a contaminated industrial area allowed identification of the source of the As and of the nature of secondary As-bearing phases. The results obtained both on solid and water samples were used to model As behavior during waste leaching on carbonate rocks. At the upper end of a topographic transect across the site, run-off waters (pH=7.9) interact with surficial waste piles (containing arsenolite, arsenopyrite and pyrite), becoming acidic (pH=2.2) and concentrated in dissolved arsenate species (As⁵⁺) (ΣAs ranging from 0.961 to 3.149·10⁻³ mol/l). Those acidic waters interact with the limestone substratum, providing dissolved Ca which reacts with As to precipitate 1:1 Ca arsenates (weilite CaHAsO₄, haidingerite CaHAsO₄.H₂O and pharmacolite CaHAsO₄.2H₂O) and, in minor amounts, Ca–Mg arsenates (picropharmacolite (Ca,Mg)₃(AsO₄)₂ 6H₂O). The 1:1 Ca arsenates identified are known to precipitate at low pH (3–6) and seem to be stable in media with high dissolved CO₂, in comparison with other types of Ca arsenates. However, due to their high solubilities, they are not strictly relevant candidates to immobilize As in contaminated surficial environments. Although reported solubilities decrease to values close to the French and US drinking standards in Ca-rich solutions, a thorough examination of the precipitation/dissolution kinetics of Ca arsenates should be undertaken to assess their long-term stability and their efficiency in rapidly immobilizing As in contaminated surficial environments.     

Reactivity of organic-rich sediment in seawater at 350°c, 500 bars: experimental and theoretical constraints and implications for the guaymas basin hydrothermal system

Hydrothermal alteration of organic-rich diatomaceous sediment by seawater was modelled experimentally at 350°C, 500 bars and seawater/sediment mass ratio of 3. The experiment was performed to assess the effect of organic matter reactivity on solution speciation and sediment alteration processes at an elevated temperature and pressure and provide requisite data to better understand the chemistry of hydrothermal fluids issuing from vents in the Guaymas Basin, Gulf of California.Seawater chemistry changed greatly during the experiment. In particular, Na, Mg and SO₄ decreased, while ∑ CO₂, ∑ NH₃, ∑ H₂S, SiO₂, Ca, K, H₂, CH₄ and heavy and base metals increased. Moreover, owing to the thermal alteration of sediment organic matter, organic acids, phenolic derivatives and phthlate were released to solution. Examination of solid alteration products revealed the effects of extensive dissolution and precipitation processes characterized by total elimination of diatoms and formation of cristobalite, quartz (?), pyrite, pyrrhotite, mixed layer chlorite/smectite and calcite. Plagioclase feldspar (An₄₀) recrystallized to a more albitic form owing to Na fixation and Ca cycling to calcite. A graphitic residue was also present in the products of the experiment.Mg and Na fixation reactions during the experiment generated significant H⁺, although the pH measured at 25°C was approximately 6.2. SO₄ reduction and thermal alteration and dissolution of organics, however, consume H⁺ and are chiefly responsible for the near neutral pH for the overall reaction. Speciation calculations including ammine and acetate protonation reactions give a pH at experimental conditions of approximately 5.1, while mineral solubility relations involving virtually all alteration phases require a pH of 5.57 to 5.94. A near neutral pH at experimental conditions constrains the mobility of Fe, Mn, Zn, Cu and Ni, which existed in solution as chloro-complexes. Dissolved concentrations of Pb and Al, in contrast, covaried with dissolved organics, especially acetate, suggesting organo-metallic complex formation.     

Alteration of the upper oceanic crust,DSDP site 417: mineralogy and chemistry

Basalts from DSDP Site 417 (109 Ma) exhibit the effects of several stages of alteration reflecting the evolution of seawater-derived solution compositions and control by the structure and permeability of the crust. Characteristic secondary mineral assemblages occur in often superimposed alteration zones within individual basalt fragments. By combining bulk rock and single phase chemical analyses with detailed mineralogic and petrographic studies, chemical changes have been determined for most of the alteration stages identified in the basalts.

