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Investigation of anion-exchange and immunoaffinity particle-loaded membranes for the isolation of charged organic analytes from water

Anion-exchange and immunoaffinity particle loaded membranes (PLMs) were investigated as a mechanism for the isolation of charged organic analytes from water. Kinetic properties determined theoretically included dynamic capacity, pressure drop (Δ P ), residence and diffusion times ( T r , T d ), and total membrane porosity (ε T ). These properties were confirmed through experimental evaluation, and the PLM method showed significant improvement over conventional solid-phase extraction (SPE) and ion-exchange formats. Recoveries of more than 90% were observed for a variety of test compounds at flow rates up to 70 mL/min (equipment-limited maximum flow rate). A fast-flow immunoaffinity column was developed using antibodies (Abs) attached to the PLMs. Reproducible recoveries (88% ± 4%) were observed at flow rates up to 70 mL/min for the antibody (Ab)-loaded PLMs. Findings indicate increased selectivity over anion-exchange PLMs and conventional SPE or ion-exchange methods and rapid Ab−antigen binding rates given the excellent mass-transfer characteristics of the PLMs.

Analytical Chemistry

A selected bibliography of water-related research in the upper Klamath Basin, Oregon

A bibliography containing 165 selected references was compiled to assist local, State, and Federal agencies that have ongoing water-related research interests in the Upper Klamath Basin. The report has two parts. Part 1 is a list of bibliographic citations alphabetized by author, and Part 2 is a subject index that references bibliographic entries. Categories of the subject index include chemistry, ecology, geology, hydrology, land use, and water management related reports. Maps, reports, proposals, theses, dissertations, and journal articles are referenced. Some of the environmental issues addressed by references in the bibliography are hypereutrophication, nuisance algal blooms, endangered fish species, water allocation questions, wetland and riparian habitat restoration, and pesticide and fertilizer utilization.

Open-File Report

Aqueous geochemical data from the analysis of stream-water samples collected in June and July 2006 — Taylor Mountains 1:250,000-scale quadrangle, Alaska

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000-scale quadrangle, Alaska. Parameters for which data are reported include pH, conductivity, water temperature, major cation and anion concentrations, trace-element concentrations, and dissolved organic-carbon concentrations. Samples were collected as part of a multiyear U.S. Geological Survey project entitled ?Geologic and Mineral Deposit Data for Alaskan Economic Development.? Data presented here are from samples collected in June and July 2006. The data are being released at this time with minimal interpretation. This is the third release of aqueous geochemical data from this project; aqueous geochemical data from samples collected in 2004 and 2005 were published previously. The data in this report augment but do not duplicate or supersede the previous data release. Site selection was based on a regional sampling strategy that focused on first- and second-order drainages. Water sample site selection was based on landscape parameters that included physiography, wetland extent, lithological changes, and a cursory field review of mineralogy from pan concentrates. Stream water in the Taylor Mountains quadrangle is dominated by bicarbonate (HCO3-), although in a few samples more than 50 percent of the anionic charge can be attributed to sulfate (SO42-). The major-cation chemistry ranges from Ca2+/Mg2+ dominated to a mix of Ca2+/Mg2+/Na++K+. Generally, good agreement was found between the major cations and anions in the duplicate samples. Many trace elements in these samples were at or near the analytical method detection limit, but good agreement was found between duplicate samples for elements with detectable concentrations. All field blank major-ion and trace-element concentrations were below detection.

Alaska

Characterization of major-ion chemistry and nutrients in headwater streams along the Appalachian National Scenic Trail and within adjacent watersheds, Maine to Georgia

