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Spatial variation in total element concentration in soil within the Northern Great Plains coal region and Regional soil chemistry in Bighorn and Wind River basins, Wyoming and Montana

PART A: To objectively determine the changes in chemical character of an area subjected to mining and reclamation, prior information is needed. This study represents a broadscale inventory of total chemical composition of the surficial materials of the Northern Great Plains coal region (western North and South Dakota, eastern Montana, and northeastern Wyoming); data are given for 41 elements in A and C soil horizons. An unbalanced, nested, analysis-of-variance design was used to quantify variation in total content of elements between glaciated and unglaciated terrains, for four increasingly smaller geographic scales, and to quantify variation due to sample preparation and analysis. From this statistical study, reliable maps on a regional basis (>100 km) were prepared for C, K, and Rb in A and C soil horizons; for N a, Si, Th, D, and Zn in A-horizon soil; and for As, Ca, Ge, and Mg in C-horizon soil. The distribution of variance components for the remaining 29 elements did not permit the construction of reliable maps. Therefore, a baseline value for each of these elements is given as a measure of the total element concentration in the soils of the Northern Great Plains coal region. The baseline is expressed as the 95-percent range in concentration to be expected in samples of natural soils. PART B: A reconnaissance study of total concentrations of 38 elements in samples of soils (0-40 cm deep, composite) from the Bighorn and Wind River Basins of Montana and Wyoming indicates that the geographic variation for most elements occurs locally (5 km or less). However, in the Bighorn Basin, Zn exhibits significant regional variation (between geologic units); and in the Wind River Basin, AI, Cr, K, Mn, Mo, Ni, U, and V exhibit similar variation. For the remaining elements, the lack of regional variation suggests that a single summary statistic can be used to estimate a baseline value that reflects the range in concentration to be expected in samples of soils in each basin. The concentrations of most of these elements in both basins are not much different from those measured independently in the Powder River Basin of Wyoming or in the Western United States. In addition, data from an analysis of variance provide an estimate of the number of random samples within an area of specified size (10 km square, approximately a township) that are needed to prepare a reliable map of total element concentration in soils for each of the elements in each of the basins.

Montana, North Dakota, Saskatchewan, South Dakota,↗

Mineralogy, mineral chemistry, and paragenesis of gold, silver, and base-metal ores of the North Amethyst vein system, San Juan Mountains, Mineral County, Colorado

Gold-rich adularia-sericite-type mineralization occurs near the southern margin of the San Luis caldera, at the intersection of the Equity fault and the northern extension of the Amethyst fault system. Mineralized rock is confined primarily to steeply dipping structures in silicified rhyolite and dacite. Intense sericitic alteration occurs at higher levels in the vein system, and wall rock adjacent to some veins is bleached. The ores are multiply brecciated, and vein filling locally shows sedimentary textures. Textural, mineralogical, and chemical criteria indicate that there are at least two partially coextensive associations of mineral assemblages separated by periods of brecciation and sedimentation. An older gold-bearing association consists of two fine-grained ore stages, both of which contain electrum, uytenbogaardtite, tetrahedrite, silver sulfosalts, silver sulfides and base-metal sulfides, and a manganese-rich stage containing the assemblages (1) manganese silicate + manganese carbonate minerals + quartz and (2) magnetite + hematite + pyrite + quartz. A younger crosscutting association contains calcite, adularia, fluorite, and quartz, plus the assemblages (1) coarse-grained basemetal sulfides and (2) hematite + chlorite + quartz. Quartz, manganese-rich calcite, and trace pyrite line late-stage vugs. Mineralogic, lead-isotopic, and fluid-inclusion characteristics of the younger association are similar to those of ores of the southern and central parts of the Creede mining district. In contrast, the gold and manganese-silicate assemblages of the older association are rare to absent in the southern and central parts of the district. The local and early occurrence of the manganese and gold assemblages may indicate that they formed in a small hydrothermal cell that predated the extensive hydrothermal system from which ores of the central and southern parts of the Creede district are proposed to have been deposited (Bethke, 1988). If similar early-stage cells were present in the southern and central parts of the district, they may have been replaced or overprinted by later assemblages, and they may remain to be discovered. In the latter case, mineral assemblages that formed at early stages in the paragenesis hold the most promise for gold exploration.

