Geology topics

D.C. Thorstenson

Publications and source records attributed to D.C. Thorstenson.

8 recordsLinked to original sources

USGS2010

Gas transport in unsaturated porous media: The adequacy of Fick's law

The increasing use of natural unsaturated zones as repositories for landfills and disposal sites for hazardous wastes (chemical and radioactive) requires a greater understanding of transport processes in the unsaturated zone. For volatile constituents an important potential transport mechanism is gaseous diffusion. Diffusion, however, cannot be treated as an independent isolated transport mechanism. A complete understanding of multicomponent gas transport in porous media (unsaturated zones) requires a knowledge of Knudsen transport, the molecular and nonequimolar components of diffusive flux, and viscous (pressure driven) flux. The constitutive equations relating these flux components are available from the “dusty gas” model of Mason et al. (1967). This review presents a brief discussion of the underlying principles and interrelationships among each of the above flux mechanisms. Some aspects of these transport mechanisms are, to our knowledge, generally unrecognized in the Earth science literature. The principles underlying the transport mechanisms are illustrated with binary systems; the constitutive equations are then cast in forms thought to be most useful for the study of natural unsaturated zones. The viscous and diffusive fluxes are coupled in the constitutive equations through the Knudsen diffusivities; a knowledge of Knudsen diffusivities is necessary to calculate the viscous component of flux and pressure gradients. The Knudsen diffusivities can be calculated from measurements of the Klinkenberg effect. Two examples are presented showing that in natural systems, very small pressure gradients (1 Pa/m or less) can produce viscous fluxes greater than or equal to diffusive fluxes and that, conversely, pressure gradients of this magnitude can be generated by diffusive processes. The example calculations show that major concentration gradients can be developed for stagnant (zero flux, nonreactive) gases. A method is presented for approximating the viscous and diffusive flux components of gases in a multicomponent system from a knowledge of the concentration profiles of stagnant gases. In subsoil environments, argon and nitrogen are considered to be stagnant gases. Fick's laws are essentially, by definition, inadequate to deal with stagnant gases. In the examples presented, the error associated with estimating the total fluxes of nonstagnant gases by Fick's law, relative to stationary coordinates, ranges from a few percent to orders of magnitude.

Reviews of Geophysics↗

USGS1998

Flow and geochemistry along shallow ground-water flowpaths in an agricultural area in southeastern Wisconsin

Water-quality and geohydrologic data were collected from 19 monitor wells and a stream in an agricultural area in southeastern Wisconsin. These sites were located along a 2,700-ft transect from a local ground-water high to the stream. The transect is approximately parallel to the horizontal direction of ground-water flow at the water table. Most of the wells were installed in unconsolidated deposits at five locations along the transect and include an upgradient well nest, a midgradient well nest, a downgradient well nest, wells in the lowland area near the stream, and wells installed in the stream bottom. The data collected from this study site were used to describe the water quality and geohydrology of the area and to explain and model the variations in water chemistry along selected ground-water flowpaths. Water samples from most wells and the stream were analyzed for major ions, nutrients, pesticides, dissolved organic carbon, aluminum, tritium, CFCs, 15N, 18O, and dissolved gases. Measurements of temperature, pH, specific conductance, and dissolved oxygen were made in the field. Concentrations of all dissolved constituents were below Wisconsin ground-water quality enforcement standards. The concentrations of both nitrate and ammonium in precipitation concentrated by evapotranspiration are roughly equal to the concentrations of either in the shallow ground waters. The nitrogen and oxygen isotope data, however, indicate that soil ammonium, ammonium fertilizer, and animal waste are possible nitrate sources. Concentrated precipitation can also supply dissolved sulfate to the shallow ground waters and may be a principal source of pesticides to the ground water. However, some input of dissolved chloride to the ground water from mineral or anthropogenic sources is necessary. X-ray diffraction analyses of samples from 2 cores show the most abundant mineral to be dolomite, with subordinate quartz, microclme, and plagioclase, and minor amounts of mica, hornblende, and chlorite. Hydraulic conductivities determined from slug tests at selected wells range from 0.006 to 55 feet per day, with most values between 0.4 and 12 feet per day. A cross-sectional ground-water flow model, representing the water-table flow system, was developed for the site and was used to identify possible ground-water flowpaths for geocli^mical modeling. The model was calibrated against measured water levels and was most sensitive to variation in recharge and hydraulic conductivity. The calibrated model shows that downward flow from shallow to deeper wells within a nest may occur at the upgradient and midgradient well nests, but that flow from each well nest travels beneath downgradient nests to the stream. Pathline and travel-time analysis performed on the calibrated flow-model output yielded travel times to well screens that range from 5.8 to 59 years with a recharge of 4 inches per yr. Recharge dates based on tritium and CFC concentrations range from pre-1955 to 1986 and are consistent with flowpaths1 and travel times in the calibrated flow model. Changes in water quality along ground-water flowpaths were evaluated using the geochemical model PHREEQC. Geochemical mole balance models of shallow ground-water formation show that the principal reaction, by an order of magnitude, is dissolution of dolomite with CO2 . Concentration factors in the mole-balance models range from 1 to 11, with most values between 5 and 10, which provides independent support for the concentration factor of 8 based on recharge estimates used in the flow model. Ground water recharging at mid- and downgradient wells is oxic and contains dissolved nitrate, whereas the ground water discharging to the stream is anoxic and contains dissolved ammonium. Redox environments were defined at each well on the basis of relative concentrations of various dissolved redox-active species. Chemically permissible flowpaths inferred from the observed sequence of redox environments at well sites are consistent with flowpaths in the ground-water flow model. The transition from nitrate in recharging ground water to ammonium in ground water discharging to the stream suggests the possibility of nitrate reduction along the flowpath. None of the techniques employed in this study, however, were able to prove the occurrence of this reaction.