1. Minor amounts of saponite, chlorite, and pyrite formed locally in coarse grained portions of massive units, possibly at high temperatures during initial cooling of the basalts. No chemical changes could be determined for this stage.
2. Possible mixing of cooled hydrothermal fluids with seawater resulted in the formation of celadonite-nontronite and Fe-hydroxide-rich black halos around cracks and pillow rims. Gains of K, Rb, H₂O, increase of Fe³⁺/Fe^T, and possibly some losses of Ca and Mg occurred during this stage.
3. Extensive circulation of oxygenated seawater resulted in the formation of various smectites, K-feldspar, and Fe-hydroxides in brown and light grey alteration zones around formerly exposed surfaces. K, Rb, H₂O, and occasionally P were added to the rocks, Fe³⁺/Fe^T increased, and Ca, Mg, Si and occasionally Al and Na were lost.
4. Anoxic alteration occurred during reaction of basalt with seawater at low water-rock ratios, or with seawater that had previously reacted with basalt. Saponite-rich dark grey alteration zones formed which exhibit very little chemical change: generally only slight increases in Fe³⁺/Fe^T and H₂O occurred.
5. Zeolites and calcite formed from seawater-derived fluids modified by previous reactions with basalt. Chemical changes involved increases of Ca, Na, H₂O, and CO₂ in the rocks.
6. A late stage of anoxic conditions resulted in the formation of minor amounts of Mn-calcites and secondary sulfides in previously oxidized rocks. No chemical changes were determined for this stage.

Recognition of such alteration sequences is important in understanding the evolution of submarine hydrothermal systems and in interpreting chemical exchange due to seawater-basalt reactions.     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.     

Stable Carbon Isotope Biogeochemistry and Anthropogenic Impacts on Karst Ground Water, Zunyi, Southwest China

Natural and anthropogenic impacts on karst ground water, Zunyi, Southwest China, are discussed using the stable isotope composition of dissolved inorganic carbon and particulate organic carbon, together with carbon species contents and water chemistry. The waters can be mainly characterized as HCO₃–Ca type, HCO₃ · SO₄–Ca type, or HCO₃ · SO₄–Ca · Mg type, according to mass balance considerations. It is found that the average δ¹³C_DIC values of ground waters are higher in winter (low-flow season) than in summer (high-flow season). Lower contents of dissolved inorganic carbon (DIC) and lower values of δ¹³C_DIC in summer than in winter, indicate that local rain events in summer and a longer residence time of water in winter play an important role in the evolution of ground water carbon in karst flow systems; therefore, soil CO₂ makes a larger contribution to the DIC in summer than in winter. The range of δ¹³C_DIC values indicate that dissolved inorganic carbon is mainly controlled by the rate of carbonate dissolution. The concentrations of dissolved organic carbon and particulate organic carbon in most ground water samples are lower than 2.0 mg C L⁻¹ and 0.5 mg C L⁻¹, respectively, but some waters have slightly higher contents of organic carbon. The waters with high organic carbon contents are generally located in the urban area where lower δ¹³C_DIC values suggest that urbanization has had an effect on the ground water biogeochemistry and might threaten the water quality.     

Geochemical constraints for the origin of thermal waters from western Turkey

The combined chemical composition, B and Sr isotopes, and the basic geologic setting of geothermal systems from the Menderes Massif in western Turkey have been investigated to evaluate the origin of the dissolved constituents and mechanisms of water–rock interaction. Four types of thermal water are present: (1) a Na–Cl of marine origin; (2) a Na–HCO₃ type with high CO₂ content that is associated with metamorphic rocks of the Menderes Massif; (3) a Na–SO₄ type that is also associated with metamorphic rocks of the Menderes Massif with H₂S addition; and (4) a Ca–Mg–HCO₃–SO₄ type that results from interactions with carbonate rocks at shallow depths. The Na–Cl waters are further subdivided based on Br/Cl ratios. Water from the Cumalı Seferihisar and Bodrum Karaada systems are deep circulated seawater (Br/Cl=sea water) whereas water from Çanakkale–Tuzla (Br/Cl<sea water) are from dissolution of Messinian evaporites. Good correlations between different dissolved salts and temperature indicate that the chemical composition of the thermal waters from non-marine geothermal systems is controlled by: (1) temperature dependent water–rock interactions; (2) intensification of reactions due to high dissolved CO₂ and possibly HCl gasses; and (3) mixing with overlying cold groundwater. All of the thermal water is enriched in B. The B isotopic composition (δ¹¹B=2.3‰ to 18.7‰; n=6) can indicate either leaching of B from the rocks, or B(OH)₃ degassing flux from deep sources. The large ranges in B concentrations in different rock types as well as in thermal waters from different systems suggest the water-rock mechanism. ⁸⁷Sr/⁸⁶Sr ratios of the thermal water are used to differentiate between solutes that have interacted with metamorphic rocks (⁸⁷Sr/⁸⁶Sr ratio as high as 0.719479) and carbonate rocks (low ⁸⁷Sr/⁸⁶Sr ratio of 0.707864).     