Colorado↗

Chemistry, mineralogy, and petrology of amphibole in Mount St. Helens 2004-2006 dacite

Textural, compositional, and mineralogical data are reported and interpreted for a large population of clinoamphibole phenocrysts in 22 samples from the seven successive dacite spines erupted at Mount St. Helens between October 2004 and January 2006. Despite the uniformity in bulk composition of magma erupted since 2004, there is striking textural and compositional diversity among amphibole phenocrysts and crystal fragments that have grown from, partly dissolved in, or been accidentally incorporated in the new dacite. This study demonstrates that magma erupted throughout the current dome-building episode is the end product of small-scale, thorough mixing of multiple generations of crystal-laden magma. The mixed amphibole population provides important clues to magma conditions within the dacite magma reservoir prior to ascent and, to some extent, the dynamics of mixing and ascent. The predominant amphibole in new dome rock ranges from moderate- to high-alumina tschermakite and magnesiohastingsite compositions. As substantiated by major- and trace-element geochemistry and barometry calculations, this compositional range of crystals, along with plagioclase, orthopyroxene, and iron-titanium oxide, is likely to have precipitated from dacite magma over a range of pressures and temperatures consistent with experimentally determined phase relations (~900&deg;C to ~800&deg;C between 100 MPa and ~350-400 MPa or ~4-km and 13.5-15-km depth). Along with traceelement characteristics, textural and compositional data help to distinguish some low-alumina magnesiohornblende crystals as xenocrysts. The diverse range in composition of amphibole in all samples of 2004-6 dacite, and the complex zonation observed in many phenocrysts, suggests a well-mixed source magma with components that are subjected to repeated heating and (or) pressurization within this pressure-temperature window. Amphibole textural and compositional diversity suggest dynamic conditions in the upper-reservoir zone, which has been tapped steadily during ~2 years of continuous and monotonous eruption. This well-mixed crystal mush is likely to have been subjected to repeated injection of hotter magma into cooler crystal-laden magma while simultaneously assimilating earlier generations of dacitic roof material and surrounding gabbroic rock. Decompression-related reaction rims around subhedral, rounded, resorbed, and fragmented amphibole phenocrysts, regardless of composition, indicate that this mixed-crystal assemblage was being broken, abraded, and dissolved in the magma as a result of mechanical mixing before and during early stages of ascent from conduit roots extending into a mushy cupola of the shallow reservoir. In the earliest lava samples (October 2004), amphiboles with <3-&mu;m rims associated with a glassier matrix than later samples suggest a slightly faster ascent rate consistent with the relatively high eruptive flux of the earliest phases of dome extrusion. Reaction rim widths of ~5 &mu;m on amphibole in all subsequently extruded lava result from a steady influx and upward transport of magma from 3.5-2.5-km to ~1-km depth at rates of ~600 to ~1,200 m/day, through a conduit less than 10 m in radius. Slower ascent rates inferred from volumetric-flux and matrixcrystallization parameters are explained by a widening of the conduit to greater than 60 m radius within 1 km of the surface.