An inventory of water-quality data on field parameters, major ions, and nutrients provided a summary of water quality in headwater (first- and second-order) streams within watersheds along the Appalachian National Scenic Trail (Appalachian Trail). Data from 1,817 sampling sites in 831 catchments were used for the water-quality summary. Catchment delineations from NHDPlus were used as the fundamental geographic units for this project. Criteria used to evaluate sampling sites for inclusion were based on selected physical attributes of the catchments adjacent to the Appalachian Trail, including stream elevation, percentage of developed land cover, and percentage of agricultural land cover. The headwater streams of the Appalachian Trail are generally dilute waters, with low pH, low acid neutralizing capacity (ANC), and low concentrations of nutrients. The median pH value was slightly acidic at 6.7; the median specific conductance value was 23.6 microsiemens per centimeter, and the median ANC value was 98.7 milliequivalents per liter (μeq/L). Median concentrations of cations (calcium, magnesium, sodium, and potassium) were each less than 1.5 milligrams per liter (mg/L), and median concentrations of anions (bicarbonate, chloride, fluoride, sulfate, and nitrate) were less than 10 mg/L. Differences in water-quality constituent levels along the Appalachian Trail may be related to elevation, atmospheric deposition, geology, and land cover. Spatial variations were summarized by ecological sections (ecosections) developed by the U.S. Forest Service. Specific conductance, pH, ANC, and concentrations of major ions (calcium, chloride, magnesium, sodium, and sulfate) were all negatively correlated with elevation. The highest elevation ecosections (White Mountains, Blue Ridge Mountains, and Allegheny Mountains) had the lowest pH, ANC, and concentrations of major ions. The lowest elevation ecosections (Lower New England and Hudson Valley) generally had the highest pH, ANC, and concentrations of major ions. The geology in discrete portions of these two ecosections was classified as containing carbonate minerals which has likely influenced the chemical character of the streamwater. Specific conductance, pH, ANC, and concentrations of major ions (calcium, chloride, magnesium, sodium, and sulfate) were all positively correlated with percentages of developed and agricultural land uses at the lower elevations of the central region of the Appalachian Trail (including the Green-Taconic-Berkshire Mountains, Lower New England, Hudson Valley, and Northern Ridge and Valley ecosections). The distinctly different chemical character of the streams in the central sections of the Appalachian Trail is likely related to the lower elevations, the presence of carbonate minerals in the geology, higher percentages of developed and agricultural land uses, and possibly the higher inputs of sulfate and nitrate from atmospheric deposition. Acid deposition of sulfate and nitrate are important influences on the acid-base chemistry of the surface waters of the Appalachian Trail. Atmospheric deposition estimates are consistently high (more than 18 kilograms per hectare (kg/ha) for sulfate, and more than 16 kg/ha for nitrate) at both the highest and lowest elevations. However, the lowest elevation (Green-Taconic-Berkshire Mountains, Lower New England, Hudson Valley, Northern Glaciated Allegheny Plateau, and Northern Ridge and Valley ecosections) included the largest spatial area of sustained high estimates of atmospheric deposition. Calcium-bicarbonate was the most frequently calculated water type in the Lower New England and Hudson Valley ecosections. In the northern and southern sections of the Appalachian Trail mix-cation water types were most prevalent and sulfate was the predominate anion. The predominance of the sulfate anion in the surface waters of the northern and southern ecosections likely reflects the influence of sulfate deposition. Although the central portion of the Appalachian Trail has the largest spatial area of high atmospheric acid deposition, the lower ionic strength waters in the northern and southern ecosections of the Appalachian Trail may have been more adversely affected by acid deposition. The low ionic strength of the streams in the White Mountains, Blue Ridge Mountains, and Allegheny Mountains ecosections makes parts of these regions susceptible to seasonal or event-driven episodic acidification, which can be detrimental to health of aquatic and terrestrial ecosystems. Median catchment ANC values were classified into three groups - acidic, sensitive, and insensitive. The White Mountains, Blue Ridge Mountains, and Allegheny Mountains ecosections included the highest frequency of catchments classified as acidic or sensitive. More than 56 percent of the catchments from the White Mountains ecosection were classified as sensitive to acidic inputs. In the Blue Ridge ecosection, 1.6 percent of the catchments were classified as acidic, and 38.2 percent of the catchments were classified as sensitive to acidic inputs. In the Allegheny Mountains ecosection, 17.6 percent of the catchments were classified as acidic, and 29.4 percent of the catchments were classified as sensitive to acidic inputs. Median concentrations of nitrogen species were less than 0.4 mg/L, and median concentrations of total phosphorus were less than 0.02 mg/L along the Appalachian Trail. A comparison of median catchment concentrations of nutrients to estimated national background concentrations demonstrated that concentrations along the Appalachian Trail are generally lower. A comparison of median concentrations of total nitrogen and total phosphorus to the U.S. Environmental Protection Agency's (USEPA) nutrient criteria for the Eastern U.S. ecoregions showed that the concentrations of total nitrogen in the northern section of the Appalachian Trail were generally higher than the USEPA criterion. Similarly, median concentrations of total phosphorus in the southern regions of the Appalachian Trail were approximately twice as high as USEPA criteria. Sections of the Appalachian Trail are adjacent to modest amounts of agricultural and developed land areas. These nonforested land areas may be contributing to the percentage of catchments in which concentrations of total nitrogen and total phosphorus are higher than USEPA nutrient ecoregion criteria.

