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Y.K. Kharaka

Publications and source records attributed to Y.K. Kharaka.

At least 19 recordsLinked to original sources
USGS2012

Geochemistry of water at Cajon Pass, California: Preliminary results

Samples of water and associated gases were collected from the Cajon Pass well using downhole samplers, and from the pipe stands at the completion of drill stem tests. The fluids were recovered from fracture systems in granitic rocks from two uncased test intervals located at 1,829 to 1,905 m and 1,829 to 2,115 m. Results of chemical analysis indicate major differences in the composition of water from different fracture systems. Water from one fracture system in the first test interval has a salinity of 2,150 mg/L dissolved solids and is relatively high in Cl, Ca and Fe, but low in HCO 3 and SO 4 ; water salinity from a second fracture system is only 950 mg/L and is dominated by Na, HCO 3 and SO 4 . Most of the water from the second interval likely originated from one fracture system; it is alkaline, low in HCO 3 , has a salinity of 1,150 mg/L, and is a NaSO 4 type water characteristic of pore water in the granitic rocks of the area. The differences in water composition indicate different evolutionary paths and isolation of water within relatively proximal fracture systems.

Geophysical Research Letters↗
USGS2012

Dissolved gases in the DOSECC Cajon Pass well: First year results

Fluid sampled from granitic rock near the 2 km depth in the DOSECC Cajon Pass well contained He, H 2 , CH 4 , C 2 H 6 , and C 2 H 4 in concentrations much greater than in air-saturated water. The dissolved helium, which ranged in concentration from 0.6 to 0.8 µmole/kg-fluid, was almost entirely radiogenic (³He/ 4 He = 0.06 Ra). The δ 13 C-CH 4 value (−36 per mil) and (C 2 H 6 + C 2 H 4 )/CH 4 ratios (0.02 - 0.05) indicate that the dissolved methane (50-55 µmoles/kg-fluid) was produced by thermogenic breakdown of organic matter. Measured pCO 2 values were very low, about 10 −5 atm., and the carbon isotopes (δ 13 C = −18.9 per mil) point to an organic source such as plant root respiration for the dissolved carbonate species. No evidence of mantle volatiles was found despite proximity of the well to the San Andreas fault.

Geophysical Research Letters↗
USGS2007

Subsurface monitoring of anthropogenic CO 2 injected in sedimentary basins: Results from the Frio-I brine test, Texas, USA

To investigate the potential for the long-term storage of CO 2 in deep saline aquifers, 1600 t of CO 2 were injected at 1500m depth into a 24-m-thick "C" sandstone of the Frio Formation near Houston, Texas. Fluid samples obtained before CO 2 injection from the injection well and an observation well 30m updip showed a Na-Ca-Cl type brine with ∼93,000 mg/L TDS at saturation with CH 4, but only 0.3% CO 2. Following CO 2 breakthrough, samples showed sharp drops in pH, pronounced increases in alkalinity and Fe, and significant shifts in the isotopic compositions of H 2O, and DIC. These parameters, together with perfluorocarbon tracer gases were used for monitoring migration of injected CO 2 into the overlying Frio "B", a 4-m-thick sandstone, separated from the "C" by ∼15m of shale and siltstone beds. Results from "B" 6 mo after injection show significant CO 2 (2.9% vs. 0.3% CO 2) migration into the "B" sandstone. Results of samples collected 15 mo after injection, however, show no indications of additional CO 2 in the "B" sandstone.

Conference Paper↗
USGS2006

Gas-water-rock interactions in sedimentary basins: CO2 sequestration in the Frio Formation, Texas, USA

To investigate the potential for the geologic storage of CO2 in saline sedimentary aquifers, 1600??ton of CO2 were injected at ???1500 m depth into a 24-m sandstone section of the Frio Formation - a regional reservoir in the US Gulf Coast. Fluid samples obtained from the injection and observation wells before, during and after CO2 injection show a Na-Ca-Cl type brine with 93,000??mg/L TDS and near saturation of CH4 at reservoir conditions. As injected CO2 gas reached the observation well, results showed sharp drops in pH (6.5 to 5.7), pronounced increases in alkalinity (100 to 3000??mg/L as HCO3) and Fe (30 to 1100??mg/L), and significant shifts in the isotopic compositions of H2O and DIC. Geochemical modeling indicates that brine pH would have dropped lower, but for buffering by dissolution of calcite and Fe oxyhydroxides. Post-injection results show the brine gradually returning to its pre-injection composition. ?? 2006 Elsevier B.V. All rights reserved.

