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Preliminary geological investigation of the Bir Hayzan diatomite deposit, Kingdom of Saudi Arabia, with a section on selected physical properties and implications for future geophysical exploration

A 2.2-m-thick lake bed composed entirely of diatomite was found in the southwestern arm of the Nafud sand sea, about 67 km east of Tayma in northwestern Saudi Arabia. Its stratigraphic position above eolian sand and below a large barchanoid dune indicates deposition during an exceptional period of pluvial climate in an otherwise arid sand desert. Radiocarbon-dated carbonate lake beds found in similar stratigraphic settings in other parts of the Nafud suggest that the diatomite was deposited in the late Pleistocene epoch sometime between 32,000 and 20,000 years ago. Diatomite of the same pluvial episode has also been found in the Afar region of Ethiopia. Four samples of the diatomite were analyzed for major chemical components and 32 minor and trace elements. Two of the samples appeared to be representative of the lake bed. These samples contained about 85 percent SiO2, 2.34 percent Fe2O3, 1 4 percent Al2O3, and 8.27 percent ignition loss, with only traces of CaO, P2O5, MgO, Na2O, and TiO2. The high content of silica and low contents of alumina, iron oxide, lime, and other constituents indicate low contamination. Analyses of samples from the two atypical units indicate a small amount of contamination, probably clay or mica, in the basal unit and addition of iron oxide and carbonate by ground water in an isolated green-colored unit. Chemically the Bi'r Hayzan diatomite compares favorably with commercial deposits from other parts of the world. Low bulk densities of 0.64 g/cm3 (30-40 lbs/ft3) and an average porosity of 63 percent for five samples also suggest the deposit is of industrial grade. Further studies are recommended to determine: (1) the size and extent of the deposit and (2) the suitability of the diatomite for commercial applications. As means to these ends, electrical-resistivity surveys following winter rains are suggested to determine both the extent and thickness of the lake bed beneath the overlying sand dunes. A complete species identification of the diatom association and further laboratory testing of physical properties of the diatomite also should be made. Further exploration in the Nafud is recommended to locate other possible diatomite deposits.

Open-File Report↗

Urban stormwater quality, event-mean concentrations, and estimates of stormwater pollutant loads, Dallas-Fort Worth area, Texas, 1992-93

The quality of urban stormwater is characterized with respect to 188 properties and constituents. Event-mean concentrations and loads for three land uses (residential, industrial, commercial), and annual loads for 12 selected properties and constituents for 26 gaged basins in the DallasFort Worth study area are presented. During February 1992–June 1993, 182 water samples from the 26 gaged basins (each basin classified as primarily residential, industrial, or commercial) were collected and analyzed. Residential land-use basins had greater median concentrations of bacteria, nutrients, and total arsenic. Industrial land-use basins had greater median concentrations of suspended and dissolved solids, and total recoverable chromium, copper, nickel, and zinc. Diazinon was the most frequently detected pesticide in all three land-use basins. Diazinon was detected in 93 percent of samples from residential land-use basins, 70 percent from commercial land-use basins, and 33 percent from industrial land-use basins. Volatile organic compounds and base/neutral and acid extractable semivolatile organic compounds were detected more frequently in samples from industrial land-use basins than residential or commercial land-use basins. Event-mean concentrations (EMCs) were computed for each land use for biochemical oxygen demand; chemical oxygen demand; suspended and dissolved solids; total nitrogen and ammonia plus organic nitrogen; total and dissolved phosphorus; total recoverable copper, lead, and zinc; and total diazinon. The EMCs of chemical oxygen demand; total nitrogen and ammonia plus organic nitrogen; total and dissolved phosphorus; and total diazinon were greatest in samples from residential land-use basins. The EMCs of biochemical oxygen demand; suspended and dissolved solids; and total copper, lead, and zinc were greatest in samples from industrial land-use basins. Loads per square mile for the three land uses were estimated for the same properties and constituents from flow-weighted EMCs and runoff volume on the basis of seven sampled storms at each gaged site. Chemical oxygen demand and dissolved and suspended solids had the greatest mean loads per square mile. Mean loads per square mile were greatest for trace elements in industrial land-use basins and for total diazinon in residential land-use basins. Mean loads per square mile for total nitrogen in the three land-use basins were dissimilar. Local regression equations were developed to estimate loads produced by individual storms. Mean annual loads were estimated by applying the storm-load equations for all runoff-producing storms in an average climatic year and summing individual storm loads to determine the annual load.

Texas↗

Arsenic, Boron, and Fluoride Concentrations in Ground Water in and Near Diabase Intrusions, Newark Basin, Southeastern Pennsylvania