Connecticut, Georgia, Maine, Massachusetts, Maryla

Aqueous geochemical data from the analysis of stream water samples collected in August 2004: Taylor Mountains 1:250,000 scale quadrangle, Alaska

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000 quadrangle. Samples were collected as part of the multi-year U.S. Geological Survey's project -- Geologic and Mineral Deposit Data for Alaskan Economic Development. Data presented here are from water samples collected primarily in the northeastern part of the Taylor Mountains quadrangle. The data include samples taken from the Taylor Mountains C1, C2, D1, D2, and D4 1:63,360 scale quadrangles. The data are being released at this time with minimal interpretation. Site selection was based on a regional sampling strategy that focused on first and second order drainages. Water sampling site selection was based on landscape parameters that included physiography, wetland extent, lithological changes, and the cursory field review of the mineralogy from the pan concentrates. Stream water in the Taylor Mountians quadrangle is dominated by bicarbonate (HCO3-), though in a few samples more than 50% of the anionic charge can be attibuted to sulfate ( SO42-). The major-cation chemistry range from Ca/Mg dominated to a mix of Ca/Mg/Na+K. Good agreement was found between the major cation and anions in the duplicate samples. Many trace elements were at or near the method detection limit in these samples but good agreement was found between duplicate samples for elements with detectable concentrations. Major ion concentrations were below detection in all field blanks and the trace elements concentrations generally were below detection. However, Ta (range 0.9 -.1 ug/L) and Zn (1 to 3.5 ug/L) were detected in all blanks and Ba ( 0.24 ug/L) and Th (0.2 ug/L) were detected in one blank. There was good agreement between dupilicate total- and methyl- mercury and DOC samples; however, total mercury, methyl-mercury and dissolve organic carbon (DOC) were detected in the blank at 2.35 ng/L, 0.07 ng/L and 0.57 mg/L, respectively.

Alaska

Geochemical mass-balance relationships for selected ions in precipitation and stream water, Catoctin Mountains, Maryland

Results of a study of input/output mass balances for major ions based on the chemical composition of precipitation and stream-water, geochemical reactions with different loading rates of hydrogen ion, and watershed processes influencing the chemical character of stream-waters in two small watershed areas are reported with a view to predicting the effect of additions of acidic rain to the watershed systems. Geochemical weathering processes account for the observed changes in the chemistry of stream flow. Although present in bedrock in extremely small quantities, calcite plays an important role in neutralization of the total hydrogen-ion input.

Maryland

User's Guide to Handlens - A Computer Program that Calculates the Chemistry of Minerals in Mixtures

