A study of celestine equilibrium in marine sediments using the entire ODP/IODP porewater data base

The stability of celestine (SrSO₄) in marine sediments has been investigated through the calculation of its saturation index at the in situ temperature and pressure, using the entire ODP/IODP porewater composition data base (14,416 samples recovered from sediments collected during 95 ODP and IODP Legs) that has been thoroughly corrected for missing data and inconsistencies. The porewater in situ pressure has been obtained from depth data, and the in situ sample temperature has been calculated from the bottom seawater temperature and from the measured thermal gradient. When the latter is unavailable, a default value of 35 °C/km or an assumed gradient similar to that of a site located close to the study area has been used. Molarities have been converted to molalities through the calculation of the porewater densities, which have represented by an empirical function of the total dissolved solids load up to 150 g/L.Ocean bottom waters are largely undersaturated with respect to celestine. Yet sediment porewater saturation is not uncommon: it is reached in 83 boreholes (i.e. about 10% of all boreholes) drilled during 22 ODP/IODP Legs. Celestine equilibrium can be reached through two different non-exclusive causes: a strontium increase in porewater linked to the dissolution of Sr-rich aragonite or biogenic calcite and precipitation of Sr-poor calcite (carbonate recrystallization), or an increase in the strontium and sulfate porewater concentrations linked to a salinity increase due to the presence of brines.Sediments at most of the sites exhibiting celestine equilibrium share common characteristics such as a carbonate-rich lithology (typically higher than 80 wt.%) and a low organic carbon content (generally below 1 wt.%). These results indicate that modification of porewaters during burial diagenesis can easily lead to celestine saturation, especially in carbonate-rich sediments. We then briefly discuss former interpretations of the presence of celestine in ancient and recent marine sediments, as well as the consequences of the incorporation of celestine formation in diagenetic models using the porewater Sr content and Sr isotopic composition.     

Hydrogeochemical factors effecting the scaling problem in Balçova geothermal field,İzmir, Turkey

Reservoir fluid compositions have been assessed from analytical data on water samples collected from thermal and cold waters in Balçova geothermal field. The results of mineral equilibrium modelling indicate that the waters, with some exceptions, are systematically supersaturated with respect to calcite, aragonite, dolomite, chalcedony and quartz, but undersaturated with respect to amorphous silica, celestite, anhydrite and gypsum and undersaturated or supersaturated with respect to barite, low-albite, K-feldspar, gibbsite and Fe(OH)₃(a). Calculation of mineral saturation states and geochemical analyses of scale and field observations show that carbonate minerals (calcite, aragonite and dolomite) are most likely to be precipitated as a scale type. Besides carbonates, scale formation risk of amorphous silica, Fe(OH)₃(a), anhydrite, barite and celestite minerals should be taken into account in some wells and surface equipment. Most of the waters, with some exceptions, have carbonate scaling risk at all temperatures, whereas the other scaling risks only exist over a limited temperature range. While silica, Fe(OH)₃(a) and barite show a scaling tendency at low temperatures, anhydrite and celestite scaling occurs at higher temperatures.     

Characterization of calcium isotopes in natural and synthetic barite

The mineral barite (BaSO₄) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (δ^44/40Ca = −2.01 ± 0.15‰) but are different from hydrothermal and cold seep barite samples (δ^44/40Ca = −4.13 to −2.72‰). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, Δ^44/40Ca = −3.42 to −2.40‰. Temperature, saturation state, , and aCa²⁺/aBa²⁺ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower ⁴⁴Ca/⁴⁰Ca than calcite, by −9‰ at 0 °C and −8‰ at 25 °C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower δ^44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca²⁺ substitution for Ba²⁺ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca²⁺ and other elements in inorganic and biogenic minerals.     

