Robert J. Rosenbauer

Experimental oxygen isotope fractionation between siderite-water and phosphoric acid liberated CO2-siderite

The equilibrium fractionation of O isotopes between synthetic siderite and water has been measured at temperatures ranging from 33° to 197°C. The fractionation between siderite and water over this temperature range can be represented by the equation: 103 ln α = 3.13 × 106T−2 − 3.50. Comparison between the experimental and theoretical fractionations is favorable only at approximately 200°C; at lower temperatures, they generally differ by up to 2 permil. Siderite was prepared by the slow addition of ferrous chloride solutions to sodium bicarbonate solutions at the experimental temperatures. It was also used to determine the O isotope fractionation factors between phosphoric acid liberated CO2 and siderite. The fractionation factors for this pair at 25° and 50°C are 1.01175 and 1.01075, respectively. Preliminary results of the measured C isotope fractionation between siderite and Co2 also indicate C isotopic equilibrium during precipitation of siderite. The measured distribution of 13C between siderite and CO2 coincides with the theoretical values only at about 120°C. Experimental and theoretical C fractionations differ up to 3 permil at higher and lower temperatures.

The critical point and two-phase boundary of seawater, 200-500°C

Abstract The two-phase boundary of seawater was determined by isothermal decompression of fully condensed seawater in the range of 200–500°C. The pressure at which phase separation occurred for each isotherm was determined by a comparison of the refractive index of fluid removed from the top and bottom of the reaction vessel. The critical point was determined to be in the range of 403–406°C, 285–302 bar and was located by the inflection in the two-phase boundary and by the relative volume of fluid and vapor as a function of temperature. The two-phase boundary of 3.2% NaCl solution was found to coincide exactly with that of seawater over the range tested in the present study. The boundary for both is described by a single seventh-order polynomial equation. The two-phase boundary defines the maximum temperature of seawater circulating at depth in the oceanic crust. Thus the boundary puts a limit of about 390°C for seawater circulating near the seafloor at active ocean ridges (2.5 km water depth), and about 465°C at the top of a magma chamber occurring at 2 km below the seafloor.

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.

Thermal decarboxylation of acetic acid: Implications for origin of natural gas

Abstract Laboratory experiments on the thermal decarboxylation of solutions of acetic acid at 200°C and 300°C were carried out in hydrothermal equipment allowing for on-line sampling of both the gas and liquid phases for chemical and stable-carbon-isotope analyses. The solutions had ambient pH values between 2.5 and 7.1; pH values and the concentrations of the various acetate species at the conditions of the experiments were computed using a chemical model. Results show that the concentrations of acetic acid, and not total acetate in solution, control the reaction rates which follow a first order equation based on decreasing concentrations of acetic acid with time. The decarboxylation rates at 200°C (1.81 × 10−8 per second) and 300°C (8.17 × 10−8 per second) and the extrapolated rates at lower temperatures are relatively high. The activation energy of decarboxylation is only 8.1 kcal/mole. These high decarboxylation rates, together with the distribution of short-chained aliphatic acid anions in formation waters, support the hypothesis that acid anions are precursors for an important portion of natural gas. Results of the δ13C values of CO2, CH4, and total acetate show a reasonably constant fractionation factor of about 20 permil between CO2 and CH4 at 300°C. The δ13C values of CO2 and CH4 are initially low and become higher as decarboxylation increases.

Salinity Variations in Submarine Hydrothermal Systems by Layered Double-Diffusive Convection

Various mechanisms have been proposed to explain the salinity variations in vent fluids of seafloor geothermal systems. New experiments reacting diabase and evolved seawater were carried out to reproduce earlier published observations of Cl depletions attributed to formation of an ephemeral Cl-bearing mineral. The absence of any Cl depletions in the present study suggests that the formation of Cl-bearing minerals is not sufficiently widespread to account for the observed salinity variations in the vent fluids. A re-evaluation of both field and laboratory evidence has led to a new model for subseafloor circulation that accounts for salinity variations as well as other chemical and mineralogic observations. In place of a simple single-pass convection system, we propose that the seafloor systems consist of two vertically nested convection cells in which a brine layer at depth heats and drives an overlying seawater cell. Such layering of salinities, a process known in fluid mechanics as double-diffusive convection, is an expected result when convection is induced in saline fluids. The process provides for stable high-temperature heat transfer upward from the cracking front adjacent to the magma, and for limited chemical exchange of the brine with the overlying seawater to explain salinity variations and high metal contents in the vent fluids. The brine also provides an effective medium to produce the secondary mineral assemblages observed in rocks from the mid-ocean ridges and ophiolites unsuccessfully produced in laboratory studies using seawater. The brine originates from the two-phase separation of seawater during magmatic/tectonic events and accumulates and remains relatively stable in the region immediately above the magma chamber.

Liquid-vapor relations in the critical region of the system NaCl-H2O from 380 to 415°C: A refined determination of the critical point and two-phase boundary of seawater

Pressure-temperature-composition (P-T-x) relations for coexisting vapor and liquid phases in the system NaCl-H2O were determined experimentally in the critical region from 380 to 415°C. The results provide much improved control on the P-T-x critical line in this region. The critical point of seawater (3.2 wt% NaCl solution), which is bracketed in the present study, is at 407°C and 298.5 bar. In addition, the P-T two-phase boundary of seawater was re-determined. These results provide increased precision and accuracy for theoretical models of critical phenomena in this important two-component system and of the limiting P- T conditions of seawater in seafloor geothermal systems.

The Solubility and Stabilization of Ikaite (CaCO3·6H2O) from 0° to 25°C: Environmental and Paleoclimatic Implications for Thinolite Tufa

We determined the solubility of ikaite from 0° to 25°C to model its saturation state in natural waters and test the hypothesis that it is the precursor of the calcite pseudomorphs in thinolite tufa of Quaternary Lake Lahontan. Reversible solubility at buffered

Experimental study of boron geochemistry: implications for fluid processes in subduction zones

P_{CO_{2}}

The system NaCl-H2O: Relations of vapor-liquid near the critical temperature of water and of vapor-liquid-halite from 300° to 500°C

yields the following expression for the dissolution constant of ikaite:

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log K_{ikaite} = 0.15981 - 2011.1/T