HandLens is a computer program, written in Excel macro language, that calculates the chemistry of minerals in mineral mixtures (for example, in rocks, soils and sediments) for related samples from inputs of quantitative mineralogy and chemistry. For best results, the related samples should contain minerals having the same chemical compositions; that is, the samples should differ only in the proportions of minerals present. This manual describes how to use the program, discusses the theory behind its operation, and presents test results of the program's accuracy. Required input for HandLens includes quantitative mineralogical data, obtained, for example, by RockJock analysis of X-ray diffraction (XRD) patterns, and quantitative chemical data, obtained, for example, by X-ray florescence (XRF) analysis of the same samples. Other quantitative data, such as sample depth, temperature, surface area, also can be entered. The minerals present in the samples are selected from a list, and the program is started. The results of the calculation include: (1) a table of linear coefficients of determination (r2's) which relate pairs of input data (for example, Si versus quartz weight percents); (2) a utility for plotting all input data, either as pairs of variables, or as sums of up to eight variables; (3) a table that presents the calculated chemical formulae for minerals in the samples; (4) a table that lists the calculated concentrations of major, minor, and trace elements in the various minerals; and (5) a table that presents chemical formulae for the minerals that have been corrected for possible systematic errors in the mineralogical and/or chemical analyses. In addition, the program contains a method for testing the assumption of constant chemistry of the minerals within a sample set.

Open-File Report

Effects of dietary cadmium on mallard ducklings

Mallard (Anas platyrhynchos) ducklings were fed cadmium in the diet at 0, 5, 10, or 20 ppm from 1 day of age until 12 weeks of age. At 4-week intervals six males and six females from each dietary group were randomly selected, bled by jugular venipuncture, and necropsied. Significant decreases in packed cell volume (PCV) and hemoglobin (Hb) concentration and a significant increase in serum glutamic pyruvic transaminase (GPT) were found at 8 weeks of age in ducklings fed 20 ppm cadmium. Mild to severe kidney lesions were evident in ducklings fed 20 ppm cadmium for 12 weeks. No other blood chemistry measurement, hematological parameter, or tissue histopathological measurement indicated a reaction to cadmium ingestion. Body weight, liver weight, and the ratio of the femur weight to length were not affected by dietary cadmium. Femur cadmium concentration In all ducklings 12 weeks of age declined from the values detected at 4 and 8 weeks of age. Liver cadmium concentrations were significantly higher in relation to the increased dietary levels and in relation to the length of time the ducklings were fed the cadmium diets. At 12 weeks of age the cadmium concentration in liver tissue was twice that in the diet.

Environmental Research

Diagenetic fate of organic contaminants on the Palos Verdes Shelf, California

Municipal wastes discharged through deepwater submarine outfalls since 1937 have contaminated sediments of the Palos Verdes Shelf. A site approximately 6–8 km downcurrent from the outfall system was chosen for a study of the diagenetic fate of organic contaminants in the waste-impacted sediments. Concentrations of three classes of hydrophobic organic contaminants (DDT+metabolites, polychlorinated biphenyls (PCBs), and the long-chain alkylbenzenes) were determined in sediment cores collected at the study site in 1981 and 1992. Differences between the composition of effluent from the major source of DDT (Montrose Chemical) and that found in sediments suggests that parent DDT was transformed by hydrolytic dehydrochlorination during the earliest stages of diagenesis. As a result, p , p ′-DDE is the dominant DDT metabolite found in shelf sediments, comprising 60–70% of ΣDDT. The p , p -DDE/ p , p ′-DDMU concentration ratio decreases with increasing sub-bottom depth in sediment cores, indicating that reductive dechlorination of p , p ′-DDE is occurring. Approximately 9–23% of the DDE inventory in the sediments may have been converted to DDMU since DDT discharges began ca. 1953. At most, this is less than half of the decline in p , p ′-DDE inventory that has been observed at the study site for the period 1981–1995. Most of the observed decrease is attributable to remobilization by processes such as sediment mixing coupled to resuspension, contaminant desorption, and current advection. Existing field data suggest that the in situ rate of DDE transformation is 10 2 –10 3 times slower than rates determined in recent laboratory microcosm experiments (Quensen, J.F., Mueller, S.A., Jain, M.K., Tiedje, J.M., 1998. Reductive dechlorination of DDE to DDMU in marine sediment microcosms. Science, 280, 722–724.). This explains why the DDT composition (i.e. o , p ′-, p , p ′-isomers of DDE, DDD, DDT) of sediments from this site have not changed significantly since at least 1972. Congener-specific PCB compositions in shelf sediments are highly uniform and show no evidence of diagenetic transformation. Apparently, the agents/factors responsible for reductive dechlorination of DDE are not also effecting alteration of the PCBs. Two types of long-chain alkylbenzenes were found in the contaminated sediments. Comparison of chain length and isomer distributions of the linear alkylbenzenes in wastewater effluent and surficial sediment samples indicate that these compounds undergo biodegradation during sedimentation. Further degradation of the linear alkylbenzenes occurs after burial despite relatively invariant isomer compositions. The branched alkylbenzenes are much more persistent than the linear alkylbenzenes, presumably due to extensive branching of the alkyl side chain. Based on these results, p , p ′-DDE, PCBs, and selected branched alkylbenzenes are sufficiently persistent for use in molecular stratigraphy. The linear alkylbenzenes may also provide information on depositional processes. However, their application as quantitative molecular tracers should be approached with caution.