The geochemistry of Ca,Sr, Ba and Ra sulfates in some deep brines from the Palo Duro Basin,Texas

The geochemistry of Ca, Sr, Ba and Ra sulfates in some deep brines from the Palo Duro Basin of north Texas, was studied to define geochemical controls on radionuclides such as ⁹⁰Sr and ²²⁶Ra. Published solubility data for gypsum, anhydrite, celestite, barite and RaSO₄ were first reevaluated, in most cases using the ion interaction approach of Pitzer, to determine solubility products of the sulfates as a function of temperature and pressure. Ionic strengths of the brines were from 2.9 to 4.8 m, their temperatures and pressures up to 40°C and 130 bars. Saturation indices of the sulfates were computed with the ion-interaction approach in one brine from the arkosic granite wash fades and four from the carbonate Wolfcamp Formation. All five brines are saturated with respect to gypsum, anhydrite and celestite, and three of the five with respect to barite. All are undersaturated by from 5 to 6 orders of magnitude with respect to pure RaSO₄. ²²⁶Ra concentrations in the brines, which ranged from 10^?11.3 to 10^?12.7 m, are not controlled by RaSO₄ solubility or adsorption, but possibly by the solubility of trace Ra solid solutions in sulfates including celestite and barite.     

Salinization of porewater in a multiple aquitard-aquifer system in Jiangsu coastal plain,China

Chemical and isotopic compositions were analyzed in porewater squeezed from a clayey aquitard in Jiangsu coastal plain, eastern China, to interpret the salinity origin, chemical evolution and water-mass mixing process. A strong geochemical fingerprint was obtained with an aligned Cl/Br ratio of 154 in the salinized aquitard porewater over a wide Cl^? concentration range (396–9,720 mg/L), indicating that porewater salinity is likely derived from a mixing with old brine with a proportion of less than 20%. Very small contributions of brine exerted limited effects on water stable isotopes. The relationships between porewater δ¹⁸O and δD indicate that shallow and intermediate porewaters could be original seawater and were subsequently diluted with modern meteoric water, whereas deep porewaters with depleted stable isotopic values were probably recharged during a cooler period and modified by evaporation and seawater infiltration. The cation–Cl relationship and mineralogy of associated strata indicate that porewater has been chemically modified by silicate weathering and ion-exchange reactions. ⁸⁷Sr/⁸⁶Sr ratios of 0.7094–0.7112 further confirm the input source of silicate minerals. Numerical simulations were used to evaluate the long-term salinity evolution of the deep porewater. The alternations of boundary conditions (i.e., the third aquifer mixed with brine at approximately 70 ka BP, followed by recharge of glacial meltwater at 20–25 ka BP, and then mixing with Holocene seawater at 7–10 ka BP) are responsible for the shift in porewater salinity. These timeframes correspond with the results of previous studies on ancient marine transgression-regression in Jiangsu coastal plain.     

Interpretation of Mineral Zoning in Submarine Hydrothermal Ore Deposits in Terms of Coupled Fluid Flow‐Precipitation Kinetics Model

Major minerals (sulfates, sulfides, quartz) are distributed in different parts of submarine hydrothermal ore deposits. For instance, the abundance of barite increases stratigraphically upwards in the massive orebodies of the Kuroko deposits (black and yellow ores), while quartz is abundant in the lower parts (siliceous ore). The different distribution of barite and quartz in the Kuroko deposits can not be accounted for by thermochemical equilibrium calculations based on the precipitation due to mixing of ascending hydrothermal solutions with ambient cold seawater. In the present study, a coupled fluid flow‐precipitation kinetics model was used to calculate the amounts of quartz, barite, and anhydrite precipitated from a hydrothermal solution mixed with seawater, assuming reasonable values for temperature, precipitation rate, fluid flow velocity, mineral surface area/fluid mass ratio (A/M), and initial concentrations of hydrothermal solution and seawater before mixing occurred. The results indicate that barite precipitates more efficiently than quartz from discharging fluids with relatively higher flow velocity, lower temperatures and under the condition of lower A/M ratios on the seafloor (black ore), whereas quartz precipitates more effectively from solutions with lower flow velocity, higher temperatures and higher A/M ratios beneath the seafloor (siliceous ore) and in the orebody (barite ore, ferruginous chert ore). Anhydrite precipitates in shallow sub‐seafloor environments with lower precipitation rates and higher A/M ratios than barite and higher precipitation rates and lower A/M ratios than quartz. These results explain the observed occurrences of barite, anhydrite, and quartz in the Kuroko deposits. Namely, barite is abundant in black ore and barite ore which formed above the seafloor, anhydrite formed in high‐permeability tuff breccias, and quartz formed in low permeability dacite intrusive bodies in the sub‐seafloor environment.     

