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USGS1986

The origin of fluids in the salt beds of the Delaware Basin, New Mexico and Texas

Oxygen and hydrogen isotope analyses have been made of (1) brines from several wells in the salt deposits of the Delaware Basin, (2) inclusion fluids in halite crystals from the ERDA No. 9 site, and (3) local ground waters of meteoric origin. The isotopic compositions indicate that the brines are genetically related and that they probably originated from the evaporation of paleo-ocean waters. Although highly variable in solute contents, the brines have rather uniform isotopic compositions. The stable isotope compositions of brine from the ERDA No. 6 site (826.3 m depth) and fluid inclusions from the ERDA No. 9 site are variable but remarkably regular and show that (1) mixing with old or modern meteoric waters has occurred, the extent of mixing apparently decreasing with depth, and (2) water in the ERDA No. 6 brine may have originated from the dehydration of gypsum. Alternatively, the data may reflect simple evaporation of meteoric water on a previously dry marine flat. Stable isotope compositions of all the waters analyzed indicate that there has been fairly extensive mixing with ground water throughout the area, but that no significant circulation has occurred. The conclusions bear importantly on the suitability of these salt beds and others as repositories for nuclear waste.

New Mexico, Texas↗

USGS1986

Role of aquitards in hydrogeochemical systems: A synopsis

Aquitards exert significant influence on the hydrogeochemistry of aquifer systems. This influence is manifested somewhat differently depending on the relative position of aquitards within a system. In the deeper regimes, they are influential in the origin and distribution of brines and the development of geopressured zones. In intermediate regimes, they form multi-layered aquifer systems and provide a source of reactive minerals and exchangeable ions. In shallow regimes, aquitards can influence the topography and drainage patterns; this influences the relationship between the water table and the potentiometric surface of confined aquifers, controls the rates of infiltration and discharge, and controls whether the geochemical system is open or closed to exchange of carbon dioxide gas. In coastal areas, aquitards can determine the depth of the saltwater-freshwater interface, its distance from the shoreline, and the position of the mixing zone that causes geochemical alteration of minerals and development of porosity. ?? 1986.

Applied Geochemistry↗

USGS1986

Geochemical exploration for mineralized breccia pipes in northern Arizona, U.S.A.

Thousands of solution-collapse breccia pipe crop out in the canyons and on the plateaus of northern Arizona. Over 80 of these are known to contain U or Cu mineralized rock. The high-grade U ore associated with potentially economic concentrations of Ag, Pb, Zn, Cu, Co and Ni in some of these pipes has continued to stimulate mining and exploration activity in northern Arizona, despite periods of depressed U prices. Large expanses of northern Arizona are comprised of undissected high plateaus; recognition of pipes in these areas is particularly important because mining access to the plateaus is far better than to the canyons. The small size of the pipes, generally less than 600 ft (200 m) in diameter, and limited rock outcrop on the plateaus, compounds the recognition problem. Although the breccia pipes, which bottom in the Mississippian Redwall Limestone, are occasionally exposed on the plateaus as circular features, so are unmineralized near-surface collapse features that bottom in the Permian Kaibab and Toroweap Formations. The distinction between these two classes of circular features is critical during exploration for this unique type of U deposit.

Arizona↗

USGS1986

Uranium series disequilibrium in a young surficial uranium deposit, northeastern Washington, U.S.A.