California

Hydrochemical facies and ground-water flow patterns in northern part of Atlantic Coastal Plain

The part of the Atlantic Coastal Plain that extends from New Jersey through Virginia was selected as a suitable field model in which to study the relationships between geology, hydrology, and chemical character of ground water. The ground-water flow pattern is the principal hydrologic control on the chemical character of the water. Within the Coastal Plain sediments, the proportions of clay, glauconitic sand, and calcareous material are the principal lithologic controls over the chemistry of the water. A subsurface body of salt water extends from southern New Jersey through southern Virginia and occupies the deposits deeper than about 500 feet below land surface in the eastern part of the Coastal Plain. The position of its top is determined by the relative head, which in turn is influenced by topography, drainage density, and the thickness and permeability of the Coastal Plain sediments. Hydrochemical facies is a term used in this paper to denote the diagnostic chemical aspect of ground-water solutions occurring in hydrologic systems. The facies reflect the response of chemical processes operating within the lithologic framework and also the pattern of flow of the water. The distribution of these facies is shown in trilinear diagrams and isometric fence diagrams and on maps showing isopleths of chemical constituents within certain formations. The occurrence of the various facies within one formation or within a group of formations of uniform mineralogy indicates that the ground-water flow through the aquifer system modifies the distribution of the facies. Flow patterns of fresh ground water shown on maps and in cross sections have been deduced from available water-level data. These patterns are controlled by the distribution of the higher landmasses and by the depth to either bedrock or to the salt-water interface. The mapping of hydrochemical facies shows that at shallow depths within the Coastal Plain (less than about 200 ft) the calcium-magnesium cation facies generally predominates. The bicarbonate anion facies occurs within more of the shallow Coastal Plain sediments than does the sulfate or the chloride facies. In deeper formations, the sodium chloride character predominates. The lower dissolved-solids content of the ground water in New Jersey indicates less upward vertical leakage than in Maryland and Virginia, where the shallow formations contain solutions of higher concentration.

Delaware, Maryland, New Jersey, Pennsylvania, Virg

Identifying calcium sources at an acid deposition-impacted spruce forest: A strontium isotope, alkaline earth element multi-tracer approach

Depletion of calcium from forest soils has important implications for forest productivity and health. Ca is available to fine feeder roots from a number of soil organic and mineral sources, but identifying the primary source or changes of sources in response to environmental change is problematic. We used strontium isotope and alkaline earth element concentration ratios of trees and soils to discern the record of Ca sources for red spruce at a base-poor, acid deposition-impacted watershed. We measured 87 Sr/ 86 Sr and chemical compositions of cross-sectional stemwood cores of red spruce, other spruce tissues and sequential extracts of co-located soil samples. 87 Sr/ 86 Sr and Sr/Ba ratios together provide a tracer of alkaline earth element sources that distinguishes the plant-available fraction of the shallow organic soils from those of deeper organic and mineral soils. Ca/Sr ratios proved less diagnostic, due to within-tree processes that fractionate these elements from each other. Over the growth period from 1870 to 1960, 87 Sr/ 86 Sr and Sr/Ba ratios of stemwood samples became progressively more variable and on average trended toward values that considered together are characteristic of the uppermost forest floor. In detail the stemwood chemistry revealed an episode of simultaneous enhanced uptake of all alkaline earth elements during the growth period from 1930 to 1960, coincident with reported local and regional increases in atmospheric inputs of inorganic acidity. We attribute the temporal trends in stemwood chemistry to progressive shallowing of the effective depth of alkaline earth element uptake by fine roots over this growth period, due to preferential concentration of fine roots in the upper forest floor coupled with reduced nutrient uptake by roots in the lower organic and upper mineral soils in response to acid-induced aluminum toxicity. Although both increased atmospheric deposition and selective weathering of Ca-rich minerals such as apatite provide possible alternative explanations of aspects of the observed trends, the chemical buffering capacity of the forest floor-biomass pool limits their effectiveness as causal mechanisms.