An experimental investigation of barite formation in seawater

We report results from time-series decay and sequential leaching experiments of laboratory cultured and coastal plankton to elucidate the mechanisms controlling barite formation in seawater. Batch-cultured diatoms (Stephanopyxis palmerina) and coccolithophorids (Emiliania huxleyi) were let to decay in the dark for 8-10 weeks, suspended in aerated seawater. The development of barite crystals was monitored by Scanning Electron Microscopy (SEM). A similar experiment was conducted with plankton collected during the spring-bloom in Vineyard Sound (MA). In addition to SEM, suspended particles were sequentially leached for Ba (distilled water rinse; 10% (v/v) HNO₃ rinse at room temperature; 30% (v/v) HCl at 80°C overnight; 50% (v/v) HNO₃ at 80°C overnight) immediately after collection, and after 10-week decay in seawater, in seawater poisoned with HgCl₂, and in seawater spiked with ¹³⁵Ba.Both experiments showed an increase in the number of barite crystals during decay. The spring-bloom plankton had initially a large pool of labile Ba, soluble in distilled water and cold dilute HNO₃ that was lost from the plankton after 10-week decay in both axenic and nonaxenic conditions. In contrast, Ba in the decayed plankton samples was predominantly in forms extracted by hot HCl and hot HNO₃ acids, which were attributed to presence of barite Ba and refractory organic Ba respectively. The increase in barite crystal counts under a Scanning Electron Microscope (SEM), the increase in HCl extractable Ba relative to organic carbon, and the loss of a large fraction of Ba during plankton decay suggest that living plankton consists of a relatively large pool of labile Ba, which is rapidly released during plankton decomposition and acts as the main source of Ba for barite formation in supersaturated microenvironments. Since mass balance indicates that only a small proportion (2 to 4%) of the labile-Ba pool is converted to barite, the availability of microenvironments that could locally concentrate Ba released by plankton decay seems to be the main limiting factor in barite precipitation.     

The Escanaba Trough, Gorda Ridge hydrothermal system: Temporal stability and subseafloor complexity

The composition and temperature of vent fluids sampled from the active hydrothermal system in Escanaba Trough, Gorda Ridge in 2000 and 2002 remain unchanged from the only time this field was previously sampled, in 1988. ODP Leg 169 drilled nine bore holes at this site in 1996, some within meters of the vents, yet this disturbance has not impacted the measured compositions or temperatures of the fluids exiting at the seafloor. The fluids have maximum measured temperatures of 218°C and contain ∼20% more chloride than local ambient seawater. Our interpretation is that the fluid compositions are generated by supercritical phase separation of seawater, with much of the water-rock reaction occurring within the ∼400m thick sedimentary section that overlies the basalt at this site. The ODP drilling results provide information on the mineralogy and composition of materials below the seafloor, as well as direct constraints not typically available on the physical conditions occurring below the seafloor hydrothermal system. Calculations utilizing geochemical modeling software suggest the fluids are close to saturation with a suite of minerals found subsurface, suggesting equilibrium between the fluids and substrate. These results provide an explanation for why the fluids have remained chemically stable for 14 yrs. The pore water data from drilling suggest that the hydrology and chemistry of the hydrothermal system are much more complex within the sediment cover than would be expected from the surface manifestations of the hydrothermal system. While the pore waters have chloride contents both greater and less than the local seawater, only fluids with higher chloride contents vent at the seafloor. Our calculations suggest that at the current conditions the “brines” (fluids with chlorinity greater than seawater) are actually less dense than the “vapors” (fluids with chlorinity less than seawater). These density relationships may provide an explanation for why the “brines” are now venting preferentially to the “vapors,” a situation opposite to what is usually observed or inferred.     