During an investigation in 2000 by the U.S. Environmental Protection Agency (USEPA) of possible contaminant releases from an industrial facility on Congo Road near Gilbertsville in Berks and Montgomery Counties, southeastern Pennsylvania, concentrations of arsenic and fluoride above USEPA drinking-water standards of 10 ?g/L and 4 mg/L, respectively, and of boron above the USEPA health advisory level of 600 ?g/L were measured in ground water in an area along the northwestern edge of the Newark Basin. In 2003, the USEPA requested technical assistance from the U.S. Geological Survey (USGS) to help identify sources of arsenic, boron, and fluoride in the ground water in the Congo Road area, which included possible anthropogenic releases and naturally occurring mineralization in the local bedrock aquifer, and to identify other areas in the Newark Basin of southeastern Pennsylvania with similarly elevated concentrations of these constituents. The USGS reviewed available data and collected additional ground-water samples in the Congo Road area and four similar hydrogeologic settings. The Newark Basin is the largest of the 13 major exposed Mesozoic rift basins that stretch from Nova Scotia to South Carolina. Rocks in the Newark Basin include Triassic through Jurassic-age sedimentary sequences of sandstones and shales that were intruded by diabase. Mineral deposits of hydrothermal origin are associated with alteration zones bordering intrusions of diabase and also occur as strata-bound replacement deposits of copper and zinc in sedimentary rocks. The USGS review of data available in 2003 showed that water from about 10 percent of wells throughout the Newark Basin of southeastern Pennsylvania had concentrations of arsenic greater than the USEPA maximum contaminant level (MCL) of 10 ?g/L; the highest reported arsenic concentration was at about 70 ?g/L. Few data on boron were available, and the highest reported boron concentration in well-water samples was 60 ?g/L in contrast to concentrations over 5,000 ?g/L in the Congo Road area. Although concentrations of fluoride up to 4 mg/L were reported for a few well-water samples collected throughout the Newark Basin, about 90 percent of the samples had concentrations of 0.5 mg/L or less. The USGS sampled 58 wells primarily in 5 areas in the Newark Basin, southeastern Pennsylvania, from February 2004 through April 2005 to identify other possible areas of elevated arsenic, boron, and fluoride and to characterize the geochemical environment associated with elevated concentrations of these constituents. Sampled wells included 12 monitor wells at an industrial facility near Congo Road, 45 private-supply wells in Berks, Montgomery, and Bucks Counties, and 1 private-supply well near Dillsburg, York County, an area where elevated fluoride in ground water had been reported in the adjacent Gettysburg Basin. Wells were sampled in transects from the diabase through the adjacent hornfels and into the unaltered shales of the Brunswick Group. Field measurements were made of pH, temperature, dissolved oxygen concentration, and specific conductance. Samples were analyzed in the laboratory for major ions, nutrients, total organic carbon, dissolved and total concentrations of selected trace elements, and boron isotopic composition. Generally, the ground water from the 46 private-supply wells had relatively neutral to alkaline pH (ranging from 6.1 to 9.1) and moderate concentrations of dissolved oxygen. Most water samples were of the calcium-bicarbonate type. Concentrations of arsenic up to 60 ?g/L, boron up to 3,950 ?g/L, and fluoride up to 0.70 mg/L were measured. Drinking-water standards or health advisories (for constituents that do not have standards established) were exceeded most frequently (about 20 percent of samples) for arsenic and boron and less frequently (6 percent or less of samples) for total iron, manganese, sulfate, nitrate, lead, molybdenum, and strontium. In water from 12 monitor

Scientific Investigations Report↗

Investigation of Ground-Water Availability and Quality in Orange County, North Carolina

A countywide inventory was conducted of 649 wells in nine hydrogeologic units in Orange County, North Carolina. As a result of this inventory, estimates of ground-water availability and use were calculated, and water-quality results were obtained from 51 wells sampled throughout the County from December 1998 through January 1999. The typical well in Orange County has an average depth of 208 feet, an average casing length of 53.6 feet, a static water level of 26.6 feet, a yield of 17.6 gallons per minute, and a well casing diameter of 6.25 inches. The saturated thickness of the regolith averages 27.0 feet and the yield per foot of total well depth averages 0.119 gallon per minute per foot. Two areas of the County are more favorable for high-yield wells—a west-southwest to east-northeast trending area in the northwestern part of the County, and a southwest to northeast trending area in the southwestern part of the County. Well yields in Orange County show little correlation with topographic or hydrogeologic setting. Fifty-one sampling locations were selected based on (a) countywide areal distribution, (b) weighted distribution among hydrogeologic units, and (c) permission from homeowners. The list of analytes for the sampling program consisted of common anions and cations, metals and trace elements, nutrients, organic compounds, and radon. Samples were screened for the presence of fuel compounds and pesticides by using immuno-assay techniques. Dissolved oxygen, pH, temperature, specific conductance, and alkalinity were measured in the field. The median pH was 6.9, which is nearly neutral, and the median hardness was 75 milligrams per liter calcium carbonate. The median dissolved solids concentration was 125 milligrams per liter, and the median specific conductance was 175 microsiemens per centimeter at 25 degrees Celsius. Orange County ground water is classified as a calcium-bicarbonate type. High nutrient concentrations were not found in samples collected for this study. Nitrate was detected in 82 percent of the samples at concentrations ranging up to 7.2 milligrams per liter, although the median concentration was 0.49 milligram per liter; all other samples had a concentration of 2.9 milligrams per liter or less. In general, trace elements were detected infrequently or at concentrations less than State drinking-water standards. However, exceedances of North Carolina drinking-water standards were observed for iron (3 exceedances of 51 analyses, detection up to 1,100 micrograms per liter), manganese (12 exceedances of 51 analyses, detection up to 890 micrograms per liter), and zinc (4 exceedances of 31 analyses, detection up to 4,900 micrograms per liter). Lead was detected in 8 of 31 samples with a concentration up to 3.5 micrograms per liter. Zinc, manganese, iron, and copper were the most frequently detected trace metals at 100, 94, 80, and 61 percent, respectively. Lead, arsenic, bromide, alum inum, and selenium were detected in 13 to 26 percent of the analyses. No benzene, toluene, ethylbenzene, and xylene (BTEX) or atrazine compounds were detected in any of the samples. Radon activities in ground water can be high because of the rock units present in Orange County. Radon activity ranged from 38 to 4,462 picocuries per liter countywide, with a median activity of 405 picocuries per liter. Median radon activities in Orange County were highest in felsic rocks (487 picocuries per liter) and lowest in mafic rocks (357 picocuries per liter). When evaluated by individual hydrogeologic units, the median radon activity was highest in the phyllite unit (1,080 picocuries per liter in 2 samples) and the felsic metaigneous unit (571 picocuries per liter in 13 samples). Overall, water-quality data in Orange County indicate few drinking-water concerns. No organic contaminants analyzed (total BTEX and atrazine) or excessive nutrient concentrations were detected, and few exceedances of North Carolina drinking- water standards were detected.