Biogeochemistry

Aqueous geochemical data from the analysis of stream-water samples collected in June and July 2005 — Taylor Mountains 1:250,000 scale quadrangle, Alaska

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000-scale quadrangle. Parameters for which data are reported include pH, conductivity, water temperature, major cation and anion concentrations, trace-element concentrations, and dissolved organic-carbon concentrations. Samples were collected as part of a multiyear U.S. Geological Survey project "Geologic and Mineral Deposit Data for Alaskan Economic Development." Data presented here are from samples collected in June and July of 2005. The data are being released at this time with minimal interpretation. This is the second release of aqueous geochemical data from this project; 2004 aqueous geochemical data were published previously ( Wang and others, 2006 ). The data in this report augment but do not duplicate or supersede the previous data release. Site selection was based on a regional sampling strategy that focused on first- and second-order drainages. Water sample site selection was based on landscape parameters that included physiography, wetland extent, lithological changes, and a cursory field review of mineralogy from pan concentrates. Stream water in the Taylor Mountians quadrangle is dominated by bicarbonate (HCO 3- ), though in a few samples more than 50 percent of the anionic charge can be attributed to sulfate (SO 4 2- ). The major-cation chemistry ranges from Ca 2+ /Mg 2+ dominated to a mix of Ca 2+ /Mg 2+ /Na + +K + . In general, good agreement was found between the major cations and anions in the duplicate samples. Many trace elements in these samples were at or near the analytical method detection limit, but good agreement was found between duplicate samples for elements with detectable concentrations. With the exception of a total mercury concentration of 0.33 ng/L detected in a field blank, field blank major-ion and trace-elements concentrations were below detection.

Alaska

Aqueous geochemical data from the analysis of stream-water samples collected in June and August 2008—Taylor Mountains 1:250,000- and Dillingham D-4 1:63,360-scale quadrangles, Alaska

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000- and Dillingham D-4 1:63,360-scale quadrangles, Alaska. Reported parameters include pH, conductivity, water temperature, major cation and anion concentrations, and trace-element concentrations. We collected the samples as part of a multiyear U.S. Geological Survey project entitled "Geologic and Mineral Deposit Data for Alaskan Economic Development." Data presented here are from samples collected in June and August 2008. Minimal interpretation accompanies this data release. This is the fourth release of aqueous geochemical data from this project; data from samples collected in 2004, 2005, and 2006 were published previously. The data in this report augment but do not duplicate or supersede the previous data releases. Site selection was based on a regional sampling strategy that focused on first- and second-order drainages. Water sample sites were selected on the basis of landscape parameters that included physiography, wetland extent, lithological changes, and a cursory field review of mineralogy from pan concentrates. Stream water in the study area is dominated by bicarbonate (HCO 3 - ), although in a few samples more than 50 percent of the anionic charge can be attributed to sulfate (SO 4 2- ). The major-cation chemistry of these samples ranges from Ca 2+ -Mg 2+ dominated to a mix of Ca 2+ -Mg 2+ -Na + +K 2+ . In most cases, analysis of duplicate samples showed good agreement for the major cation and major anions with the exception of the duplicate samples at site 08TA565. At site 08TA565, Ca, Mg, Cl, and CaCO 3 exceeded 25 percent and the concentrations of trace elements As, Fe and Mn also exceeded 25 percent in this duplicate pair. Chloride concentration varied by more than 25 percent in 5 of the 11 duplicated samples. Trace-element concentrations in these samples generally were at or near the detection limit for the method used and, except for Co at site 08TA565, generally good agreement was determined between duplicate samples for elements with detectable concentrations. Major-ion concentrations were below detection limits in all field blanks, and the trace-element concentrations also were generally below detection limits; however, Co, Mn, Na, Zn, Cl, and Hg were detected in one or more field blank samples.