A recently discovered ore-grade accumulation of U in organic-rich sediments of late Quaternary age provides an opportunity for studying the early association of U, U-daughters, and organic matter in a natural setting. The U occurs in valley-fill sediments of peat, peaty clay, silt, and sand along the north fork of Flodelle Creek, Stevens County, Washington. Radiometric techniques (delayed neutron, high-resolution gamma-ray spectrometry, thin-source alpha spectrometry) were employed to determine the abundance and distribution of U-series nuclides, the extent of secular equilibrium within the U decay series, and the apparent U-series ages of U incorporation. Sixteen lithologically distinct intervals were sampled from a 292 cm core. Uranium contents range from 140 to 2790 ppm and are positively correlated with organic contents. Measured alpha activity ratios of 234 U/ 238 U (1.31–1.38) are very similar to those reported in coexisting waters, suggesting a rather constant isotopic composition of introduced U. Much lower Th contents of <10–40 ppm are controlled by the type and abundance of silicate detritus. The youth of the host sediments (<15 000 a) and the paucity of associated radioactivity suggested large excesses of U relative to radioactive daughters and such excesses were observed, particularly in the shallowest intervals. Apparent ages of U emplacement determined by the (alpha) activity ratio of 230 Th daughter to 234 U parent show a general increase with depth and fair agreement with estimated depositional ages. This observation suggests dominantly syndepositional or early post depositional emplacement of U followed by decay-generated buildup of 230 Th daughter with time. However, interval by interval comparisons of the relative abundances of other daughters, particularly 226 Ra and 210 Pb, indicate variability caused by processes other than closed-system growth and decay, probably because chemically diverse daughters that are decay-generated in situ have differing mobilities and because upwelling ground water continuously adds more U and minor amounts of daughters. If 230 Th is considered the least susceptible to these modifications, the data suggest some addition of 234 U in the deepest intervals and some loss of 226 Ra and/or gain of 222 Rn throughout the studied core.

Washington↗

USGS1987

The relation of stream sediment surface area, grain size and composition to trace element chemistry

Intensive studies of 17 geographically and hydrologically diverse stream bed sediments provide information on the relation between grain size, surface area, and operationally defined geochemical phases (e.g. Mn oxides, amorphous Fe oxides) to trace element concentrations. Of the size fractions investigated (<2, <16, <63and<125 μm), the strongest correlation with trace elements occurs with the percent <63 μm or<125 μm fractions. As the proportion of these size fractions increases in the samples, so do the trace element concentrations. When surface area (as defined by nitrogen adsorption and the BET equations) increases, trace element levels also increase. Correlations between bulk sediment chemistry and surface area are as strong as those between sediment chemistry and the proportion of the <63or<125 μm fractions. Surface area appears to serve as a proxy for grain size. The strongest correlations between grain size and surface area are the same as for trace elements and grain size (with the <63or<125 μm fractions). Surface area also is affected by geochemical phase, as are the trace elements associated with sediments. Of the phases considered (carbonates, Mn oxides, reactive Fe, amorphous Fe, organic matter), amorphous Fe oxides appear to exert the greatest control over both surface area and trace element levels. The concentrations of various geochemical phases affect surface area, grain size, and trace element chemistry. However, the effect of phase is grain-size dependent. For material with mean grain sizes in the fine sand range and coarser (> 125 μm), each of the various phases contribute to overall sample surface area. For material having mean grain sizes in the very fine sand range and finer (<125 μm), the same phases act as surface-area inhibitors by cementing fine grains together to form aggregates. This increases the mean grain size of the sample and reduces the surface area. The presence of these aggregates may explain why the <63 μm or<125 μm size fractions are more important to sediment-trace element levels and surface area than other finer fractions.

Applied Geochemistry↗

USGS1987

Inter-laboratory comparison of X-ray fluorescence analyses of eruptive products of El Chichón Volcano, Chiapas, Mexico

An inter-laboratory comparison has been made of X-ray fluorescence analyses of 10 samples of lava and pumices from El Chichón Volcano, Chiapas, Mexico. Some determinations of major-element constituents agree within analytical uncertainty, whereas others exchibit significant bias. Analyses carried out at the Michigan Technological University (MTU) laboratory are systematically lower in MgO (26–48%), Fe total (5–18%), CaO (4–15%) and higher in K 2 O (0–15%) than analyses made at the U.S. Geological Survey (USGS) Denver laboratory. These differences are ascribed in part to a complex combination of calibration assumptionsand mineralogical and particle-size effects inherent in the use of pressed rock-powder pellets in the analytical procedure of the MTU laboratory. Other, but as yet unknown, differences in sample preparation and/or analytical technique may also be important; effects related to natural sample inhomogeneityare believed to be insignificant. The inter-laboratory differences in the analytical data complicated accurate assessment of whether El Chichón magmas have changed composition during the past 300 000 a. Knowledge of such change is needed for understanding petrogenetic history and for such related studies as evaluation of volcanic hazards.