Washington↗

Groundwater chemistry and hexavalent chromium

Water samples collected by the U.S. Geological Survey from more than 100 wells between March 2015 and November 2017 in Hinkley and Water Valleys, in the Mojave Desert 80 miles northeast of Los Angeles, California, were analyzed for field parameters, major ions, nutrients, and selected trace elements, including hexavalent chromium, Cr(VI). Water from most wells was alkaline and oxic. The pH ranged from 6.9 in water-table wells near recharge areas along the Mojave River to 9.4 in deeper wells farther downgradient in the northern subarea. Hexavalent chromium concentrations measured by ion chromatography using U.S. Environmental Protection Agency Method 218.6 and a version of that method used for detection of Cr(VI) concentrations as low as 0.06 micrograms per liter (μg/L), produced results comparable to field speciation with subsequent analyses by graphite furnace atomic absorption spectroscopy (coefficient of determination, R 2 , of 0.97). Hexavalent chromium concentrations ranged from less than the study reporting level of 0.10 to 2,500 μg/L. The highest concentrations were within the October–December 2015 (Q4 2015) regulatory Cr(VI) plume downgradient from the Hinkley compressor station. Hexavalent chromium concentrations outside the Q4 2015 regulatory Cr(VI) plume were as high as 11 μg/L. Hexavalent chromium concentrations in water from most wells were distributed in a narrow redox potential and pH band within the overlapping chromate ion, CrO 4 2− (aqueous) , and manganese-3, Mn(III) (solid) , stability fields. The redox potential of water from some wells completed in carbonate-rich mudflat/playa deposits approached the more oxic manganese-4, Mn(IV) (solid) , stability field. However, Cr(VI) concentrations in porewater pressure-extracted from Mn(IV)-containing deposits in the eastern subarea did not exceed 3.3 μg/L, and porewater does not appear to be a source of Cr(VI) concentrations greater than this concentration in water from wells in the eastern subarea. On the basis of comparison with California-wide data, Cr(VI) concentrations at the measured pH were higher than expected for uncontaminated water from wells (1) within the Q4 2015 regulatory Cr(VI) plume, (2) within the eastern subarea nominally crossgradient from the Hinkley compressor station and upgradient from the Q4 2015 regulatory Cr(VI) plume, and (3) from shallow wells in the northern subarea downgradient from the leading edge of the Q4 2015 regulatory Cr(VI) plume. Hexavalent chromium concentrations in alkaline water from wells in the northern subarea of Hinkley Valley and in Water Valley were within ranges expected for uncontaminated water elsewhere in California given their pH and trace-element composition. Hexavalent chromium concentrations were higher than expected on the basis of selected trace-element concentrations that co-occur with Cr(VI) in water from wells within the Q4 2015 regulatory Cr(VI) plume and from wells in the eastern and northern subareas near the plume margins. Hexavalent chromium concentrations did not exceed 4 μg/L in water from domestic wells sampled in Hinkley and Water Valleys and were generally within ranges expected for uncontaminated groundwater given their pH and trace-element composition. Interpretations derived from Cr(VI) and pH, and from Cr(VI) and selected trace-element concentrations collected between March 2015 and November 2017 were used within a summative-scale analysis to determine the Cr(VI) plume extent (chapter G). However, Cr(VI) background concentrations (chapter G) were calculated from regulatory data collected from selected wells between April 2017 and January 2018.

California↗

Chemistry of ground water in the Silver Springs basin, Florida, with an emphasis on nitrate