Alaska

Questa baseline and pre-mining ground-water quality investigation 22 — Groundwater budget for the Straight Creek drainage basin, Red River Valley, New Mexico, with a section on Sulphur Gulch water budget

In April 2001, the U.S. Geological Survey (USGS) and the New Mexico Environment Department (NMED) began a cooperative study to infer the pre-mining ground-water chemistry at the Molycorp molybdenum mine site in the Red River Valley. The Molycorp mine has been in operation since the 1920s. Because ground-water conditions prior to mining are not available, sites analogous to the pre-mining conditions at the mine site must be studied to infer those pre-mining conditions. The Straight Creek drainage basin (watershed) was selected as the primary analog site for this study because of its similar terrain and geology to the mine site, accessibility, potential for well construction, and minimal anthropogenic activity. The purpose of this report is to present results of a water-budget analysis of the debris-flow aquifer in the Straight Creek watershed. The water budget is based on mean annual conditions and is assumed to be steady state. For this study, the Straight Creek watershed was divided into sub-watersheds on the basis of locations of seismic lines, which were used to calculate cross-section area through the Straight Creek debris-flow deposits and underlying fractured and weathered bedrock (regolith). Water-budget components were calculated for areas upstream from and between the seismic lines. Components of the water budget were precipitation, evapotranspiration, surface-water flow, and ground-water flow under a steady-state mean annual condition. Watershed yield, defined as precipitation minus evapotranspiration, was separated into surface-water flow, ground-water flow through the debris-flow deposits and regolith, and ground-water flow through fractured bedrock. The approach to this calculation was to use Darcy's Law to calculate the flow through the cross-section area of the saturated debris-flow deposits and underlying regolith as defined by the interpreted seismic data. The amount of watershed yield unaccounted for through this section then was attributed to either surface-water flow or the component of ground-water flow through fractured bedrock. The inflow to the watershed, calculated to be 701 gallons per minute, is from precipitation. The calculated outflow from the watershed at or upstream from seismic-line 5 (the downstream-most line in Straight Creek prior to entering the Red River Valley) is 540 gallons per minute of evapotranspiration in the watershed upstream from line 5 (77.0 percent of precipitation), 5 gallons per minute of surface-water flow (0.7 percent of precipitation), 122 gallons per minute of ground-water flow through the debris-flow deposits and underlying regolith defined by the seismic data (17.4 percent of precipitation), and 34 gallons per minute of ground-water flow through fractured bedrock below the defined seismic line (4.9 percent of precipitation). The ground-water flow through the alluvium and inter-tonguing debris-flow deposits of the Red River Valley was calculated to be 5,227 gallons per minute at seismic-line 7, the first seismic line in the Red River Valley downstream from Straight Creek. The water budget indicates the amount of ground-water flow that enters the Red River alluvium from the debris-flow deposits and regolith in Straight Creek is small (about 2.3 percent; 122 gallons per minute) compared to the volume of flow that moves through the Red River alluvium. The total amount of ground-water flow from Straight Creek (156 gallons per minute; 122 gallons per minute from debris-flow deposits and regolith plus 34 gallons per minute through fractured bedrock) is about 3.0 percent of the ground-water flow calculated at line 7 for the Red River alluvium.

