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Results for “Geochimica et Cosmochimica Acta”

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At least 199 records · Page 11Linked to original sources
USGS1983

An interpretation of carbon and sulfur relationships in Black Sea sediments as indicators of environments of deposition

Syngenetic iron sulfides in sediments are formed from dissolved sulfide resulting from sulfate reduction and catabolism of organic matter by anaerobic bacteria. It has been shown that in recent marine sediments deposited below oxygenated waters there is a constant relationship between reduced sulfur and organic carbon which is generally independent of the environment of deposition. Reexamination of data from recent sediments from euxinic marine environments ( e.g. , the Black Sea) also shows a linear relationship between carbon and sulfur, but the slope is variable and the line intercepts the S axis at a value between 1 and 2 percent S. It is proposed that the positive S intercept is due to watercolumn microbial reduction of sulfate using metabolizable small organic molecules and the sulfide formed is precipitated and accumulates at the sediment-water interface. The variation in slope and intercept of the C to S plots for several cores and for different stratigraphic zones for the Black Sea can be interpreted in relation to thickness of the aqueous sulfide layer or thinness of the oxygen containing layer and to deposition rate, but also may be influenced by availability of iron, and perhaps the type of organic matter (Leventhal, 1979).

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USGS1983

A note on the chemistry of seawater in the range 350°-500°C

The chemistry of seawater at conditions of 350° to 500°C, 220 to 1000 bars (22 to 100 MPa) is controlled by reactions involving magnesium hydroxide sulfate (MHSH) and anhydrite. During progressive heating from 350° to 500°C at 1000 bars (100 MPa), MHSH with a ratio of 1.25 is formed via precipitation from solution and via reaction of solution with pre-existing anhydrite. During adiabatic expansion the MHSH extracts additional SO 4 from seawater and converts to a stoichiometry in which . These reactions control and greatly change the concentrations of Ca, Mg, SO 4 in solution and produce significant ionizable hydrogen, attaining 11.7 mmoles kg −1 at maximum conditions.

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USGS1983

Development of reaction models for ground-water systems

Methods are described for developing geochemical reaction models from the observed chemical compositions of ground water along a hydrologic flow path. The roles of thermodynamic speciation programs, mass balance calculations, and reaction-path simulations in developing and testing reaction models are contrasted. Electron transfer is included in the mass balance equations to properly account for redox reactions in ground water. The mass balance calculations determine net mass transfer models which must be checked against the thermodynamic calculations of speciation and reaction-path programs. Although reaction-path simulations of ground-water chemistry are thermodynamically valid, they must be checked against the net mass transfer defined by the mass balance calculations. An example is given testing multiple reaction hypotheses along a flow path in the Floridan aquifer where several reaction models are eliminated. Use of carbon and sulfur isotopic data with mass balance calculations indicates a net reaction of incongruent dissolution of dolomite (dolomite dissolution with calcite precipitation) driven irreversibly by gypsum dissolution, accompanied by minor sulfate reduction, ferric hydroxide dissolution, and pyrite precipitation in central Florida. Along the flow path, the aquifer appears to be open to CO 2 initially, and open to organic carbon at more distant points down gradient.

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USGS1983

Selective concentration of cesium in analcime during hydrothermal alteration, Yellowstone National Park, Wyoming

Chemical and mineralogical studies of fresh and hydrothermally altered rhyolitic material in Upper and Lower Geyser Basins, Yellowstone National Park, show that all the altered rocks are enriched in Cs and that Cs is selectively concentrated in analcime. The Cs content of unaltered rhyolite lava flows, including those from which the altered sediments are derived, ranges from 2.5 to 7.6 ppm. The Cs content of analcime-bearing altered sedimentary rocks is as high as 3000 ppm, and in clinoptilolite-bearing altered sedimentary rocks Cs content is as high as 180 ppm. Altered rhyolite lava flows which were initially vitrophyres, now contain up to 250 ppm Cs, and those which were crystallized prior to hydrothermal alteration contain up to 14 ppm. Mineral concentrates of analcime contain as much as 4700 ppm Cs. The Cs must have been incorporated into the analcime structure during crystallization, rather than by later cation substitution, because analcime does not readily exchange Cs. The Cs Cl "> CsCl of the fluids circulating through the hydrothermal system varies, suggesting that Cs is not always a conservative ion and that Cs is lost from upflowing thermal waters due to water-rock interaction resulting in crystallization of Cs-bearing analcime. The source of Cs for Cs enrichment of the altered rocks is from leaching of rhyolitic rocks underlying the geyser basins, and from the top of the silicic magma chamber that underlies the area. Analcime is an important natural Cs sink, and the high Cs concentrations reported here may prove to be an important indicator of the environment of analcime crystallization.

