Geology topics

W.W. Carothers

Publications and source records attributed to W.W. Carothers.

7 recordsLinked to original sources

USGS1988

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: 10 3 ln α = 3.13 × 10 6 T −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 CO 2 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 Co 2 also indicate C isotopic equilibrium during precipitation of siderite. The measured distribution of 13 C between siderite and CO 2 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.

Geochimica et Cosmochimica Acta↗

USGS1987

Geochemistry of metal-rich brines from central Mississippi Salt Dome basin, U.S.A.

Oil-field brines are the most favored ore-forming solutions for the sediment-hosted Mississippi Valley-type ore deposits. Detailed inorganic and organic chemical and isotope analyses of water and gas samples from six oil fields in central Mississippi, one of the very few areas with high metal brines, were conducted to study the inorganic and organic complexes responsible for the high concentrations of these metals. The samples were obtained from production zones consisting of sandstone and limestone that range in depth from 1900 to 4000 m (70–120°C) and in age from Late Cretaceous to Late Jurassic. Results show that the waters are dominantly bittern brines related to the Louann Salt. The brines have extremely high salinities that range from 160,000 to 320,000 mg/l total dissolved solids and are Na Ca Cl-type waters with very high concentrations of Ca (up to 48,000 mg/l) and other alkaline-earth metals, but with low concentrations of aliphatic acid anions. The concentrations of metals in many water samples are very high, reaching values of 70 mg/l for Pb, 245 mg/l for Zn, 465 mg/l for Fe and 210 mg/l for Mn. The samples with high metal contents have extremely low concentrations (<0.02 mg/l) of H 2 S. Samples obtained from the Smackover Formation (limestone) have low metal contents that are more typical of oil-field waters, but have very high concentrations (up to 85 mg/l) of H 2 S. Computations with the geochemical code SOLMINEQ.87 give the following results: (1) both Pb and Zn are present predominantly as aqueous chloride complexes (mainly as PbCl 4 2− and ZnCl 4 2− , respectively); (2) the concentrations of metals complexed with short-chained aliphatic acid anions and reduced S species are minor; (3) organic acid anions are important in controlling the concentrations of metals because they affect the pH and buffer capacity of the waters at subsurface conditions; and (4) galena and sphalerite solubilities control the concentrations of Pb and Zn in these waters.

Applied Geochemistry↗

USGS1987

Isotope geochemistry of minerals and fluids from Newberry volcano, Oregon

Isotopic compositions were determined for hydrothermal quartz, calcite, and siderite from core samples of the Newberry 2 drill hole, Oregon. The ??15O values for these minerals decrease with increasing temperatures. The values indicate that these hydrothermal minerals precipitated in isotopic equilibrium with water currently present in the reservoirs. The ??18O values of quartz and calcite from the andesite and basalt flows (700-932 m) have isotopic values which require that the equilibrated water ??18O values increase slightly (- 11.3 to -9.2???) with increasing measured temperatures (150-265??C). The lithic tuffs and brecciated lava flows (300-700 m) contain widespread siderite. Calculated oxygen isotopic compositions of waters in equilibrium with siderite generally increase with increasing temperatures (76-100??C). The ??18O values of siderite probably result from precipitation in water produced by mixing various amounts of the deep hydrothermal water (- 10.5 ???) with meteoric water (- 15.5 ???) recharged within the caldera. The ??13C values of calcite and siderite decrease with increasing temperatures and show that these minerals precipitated in isotopic equilibrium with CO2 of about -8 ???. The ??18O values of weakly altered (<5% alteration of plagioclase) whole-rock samples decrease with increasing temperatures above 100??C, indicating that exchange between water and rock is kinetically controlled. The water/rock mass ratios decrease with decreasing temperatures. The ??18O values of rocks from the bottom of Newberry 2 show about 40% isotopic exchange with the reservoir water. The calculated ??18O and ??D values of bottom hole water determined from the fluid produced during the 20 hour flow test are -10.2 and -109???, respectively. The ??D value of the hydrothermal water indicates recharge from outside the caldera. ?? 1987.