Applied Geochemistry↗

USGS1988

The solubility of noble gases in crude oil at 25-100°C

The solubility of the noble gases He, Ne, Ar, Kr and Xe was measured in two typical crude oils at temperatures of 25–100°C. The oil samples were obtained from the Elk Hills oil field located in southern San Joaquin Valley, California. The experimental procedure consisted of placing a known amount of gas with a known volume of crude oil in a stainless steel hydrothermal pressure vessel. The vessel was housed inside an oven and the entire unit rotates providing continuous mixing. The amount of gas dissolved in oil at a measured temperature and partial pressure of gas was used to calculate the solubility constants for these gases. Results show that the solubility of He and Ne in both oils is approximately the same; solubility then increases with atomic mass, with the solubility of Xe at 25°C being two orders of magnitude higher than that of He. The gas solubilities are somewhat higher in the lower density (higher API gravity) oil. The solubility of Ar is approximately constant in the range of temperatures of this study. The solubilities of He and Ne increase, but those of Kr and Xe decrease with increasing temperatures. Solubilities of noble gases in crude oil are significantly higher than their solubilities in water. For example, the solubilities of He and Xe at 25°C in the light oil of this study are, respectively, 3 and 24 times higher than their solubilities in pure water, and they are 15 and 300 times higher than in a brine with a salinity of 350,000 mg/l dissolved solids. These large and variable differences in the solubilities of noble gases in oil and water indicate that, in sedimentary basins with oil, these gases must be partitioned between oil, water and natural gas before they are used to deduce the origin and residence time of these fluids.

Applied Geochemistry↗

USGS1988

A test of uranium-series dating of fossil tooth enamel: Results from Tournal Cave, France

A series of well preserved mammal bones and horse teeth was analyzed from archaeological levels of Tournal Cave (Magdalenian, Aurignacian, and Mousterain) to test the hypothesis that well-crystallized enamel behaves more as a closed system than does whole bone. The isotopic composition of bones and tooth enamels from this deposit meet criteria for confidence, and gave no reasons to suspect contamination or open-system behavior. Two samples for which 231 Pa could be analyzed showed internal concordance with the respective 230 Th ages. In spite of the favourable isotopic criteria, however, comparison of the U-series ages of the bones and the tooth enamel with stratigraphic position and 14 C control indicated the dates were not meaningful. In general, both bones and tooth enamels gave ages too young, although some were clearly too old. Neither group showed any systematic increase of age with stratigraphic depth. Tooth enamel, therefore, shows no advantage over bone for U-series dating for this site. In Tournal cave both bones and enamel are apparently open to U, which is probably cycling as a consequences of post-depositional groundwater movement.

Applied Geochemistry↗

USGS1988

Leaching characteristics of a high-calcium fly ash as a function of pH: A potential source of selenium toxicity

Using a modified extraction procedure, the effect of pH on the leaching of selected elements from Ca-rich (Type C) power plant fly ash was studied. Continuous additions of acetic acid were used to maintain pH values of fly ash slurries at 4.0, 6.0 and 8.0 for 24 h and an additional set was leached at its natural pH (average 11.8) value. Analyses for Se, As, Ca, Cd, Cr, Fe, Na and Pb showed that the highest concentrations occur in the leachate at pH 4.0 and decline with increasing pH. Concentrations of Cr and Fe increased slightly between neutral and high pH. Arsenic, Cd, Cr, Pb and Se concentrations exceeded the Environmental Protection Agency's toxicity criteria at pH 4.0. Selenium was above its toxicity level at pH values near 7 but the other elements were below their respective toxicity levels near neutral pH. Because recent studies show adverse effects of Se on aquatic life at far lower concentrations than the current Environmental Protection Agency's standard, high-Ca, power plant fly ashes represent a potentially hazardous pollutant to surface and subsurface waters.