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USGS1983

Phase relations in the system NaCl-KCl-H 2 O II: Differential thermal analysis of the halite liquidus in the NaCl-H 2 O binary above 450°c

Thermal analysis of the halite liquidus in the system NaCl-H 2 O has been conducted for NaCl mole fractions ( X NaCl ) greater than 0.25 ( i.e. , > 50 wt. % NaCl) at pressures between 0.3 and 4.1 kb and temperatures greater than 450&deg;C. The position of the liquidus was located by differential thermal analysis (DTA) of cooling scans only, as heating scans did not produce definitive DTA peaks. The dP/dT slope of the liquidus is positive and steep at high pressures, but at high X NaCl , and pressures below 0.5 kb it appears to reverse slope and intersects the three-phase curve (liquid-halite-vapour) at a shallow angle. However, due to the complex nature of the DTA signal when P <- 0.5 kb, there is considerable doubt about exactly what event has been recorded in the experiments conducted at these low pressures. The solubility of halite can be expressed as a function of the mole-fractional-based activity of NaCl in the liquid phase ( L ) in temperature (T, &deg;K) and pressure (P, bars) In Our liquidus data (based on 10 compositions) above 500 bars for these brines were combined with this equation to generate activity coefficients of NaCl which were fit within their experimental uncertainties to the following one parameter Margules equation In . Concentrated solutions of NaCl show negative deviations from ideality which rapidly increase in magnitude with decreasing X NaCl .

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USGS1983

The contribution of humic substances to the acidity of colored natural waters

An operationally defined carboxyl content of humic substances extracted from rivers, streams, lakes, wetlands, and groundwaters throughout the United States and Canada is reported. Despite the diversity of the samples, only small variations were observed in this humic carboxyl content. The dissociation behavior of two combined fulvic/humic acid extracts was studied and it was found that the dissociation of the humics varied in a predictable manner with pH. Using a carboxyl content of 10 μeq/ mg humic organic carbon, and mass action quotient calculated from sample pH, the ionic balances of three highly colored Nova Scotia rivers were estimated.

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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.

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USGS1983

Chemical reactions accompanying fluid flow through granite held in a temperature gradient

Distilled water was passed at a low rate down a temperature gradient through cylinders of Barre and Westerly Granite. Temperatures ranged from 80–100°C at the outer edges of the cylinders to 250–300°C in central, drilled holes which housed the heating coils. The measured permeabilities of the granite cylinders decreased by as much as two orders of magnitude in experiments of 1–3 weeks' duration. The amount of permeability decrease varied directly with temperature and inversely with the rate of fluid flow. The compositions of the fluids discharged from the granites were functions of temperature and flow rate as well as mineral composition, with dissolved silica concentrations showing trends different from those of the other analyzed species. Fluids from experiments run at higher temperatures but at much lower initial rates of fluid flow had higher concentrations of most ions but substantially lower dissolved silica contents. In contrast, an increase in temperature at similar rates of fluid flow resulted in higher silica concentrations. In the experiments, the distilled water acquired enough dissolved materials at high temperatures to become supersaturated with respect to several minerals at the low-temperature edges of the cylinders. Some of this material, particularly silica, was deposited along grain boundaries and microfractures, causing the observed permeability decreases. The very low rates of fluid flow in some high-temperature experiments significantly increased the rates of SiO 2 precipitation and reduced dissolved silica concentrations relative to other species in the discharged fluids.

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USGS1983

Sterane distribution of solid bitumen pyrolyzates. Changes with biodegradation of crude oil in the Ouachita Mountains, Oklahoma

Solid bitumens (grahamite and impsonite) of southeastern Oklahoma have been shown to originate from near-surface alteration of crude oil ( Curiale , 1981; Curiale and Harrison , 1981). Pyrolysis of these solids has been employed to compare the sterane distribution of geographically proximate oils to that of the bitumens. The ratio of rearranged to regular steranes is higher in the pyrolyzates than in the oils, a finding consistent with a bitumen origin due to biodegradation of oil. The remaining presence of steranes, particularly regular steranes, in the bitumens suggests that sterane occlusion may have occurred prior to or during the alteration process, thus removing tetracyclic compounds from the influence of microbial attack. These data suggest that pyrolysis- GC MS "> GCMS offers a viable approach to correlation problems involving solid bitumens.