Michigan, Wisconsin↗

USGS1996

Factors affecting tritium and 14carbon distributions in the unsaturated zone near the low-level radioactive-waste burial site south of Beatty, Nevada

Interpretations of the distributions of tritiated water vapor (HTO V ) and 14 carbon dioxide gas ( 14 CO 2 ) concentrations in the unsaturated zone adjacent to the low-level radioactive-waste burial site south of Beatty, Nevada, suggest that observed concentrations of 14 CO 2 could be explained by either diffusive or advective transport of the radioactive gas from the site. The distribution of HTO V cannot be explained by vapor transport, either by diffusive or advective mechanisms. Thus, liquid transport appears to have played a role in moving HTO V to well UZB-2. Although the process by which this occurred cannot be determined from available data (and indeed may never be known), it is likely that liquid wastes disposed directly into the trenches during the period from 1962 to 1975 contributed to the offsite contamination. Liquid transport may have been enhanced by precipitation and runoff into open trenches that resulted in the occasional accumulation of ponded water in the trenches and flow along preferential pathways in the underlying unsaturated zone

Nevada↗

USGS1993

Carbon isotopic data from test hole USW UZ-1, Yucca Mountain, Nevada

Rock-CO2-gas analyses in test hole USW UZ-1 at Yucca Mountain indicate that gas movement in the unsaturated zone is likely through a dry-fracture system with little porewater or caliche-calcite interaction. This is because near-surface ??13C values are of biogenic origin and have changed little throughout the total depth. Post-bomb 14C activity is observed to the depth of about 12 m. An abrupt change in plotted 14C/depth slope is seen at 61 m. The less steep upper segment corresponds to the zone with greater porosity and moisture content, and consequently more tortuosity, with an estimated traveltime of 1.27 cm/yr; the steeper sloped zone corresponding to the lower segment has smaller porosity and moisture content but larger fracture density for gas transport, with an estimated traveltime of 3.26 cm/yr.