The Silver Springs group, in central Marion County, Florida, has a combined average discharge rate of 796 cubic feet per second and forms the headwaters of the Silver River. The springs support a diverse ecosystem and are an important cultural and economic resource. Concentrations of nitrite-plus-nitrate (nitrate-N) in water from the Main Spring increased from less than 0.5 milligrams per liter (mg/L) in the 1960s to about 1.0 mg/L in 2003. The Upper Floridan aquifer supplies the ground water to support spring discharge. This aquifer is at or near land surface in much of the ground-water basin; nutrients leached at land surface can easily percolate downward into the aquifer. Sources of nitrogen in ground water in the Silver Springs basin include atmospheric deposition, fertilizers used by agricultural and urban activities, and human and animal wastes. During 2000-2001, 56 wells in the area contributing recharge to Silver Springs were sampled for major ions, nutrients, and some trace constituents. Selected wells also were sampled for a suite of organic constituents commonly found in domestic and industrial wastewater and for the ratio of nitrogen isotopes (15N/14N) to better understand the sources of nitrate. Wells were selected to be representative of both confined and unconfined conditions of the Upper Floridan aquifer, as well as a variety of land-use types. Data from this study were compared to data collected from 25 wells in 1989-90. Concentrations of nitrate-N in ground water during this study ranged from less than the detection limit of 0.02 to 12 mg/L, with a median of 1.2 mg/L. For data from 1989-90, the range was from less than 0.02 to 3.6 mg/L, with a median of 1.04 mg/L. Water from wells in agricultural land-use areas had the highest median nitrate-N concentration (1.7 mg/L), although it is uncertain if the 12 mg/L maximum concentration was influenced by land-use activities or proximity to a septic tank. The median value for all urban land-use areas was 1.15 mg/L. Because fewer wells were in rangeland or forested areas, those categories were grouped together. The median concentration for that group was 0.09 mg/L. The ratio of 15N/14N in ground-water samples ranged from -0.5 to 11.5 per mil. The median value for ground-water samples from 35 wells, 4.9 per mil, is near the top of the range that indicates inorganic nitrogen sources. In agricultural areas, the median 15N/14N was 4.8 per mil, indicating mostly inorganic (fertilizer) sources. In urban areas, the median 15N/14N was 5.4 per mil, indicating more influence of organic nitrogen (N) sources. Thus, in both agricultural and urban areas, fertilizer is an important inorganic source of N in ground water (and, therefore, in spring water as well). The influence of organic N is more apparent in urban areas than in agricultural areas. Two distinct 15N/14N values were observed in water from the Main Spring, one indicating an inorganic nitrogen source and the other indicating a mixture of sources with a strong influence of organic nitrogen. Thirty-five wells and three springs of the Silver Springs group (the Main Spring, the Abyss, and the Blue Grotto) were sampled for a suite of 63 compounds common in wastewater. A total of 38 compounds was detected, nearly all in very low concentrations. The most frequently detected compound was the insecticide N,N-diethyl-meta-toluamide (DEET), which was detected in water from 27 wells and all three springs. The presence or absence of DEET in ground-water samples did not seem to be related to land use; however, hydrogeologic conditions at the well sites (confined or unconfined) generally did affect the presence or absence of DEET in the ground water. DEET also appears to be a useful tracer for the presence of reused water. Water samples were collected from the Main Spring and two other springs of the Silver Springs group and analyzed for concentrations of dissolved gasses and for chlorofluorocarbons (CFCs), sulfur hexaflu

Scientific Investigations Report↗

Hydrogeologic investigation, water chemistry analysis, and model delineation of contributing areas for City of Tallahassee public-supply wells, Tallahassee, Florida