Fluid inclusion study of the Fiumarella barite deposit (Catanzaro — S. Italy)

Samples from a barite vein deposit, located in the Catanzaro Fiumarella (Calabria) were examined by fluid inclusion and ore minerographic techniques. The barite vein occur in plutonic rocks of the Stilo Unit, where some Mo mineralizations were reported. The purpose of the study was to determine the characteristics of the fluid inclusions and to compare them to those of typical porphyry Cu/Mo systems. The ore minerographic study shows that the sulfides, associated to the barite, are clearly post-barite. The fluid inclusion results indicate that the average minimum temperature of the barite formation can be assumed to be about 210°C, with a range of 190–235°C. The salinity of the barite forming solutions is in the range 0–19.5 wt% NaCl and the average minimum pressure on the system was of 18.04 bars equivalent to a minimum depth of 201 m of barite formation below the paleowatertable. No genetic link is suggested to exist between the fluid inclusions of the Fiumarella barite deposit and those characteristic of typical porphyry Cu/Mo systems, whereas a close relation with epithermal precious metal (with base metals) vein deposits or with their distant cousins, the Kuroko deposits, is suggested to exist.Work carried out with the financial assistance of the "Progetto Finalizzato Geodinamica" (n^o 79.00597.89.115.6291). Publ. n^o 353     

Formation,diagenesis and palaeoenvironmental significance of upper Ediacaran fibrous dolomite cements

Neoproterozoic marine dolomite cements represent reliable, albeit complex, archives of their palaeoenvironment. Petrological and high-resolution geochemical data from well-preserved fibrous dolomite and pyrite in the upper Ediacaran (ca 551·1 to 548·0 Ma) Dengying Formation in south-west China are presented and discussed here. The aim of this research is to reconstruct the redox state of late Ediacaran shallow seawater and porewater in the Sichuan Basin using early marine diagenetic fabrics. Based on crystalline texture and axis, four basic types of fibrous dolomite cements formed penecontemporaneously in a microbialite reef setting at the platform margin: (i) bladed dolomites (replacement from a high-Mg calcite precursor); (ii) fascicular fast dolomites (replacement from an aragonitic precursor); (iii) fascicular slow dolomites; and (iv) radial slow dolomites. The latter two fabrics are considered direct marine porewater precipitates due to their length-slow character, cathodoluminescent zonation, and enriched copper and cobalt concentrations. Marine cements yield rare earth element and yttrium patterns comparable to modern seawater and represent a refined set of archive data relative to previously published bulk dolostones. Redox-sensitive elements and cathodoluminescence indicate that the fascicular fast dolomites formed in suboxic seawater, while fascicular slow and radial slow dolomites formed in euxinic marine porewaters. Microbial sulphate reduction during the formation of fascicular slow and radial slow dolomites is recognized by nanometre-scale spheroidal ankerite and sulphur-containing dolomite, and intergrown pyrite grains with U-shaped δ³⁴S transects. Data shown here suggest predominantly suboxic shallow late Ediacaran seawater and euxinic marine porewaters, with microbial activity promoting the direct precipitation of dolomite.     