Conference Paper↗

USGS1992

Consumption of atmospheric methane by desert soils

Atmospheric concentrations of methane, a greenhouse gas, are increasing at a rate of about 1% yr -1 (refs 1–4). Oxidation by methylotrophic bacteria in soil is the largest terrestrial sink for atmospheric CH 4 , and is estimated to consume about 30 x 10 12 g CH 4 yr -1 (refs 4–6). Spatial and temporal variability in the rate of soil CH 4 consumption are incompletely understood 6–19 , as are the apparent inhibitory 12,13,18 or enhancing 20 effects of changes in land use. Dry deserts, which constitute 20% of total land surface, are not currently included in global soil uptake estimates. Here we describe measurements of the rate of uptake of atmospheric CH 4 by undisturbed desert soils. We observed rates as great as 4.38 mg CH 4 m -2 day -1 ; 50% of the measured rates were between 0.24 and 0.92 mg CH 4 m -2 d -1 . Uptake of CH 4 by desert soil is enhanced by rainfall after an initial soil-drainage period—opposite to the response of temperate forest soils 12 . Methane is consumed to a depth of about 2 m, allowing for deep removal of atmospheric CH 4 if near-surface conditions are unfavourable for consumption. On the basis of an annual average CH 4 consumption rate of 0.66 mg CH 4 m -2 d -1 , we estimate that the global CH 4 sink term needs to be increased by about 7 x 10 12 g yr -1 to account for the contribution of desert soils.

Nevada↗

USGS1984

The concept of electron activity and its relation to redox potentials in aqueous geochemical systems

The definition of a formal thermodynamic activity of electrons in redox reactions appears in the literature of the 1920's. The concept of pe as -log (electron activity) was introduced by Jorgensen in 1945 and popularized in the geochemical literature by Sillen, who considered pe and pH as master variables in geochemical reactions. The physical significance of the concept of electron activity was challenged as early as 1928. However, only in the last two decades have sufficient thermodynamic data become available to examine this question quantitatively. The chemical nature of hydrated electrons differs greatly from that of hydrated protons, and thermodynamic data show that hydrated electrons cannot exist at physically meaningful equilibrium concentrations under natural conditions. This has important consequences for the understanding of redox processes in natural waters. These are: (1) the analogy between pe and pH as master variables is generally carried much further than is justified; (2) a thermodynamically meaningful value of redox potential cannot be assigned to disequilibrium systems; (3) the most useful approach to the study of redox characteristics is the analysis and study of multiple redox couples in the system; and (4) for all practical purposes, thermodynamically defined redox potentials do not exist (and thus cannot be measured) in natural waters. The overall implication for natural systems is that, in terms of redox reactions, each case must be considered on an individual and detailed basis. Field studies would appear to be a mandatory part of any site-specific study; conclusions regarding redox processes cannot be based solely on electrode measurements or thermodynamic stability calculations. (USGS)

Open-File Report↗

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.

Geochimica et Cosmochimica Acta↗

USGS1982

Organic geochemistry and pore water chemistry of sediments from Mangrove Lake, Bermuda

Mangrove Lake, Bermuda, is a small coastal, brackish-water lake that has accumulated 14 m of banded, gelatinous, sapropelic sediments in less than 10 4 yr. Stratigraphic evidence indicates that Mangrove Lake's sedimentary environment has undergone three major depositional changes (peat, freshwater gel, brackish-water gel) as a result of sea level changes. The deposits were examined geochemically in an effort to delineate sedimentological and diagenetic changes. Gas and pore water studies include measurements of sulfides, ammonia, methane, nitrogen gas, calcium, magnesium, chloride, alkalinity, and pH. Results indicate that sulfate reduction is complete, and some evidence is presented for bacterial denitrification and metal sulfide precipitation. The organic-rich sapropel is predominantly algal in origin, composed mostly of carbohydrates and insoluble macromolecular organic matter called humin with minor amounts of proteins, lipids, and humic acids. Carbohydrates and proteins undergo hydrolysis with depth in the marine sapropel but tend to be preserved in the freshwater sapropel. The humin, which has a predominantly aliphatic structure, increases linearly with depth and composes the greatest fraction of the organic matter. Humic acids are minor components and are more like polysaccharides than typical marine humic acids. Fatty acid distributions reveal that the lipids are of an algal and/or terrestrial plant source. Normal alkanes with a total concentration of 75 ppm exhibit two distribution maxima. One is centered about n -C 22 with no odd/even predominance, suggestive of a degraded algal source. The other is centered at n -C 31 with a distinct odd/even predominance indicative of a vascular plant origin. Stratigraphic changes in the sediment correlate to observed changes in the gas and pore water chemistry and the organic geochemistry.

Mangrove Lake↗