Ground water from the Upper Floridan aquifer is the sole source of water supply for Tallahassee, Florida, and the surrounding area. The City of Tallahassee (the City) currently operates 28 water-supply wells; 26 wells are distributed throughout the City and 2 are located in Woodville, Florida. Most of these wells yield an ample supply of potable water; however, water from several wells has low levels of tetrachloroethylene (PCE). The City removes the PCE from the water by passing it through granular-activated carbon units before distribution. To ensure that water-supply wells presently free of contamination remain clean, it is necessary to understand the ground-water flow system in sufficient detail to protect the contributing areas. Ground-water samples collected from four public-supply wells were analyzed for tritium ( 3 H), chlorofluorocarbons (CFCs), and sulfur hexafluoride (SF 6 ). Using data for the CFC compounds, apparent ground-water ages ranged from 7 to 31 years. For SF 6 , the apparent ages tended to be about 5 to 10 years younger than those from CFCs. Apparent ages based on the tritium/tritiogenic helium-3 ( 3 H/ 3 He trit ) method ranged from 26 to 33 years. The three dating methods indicate that the apparent age of ground water generally decreases from northern to southern Leon County. This southward trend of decreasing ages is consistent with increasing amounts of recharge that occur as ground water moves from north to south. The ground-water age data derived by geochemical and tracer analyses were used in combination with the flow model and particle tracking to determine an effective porosity for the Hawthorn clays and Upper Floridan aquifer. The effective porosities for the Upper Floridan aquifer that resulted in best model matches were averaged to produce an effective porosity of 7 percent, and the effective porosities for the Hawthorn clays that resulted in a match were averaged to produce an effective porosity of 22 percent. Probabilistic contributing areas were determined for 26 City wells using MODFLOW and MODPATH. For each probabilistic contributing area delineated, the model was run 100 times and the results were analyzed statistically. For each of the 100 runs, a different hydraulic conductivity for each of the zones was assigned to the Upper Floridan aquifer. The hydraulic conductivities were generated randomly assuming a lognormal probability distribution; the mean of the distribution was equal to the hydraulic conductivity from the calibrated model. The 5-year time-dependent capture zones (TDCZs), assuming effective porosities of 0.1, 1, and 7 percent for four representative wells, were delineated. The higher probabilities of capture (greater than 40, 60, and 80 percent) were similar for all effective porosities, and the TDCZ delineated using a 7-percent porosity was slightly smaller; the lower probabilities of capture (greater than 10 and 20 percent) showed a large range of variability.

Florida↗

Evaluation of ground-water and boron sources by use of boron stable-isotope ratios, tritium, and selected water-chemistry constituents near Beverly Shores, northwestern Indiana, 2004