Geochemistry of thermal springs,Alhama de Granada (southern Spain)

The waters of the thermal springs at Alhama de Granada vary in temperature between 27 and 45°C. Temporal changes in the composition of the principal spring (Baños Viejos) indicate that a small degree of mixing may occur between deep thermal waters and shallow groundwater. Slight compositional variations also occur between the various thermal springs in the study area. These spatial variations are due to the different local hydrodynamic conditions in the springs. Towards the north in less hydraulically transmissive rocks, cooling of the rising water is more noticeable, as are ion exchange and processes of SO₄ reduction. The chemical composition of the water is related to the dissolution of evaporites (SO₄ and Cl salts), carbonates and silicates, and to the possible existence of sources of S within the rock. Estimates of the mean residence times have been obtained based on ¹⁴C_DIC and T. The state of thermodynamic equilibrium at the spring discharge was calculated using the SOLMINEQ.88 program. The results indicate that all the samples are supersaturated with respect to quartz, chalcedony, cristobalite, calcite, aragonite and dolomite, and undersaturated with respect to gypsum, anhydrite and halite. The use of different geothermometers and modelling of saturation indices for quartz, albite and anhydrite indicate temperatures of about 110°C.     

The mechanism and kinetics of DTPA-promoted dissolution of barite

The dissolution rate of natural barite, BaSO₄, was measured in solutions of DTPA (diethylene triamine penta-acetic acid) to investigate the mechanism of ligand-promoted dissolution using a strong chelating agent. Experiments were carried out over a range of DTPA concentrations 0.5–0.0001 M solutions, at room temperature (22 °C), as well as a range of temperatures, 22–80 °C at 1 atm. The dissolution rate is inversely related to the DTPA concentration in solution. A more dilute DTPA solution is shown to be more efficient as a solvent in terms of the approach to the equilibrium saturation value for the dissolution of Ba²⁺. An analysis of the temperature dependence of the dissolution rate at high pH by the determination of activation energies indicates that the reaction is probably controlled by the pre-exponential term in the rate constant. This indicates that reaction frequency mostly controls differences in reactivity and suggests an explanation for the results in terms of stearic hindrance due to adsorbed DTPA molecules at the barite surface. The effect of DTPA on the solvation of the Ba²⁺ ion may also influence the dissolution rate.     

Experimental evidence for carbonate precipitation and CO2 degassing during sea ice formation

Chemical and stable carbon isotopic modifications during the freezing of artificial seawater were measured in four 4 m³ tank incubations. Three of the four incubations were inoculated with a nonaxenic Antarctic diatom culture. The 18 days of freezing resulted in 25 to 27 cm thick ice sheets overlying the residual seawater. The ice phase was characterized by a decrease in temperature from −1.9 to −2.2°C in the under-ice seawater down to −6.7°C in the upper 4 cm of the ice sheet, with a concurrent increase in the salinity of the under-ice seawater and brine inclusions of the ice sheet as a result of physical concentration of major dissolved salts by expulsion from the solid ice matrix. Measurements of pH, total dissolved inorganic carbon (C_T) and its stable isotopic composition (δ¹³C_T) all exhibited changes, which suggest minimal effect by biological activity during the experiment. A systematic drop in pH and salinity-normalized C_T by up to 0.37 pH_SWS units and 376 μmol C kg⁻¹ respectively at the lowest temperature and highest salinity part of the ice sheet were coupled with an equally systematic ¹³C enrichment of the C_T. Calculations based on the direct pH and C_T measurements indicated a steady increase in the in situ concentration of dissolved carbon dioxide (CO₂(aq)) with time and increasing salinity within the ice sheet, partly due to changes in the dissociation constants of carbonic acid in the low temperature-high salinity range within sea ice. The combined effects of temperature and salinity on the solubility of CO₂ over the range of conditions encountered during this study was a slight net decrease in the equilibrium CO₂(aq) concentration as a result of the salting-out overriding the increase in solubility with decreasing temperature. Hence, the increase in the in situ CO₂(aq) concentration lead to saturation or supersaturation of the brine inclusions in the ice sheet with respect to atmospheric pCO₂ (≈3.5 × 10⁻⁴ atm). When all physico-chemical processes are considered, we expect CO₂ degassing and carbonate mineral precipitation from the brine inclusions of the ice sheet, which were saturated or highly supersaturated with respect to both the anhydrous (calcite, aragonite, vaterite) and hydrated (ikaite) carbonate minerals.     