North Carolina↗

Chemical analysis of water samples and geophysical logs from cored test holes drilled in the central Oklahoma Aquifer, Oklahoma

Chemical analyses of water from eight test holes and geophysical logs for nine test holes drilled in the Central Oklahoma aquifer are presented. The test holes were drilled to investigate local occurrences of potentially toxic, naturally occurring trace substances in ground water. These trace substances include arsenic, chromium, selenium, residual alpha-particle activities, and uranium. Eight of the nine test holes were drilled near wells known to contain large concentrations of one or more of the naturally occurring trace substances. One test hole was drilled in an area known to have only small concentrations of any of the naturally occurring trace substances. Water samples were collected from one to eight individual sandstone layers within each test hole. A total of 28 water samples, including four duplicate samples, were collected. The temperature, pH, specific conductance, alkalinity, and dissolved-oxygen concentrations were measured at the sample site. Laboratory determinations included major ions, nutrients, dissolved organic carbon, and trace elements (aluminum, arsenic, barium, beryllium, boron, cadmium, chromium, hexavalent chromium, cobalt, copper, iron, lead, lithium, manganese, mercury, molybdenum, nickel, selenium, silver, strontium, vanadium and zinc). Radionuclide activities and stable isotope (5 values also were determined, including: gross-alpha-particle activity, gross-beta-particle activity, radium-226, radium-228, radon-222, uranium-234, uranium-235, uranium-238, total uranium, carbon-13/carbon-12, deuterium/hydrogen-1, oxygen-18/oxygen-16, and sulfur-34/sulfur-32. Additional analyses of arsenic and selenium species are presented for selected samples as well as analyses of density and iodine for two samples, tritium for three samples, and carbon-14 for one sample. Geophysical logs for most test holes include caliper, neutron, gamma-gamma, natural-gamma logs, spontaneous potential, long- and short-normal resistivity, and single-point resistance. Logs for test-hole NOTS 7 do not include long- and short-normal resistivity, spontaneous-potential, or single-point resistivity. Logs for test-hole NOTS 7A include only caliper and natural-gamma logs.

Oklahoma↗

The occurrence of trace elements in bed sediment collected from areas of varying land use and potential effects on stream macroinvertebrates in the conterminous western United States, Alaska, and Hawaii, 1992-2000

As part of the National Water-Quality Assessment Program of the U.S. Geological Survey, this study examines the occurrence of nine trace elements in bed sediment of varying mineralogy and land use and assesses the possible effects of these trace elements on aquatic-macroinvertebrate community structure. Samples of bed sediment and macroinvertebrates were collected from 154 streams at sites representative of undeveloped, agricultural, urban, mined, or mixed land-use areas and 12 intermediate-scale ecoregions within the conterminous western United States, Alaska, and Hawaii from 1992 to 2000. The nine trace elements evaluated during this study—arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb), mercury (Hg), nickel (Ni), selenium (Se), and zinc (Zn)—were selected on the basis of potential ecologic significance and availability of sediment-quality guidelines. At most sites, the occurrence of these trace elements in bed sediment was at concentrations consistent with natural geochemical abundance, and the lowest concentrations were in bed-sediment samples collected from streams in undeveloped and agricultural areas. With the exception of Zn at sampling sites influenced by historic mining-related activities, median concentrations of all nine trace elements in bed sediment collected from sites representative of the five general land-use areas were below concentrations predicted to be harmful to aquatic macroinvertebrates. The highest concentrations of As, Cd, Pb, and Zn were in bed sediment collected from mined areas. Median concentrations of Cu and Ni in bed sediment were similarly enriched in areas of mining, urban, and mixed land use. Concentrations of Cr and Ni appear to originate largely from geologic sources, especially in the western coastal states (California, Oregon, and Washington), Alaska, and Hawaii. In these areas, naturally high concentrations of Cr and Ni can exceed concentrations that may adversely affect aquatic macroinvertebrates. Generally, Hg concentrations were below the sediment-quality guideline for this trace element but appeared elevated in urbanized areas and at sites contaminated by historic mining practices. Lastly, although there was no distinctive pattern in Se concentrations with land use, median bed-sediment concentrations were slightly elevated in urbanized areas. Macroinvertebrate community structure was influenced by topographic, geologic, climatic, and in-stream characteristics. To account for inherent distribution patterns resulting from these influences, samples of macroinvertebrates were stratified by ecoregion to assess the influence of trace elements on community structure. Cumulative toxic units (CTUs) were used to evaluate gradients in trace-element concentrations in mixture. Correlation analyses among the trace elements under different land-use conditions indicate that trace-element mixtures vary among bed sediment and can have a marked influence on CTU composition. Macroinvertebrate response to bed-sediment trace-element exposure was evident only at the most highly contaminated sites, notably at sites classified as contaminated by the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) as a result of historic mining activities. Results of this study agree with the findings of other studies evaluating trace-element exposure to in-stream macroinvertebrate community structure in that generally lower richness metrics and taxa dominance occur in streams where high trace-element enrichment occurs; however, not all streams in all areas have the same characterizing taxa. In the mountain and xeric ecosystems, the mayfly, Baetis sp.; the Diptera, Simulium sp.; caddisflies in the family Hydropsychiidae; midges in the family Orthocladiinae; and the worms belonging to Turbellaria and Naididae all demonstrated resilience to trace-element exposure and, in some cases, possible changes in physical habitat within stream ecosystems. The taxa characteristics within the Ozark Highland ecoregion were different than other ecoregions as evidenced by generally more diverse mayfly populations. In addition, Baetis sp. was common and dominated many of the mayfly populations found in the Rocky Mountain streams within the Mountain Southern Rockies and Mountain Northern Rockies ecoregions; however, within the Ozark Highland ecoregion, Tricorythodes sp. appeared to be more common than Baetis sp.