Journal of Volcanology and Geothermal Research↗

USGS1986

Flow testing of the Newberry 2 research drillhole, Newberry volcano, Oregon

A 20 hour flow test of the Newberry 2 research drillhole at Newberry Volcano produced about 33,000 kilograms of fluid. The flow rate declined from about 0.8 kilograms per sec to less than 0.3 kilograms per sec during the course of the test. The mass ratio of liquid water to vapor was about 3:2 at the separator and stayed fairly constant throughout the test. The vapor phase was about half steam and half CO2 by weight. The average enthalpy of the steam/water mixture at the separator was about 1 ,200 kilojoules per kilogram. Because of the low flow rate and the large temperature gradient into the surrounding rocks, heat loss from the wellbore was high; a simple conductive model gives overall losses of about 1,200 kilojoules per kilogram of H2O produced. The actual heat loss may have been even higher due to convective effects, and it is likely that the fluid entering the bottom of the wellbore was largely or entirely steam and CO2. (Author 's abstract)

Water-Resources Investigations Report↗

USGS1984

Hydrogeochemistry of Big Soda Lake, Nevada: An alkaline meromictic desert lake

Big Soda Lake, located near Fallon, Nevada, occupies an explosion crater rimmed by basaltic debris; volcanic activity apparently ceased within the last 10,000 years. This lake has been selected for a detailed multidisciplinary study that will ultimately cover the organic and inorganic hydrogeochemistry of water and sediments because the time at which chemical stratification was initiated is known (~1920) and chemical analyses are available for a period of more than 100 years. Detailed chemical analyses of the waters show that the lake is at present alkaline ( pH = 9.7 "> pH = 9.7 ), chemically stratified (meromictic) and is extremely anoxic (total reduced sulfur—410 mg/L as H 2 S) below a depth of about 35 m. The average concentrations (in mg/L) of Na, K, Mg, Ca, NH 3 , H 2 S, alkalinity (as HCO 3 ), Cl, SO 4 , and dissolved organics (as C) in waters of the upper layer (depth 0 to 32 m) are 8,100, 320, 150, 5.0, < 0.1 "> < 0.1 , < 0.5 "> < 0.5 , 4,100, 7,100, 5,800, and 20 respectively; in the deeper layer (depth 37 to 64 m) they are 27,000, 1,200, 5.6, 0.8, 45, 410, 24,000, 27,500, 6,800, and 60, respectively. Chemical and stable isotope analyses of the waters, δ 13 C "> δ13C and Δ 14 C "> Δ14C values of dissolved total carbonate from this lake and surface and ground waters in the area together with mineral-water equilibrium computations indicate that the waters in the lake are primarily meteoric in origin with the present chemical composition resulting from the following geochemical processes: 1. (1) evaporation and exchange with atmosphere, the dominant processes, 2. (2) mineral-water interactions, including dissolution, precipitation and ion exchange, 3. (3) inflow and outflow of ground water and 4. (4) biological activity of macro- and microorganisms, including sulfate reduction in the water column of the deeper layer at a very high rate of 6.6 μmol L −1 day −1 .

Geochimica et Cosmochimica Acta↗

USGS1983

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

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 δ 13 C values of CO 2 , CH 4 , and total acetate show a reasonably constant fractionation factor of about 20 permil between CO 2 and CH 4 at 300°C. The δ 13 C values of CO 2 and CH 4 are initially low and become higher as decarboxylation increases.

Geochimica et Cosmochimica Acta↗

USGS1980

Stable carbon isotopes of HCO3- in oil-field waters-implications for the origin of CO2

The δ 13 C values of dissolved HCO 3 − in 75 water samples from 15 oil and gas fields (San Joaquin Valley, Calif., and the Houston-Galveston and Corpus Christi areas of Texas) were determined to study the sources of CO 2 of the dissolved species and carbonate cements that modify the porosity and permeability of many petroleum reservoir rocks. The reservoir rocks are sandstones which range in age from Eocene through Miocene. The δ 13 C values of total HCO 3 − indicate that the carbon in the dissolved carbonate species and carbonate cements is mainly of organic origin. The range of δ 13 C values for the HCO 3 − of these waters is −20–28 per mil relative to PDB. This wide range of δ 13 C values is explained by three mechanisms. Microbiological degradation of organic matter appears to be the dominant process controlling the extremely low and high δ 13 C values of HCO 3 − in the shallow production zones where the subsurface temperatures are less than 80°C. The extremely low δ 13 C values (< −10 per mil) are obtained in waters where concentrations of SO 4 2− are more than 25 mg/l and probably result from the degradation of organic acid anions by sulfate-reducing bacteria ( SO 4 2− + CH 3 COO − → 2 HCO 3 − + HS − ). The high δ 13 C values probably result from the degradation of these anions by methanogenic bacteria ( CH 3 COO − + H 2 O ai HCO 3 − + CH 4 ). Thermal decarboxylation of short-chain aliphatic acid anions (principally acetate) to produce CO 2 and CH 4 is probably the major source of CO 2 for production zones with subsurface temperatures greater than 80°C. The δ 13 C values of HCO 3 − for waters from zones with temperatures greater than 100°C result from isotopic equilibration between CO 2 and CH 4 . At these high temperatures, δ 13 C values of HCO 3 − decrease with increasing temperatures and decreasing concentrations of these acid anions.

Geochimica et Cosmochimica Acta↗