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USGS1983

A method of calculating quartz solubilities in aqueous sodium chloride solutions

The aqueous silica species that form when quartz dissolves in water or saline solutions are hydrated. Therefore, the amount of quartz that will dissolve at a given temperature is influenced by the prevailing activity of water. Using a standard state in which there are 1,000 g of water (55.51 moles) per 1,000 cm 3 of solution allows activity of water in a NaCl solution at high temperature to be closely approximated by the effective density of water, p e , in that solution, i.e. the product of the density of the NaCl solution times the weight fraction of water in the solution, corrected for the amount of water strongly bound to aqueous silica and Na + as water of hydration. Generally, the hydration of water correction is negligible. The solubility of quartz in pure water is well known over a large temperature-pressure range. An empirical formula expresses that solubility in terms of temperature and density of water and thus takes care of activity coefficient and pressure-effect terms. Solubilities of quartz in NaCl solutions can be calculated by using that equation and substituting p e , for the density of pure water. Calculated and experimentally determined quartz solubilities in NaCl solutions show excellent agreement when the experiments were carried out in non-reactive platinum, gold, or gold plus titanium containers. Reactive metal containers generally yield dissolved silica concentrations higher than calculated, probably because of the formation of metal chlorides plus NaOH and H 2 . In the absence of NaOH there appears to be no detectable silica complexing in NaCl solutions, and the variation in quartz solubility with NaCl concentration at constant temperature can be accounted for entirely by variations in the activity of water. The average hydration number per molecule of dissolved SiO 2 in liquid water and NaCl solutions decreases from about 2.4 at 200°C to about 2.1 at 350°C. This suggests that H 4 SiO 4 may be the dominant aqueous silica species at 350°C, but other polymeric forms become important at lower temperatures.

Geochimica et Cosmochimica Acta↗
USGS1983

The past is the key to the future

A new major frontier of geological research, which was initiated in the 1970's, involves predicting future geologic trends or events through study of the present and past, rather than trying to understand the past, often using what one knows about the present. Like most scientific frontiers, this one began from practical considerations—environmental concerns. The lack of formal recognition of this frontier results from fragmentation among many Federal agencies and highly focused mission-oriented programs ( e.g. , earthquake prediction, CO 2 , nuclear-energy safety, etc.). Most programs aim to predict only the next 50–100 years, but much longer periods of the past need to be studied to do this. Nuclear-waste disposal has sometimes been considered in terms of the next million years, a period of time permitting significant and broad geologic changes. Decreasing public interest in environmental concerns relegates many questions from the realm of applied research back to that of basic research. Most of these questions are so fascinating, however, that the frontier is still worth pursuing. Such questions include whether a phenomenon will or will not take place and the rates at which it can develop ( e.g. , how fast do rifts form, how fast can a caldera event begin, and how quickly can a glacial maximum arrive?). Common elements of all studies include the historic record, trends in the Quaternary, analogues in various periods of the geologic time scale, and allowance for phenomena never experienced before. Other examples of studies include the Cretaceous as a period of a climatic extreme, an especially interesting time period; establishing the amount of paleocloudiness, a particularly challenging and important research area; acid rain as a possible new phenomenon. Geochemistry has much to contribute to this frontier science.

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USGS1984

Complexation of trace metals by adsorbed natural organic matter

The adsorption behavior and solution speciation of Cu(II) and Cd(II) were studied in model systems containing colloidal alumina particles and dissolved natural organic matter. At equilibrium a significant fraction of the alumina surface was covered by adsorbed organic matter. Cu(II) was partitioned primarily between the surface-bound organic matter and dissolved Cu-organic complexes in the aqueous phase. Complexation of Cu2+ with the functional groups of adsorbed organic matter was stronger than complexation with uncovered alumina surface hydroxyls. It is shown that the complexation of Cu(II) by adsorbed organic matter can be described by an apparent stability constant approximately equal to the value found for solution phase equilibria. In contrast, Cd(II) adsorption was not significantly affected by the presence of organic matter at the surface, due to weak complex formation with the organic ligands. The results demonstrate that general models of trace element partitioning in natural waters must consider the presence of adsorbed organic matter.

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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 .