Alaska, Arizona, California, Colorado, Hawai'i, Id↗

Final synthesis report for factors controlling DDE dechlorination rates on the palos verdes shelf: A field and laboratory investigation

This project was organized into separate field and laboratory studies aimed at answering “18 questions” in the original Scope of Work (cf., section 2 of this report, Background, for explanation). Because of some early results, certain questions became irrelevant and were, therefore, not pursued. In other cases, there simply was not enough time to complete the originally planned studies. On the other hand, additional work, not identified in any of the original “18 questions”, was carried out for purposes of addressing specific issues of concern to the USEPA (United States Environmental Protection Agency). Examples of the latter include: 1) the analysis of an expanded list of sediment cores for DDX (DDX refers to the ten DDT-related compounds of interest in this study; cf., Eganhouse et al., [1]) and selected PCB congeners to facilitate estimation of site-specific reductive dechlorination (RDC) and total loss rates, 2) analysis of gravity and box cores for trace elements to allow stratigraphic alignment, and 3) determination of the extent of mineralization of p,p’-DDE (1-chloro-2-[2,2-dichloro-1-(4- chlorophenyl)ethyl]benzene) in microcosm experiments. In this Executive Summary, we offer a brief recapitulation of what was learned about the factors controlling reductive dechlorination of p,p’-DDE in Palos Verdes Shelf (PVS) sediments using the “18 questions” as a structural guide. The summary is written in narrative form, but references to specific sections (corresponding to the “18 questions”) are identified parenthetically in the text so that the reader can explore the expanded answers that appear later in the report.

Palos Verdes Shelf↗

Hydrothermal contamination of public supply wells in Napa and Sonoma Valleys, California

Groundwater chemistry and isotope data from 44 public supply wells in the Napa and Sonoma Valleys, California were determined to investigate mixing of relatively shallow groundwater with deeper hydrothermal fluids. Multivariate analyses including Cluster Analyses, Multidimensional Scaling (MDS), Principal Components Analyses (PCA), Analysis of Similarities (ANOSIM), and Similarity Percentage Analyses (SIMPER) were used to elucidate constituent distribution patterns, determine which constituents are significantly associated with these hydrothermal systems, and investigate hydrothermal contamination of local groundwater used for drinking water. Multivariate statistical analyses were essential to this study because traditional methods, such as mixing tests involving single species (e.g. Cl or SiO 2 ) were incapable of quantifying component proportions due to mixing of multiple water types. Based on these analyses, water samples collected from the wells were broadly classified as fresh groundwater, saline waters, hydrothermal fluids, or mixed hydrothermal fluids/meteoric water wells. The Multivariate Mixing and Mass-balance (M3) model was applied in order to determine the proportion of hydrothermal fluids, saline water, and fresh groundwater in each sample. Major ions, isotopes, and physical parameters of the waters were used to characterize the hydrothermal fluids as Na–Cl type, with significant enrichment in the trace elements As, B, F and Li. Five of the wells from this study were classified as hydrothermal, 28 as fresh groundwater, two as saline water, and nine as mixed hydrothermal fluids/meteoric water wells. The M3 mixing-model results indicated that the nine mixed wells contained between 14% and 30% hydrothermal fluids. Further, the chemical analyses show that several of these mixed-water wells have concentrations of As, F and B that exceed drinking-water standards or notification levels due to contamination by hydrothermal fluids.

California↗

Mineral stimulation of subsurface microorganisms: release of limiting nutrients from silicates

Microorganisms play an important role in the weathering of silicate minerals in many subsurface environments, but an unanswered question is whether the mineral plays an important role in the microbial ecology. Silicate minerals often contain nutrients necessary for microbial growth, but whether the microbial community benefits from their release during weathering is unclear. In this study, we used field and laboratory approaches to investigate microbial interactions with minerals and glasses containing beneficial nutrients and metals. Field experiments from a petroleum-contaminated aquifer, where silicate weathering is substantially accelerated in the contaminated zone, revealed that phosphorus (P) and iron (Fe)-bearing silicate glasses were preferentially colonized and weathered, while glasses without these elements were typically barren of colonizing microorganisms, corroborating previous studies using feldspars. In laboratory studies, we investigated microbial weathering of silicates and the release of nutrients using a model ligand-promoted pathway. A metal-chelating organic ligand 3,4 dihydroxybenzoic acid (3,4 DHBA) was used as a source of chelated ferric iron, and a carbon source, to investigate mineral weathering rate and microbial metabolism. In the investigated aquifer, we hypothesize that microbes produce organic ligands to chelate metals, particularly Fe, for metabolic processes and also form stable complexes with Al and occasionally with Si. Further, the concentration of these ligands is apparently sufficient near an attached microorganism to destroy the silicate framework while releasing the nutrient of interest. In microcosms containing silicates and glasses with trace phosphate mineral inclusions, microbial biomass increased, indicating that the microbial community can use silicate-bound phosphate inclusions. The addition of a native microbial consortium to microcosms containing silicates or glasses with iron oxide inclusions correlated to accelerated weathering and release of Si into solution as well as the accelerated degradation of the model substrate 3,4 DHBA. We propose that silicate-bound P and Fe inclusions are bioavailable, and microorganisms may use organic ligands to dissolve the silicate matrix and access these otherwise limiting nutrients.