Applied Geochemistry↗

USGS1988

The association of uranium with organic matter in Holocene peat: An experimental leaching study

Uraniferous peat was sampled from surface layers of a Holocene U deposit in northeastern Washington State. Dried, sized, and homogenized peat that contained5980 ±307 ppm U was subjected to a variety of leaching conditions to determine the nature and strength of U-organic bonding in recently accumulated organic matter. The results complement previous experimental studies of U uptake on peat and suggest some natural or anthropogenic disturbances that are favorable for remobilizing U. The fraction of U leached in 24 h experiments at 25°C ranged from 0 to 95%. The most effective leach solutions contained anions capable of forming stable dissolved complexes with uranyl (UO 2 +2 ) cation. These included H 2 SO 4 ( pH = 1.5) and concentrated (0.01M) solutions of sodium bicarbonate-carbonate ( pH = 7.0–10.0), or sodium pyrophosphate ( pH = 10). Effective leaching by carbonate and pyrophosphate in the absence of added oxidant, and the insignificant effect of added oxidant (as pressurized O 2 ) strongly suggest that U is initially fixed on organic matter as an oxidized U(VI) species. Uranium is more strongly bound than some other polyvalent cations, based on its resistance to exchange in the presence of large excesses of dissolved Ca 2+ and Cu 2+ . Measurements of the rate of U leaching indicate faster rates in acid solution compared to carbonate solution, and are consisten with simultaneous attack of sites with different affinities for U. Sulfuric acid appears a good choice for commercial extraction of U from mined peat. In situ disturbances such as overliming of peat soils, addition of fertilizers containing pyrophosphate, or incursions of natural carbonate-rich waters could produce significant remobilization of U, and possibly compromise the quality of local domestic water supplies.

Applied Geochemistry↗

USGS1988

Acid neutralizing processes in an alpine watershed front range, Colorado, U.S.A.-1: Buffering capacity of dissolved organic carbon in soil solutions

Soil interstitial waters in the Green Lakes Valley, Front Range, Colorado were studied to evaluate the capacity of the soil system to buffer acid deposition. In order to determine the contribution of humic substances to the buffering capacity of a given soil, dissolved organic carbon (DOC) and pH of the soil solutions were measured. The concentration of the organic anion, Ai − , derived from DOC at sample pH and the concentration of organic anion, Ax − at the equivalence point were calculated using car☐yl contents from isolated and purified humic material from soil solutions. Subtracting Ax − from Ai − yields the contribution of humic substances to the buffering capacity (A equiv. − ). Using this method, one can evaluate the relative contribution of inorganic and organic constituents to the acid neutralizing capacity (ANC) of the soil solutions. The relative contribution of organic acids to the overall ANC was found to be extremely important in the alpine wetland (52%) and the forest-tundra ecotone (40%), and somewhat less important in the alpine tundra sites (20%). A failure to recognize the importance of organic acids in soil solutions to the ANC will result in erroneous estimates of the buffering capacity in the alpine environment of the Front Range, Colorado.

Colorado↗

USGS1988

The role of mantle CO2 in volcanism

Carbon dioxide is the propellant gas in volcanic eruptions and is also found in mantle xenoliths. It is speculated that CO2 occurs as a free gas phase in the mantle because there is no reason to expect CO2 to be so universally associated with volcanic rocks unless the CO2 comes from the same source as the volcanic rocks and their xenoliths. If correct, the presence of a free gas in the mantle would lead to physical instability, with excess gas pressure providing the cause of both buoyancy of volcanic melts and seismicity in volcanic regions. Convection in the mantle and episodic volcanic eruptions are likely necessary consequences. This suggestion has considerable implications for those responsible for providing warnings of impending disasters resulting from volcanic eruptions and earthquakes in volcanic regions.