Concentrations of boron greater than the U.S. Environmental Protection Agency (USEPA) 900 μg/L removal action level (RAL) standard were detected in water sampled by the USEPA in 2004 from three domestic wells near Beverly Shores, Indiana. The RAL regulates only human-affected concentrations of a constituent. A lack of well logs and screened depth information precluded identification of whether water from sampled wells, and their boron sources, were from human-affected or natural sources in the surficial aquifer, or associated with a previously defined natural, confined aquifer source of boron from the subtill or basal sand aquifers. A geochemically-based classification of the source of boron in ground water could potentially determine the similarity of boron to known sources or mixtures between known sources, or classify whether the relative age of the ground water predated the potential sources of contamination. The U.S. Geological Survey (USGS), in cooperation with the USEPA, investigated the use of a geochemical method that applied boron stable isotopes, and concentrations of boron, tritium, and other constituents to distinguish between natural and human-affected sources of boron in ground water and thereby determine if the RAL was applicable to the situation. Boron stable-isotope ratios and concentrations of boron in 17 ground-water samples and tritium concentrations in 9 ground-water samples collected in 2004 were used to identify geochemical differences between potential sources of boron in ground water near Beverly Shores, Indiana. Boron and δ 11 B analyses for this investigation were made on unacidified samples to assure consistency of the result with unacidified analyses of δ 11 B values from other investigations. Potential sources of boron included surficial-aquifer water affected by coal-combustion products (CCP) or domestic-wastewater, upward discharge of ground water from confined aquifers, and unaffected water from the surficial aquifer that was distant from human-affected boron sources. Boron concentrations in potential ground-water sources of boron were largest (15,700 to 24,400 μg/L) in samples of CCP-affected surficial aquifer water from four wells at a CCP landfill and smallest (27 to 63 μg/L) in three wells in the surficial aquifer that were distant from human-affected boron sources. Boron concentrations in water from the basal sand aquifer ranged from 656 μg/L to 1,800 μg/L. Boron concentrations in water from three domestic-wastewater-affected surficial aquifer wells ranged from 84 to 387 μg/L. Among the representative ground-water samples, boron concentrations from all four samples of CCP-affected surficial aquifer water and four of five samples of water from the basal sand aquifer had concentrations greater than the RAL. A comparison of boron concentrations in acid-preserved and unacidified samples indicated that boron concentrations reported for this investigation may be from about 11 to 16 percent less than would be reported in a standard analysis of an acidified sample. The stable isotope boron-11 was most enriched in comparison to boron-10 in ground water from a confined aquifer, the basal sand aquifer (δ 11 B, 24.6 to 34.0 per mil, five samples); it was most depleted in CCP-affected water from the surficial aquifer (δ 11 B, 0.1 to 6.6 per mil, four samples). Domestic-wastewater-affected water from the surficial aquifer (δ 11 B, 8.7 to 11.7 per mil, four samples) was enriched in boron-11, in comparison to individual samples of a borax detergent additive and a detergent with perborate bleach; it was intermediate in composition between basal sand aquifer water and CCP-affected water from the surficial aquifer. The similarity between a ground-water sample from the surficial aquifer and a hypothetical mixture of unaffected surficial aquifer and basal sand aquifer waters indicates the potential for long-term upward discharge of ground water into the surficial aquifer from one or more confined aquifers. Estimated δ 11 B values for acidified samples were depleted by 1.9 to 2.8 per mil in comparison to unacidified samples from the four wells sampled; those differences were small in comparison to the differences between δ 11 B values of representative sources of boron in ground water. Tritium concentrations ranged from 7.0 to 10.3 tritium units in six samples from the surficial aquifer and were less than 0.8 tritium units in three samples from the basal sand aquifer. Water from wells in the surficial aquifer represents predominantly modern, post-1972 recharge and sources of boron and other constituents. Water from the basal sand aquifer is associated with pre-1952 recharge from sources not affected by local boron inputs. Ground water from six wells (five domestic wells and one public-supply well) where the ground-water source was unknown had boron concentrations, boron isotope ratios, and tritium concentrations similar to water from the basal sand aquifer. Boron concentrations greater than the RAL were found in water from four of these six wells. The boron isotope and tritium data from these four wells indicate a natural source of boron in ground water; therefore, the RAL does not apply to boron concentrations in water from these wells. Water samples from two domestic wells where the ground-water source was unknown had boron concentrations less than the RAL and boron isotope ratios and tritium concentrations that were similar to domestic-wastewater-affected water from the surficial aquifer. The boron isotope ratio for a sample from one domestic well was similar to that of CCP-affected water from the surficial aquifer and detergent compositions; the boron concentration of that sample was less than the RAL. The classifications of differences among representative sources of boron in ground water and water samples from wells where the ground-water source was unknown generally agreed with distinctions based on strontium-87/strontium-86 ratios and concentrations of strontium, chloride, nitrate, and ammonia. This application of boron concentrations, boron isotope ratios, and tritium concentrations to classify differences in relation to potential sources of boron in ground water was able to distinguish between boron from natural sources and from human-affected sources that are subject to regulation.

Indiana↗

Effect of agricultural practices on hydrology and water chemistry in a small irrigated catchment, Yakima River Basin, Washington

The role of irrigation and artificial drainage in the hydrologic cycle and the transport of solutes in a small agricultural catchment in central Washington's Yakima Valley were explored using hydrologic, chemical, isotopic, age-dating, and mineralogical data from several environmental compartments, including stream water, ground water, overland flow, and streambed pore water. A conceptual understanding of catchment hydrology and solute transport was developed and an inverse end-member mixing analysis was used to further explore the effects of agriculture in this small catchment. The median concentrations of major solutes and nitrates were similar for the single field site and for the catchment outflow site, indicating that the net effects of transport processes for these constituents were similar at both scales. However, concentrations of nutrients were different at the two sites, suggesting that field-scale variations in agricultural practices as well as nearstream and instream biochemical processes are important components of agricultural chemical transformation and transport in this catchment. This work indicates that irrigation coupled with artificial drainage networks may exacerbate the ecological effects of agricultural runoff by increasing direct connectivity between fields and streams and minimizing potentially mitigating effects (denitrification and dilution, for example) of longer subsurface pathways.

Washington↗