Sedimentary-hosted polymetallic massive sulfide deposits of the Kebrit and Shaban Deeps,Red Sea

Massive sulfides recovered from the Kebrit Deep carbonaceous sedimentary succession represent black smoker fragments, novel to any Red Sea brine pool deposit. Chimneys, which were also observed in situ near the seawater/brine interface of the Kebrit Deep pool, are primarily comprised of Fe-, Zn- and Pb-bearing phases, and are often tar and asphalt impregnated. Cu-sulfides are virtually absent from parageneses, contrasting rift-related smoker and Red Sea metalliferous sediment deposits. Concentration of nickel in discrete bravoite points to a basalt/seawater leaching process as a source for most metals. The sedimentary package, which probably hosts Cu-mineralization in lower stockworks of the smoker deposit, is considered the major source of lead. Prevention of boiling of hydrothermal fluids, passing through a succession of organic-rich carbonate and clay horizons prior to discharge, is essential for smoker formation. Shaban Deep sedimentary-hosted massive sulfides are less frequent, with pyrite being the dominant ore mineral. Sulfur isotope data indicate both high temperature inorganic as well as biogenic sulfate (seawater and/or evaporite) reduction in sulfide-forming processes. Cogenetic sulfates formed from residual, bacteriogenically reduced seawater sulfate. Rather low sulfide/sulfate precipitation temperatures of 110–130 °C for the Kebrit brine pool and 100 °C for Shaban Deep massive sulfides are evident.     

High temperature alteration minerals and thermal brines,Reykjanes, Iceland

The geothermal area on Reykjanes, Iceland has been investigated mineralogically. The temperature within the studied area is very variable from 30–300° C. Mineral zones corresponding to the temperature conditions in the area are found. Accidental changes in the geothermal system are also reflected in the mineralogy by formation of anhydrite. Changes in temperature conditions in the field are indicated by epidote occurrence at 40° C and retrograd formation of montmorillonite.     

Formation of massive sulfide deposits on oceanic ridge crests: Incremental reaction models for mixing between hydrothermal solutions and seawater

Equilibrium path calculations have been used to model mixing between hot (350°C) hydrothermal solutions and ambient seawater, in an attempt to simulate mineral precipitation at seafloor vents. These calculations predict temperatures of precipitation, paragenetic sequence of minerals, and chemical composition of chimney deposits associated with vents on the seafloor at 21°N, EPR. Assuming sulfate-sulfide disequilibrium during mixing, the paragenetic sequence revealed is: chalcopyrite, anhydrite, pyrrhotite, pyrite, sphalerite, graphite, and barite. When sulfate-sulfide equilibria is permitted during mixing, however, reduction of small amounts of sulfate results in early precipitation of pyrite and a sequence of Cu-rich sulfide minerals (chalcopyrite-bornite-chalcocite-covellite). This sequence is analogous to that observed in thin chimney walls. The calculations indicate that sulfide mineral precipitation occurs in response to both cooling and change in composition of the hydrothermal solutions as a result of mixing. Varying the amount of mixing with respect to temperature, simulating conductive heating of seawater prior to mixing, results in only minor variations in the sequence and abundance of precipitated phases.Anhydrite precipitation during mixing occurs early, which is consistent with formation of an anhydrite leading edge of chimney structures. Similarly, extrapolation of warm spring data from Galapagos to zero SO₄ concentration suggests anhydrite formation due to mixing with seawater beneath the seafloor, most likely below the level of reactive calcareous sediments. Subsequent interaction of the mixed hydrothermal solution with those sediments results in elevated and variable Ca concentrations estimated for end-member solutions from the Galapagos.Precipitation of Mg hydroxide sulfate hydrate in the walls of the vent chimneys at 21°N, EPR, occurs as a result of conductive heating of ambient seawater with only very minor amounts of mixing. In contrast, precipitation of amorphous silica in the vents must be due to conductive cooling of the hydrothermal solutions.Thus, incremental reaction calculations demonstrate that reactions occurring in and associated with venting ridge crest hydrothermal solutions can be effectively modeled using the thermodynamic data and reaction modeling codes available today. Departures from equilibrium required to accurately model the mixing process are easily accommodated and consistent with data from the vents and vent forming materials.     

Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a δ³⁴S versus δ¹⁸O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The δ³⁴S versus δ¹⁸O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H₂O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.     

A thermodynamic model for the solubility of barite and celestite in electrolyte solutions and seawater to 200°C and to 1 kbar

This paper describes a model for barite and celestite solubilities in the Na–K–Ca–Mg–Ba–Sr–Cl–SO₄–H₂O system to 200°C and to 1 kbar. It is based on Pitzer's ion interaction model for the thermodynamic properties of the aqueous phase and on values of the solubility products of the solids revised in this work. It is shown how barite and celestite solubilities in electrolyte solutions can be accurately predicted as a function of temperature and pressure from previously determined Pitzer's parameters. The equilibrium constant for the BaSO₄(aq) ion pair dissociation reaction is calculated from recently reported barite solubility in Na₂SO₄ solutions from 0 to 80°C. Pressure corrections are evaluated through partial molal volume calculations and are partially validated by comparing model predictions to measured barite and celestite solubilities in pure water to 1 kbar and in NaCl solutions to 500 bars. The model is then used to investigate the tendency of ion pairing of Ca, Sr and Ba with sulfate in seawater. Finally, the activity coefficient of aqueous barium sulfate in seawater is calculated for temperature, pressure and salinity values found in the ocean and compared to published values.     

Rare earth element distribution in >400 °C hot hydrothermal fluids from 5°S, MAR: The role of anhydrite in controlling highly variable distribution patterns

Two submarine hydrothermal vent fields at 5°S, Mid-Atlantic Ridge (MAR) - Turtle Pits and Comfortless Cove - emanate vapor-phase fluids at conditions close to the critical point of seawater (407 °C, 298 bars). In this study, the concentration and distribution of rare earth element (REE) and yttrium (Y) has been investigated. Independent of the major element composition, the fluids display a strong temporal variability of their REE + Y concentrations and relative distributions at different time scales of minutes to years. Chondrite-normalized distributions range from common fluid patterns with light REE enrichment relative to the heavy REE, accompanied by positive Eu anomalies (type I), to strongly REE + Y enriched patterns with a concave-downward distribution with a maximum enrichment of Sm and weakly positive or even negative Eu anomalies (type II). The larger the sum of REE, the smaller Ce_CN/Yb_CN and Eu/Eu∗. We also observed a strong variability in fluid flow and changing fluid temperatures, correlating with the compositional variability.As evident by the positive correlation of total REE, Ca, and Sr concentrations in Turtle Pits and Comfortless Cove fluids, precipitation/dissolution of hydrothermal anhydrite controls the variability in REE concentrations and distributions in these fluids and the transformation of one fluid type to the other. The variable distribution of REE can be explained by the accumulation of particulate anhydrite (with concave-downward REE distribution and negative Eu anomaly) into a fluid with common REE distribution (type I), followed by the modification of the REE fluid signature due to dissolution of incorporated anhydrite. A second model, in which the type II fluids represent a primary REE reaction zone fluid pattern, which is variably modified by precipitation of anhydrite, can also explain the observed correlations of total REE, fractionation of LREE/HREE and size of Eu anomaly as well as Ca, Sr. The emanation of such a fluid may be favored in a young hydrothermal system in its high-activity phase with short migration paths and limited exchange with secondary minerals. However, this model is not as well constrained as the other and requires further investigations.The strongly variable REE fluid signature is restricted to the very hot, actively phase-separating hydrothermal systems Turtle Pits and Comfortless Cove at 5°S and has not been observed at the neighboring Red Lion vent field, which continuously emanates 350 °C hot fluid and displays a stable REE distribution (type I).