Abiotic formation of hydrocarbons under hydrothermal conditions: Constraints from chemical and isotope data

To understand reaction pathways and isotope systematics during mineral-catalyzed abiotic synthesis of hydrocarbons under hydrothermal conditions, experiments involving magnetite and CO₂ and H₂-bearing aqueous fluids were conducted at 400 °C and 500 bars. A robust technique for sample storage and transfer from experimental apparatus to stable isotope mass spectrometer provides a methodology for integration of both carbon and hydrogen isotope characterization of reactants and products generated during abiogenic synthesis experiments. Experiments were performed with and without pretreatment of magnetite to remove background carbon associated with the mineral catalyst. Prior to experiments, the abundance and carbon isotope composition of all carbon-bearing components were determined. Time-series samples of the fluid from all experiments indicated significant concentrations of dissolved CO and C₁-C₃ hydrocarbons and relatively large changes in dissolved CO₂ and H₂ concentrations, consistent with formation of additional hydrocarbon components beyond C₃. The existence of relatively high dissolved alkanes in the experiment involving non-pretreated magnetite in particular, suggests a complex catalytic process, likely involving reinforcing effects of mineral-derived carbon with newly synthesized hydrocarbons at the magnetite surface. Similar reactions may be important mechanisms for carbon reduction in chemically complex natural hydrothermal systems. In spite of evidence supporting abiotic hydrocarbon formation in all experiments, an “isotopic reversal” trend was not observed for ¹³C values of dissolved alkanes with increasing carbon number. This may relate to the specific mechanism of carbon reduction and hydrocarbon chain growth under hydrothermal conditions at elevated temperatures and pressures. Over time, significant ¹³C depletion in CH₄ suggests either depolymerization reactions occurring in addition to synthesis, or reactions between the C₁-C₃ hydrocarbons and carbon species absorbed on mineral surfaces and in solution.     

Genesis of Palaeoproterozoic iron skarns in the Misi region, northern Finland

Sodic alteration is widespread in Palaeoproterozoic greenstone and schist belts of the northern Fennoscandian shield. In the Misi region that forms the easternmost part of the Peräpohja schist belt, several small magnetite deposits show intimate spatial relationships with intensely albitised gabbros, raising the possibility that regional sodic alteration released iron, which was subsequently accumulated into deposits. Two of these magnetite deposits, Raajärvi and Puro display a typical paragenesis as follows (from oldest to youngest): (1) diopside, (2) actinolite/tremolite-magnetite ± chlorite, biotite, and (3) serpentine ± hematite, chlorite. Mass balance calculations suggest that significant amounts of Fe, Ca, Mg, K, Cu, V, and Ba were lost, and Na and Si gained during the albitisation of the gabbro, at near-constant Al, Ga, Ti, and Zr. Significant amounts of Si, Ca, Fe, and Na were enriched in the formation of skarn related to magnetite deposits. Fe and V leached from country rocks deposited during the skarn-alteration and formed the vanadium rich iron deposits while Cu passed through the system without significant precipitation due to low sulphur fugasity. Variations in Na, Ca, Mg, K, and Ba contents reflect the composition of the infiltrating fluid during alteration. Conventional heating-freezing measurements and proton-induced X-ray emission (PIXE) analyses of the fluid inclusions related to actinolite/tremolite-magnetite stage alteration indicate that the fluids that caused the alteration and the Fe-mineralisation were complex, oxidised, highly saline H₂O ± CO₂ fluids that contained high amounts of Na, Ca, K, Fe, and Ba as well as elevated concentrations of Cu, Zn, and Pb. The oxygen isotope thermometry suggest that temperature during the Fe-mineralisation stage was between 390 and 490°C. Calculated δ¹⁸O_fluid values of 6.1–9.8‰ SMOW and δ¹³C values of calcites in the ores and skarns were between ?7.7 and 10.9‰ PDB and most likely reflect admixture of ¹³C depleted, possibly magmatic fluids with the marble wall rocks that show δ¹³C_calcite values of 13‰ PDB. The SIMS U–Pb data on the zircons in the albitised gabbro next to the Raajärvi and Puro deposits suggest that intrusion of the gabbro took place at 2123±7 Ma and was accompanied by the formation of diopside skarn. The TIMS data on the metasomatic titanites related to sodic alteration yielded ages of 2062±3 and 2017±3 Ma. Iron was probably stripped from the mafic country rocks by sodic alteration between 2123 and 2017 Ma, driven by repeated brine influxes. Subsequently, the metal-rich brine was focused by a fault system and the iron was precipitated from this fluid by a combination of wall rock reaction, fluid mixing, and a drop in the temperature.     