Chemical Geology↗

Water-quality trend analysis and sampling design for the Devils Lake Basin, North Dakota, January 1965 through September 2003

This report presents the results of a study conducted by the U.S. Geological Survey, in cooperation with the North Dakota State Water Commission, the Devils Lake Basin Joint Water Resource Board, and the Red River Joint Water Resource District, to analyze historical water-quality trends in three dissolved major ions, three nutrients, and one dissolved trace element for eight stations in the Devils Lake Basin in North Dakota and to develop an efficient sampling design to monitor the future trends. A multiple-regression model was used to detect and remove streamflow-related variability in constituent concentrations. To separate the natural variability in concentration as a result of variability in streamflow from the variability in concentration as a result of other factors, the base-10 logarithm of daily streamflow was divided into four components-a 5-year streamflow anomaly, an annual streamflow anomaly, a seasonal streamflow anomaly, and a daily streamflow anomaly. The constituent concentrations then were adjusted for streamflow-related variability by removing the 5-year, annual, seasonal, and daily variability. Constituents used for the water-quality trend analysis were evaluated for a step trend to examine the effect of Channel A on water quality in the basin and a linear trend to detect gradual changes with time from January 1980 through September 2003. The fitted upward linear trends for dissolved calcium concentrations during 1980-2003 for two stations were significant. The fitted step trends for dissolved sulfate concentrations for three stations were positive and similar in magnitude. Of the three upward trends, one was significant. The fitted step trends for dissolved chloride concentrations were positive but insignificant. The fitted linear trends for the upstream stations were small and insignificant, but three of the downward trends that occurred during 1980-2003 for the remaining stations were significant. The fitted upward linear trends for dissolved nitrite plus nitrate as nitrogen concentrations during 1987-2003 for two stations were significant. However, concentrations during recent years appear to be lower than those for the 1970s and early 1980s but higher than those for the late 1980s and early 1990s. The fitted downward linear trend for dissolved ammonia concentrations for one station was significant. The fitted linear trends for total phosphorus concentrations for two stations were significant. Upward trends for total phosphorus concentrations occurred from the late 1980s to 2003 for most stations, but a small and insignificant downward trend occurred for one station. Continued monitoring will be needed to determine if the recent trend toward higher dissolved nitrite plus nitrate as nitrogen and total phosphorus concentrations continues in the future. For continued monitoring of water-quality trends in the upper Devils Lake Basin, an efficient sampling design consists of five major-ion, nutrient, and trace-element samples per year at three existing stream stations and at three existing lake stations. This sampling design requires the collection of 15 stream samples and 15 lake samples per year rather than 16 stream samples and 20 lake samples per year as in the 1992-2003 program. Thus, the design would result in a program that is less costly and more efficient than the 1992-2003 program but that still would provide the data needed to monitor water-quality trends in the Devils Lake Basin.

North Dakota↗

Hydrology and ground-water quality in the mine workings within the Picher Mining District, Northeastern Oklahoma, 2002-03

The Picher mining district of northeastern Ottawa County, Oklahoma, was a major site of mining for lead and zinc ores in the first half of the 20th century. The primary source of lead and zinc were sulfide minerals disseminated in the cherty limestones and dolomites of the Boone Formation of Mississippian age, which comprises the Boone aquifer. Ground water in the aquifer and seeping to surface water in the district has been contaminated by sulfate, iron, lead, zinc, and several other metals. The U.S. Geological Survey, in cooperation with the Oklahoma Department of Environmental Quality, investigated hydrology and ground-water quality in the mine workings in the mining district, as part of the process to aid water managers and planners in designing remediation measures that may restore the environmental quality of the district to pre-mining conditions. Most ground-water levels underlying the mining district had similar altitudes, indicating a large degree of hydraulic connection in the mine workings and overlying aquifer materials. Recharge-age dates derived from concentrations of chlorofluorocarbons and other dissolved gases indicated that water in the Boone aquifer may flow slowly from the northeast and southeast portions of the mining district. However, recharge-age dates may have been affected by the types of sites sampled, with more recent recharge-age dates being associated with mine-shafts, which are more prone to atmospheric interactions and surface runoff than the sampled airshafts. Water levels in streams upstream from the confluence of Tar and Lytle Creeks were several feet higher than those in adjacent portions of the Boone aquifer, perhaps due to low-permeability streambed sediments and indicating the streams may be losing water to the aquifer in this area. From just upstream to downstream from the confluence of Tar and Lytle Creeks, surface-water elevations in these streams were less than those in the surrounding Boone aquifer, indicating that seepage from the aquifer to downstream portions of Tar Creek was much more likely. Water properties and major-ion concentrations indicate that water in the mining area was very hard, with large concentrations of dissolved solids that increased from areas of presumed recharge toward areas with older ground water. Most of the ground-water samples, particularly those from the airshafts, had dissolved-oxygen concentrations less than 1.0 milligram per liter. Small concentrations of dissolved oxygen may have been introduced during the sampling process. The small dissolved-oxygen concentrations were associated with samples containing large iron concentrations that indicates possible anoxic conditions in much of the aquifer. Ground water in the mining district was dominated by calcium, magnesium, and sulfate. Sodium concentrations tended to increase relative to calcium and magnesium concentrations. Ground-water samples collected in 2002-03 had large concentrations of many trace elements. Larger concentrations of metals and sulfate occurred in ground water with smaller pHs and dissolved-oxygen concentrations. Iron was the metal with the largest concentrations in the ground-water samples, occurring at concentrations up to 115,000 micrograms per liter. Cadmium, lead, manganese, zinc, and the other analyzed metals occurred in smaller concentrations in ground water than iron. However, larger cadmium concentrations appeared to be associated with sites that have small iron concentrations and more oxygenated waters. This is noteworthy because the small sulfate and iron concentrations in these waters could lead to conclusions that the waters are less contaminated than waters with large sulfate and iron concentrations. Ground-water quality in the mining district was compared with subsets of samples collected in 1983-85 and in 2002.