Applied Geochemistry↗

USGS1989

Uranium-series nuclides in the Golden fault, Colorado, U.S.A.: Dating latest fault displacement and measuring recent uptake of radionuclides by fault-zone materials

Concentrations and isotopic ratios of U, Th and Ra were measured in a fault zone near Golden, Colorado where major displacement occurred between about 190 and 615 ka. Faulting created new surfaces for leaching and provided the pathways for U-rich ground water. Uranium and 230 Th, the latter produced by the decay of dissolved 234 U, are adsorbed by fault gouge, hematite-stained sand and brecciated sand- and claystones. The observed U enrichment is as much as six times baseline value and the simultaneous enrichment of 230 Th is estimated at about ninefold relative to 238 U. The adsorption of radionuclides chemically analogous to Th, such as Pu (IV) and Np, and 237 Np decay products, on fault-zone materials would contribute to the immobilization of high-level radioactive waste in the vicinity of a repository in the event of leakage from engineered barriers into fractured rock-mass.

Colorado↗

USGS1989

Geochemical processes controlling selenium in ground water after mining, Powder River Basin, Wyoming, U.S.A.

Geochemical data for samples of overburden from three mines in the Powder River Basin indicate a statistically significant (0.01 confidence level) positive correlation ( r = 0.74) between Se and organic C. Results of factor analysis with varimax rotation on the major and trace element data from the rock samples indicate large (>50) varimax loadings for Se in two of the three factors. In Factor 1, the association of Se with constituents common to detrital grains indicates that water transporting the detrital particles into the Powder River Basin also carried dissolved Se. The large (>50) varimax loadings of Se and organic C in Factor 2 probably are due to the organic affinities characteristic of Se. Dissolved Se concentrations in water samples collected at one coal mine are directly related to the dissolved organic C concentrations. Hydrophilic acid concentrations in the water samples from the mine ranged from 35 to 43% of the total dissolved organic C, and hydrophobic acid concentrations ranged from 40 to 49% of the total dissolved organic C. The largest dissolved organic C concentrations in water from the same mine (34–302 mg/l), coupled with the large proportion of acidic components, may saturate adsorption sites on geothite and similar minerals that comprise the aquifer material, thus decreasing the extent of selenite (SeO 3 2− ) adsorption as a sink for Se as the redox state of ground water decreases.

Wyoming↗

USGS1990

Characterization of hydrocarbon gas within the stratigraphic interval of gas-hydrate stability on the North Slope of Alaska, U.S.A.

In the Kuparuk River Unit 2D-15 well, on the North Slope of Alaska, a 60 m-thick stratigraphic interval that lies within the theoretical pressure-temperature field of gas-hydrate stability is inferred to contain methane hydrates. This inference is based on interpretations from well logs: (1) release of methane during drilling, as indicated by the mud log, (2) an increase in acoustic velocity on the sonic log, and (3) an increase of electrical resistivity on the electric logs. Our objective was to determine the composition and source of the gas within the shallow gas-hydrate-bearing interval based on analyses of cutting gas. Headspace gas from canned drill cuttings collected from within the gas-hydrate-bearing interval of this well has an average methane to ethane plus propane [C 1 /(C 2 + C 3 )] ratio of about 7000 and an average methane δ 13 C value of −46% (relative to the PDB standard). These compositions are compared with those obtained at one well located to the north of 2D-15 along depositional strike and one down-dip well to the northeast. In the well located on depositional strike (Kuparuk River Unit 3K-9), gas compositions are similar to those found at 2D-15. At the down-dip well (Prudhoe Bay Unit R-1), the C 1 /(C 2 +C 3 ) ratios are lower (700) and the methane δ 13 C is heavier (−33%). We conclude that the methane within the stratigraphic interval of gas hydrate stability comes from two sources— in situ microbial gas and migrated thermogenic gas. The thermal component is greatest at Prudhoe Bay. Up-dip to the west, the thermogenic component decreases, and microbial gas assumes more importance.