Journal of Geochemical Exploration↗
USGS2005

Ferric iron in sediments as a novel CO2 mineral trap: CO 2-SO2 reaction with hematite

Thermodynamic simulations of reactions among SO2-bearing CO 2-dominated gas, water and mineral phases predict that Fe III in sediments should be converted almost entirely to dissolved FeII and siderite (FeCO3), and that SO2 should simultaneously be oxidized to dissolved sulfate. The reactions are however, subject to kinetic constraints which may result in deviation from equilibrium and the precipitation of other metastable mineral phases. To test the prediction, a laboratory experiment was carried out in a well stirred hydrothermal reactor at 150??C and 300 bar with hematite, 1.0 m NaCl, 0.5 m NaOH, SO2 in quantity sufficient to reduce much of the iron, and excess CO2. The experiment produced stable siderite and metastable pyrite and elemental S. Changes in total dissolved Fe are consistent with nucleation of pyrite at ???17 h, and nucleation of siderite at ???600 h. Dissolution features present on elemental S at the conclusion of the experiment suggest nucleation early in the experiment. The experiment did not reach equilibrium after ???1400 h, as indicated by coexistence of hematite with metastable pyrite and elemental sulfur. However, the results confirm that FeIII can be used to trap CO2 in siderite if partly oxidized S, as SO2, is present to reduce the Fe with CO2 in the gas phase. ?? 2005 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗
USGS2005

Ferric iron-bearing sediments as a mineral trap for CO2 sequestration: Iron reduction using sulfur-bearing waste gas

We present a novel method for geologic sequestration of anthropogenic CO2 in ferrous carbonate, using ferric iron present in widespread redbeds and other sediments. Iron can be reduced by SO2 that is commonly a component of flue gas produced by combustion of fossil fuel, or by adding SO2 or H2S derived from other industrial processes to the injected waste gas stream. Equilibrium and kinetically controlled geochemical simulations at 120 bar and 50 and 100 ??C with SO2 or H2S show that iron can be transformed almost entirely to siderite thereby trapping CO2, and simultaneously, that sulfur can be converted predominantly to dissolved sulfate. If there is an insufficient amount of sulfur-bearing gas relative to CO2 as for typical flue gas, then some of the iron is not reduced, and some of the CO2 is not sequestered. If there is an excess of sulfur-bearing gas, then complete iron reduction is ensured, and some of the iron precipitates as pyrite or other solid iron sulfide, depending on their relative precipitation kinetics. Gas mixtures with insufficient sulfur relative to CO2 can be used in sediments containing Ca, Mg, or other divalent metals capable of precipitating carbonate minerals. For quartz arenite with an initial porosity of 21% and containing 0.25 wt.% Fe2O3, approximately 0.7 g of CO2 is sequestered per kg of rock, and the porosity decrease is less than 0.03%. Sequestration of CO2 using ferric iron has the advantage of disposing of SO2 that may already be present in the combustion gas. ?? 2005 Published by Elsevier B.V.

Chemical Geology↗
USGS2003

Reclaiming agricultural drainage water with nanofiltration membranes: Imperial Valley, California, USA

We conducted pilot-scale field experiments using nanofiltration membranes to lower the salinity and remove Se, As and other toxic contaminants from saline agricultural wastewater in the Imperial Valley, California, USA. Farmlands in the desert climate (rainfall - 7.4 cm/a) of Imperial Valley cover -200,000 ha that are irrigated with water (-1.7 km 3 annually) imported from the Colorado River. The salinity (-850 mg/L) and concentration of Se (-2.5 μ g/L) in the Colorado River water are high and evapotranpiration further concentrates salts in irrigation drainage water, reaching salinities of 3,000-15,000 mg/L TDS and a median Se value of -30 μ g/L. Experiments were conducted with two commercially available nanofiltration membranes, using drainage water of varying composition, and with or without the addition of organic precipitation inhibitors. Results show that these membranes selectively remove more than 95% of Se, SO 4 , Mo, U and DOC, and -30% of As from this wastewater. Low percentages of Cl, NO 3 and HCO 3 , with enough cations to maintain electrical neutrality also were removed. The product water treated by these membranes comprised more than 90% of the wastewater tested. Results indicate that the treated product water from the Alamo River likely will have less than 0.2 μ g/L Se, salinity of 300-500 mg/L TDS and other chemical concentrations that meet the water quality criteria for irrigation and potable use. Because acceptability is a major issue for providing treated wastewater to urban centers, it may be prudent to use the reclaimed water for irrigation and creation of lower salinity wetlands near the Salton Sea; an equivalent volume of Colorado River water can then be diverted for the use of increasing populations of San Diego and other urban centers in southern California. Nanofiltration membranes yield greater reclaimed-water output and require lower pressure and less pretreatment, and therefore are generally more cost effective than traditional reverse osmosis membranes.

California↗
USGS2000

Large-scale hydrothermal fluid discharges in the Norris-Mammoth corridor, Yellowstone National Park, USA

Norris–Mammoth corridor is a complex subsidence structure that extends ∼40 km northward from the 0.6 Ma Yellowstone caldera, and contains many hydrothermal features with high fluid discharges totaling ∼1000 l/s. About 150–250 l/s of hydrothermal water, which attains boiling temperature at surface and 360°C at depth, discharge from the Norris Geyser Basin, adjacent to the caldera. The highest thermal water and gas discharges in the corridor are from Mammoth Hot Springs, where 500–600 l/s thermal water with surface temperatures of up to 73°C and calculated subsurface temperatures of ∼100°C issue from ∼100 hot springs scattered over a score of step-like travertine terraces that range in age from ∼0.4 Ma to recent. All the thermal water is meteoric, likely recharged in the Gallatin Range at 2.5–3.0 km elevations. The isotopic and chemical compositions of thermal waters and solutes can be interpreted to indicate a common magmatic source for heat and volatile solutes located near Norris. However, the chemical and isotopic compositions of gases, especially the 3 He/ 4 He ratios, provide strong evidence for a separate magmatic source for the Mammoth system.