Oklahoma↗

Assessment of Energetic Compounds, Semi-volatile Organic Compounds, and Trace Elements in Streambed Sediment and Stream Water from Streams Draining Munitions Firing Points and Impact Areas, Fort Riley, Kansas, 2007-08

An assessment of energetic compounds (explosive and propellant residues) and associated semi-volatile organic compounds (SVOCs) and trace elements in streambed sediment and stream water from streams draining munitions firing points and impact areas at Fort Riley, northeast Kansas, was performed during 2007-08 by the U.S. Geological Survey (USGS) in cooperation with the U.S. Army. Streambed sediment from 16 sampling sites and stream-water samples from 5 sites were collected at or near Fort Riley and analyzed for as many as 17 energetic compounds, 65 SVOCs, and 27 trace elements. None of the energetic compounds or SVOCs were detected in streambed sediment collected from sites within the Fort Riley Military Reservation. This may indicate that these compounds either are not transported from dispersal areas or that analytical methods are not sensitive enough to detect the small concentrations that may be transported. Concentrations of munitions-associated trace elements did not exceed sediment-quality guidelines recommended by the U.S. Environmental Protection Agency (USEPA) and are not indicative of contamination of streambed sediment at selected streambed sampling sites, at least in regards to movement from dispersal areas. Analytical results of stream-water samples provided little evidence of contamination by energetic compounds, SVOCs, or associated trace elements. Perchlorate was detected in 19 of 20 stream-water samples at concentrations ranging from an estimated 0.057 to an estimated 0.236 ug/L (micrograms per liter) with a median concentration of an estimated 0.114 ug/L, substantially less than the USEPA Interim Health Advisory criterion (15 ug/L), and is in the range of documented background concentrations. Because of these small concentrations and possible natural sources (precipitation and groundwater), it is likely that the occurrence of perchlorate in stream water is naturally occurring, although a definitive identification of the source of perchlorate in stream water at Fort Riley is difficult. The only SVOCs detected in stream-water samples were bis(2-ethylhexyl) phthalate and di-n-butyl phthalate but at concentrations substantially less than the most stringent aquatic-life criteria established by the Kansas Department of Health and Environment. All trace element concentrations in stream-water samples were less than the most stringent aquatic-life criteria. The implication of these stream-water results is that contamination arising from firing-range activities, if it exists, is so small as to be nondetectable with current analytical methods or is not distinguishable from background concentrations for constituents that also are naturally occurring. Overall, the munitions-related constituents analyzed in streambed sediment and stream water, when detected, were at concentrations that were less than regulatory criteria

Scientific Investigations Report↗

Trace elements and organic compounds in streambed sediment and fish tissue of coastal New England streams, 1998-99

Streambed sediment and fish tissue were collected at 14 river sites in eastern New England during low-flow conditions in 1998 and 1999 as part of the New England Coastal Basins (NECB) study of the U.S. Geological Survey National Water-Quality Assessment (NAWQA) Program. Sampling sites were selected over a range of urban settings. Population densities at selected sites ranged from 26 to 3,585 people per square mile, and urban land use ranged from 1 to 68 percent. The streambed sediment samples were analyzed for a total of 141 contaminants, including 45 trace elements, 32 organochlorine compounds, and 64 semi-volatile organic compounds. The fish tissue samples were analyzed for 22 trace elements and 28 organochlorine compounds. Concentrations of selected contaminants in both streambed sediment and fish tissue correlated more strongly with population density than with other watershed characteristics. Cadmium, copper, lead, mercury, zinc, total polycyclic aromatic hydrocarbons (PAHs), total polychlorinated biphenyls (PCBs), dichloro diphenyl trichloroethane and metabolites (DDTM), and total chlordane in streambed sediment all showed strong positive correlations with population density (rho = 0.71 to 0.85, p value = 0.005 to <0.001). Correlations between population density and selected contaminants in fish tissue were less significant than with streambed sediment (rho = 0.62 to 0.72, p value = 0.03 to 0.008). Organic carbon concentrations were correlated with concentrations of arsenic, selenium, total PAHs, total PCBs, and DDTM in streambed sediment. The relation between concentrations of contaminants in streambed sediment and fish tissue was stronger for organochlorine compounds (rho = 0.75 to 0.55, p = 0.005 to 0.065) than for trace elements (rho = 0.63 to 0.53, p = 0.029 to 0.069). The NECB study area had the highest median concentrations of lead, mercury, total PAHs, total PCBs, and DDTM in streambed sediment and the highest median concentration of PCBs in fish tissue compared to 45 other NAWQA study units across the Nation. Concentrations of many of these constituents in streambed sediment also were frequently above the consensus-based Sediment-Quality Guidelines for the protection of wildlife, suggesting they are a threat to the health of aquatic biota in New England.

Water-Resources Investigations Report↗

Water quality in the lower Puyallup River valley and adjacent uplands, Pierce County, Washington

The quality of most ground and surface water within and adjacent to the lower Puyallup River valley is suitable for most typical uses; however, some degradation of shallow groundwater quality has occurred. High concentrations of iron and manganese were found in groundwater, sampled at depths of < 40 ft, from wells tapping alluvial aquifers and in a few wells tapping deeper aquifers. Volatile and acid- and base/neutral-extractable organic compounds were not detected in either shallow or deep groundwater samples. The quality of shallow groundwater was generally poorer than that of deep water. Deep ground water (wells set below 100 ft) appears suitable as a supplementary water supply for fish-hatchery needs. Some degradation of water quality, was observed downstream from river mile 1.7 where a municipal wastewater-treatment plant discharges into the river. In the Puyallup River, the highest concentrations of most trace elements were found in bed sediments collected downstream from river mile 1.7. Median concentrations of arsenic, lead, and zinc were higher in bed sediments from small streams compared with those from the Puyallup River, possibly because the small stream drainages, which are almost entirely within developed areas, receive more urban runoff as a percentage of total flow. Total-recoverable trace-element concentrations exceeded water-quality criteria for acute toxicity in the Puyallup River and in some of the small streams. In most cases, high concentrations of total-recoverable trace elements occurred when suspended-sediment concentrations were high. Temperatures in all streams except Wapato Creek and Fife Dutch were within limits (18 C) for Washington State class A water. Minimum dissolved oxygen concentrations were relatively low at 5.6 and 2.0 mg/L, respectively, for Wapato Creek and Fife Dutch. The poorest surface-water quality, which can be characterized as generally unsuitable for fish, was in Fife Dutch, a manmade channel and therefore uncharacteristic of other small streams. (Author 's abstract)