Saponite and celadonite in layer 2 basalts,DSDP Leg 37

Detailed examination of igneous core recovered during Leg 37 of the DSDP, has revealed that basalt diagenesis, an alteration effect resulting from low temperature interaction with seawater, is pervasive to depths of greater than 600 meters in layer 2. Phyllosilicates are among the main components of this low grade alteration effect and occur exclusively as saponite, celadonite and interlayered mixtures of these two phases. Saponites fall into two chemical groups as (a) Mg rich-Fe poor types characteristic of oxidative diagenesis and (b) Fe rich-Mg poor types characteristic of non-oxidative diagenesis. Celadonite is entirely restricted in occurrence to the oxidative diagenetic environment (oxidation halos) and rarely, if ever, occurs as a pure phase. In this respect, X-ray and electron microprobe analyses suggest the presence of interlayered smectite in some cases and iron-oxide contamination in others.Phyllosilicates generated during oxidative diagenesis of basalt occur in discrete mineralogical zones, typically arranged in the sequence Fe³⁺-oxide, celadonite, saponite proceeding outwards from a vein. The generation of these zones are modelled in terms of an infiltration dominated metasomatic process and their occurrence reflects a gradual extraction of oxygen from inflowing seawater during progressive reaction with the massive crystalline basalt.Mass balance calculations applied to the oxidative diagenetic process suggest that a source external to the immediate environment of the massive crystalline rock is required for Si, Fe, K, Mg, Ca, and Al, in order to account for the observed secondary minerals. While Mg, K, and Ca are indigenous to seawater, Si, Fe, and Al were probably enriched in the fluid during wall rock reactions in the fracture system.It is suggested that diagenesis of layer 2 basalts results in the extraction of Mg and K from seawater, in enough quantity to contribute significantly to the chemical mass balance of the oceans.     

Geochemistry of carbonated mineral waters from the Fadeevskoe deposit of the Primorye region

The geochemical study of bed rocks, underground and surface waters, and associated gases in the Fadeevskoe deposit of carbonated waters (Sikhote Alin, Primorye region) revealed that the chemical composition of these waters is formed in the zone of active water exchange in the limited area of the discharge zone, where hydro carbonate calcic waters with mineralization of up to 1 g/1 are formed in largely potassic-sodic rocks. Calculations of the saturation indices show that the mineral waters are characterized by the early stage of Ca saturation, being undersaturated with carbonates and aluminosilicates. The main factors that influence the water mineralization are the excess carbon dioxide in water and the circulation time. The oxygen and carbon isotope ratios indicate the atmospheric genesis of the aqueous component (δ²H = —117; δ¹⁸O = —15.4%o) and the carbon isotope content in the CO₂ implies the mantle nature of the carbon dioxide (δ¹³C = -9.9%o).     

Interstitial solutions and diagenesis in deeply buried marine sediments: results from the Deep Sea Drilling Project

Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments.Pelagic clays and slowly deposited (<1 cm/10³yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters.In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/10³ yr the changes chiefly involve gains of Ca²⁺ and Sr²⁺ and losses of Mg²⁺ which balance the Ca²⁺ enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr²⁺ may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg²⁺ for Ca²⁺ during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca²⁺ and Sr²⁺ enrichment is again characteristic, but Mg²⁺ losses exceed Ca²⁺ gains with the excess being balanced by SO₄^{post staggered2?} losses. The data indicate that the reactions are similar to those noted above, except that the Ca²⁺ released is not kept in solution but is precipitated by the HCO₃^{post staggered?} produced in SO₄^{post staggered2?} reduction. In both these types of pore waters Na⁺ is usually conservative, but K⁺ depletions are frequent.In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na⁺, Si and CO₂, and slight enhancement in Cl^?. The changes are attributed to exchange of Na⁺ for Ca²⁺ in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity.Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO₄^{post staggered2?}, strong HCO₃^{post staggered?} enrichment, formation of NH₄^{post staggered+}, and methane synthesis from H₂ and CO₂ once SO₄^{post staggered2?} is eliminated. K⁺ and often Na⁺ (slightly) are depleted in the interstitial waters. Ca²⁺ depletion may occur owing to precipitation of CaCO₃. In most cases interstitial Cl^? remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl^? are observed in some sediments adjacent to continents.     