Alaska↗

USGS1990

Deep-water hydrocarbon seeps in Guaymas Basin, Gulf of California

Acoustically discovered hydrocarbon seeps along a transform fault zone on the Sonoran margin of Guaymas Basin and in the Southern Trough of Guaymas Basin were examined and sampled during dives of DSV Alvin . Seepage of methane and heavier hydrocarbons occurs through shallow pockmarks along the eroding crest of a steep anticline, 1600 m below sea level. Extensive ledges of aragonite crop out around the rims of the pockmarks; isotopic analysis indicates that carbonate precipitation is a result of methane oxidation. Seepage zones within the pockmarks support dense communities of Calyptogena , half buried in the mud; tubeworms ( Lamellibracheae sp.) have colonized many of the aragonite outcrops. Though the margin site is only a few kilometers from a high-temperature sulfide-precipitating and petroleum-discharging vent system at a nearby center, its structural setting is more akin to pockmarks described from continental shelves, and its chemosynthetic fauna is more like that around low temperature seeps on other continental slopes and margins (e.g. Oregon, U.S.A., and Japan). The seep in the Southern Trough is a condensate-type petroleum (C 1 -C 40 ) and rises as a plume from a young vent-mound system about 2000 m below sea level.

Gulf of California↗

USGS1990

Organic matter in hydrothermal metal ores and hydrothermal fluids

Massive polymetallic sulfides are currently being deposited around active submarine hydrothermal vents associated with spreading centers. Chemoautolithotrophic bacteria are responsible for the high production of organic matter also associated with modern submarine hydrothermal activity. Thus, there is a significant potential for organic matter/metal interactions in these systems. We have studied modern and ancient hydrothermal metal ores and modern hydrothermal fluids in order to establish the amounts and origin of the organic matter associated with the metal ores. Twenty-six samples from modern and ancient hydrothermal systems were surveyed for their total organic C contents. Organic C values ranged from 0.01% to nearly 4.0% in these samples. Metal ores from modern and ancient sediment-covered hydrothermal systems had higher organic C values than those from modern and ancient hydrothermal systems lacking appreciable sedimentary cover. One massive pyrite sample from the Galapagos spreading center (3% organic C) had stable isotope values of −27.4% (δ 13 C) and 2.1% (δ 15 N), similar to those in benthic siphonophors from active vents and distinct from seep sea sedimentary organic matter. This result coupled with other analyses (e.g. 13 C NMR, pyrolysis/GC, SEM) of this and other samples suggests that much of the organic matter may originate from chemoautolithotrophic bacteria at the vents. However, the organic matter in hydrothermal metal ores from sediment covered vents probably arises from complex sedimentary organic matter by hydrothermal pyrolysis. The dissolved organic C concentrations of hydrothermal fluids from one site (Juan de Fuca Ridge) were found to be the same as that of background seawater. This result may indicate that dissolved organic C is effectively scavenged from hydrothermal fluids by biological activity or by co-precipitation with metal ores.

Applied Geochemistry↗

USGS1990

Thermal maturity of Jurassic shales from the Newark Basin, U.S.A.: Influence of hydrothermal fluids and implications to basin modeling

Organic geochemical investigations were conducted on a series of cores that systematically sampled the uppermost Jurassic strata from the northern Newark Basin. Each sedimentary unit consists of fluvial red sandstones and siltstones with cyclic deposits of interbedded black lacustrine shales and gray deltaic siltstones. In a suite of organic-rich shales from the Boonton, Towaco and Feltville Formations, organic maturation parameters were used to determine aspects of the thermal history of the Newark Basin. Comparisons of model calculations and measured maturities support 39 Ar/ 40 Ar-geochronometer studies that indicate a hydrothermal event occurred ∼175 Ma ago. An increase in the regional geothermal gradient to ∼7.5°C/100 m for ∼5 Ma best conforms to the organic geochemical observations. Biomarker compounds in Boonton and Towaco strata should have been relatively unaltered by this regional event, but anomalous molecular distributions in the organic-rich rocks may have resulted from localized heating by hydrothermal fluids. The effects of this interaction would be very subtle and may be indistinguishable from variations caused by differences in organic facies. Within this uncertainty, sterane and hopane isomerization and steroid aromatization reactions advanced in the Boonton and Towaco Formation strata primarily because of burial and normal geothermal heating that followed the hydrothermal event. Biomarker kinetic models indicate that ∼2400 m of Boonton and post-Boonton strata were eroded after basinal uplift commenced ∼50 Ma ago.

Applied Geochemistry↗