Water-Resources Investigations Report↗

Hydrogeology, digital solute-transport simulation, and geochemistry of the Lower Cretaceous aquifer system near Baltimore, Maryland

This study was made to develop information on the hydrogeology and ground-water geochemistry of the Patuxent and Patapsco aquifers (Lower Cretaceous) near Baltimore, Maryland. This information is needed to evaluate the availability and chemical quality of water from these aquifers. The Patuxent aquifer unconformably overlies Lower Paleozoic and Precambrian basement rocks and consists primarily of medium- to coarse-grained quartz sand. Discontinuous lenses of gravel and silty clay are commonly interbedded with the sand-sized material. The Patuxent aquifer in this area attains a thickness of 250 feet and transmissivities range from 2,000 to 8,000 feet squared per day. The Patuxent is the most productive source of ground water in the Baltimore area. In 1982, approximately 11 million gallons of water per day was produced from this unit. Several cones of depression, ranging from 30 to 50 feet below sea level, have developed in response to this pumping stress. The Arundel Formation conformably overlies the Patuxent aquifer. The Arundel is composed predominantly of clay and ranges from 0 to 150 feet thick. The Arundel exhibits very low vertical hydraulic conductivities that are on the order of 10 -9 to 10 -11 feet per second. This unit acts as the upper confining bed of the Patuxent aquifer in much of the project area. The Patapsco aquifer unconformably overlies the Arundel Formation and is a medium- to fine-grained quartz sand. The Patapsco functions as a water-table aquifer in much of the project area. Although the Patapsco has been heavily pumped in the past, pumpage from that aquifer in Baltimore was negligible in 1982. Brackish-water contamination of the Patuxent and Patapsco aquifers has been a major water-quality problem since the early 1900's. The Patuxent aquifer presently (1982) contains a circular plume of brackish-water contamination about 5 miles in diameter. This plume is centered on the Harbor district and has enlarged measurably since 1945. The Patapsco aquifer has a smaller zone of brackish-water contamination that has decreased in size since 1945. Borehole data demonstrate that the Arundel Formation has been breached by Pleistocene river channels near the Harbor district. These erosional channels provide a conduit for brackish water to intrude into the Patuxent aquifer. A two-dimensional areal solute-transport model of the Patuxent aquifer was constructed. This model was designed to estimate the future movement of the brackish-water plume based on alternative scenarios of aquifer use. Model simulations suggest that the plume will remain relatively immobile if 1982 pumping patterns continue into the foreseeable future. However, increased pumpage in the Marley Neck peninsula could draw the plume to the southeast and increase contamination of the Fairfield area. The water quality of the Patuxent aquifer is extremely variable. Because of this variability, it is useful to divide the aquifer into three water-quality zones: Zone 1 -- This zone corresponds to the plume of brackish-water contamination. Zone 2 -- This zone exhibits evidence of urbanization-related contamination such as measurable concentrations of organic chemicals and elevated concentrations of trace elements and total organic carbon. Zone 3 -- Water composition in this zone is controlled exclusively by naturally occurring chemical processes. These processes are dominated by reactions involving dissolved iron. Near the outcrop area, oxidation of pyrite and lignite consumes dissolved oxygen and produces ledges of iron hydroxide-cemented sandstones and conglomerates. The predominant dissolved iron species in oxic water is Fe(OH) 2 + . Downgradient, the water becomes anoxic and sulfate reduction becomes an important process. The predominant dissolved iron species in anoxic water is Fe 2+ .

Maryland↗

Streamflow, water-quality, and biological conditions in the Big Black Creek basin, St. Clair County, Alabama, 1997

In 1997 synoptic streamflow, water-quality, and biological investi- gations in the Big Black Creek Basin were conducted by the U.S. Geological Survey in cooperation with the City of Moody, St. Clair County, and the Birmingham Water Works Board. Data obtained during these synoptic investigations provide a one-time look at the streamflow and water-quality conditions in the Big Black Creek Basin during a stable, base-flow period when streamflow originated only from ground-water discharge. These data were used to assess the degree of water-quality degradation in the Big Black Creek Basin from land-use activities in the basin, including leakage of leachate from the Acmar Regional Land- fill. Biological data from the benthic invertebrate community investigation provided an assessment of the cumulative effects of stream conditions on organisms in the basin. The synoptic measurement of streamflow at 28 sites was made during a period of baseflow on August 27, 1997. Two stream reaches above the landfill lost water to the ground-water system, but those below the landfill had significantly higher ground-water gains. If significant leakage of leachate from the landfill had occurred during the measurement period, the distribution of ground-water discharge suggests that leachate would travel relatively short distances before resurfacing as ground-water discharge to the stream. Benthic invertebrate communities were sampled at four sites in the Big Black Creek Basin during July 16-17, 1997. Based on Alabama Department of Environmental Management criteria and on comparison with a nearby unimparied reference site, the benthic invertebrate communities at the sites sampled were considered unimpaired or only slightly impaired during the sample period. This would imply that landfill and coal-mining activities did not have a detrimental effect on the benthic invertebrate communities at the time of the study. Synoptic water-column samples were collected at nine sites on Big Black Creek and its tributaries at the same time that the synoptic streamflow measurements were made. Trace-element and organic compound concentrations in the stream water were below established water-quality standards and criteria for the State of Alabama, with the exception of secondary (aesthetic) drinking-water levels for iron and manganese. Oil and grease concentrations detected in bed sediments were below the corrective action limit of 100 milligrams per kilogram. No significant increases in chloride, specific conductance, total dissolved solids, oil and grease, color, or biochemical oxygen demand were observed at sites downgradient from the landfill. Ground-water samples were collected from three drive-point wells in the vicinity of the landfill. These samples were analyzed for a suite of volatile organic compounds. The solvent 1,1-dichloroethane (the same solvent detected in the ground-water monitoring system at the landfill) was detected in a sample from a drive-point well downgradient from the landfill--an indication of the potential risk of landfill-derived contamination migrating toward Big Black Creek. No distinguishing trend or pattern of contamination was identified that could be attributed solely to landfill activities. Landfill activities did not appear to contribute significant contamination to Big Black Creek during these streamflow conditions. Any contaminant contribution from coal-mining activities in the basin may have served to mask any leachate contributions from the landfill; however, the overall effects on stream water and benthic intervebrate communities apparently were only minimal.