Book↗
USGS1997

Mantle fluids in the San Andreas fault system, California

Fluids associated with the San Andreas and companion faults n central and south-central California have high 3He/4He ratios. The lack of correlation between helium isotopes and fluid chemistry or local geology requires that fluids enter the fault system from the mantle. Mantle fluids passing through the ductile lower crust must enter the brittle fault zone at or near lithostatic pressures; estimates of fluid flux based on helium isotopes suggest that they may thus contribute directly to fault-weakening high-fluid pressures at seismogenic depths.

Science↗
USGS1992

Hydrous pyrolysis of crude oil in gold-plated reactors

Crude oils from Iraq and California have been pyrolyzed under hydrous conditions at 200 and 300°C for time periods up to 210 days, in gold-plated reactors. Elemental (vanadium, nickel), stable isotopic (carbon), and molecular ( n -alkanes, acyclic isoprenoids, steranes, terpanes and aromatic steroid hydrocarbons) analyses were made on the original and pyrolyzed oils. Various conventional crude oil maturity parameters, including 20 S /(20 S + 20 R )-24-ethylcholestane ratios and the side-chain-length distribution of aliphatic and aromatic steroidal hydrocarbons, were measured in an effort to assess the modification of molecular maturity parameters in clay-free settings, similar to those encountered in “clean” reservoirs. Concentrations of vanadium and nickel in the Iraq oil decrease significantly and the V/(V + Ni) ratio decreases slightly, with increasing pyrolysis time/temperature. Whole oil carbon isotope ratios remain fairly constant during pyrolysis, as do hopane/sterane ratios and carbon number distribution of 5 α (H),14 α (H),17 α (H),20 R steranes. These latter three parameters are considered maturity-invariant. The ratios of short side-chain components to long side-chain components of the regular steranes [C 21 /(C 21 + C 29 R )] and the triaromatic steroid hydrocarbons [C 21 /(C 21 + C 28 )] vary systematically with increasing pyrolysis time, indicating that these parameters may be useful as molecular maturity parameters for crude oils in clay-free reservoir rocks. In addition, decreases in bisnorhopane/hopane ratio with increasing pyrolysis time, in a clay-free and kerogen-free environment, suggest that the distribution of these compounds is controlled by either differential thermal stabilities or preferential release from a higher-molecular weight portion of the oil.

Organic Geochemistry↗
USGS1992

Geochemical effects of deep-well injection of the Paradox Valley brine into Paleozoic carbonate rocks, Colorado, U.S.A.

Brine seepage into the Dolores River from ground water in Paradox Valley, Colorado constitutes a major source of salt to the Colorado River. Plants are enderway to remove this source of salt by drawing down the Paradox Valley brine (PVB) and forcibly injecting it into a deep disposal well (4.8 km). Experiments were conducted to determine the effects of deep-well injection of PVB. The results show that PVB is near saturation with anhydrite at 25°C, and that heating results in anhydrite precipitation. The amount and the rate at which anhydrite forms is temperature, pressure, and substrate dependent. Paradox Valley brine heated in the presence of Precambrian rocks from the drill core produces the same amount of anhydrite as PVB heated alone, but at a greatly accelerated rate. A 30% dilution of PVB with Dolores River water completely eliminates anhydrite precipitation when the fluid is heated with the Precambrian rocks. Interaction of PVB and Leadville Limestone is characterized by dolomitization of calcite by brine Mg which releases Ca to solution. This added Ca reacts with SO 4 to form increased amounts of anhydrite. A 20% dilution of PVB by Dolores River water has no effect on dolomitization and reduces the amount of anhydrite only slightly. A 65% dilution of PVB by Dolores River water still does not prevent dolomitization but does suppress anhydrite formation. Computer modeling of PVB by programs utilizing the Pitzer ion-interaction parameters is in general agreement with the experimental results. Ion-activity products calculated by both SOLMINEQ and PHRQPITZ are close to equilibrium with both anhydrite and dolomite whenever these phases are present experimentally, although the calculations over-estimate by a factor of 2 the degree of saturation. Some discrepancies in the calculated results between the two programs are due largely to differences in mineral solubility data.

Colorado↗
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↗
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, &lt; 0.1 "> < 0.1 , &lt; 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, &#x3B4; 13 C "> δ13C and &#x394; 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↗
USGS1976

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100–350° for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100°. Exchange rates were 3–5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O 18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O 18 exchange. At 350° kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O 18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor.

Geochimica et Cosmochimica Acta↗