Geochemical patterns and origin of alkaline thermal waters in Central Greece (Platystomo and Smokovo areas)

This study investigates the origin and chemical composition of the thermal waters of Platystomo and Smokovo areas in Central Greece as well as any possible relationships of them to the neighboring geothermal fields located in the south-eastern part of Sperchios basin. The correlations between different dissolved salts and the temperature indicate that the chemical composition of thermal waters are controlled by, the mineral dissolution and the temperature, the reactions due to CO₂ that originates possibly by diffusion from the geothermal fields of Sperchios basin and the mixing of thermal waters with fresh groundwater from karst or shallow aquifers. Two major groups of waters are recognized on the basis of their chemistry: thermal waters of Na–HCO₃–Cl type and thermal waters mixed with fresh groundwater of Ca–Mg–Na–HCO₃ type. All thermal waters of the study area are considered as modified by water–rock interaction rainwater, heated in depth and mixed in some cases with fresh groundwater when arriving to the surface. Trace elements present low concentrations. Lithium content suggests discrimination between the above two groups of waters. Boron geochemistry confirms all the above remarks. Boron concentration ranges from 60 μg L^?1 to 10 mg L^?1, while all samples’ constant isotopic composition (δ¹¹B ≈ 10 ‰) indicates leaching from rocks. The positive correlation between the chemical elements and the temperature clearly indicates that much of the dissolved salts are derived from water–rock interactions. The application of geothermometers suggests that the reservoir temperature is around 100–110 °C. Chalcedony temperatures are similar to the emergent temperatures and this is typical of convective waters in fault systems in normal thermal gradient areas.     

Stable isotopic and elemental characteristics of recent tufa from a karstic Krka River (south‐east Slovenia): useful environmental proxies?

Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO₂ degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ¹³C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO₂ degassing and tufa precipitation rate downstream. The Δ¹³C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous ¹²CO₂ degassing downstream leaving the carbon pool enriched in ¹³C. In the case of oxygen, the isotope fractionation (Δ¹⁸O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ¹⁸O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ¹⁸O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.     

Iron isotope fractionation during hydrothermal ore deposition and alteration

Iron isotopes fractionate during hydrothermal processes. Therefore, the Fe isotope composition of ore-forming minerals characterizes either iron sources or fluid histories. The former potentially serves to distinguish between sedimentary, magmatic or metamorphic iron sources, and the latter allows the reconstruction of precipitation and redox processes. These processes take place during ore formation or alteration. The aim of this contribution is to investigate the suitability of this new isotope method as a probe of ore-related processes. For this purpose 51 samples of iron ores and iron mineral separates from the Schwarzwald region, southwest Germany, were analyzed for their iron isotope composition using multicollector ICP-MS. Further, the ore-forming and ore-altering processes were quantitatively modeled using reaction path calculations. The Schwarzwald mining district hosts mineralizations that formed discontinuously over almost 300 Ma of hydrothermal activity. Primary hematite, siderite and sulfides formed from mixing of meteoric fluids with deeper crustal brines. Later, these minerals were partly dissolved and oxidized, and secondary hematite, goethite and iron arsenates were precipitated. Two types of alteration products formed: (1) primary and high-temperature secondary Fe minerals formed between 120 and 300 °C, and (2) low-temperature secondary Fe minerals formed under supergene conditions (<100 °C). Measured iron isotope compositions are variable and cover a range in δ⁵⁶Fe between −2.3‰ and +1.3‰. Primary hematite (δ⁵⁶Fe: −0.5‰ to +0.5‰) precipitated by mixing oxidizing surface waters with a hydrothermal fluid that contained moderately light Fe (δ⁵⁶Fe: −0.5‰) leached from the crystalline basement. Occasional input of CO₂-rich waters resulted in precipitation of isotopically light siderite (δ⁵⁶Fe: −1.4 to −0.7‰). The difference between hematite and siderite is compatible with published Fe isotope fractionation factors. The observed range in isotopic compositions can be accounted for by variable fractions of Fe precipitating from the fluid. Therefore, both fluid processes and mass balance can be inferred from Fe isotopes. Supergene weathering of siderite by oxidizing surface waters led to replacement of isotopically light primary siderite by similarly light secondary hematite and goethite, respectively. Because this replacement entails quantitative transfer of iron from precursor mineral to product, no significant isotope fractionation is produced. Hence, Fe isotopes potentially serve to identify precursors in ore alteration products. Goethites from oolitic sedimentary iron ores were also analyzed. Their compositional range appears to indicate oxidative precipitation from relatively uniform Fe dissolved in coastal water. This comprehensive iron isotope study illustrates the potential of the new technique in deciphering ore formation and alteration processes. Isotope ratios are strongly dependent on and highly characteristic of fluid and precipitation histories. Therefore, they are less suitable to provide information on Fe sources. However, it will be possible to unravel the physico-chemical processes leading to the formation, dissolution and redeposition of ores in great detail.