Water-Resources Investigations Report↗

Evaluation of selected information on splitting devices for water samples

Four devices for splitting water samples into representative aliquots are used by the U.S. Geological Survey's Water Resources Division. A thorough evaluation of these devices (14-liter churn, 8-liter churn, plastic cone, and Teflon cone) encompasses a wide variety of concerns, based on both chemical and physical considerations. This report surveys the existing data (as of April 1994) on cleaning efficiency and splitting capability of these devices and presents the data in a systematic framework for evaluation. From the existing data, some of these concerns are adequately or partially addressed, but the majority of concerns could not be addressed because of the lack of data. In general, the existing cleaning and transport protocols are adequate at the milligram per liter level, but the adequacy is largely unknown for trace elements and organic chemicals at lower concen- trations. The existing data indicate that better results are obtained when the splitters are cleaned in the laboratory rather than in the field. Two conclusions that can be reached on the splitting capability of solids are that more work must be done with all four devices to characterize and quantify their limitations and range of usefulness, and that the 14-liter churn (and by association, the 8-liter churn) is not useful in obtaining representative splits of sand-sized particles.

Water-Resources Investigations Report↗

Trace silicon determination in biological samples by inductively coupled plasma mass spectrometry (ICP-MS): Insight into volatility of silicon species in hydrofluoric acid digests for optimal sample preparation and introduction to ICP-MS

A method for the determination of trace levels of silicon from biological materials by inductively coupled plasma mass spectrometry (ICP-MS) has been developed. The volatility of water-soluble silicon species, hexafluorosilicic acid (H 2 SiF 6 ), and sodium metasilicate (Na 2 SiO 3 ) was investigated by evaporating respective solutions (50 µg/mL silicon) in nitric acid (HNO 3 ), nitric acid + hydrochloric acid (HNO 3 + HCl), and nitric acid + hydrochloric acid + hydrofluoric acid (HNO 3 + HCl + HF) at 120 °C on a hot-block to near dryness. The loss of silicon from H 2 SiF 6 solutions was substantial (>99%) regardless of the digestion medium. Losses were also substantial (>98%) for metasilicate solutions heated in HNO 3 + HCl + HF, while no significant loss occurred in HNO 3 or HNO 3 + HCl. These results show that H 2 SiF 6 species were highly volatile and potential losses could confound accuracy at trace level determinations by ICP-MS if digestates prepared in HF are heated to eliminate HF. Among the various matrices comprising major elements, sodium appeared to be effective in reducing silicon loss from H 2 SiF 6 solutions. Excess sodium chloride (NaCl) matrix provided better stability, improving silicon recoveries by up to about 80% in evaporated HF digestates of soil and mine waste samples, but losses could not be fully prevented. To safely remove excess acids and circumvent the adverse effects of excess HF (e.g., risk of high Si background signals), a two-step digestion scheme was adopted for the preparation of biological samples containing trace silicon levels. A closed-vessel digestion was performed either in 4 mL of concentrated HNO 3 and 1 mL of concentrated HCl or 4 mL of concentrated HNO 3 , 1 mL of concentrated HCl and 1 mL of concentrated HClO 4 on a hot plate at 140 °C. Digestates were then evaporated to incipient dryness at 120 °C to remove the acids. A second closed-vessel digestion was carried out to dissolve silicates in 0.5 mL of concentrated HNO 3 and 0.5 mL of concentrated HF at 130 °C. After digestion, digestates were diluted to 10 mL. The solution containing about 5% HNO 3 and 5% HF was directly analyzed by ICP-MS equipped with an HF-inert sample introduction system. The limit of detection was about 110 µg/L for 28 Si when using the Kinetic Energy Discrimination (KED) mode. The method was used to determine silicon in various plant and tissue certified reference materials. Data were acquired for 28 Si using KED and standard (STD) modes, and 74 Ge and 103 Rh as internal standard elements. There was not any significant difference between the accuracy and precision of the results obtained with 74 Ge and 103 Rh within the same measurement mode. Precision, calculated as relative standard deviation for four replicate analyses, varied from 5.3 (tomato leaves) to 21% (peach leaves) for plant and from 2.2 (oyster tissue) to 33% (bovine liver) for tissue SRM/CRMs. Poor precision was attributed to material heterogeneity and the large particle size distribution. An analysis of lung tissue samples from those with occupational exposure to silica dust revealed that tissues possessed substantial levels of water-soluble silicates, but the most silicon was present in the particulate matter fraction.

Minerals↗