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USGS1984

Ferromanganese nodules from MANOP Sites H, S, and R-Control of mineralogical and chemical composition by multiple accretionary processes

The chemical composition of ferromanganese nodules from the three nodule-bearing MANOP sites in the Pacific can be accounted for in a qualitative way by variable contributions of distinct accretionary processes. These accretionary modes are: 1. (1) hydrogenous, i.e ., direct precipitation or accumulation of colloidal metal oxides in seawater, 2. (2) oxic diagenesis which refers to a variety of ferromanganese accretion processes occurring in oxic sediments; and 3. (3) suboxic diagenesis which results from reduction of Mn +4 by oxidation of organic matter in the sediments. Geochemical evidence suggests processes (1) and (2) occur at all three MANOP nodule-bearing sites, and process (3) occurs only at the hemipelagic site, H, which underlies the relatively productive waters of the eastern tropical Pacific. A normative model quantitatively accounts for the variability observed in nearly all elements. Zn and Na, however, are not well explained by the three end-member model, and we suggest that an additional accretionary process results in greater variability in the abundances of these elements. Variable contributions from the three accretionary processes result in distinct top-bottom compositional differences at the three sites. Nodule tops from H are enriched in Ni, Cu, and Zn, instead of the more typical enrichments of these elements in nodule bottoms. In addition, elemental correlations typical of most pelagic nodules are reversed at site H. The three accretionary processes result in distinct mineralogies. Hydrogenous precipitation produces δMnO 2 . Oxic diagenesis, however, produces Cu-Ni-rich todorokite, and suboxic diagenesis results in an unstable todorokite which transforms to a 7 Å phase (“birnessite”) upon dehydration. The presence of Cu and Ni as charge-balancing cations influence the stability of the todorokite structure. In the bottoms of H nodules, which accrete dominantly by suboxic diagenesis, Na + and possibly Mn +2 provide much of the charge balance for the todorokite structure. Limited growth rate data for H nodules suggest suboxic accretion is the fastest of the three processes, with rates at least 200 mm/10 6 yr. Oxic accretion is probably 10 times slower and hydrogenous 100 times slower. Since these rates predict more suboxic component in bulk nodules than is calculated by the normative analysis, we propose that suboxic accretion is a non-steady-state process. Variations in surface water productivity cause pulses of particulate flux to the sea floor which result in transient Mn reduction in the surface sediments and reprecipitation on nodule surfaces.

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USGS1984

Oxidation state of marine manganese nodules

Analyses of the bulk oxidation state of marine manganese nodules indicates that more than 98% of the Mn in deep ocean nodules is present as Mn(IV). The samples were collected from three quite different areas: the hemipelagic environment of the Guatemala Basin, the pelagic area of the North Pacific, and seamounts in the central Pacific. Results of the study suggest that todorokite in marine nodules is fully oxidized and has the following stoichiometry: (K, Na, Ca, Ba) .33 (Mg, Cu, Ni) .76 Mn 5 O 22 (H 2 O) 3.2 .

Geochimica et Cosmochimica Acta↗
USGS1984

Arsenic and antimony in geothermal waters of Yellowstone National Park, Wyoming, USA

A total of 268 thermal spring samples were analyzed for total soluble As using reduced molybdenum-blue; 27 of these samples were also analyzed for total Sb using flame atomic absorption spectrometry. At Yellowstone the Cl As "> ClAs atomic ratio is nearly constant among neutral-alkaline springs with Cl > 100 mg L −1 , and within restricted geographic areas, indicating no differential effects of adiabatic vs . conductive cooling on arsenic. The Cl As "> ClAs ratio increases with silica and decreases with decreasing Cl &#x3A3;CO 3 "> ClΣCO3 ; the latter relationship is best exemplified for springs along the extensively sampled SE-NW trend within the Lone Star-Upper-Midway Basin region. The relationship between Cl As "> ClAs and Cl &#x3A3;CO 3 "> ClΣCO3 at Yellowstone suggests a possible rock leaching rather than magmatic origin for much of the Park's total As flux. Condensed vapor springs are low in both As and Cl. Very high Cl As "> ClAs ratios ( > 1000) are associated exclusively with highly diluted (Cl < 100 mg L −1 ) mixed springs in the Norris and Shoshone Basins and in the Upper White Creek and Firehole Lake areas of Lower Basin. The high ratios are associated with acidity and/or oxygen and iron; they indicate precipitation of As following massive dilution of the Asbearing high-Cl parent water. Yellowstone Sb ranged from 0.009 at Mammoth to 0.166 mg L −1 at Joseph's Coat Spring. Within basins, the Cl Sb "> ClSb ratio increases as the Cl &#x3A3;CO 3 "> ClΣCO3 ratio decreases, in marked contrast to As. Mixed springs also have elevated Cl Sb "> ClSb ratios. White (1967) and Weissberg (1969) previously reported stibnite (Sb 2 S 3 ), but not orpiment (As 2 S 3 ), precipitating in the near surface zone of alkaline geothermal systems.

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