New Mexico

Improvements in the use of aquatic herbicides and establishment of future research directions

Peer-reviewed literature over the past 20 years identifies significant changes and improvements in chemical control strategies used to manage nuisance submersed vegetation. The invasive exotic plants hydrilla (Hydrilla verticillata L.f. Royle) and Eurasian watermilfoil (Myriophyllum spicatum L.) continue to spread and remain the plant species of greatest concern for aquatic resource managers at the national scale. Emerging exotic weeds of regional concern such as egeria (Egeria densa Planch.), curlyleaf pondweed (Potamogeton crispus L.), and hygrophila (Hygrophila polysperma (Roxb.) T. Anders), as well as native plants such as variable watermilfoil (Myriophyllum heterophyllum Michx), and cabomba (Cabomba caroliniana Gray) are invasive outside their home ranges. In addition, there is always the threat of new plant introductions such as African elodea (Lagarosiphon major (Ridley) Moss) or narrow-leaf anacharis (Egeria najas Planchon). The registration of the bleaching herbicide fluridone in the mid 1980s for whole-lake and large-scale management stimulated numerous lines of research involving reduction of use rates, plant selectivity, residue monitoring, and impacts on fisheries. In addition to numerous advances, the specificity of fluridone for a single plant enzyme led to the first documented case of herbicide resistance in aquatic plant management. The resistance of hydrilla to fluridone has stimulated a renewed interest by industry and others in the registration of alternative modes of action for aquatic use. These newer chemistries tend to be enzyme-specific compounds with favorable non-target toxicity profiles. Registration efforts have been facilitated by increased cooperation between key federal government agencies that have aquatic weed control and research responsibilities, and regulators within the U.S. Environmental Protection Agency (USEPA). We reviewed past and current research efforts to identify areas in need of further investigation and to establish priorities for future research directions in chemical management of submersed plants. The priorities we identified include: (A) improving methods for evaluating non-target impacts of herbicides with an emphasis on threatened and endangered species, or species of special concern; (B) improving herbicide performance in flowing-water environments, including irrigation canals; (C) screening and developing new herbicides to supplement fluridone for large-scale or whole-lake management approaches; (D) screening and developing new organic algaecides to supplement the use of copper-based compounds; (E) developing risk assessment tools to educate the public on the risks of invasive species and chemical management options; (F) increasing cooperative research with ecologists and fisheries scientists to evaluate the long-term impacts of invasive species introductions and herbicide programs on native plant assemblages, water quality, and fish populations; and (G) improving the integration of chemical control technology with other aquatic plant management disciplines. While circumstances may dictate setting new priorities or dropping current ones, the list we have generated represents our vision of the needs that will require the greatest focus over the next several years.

Conference Paper

Toxicity of sediment cores collected from the Ashtabula River in northeastern Ohio, USA, to the amphipod Hyalella azteca

This study was conducted to support a Natural Resource Damage Assessment and Restoration project associated with the Ashtabula River in Ohio. The objective of the study was to evaluate the chemistry and toxicity of 50 sediment samples obtained from five cores collected from the Ashtabula River (10 samples/core, with each 10-cm-diameter core collected to a total depth of about 150 cm). Effects of chemicals of potential concern (COPCs) measured in the sediment samples were evaluated by measuring whole-sediment chemistry and whole-sediment toxicity in the sediment samples (including polycyclic aromatic hydrocarbons [PAHs], polychlorinated biphenyls [PCBs], organochlorine pesticides, and metals). Effects on the amphipod Hyalella azteca at the end of a 28-day sediment toxicity test were determined by comparing survival or length of amphipods in individual sediment samples in the cores to the range of responses of amphipods exposed to selected reference sediments that were also collected from the cores. Mean survival or length of amphipods was below the lower limit of the reference envelope in 56% of the sediment samples. Concentrations of total PCBs alone in some samples or concentrations of total PAHs alone in other samples were likely high enough to have caused the reduced survival or length of amphipods (i.e., concentrations of PAHs or PCBs exceeded mechanistically based and empirically based sediment quality guidelines). While elevated concentrations of ammonia in pore water may have contributed to the reduced length of amphipods, it is unlikely that the reduced length was caused solely by elevated ammonia (i.e., concentrations of ammonia were not significantly correlated with the concentrations of PCBs or PAHs and concentrations of ammonia were elevated both in the reference sediments and in the test sediments). Results of this study show that PAHs, PCBs, and ammonia are the primary COPCs that are likely causing or substantially contributing to the toxicity to sediment-dwelling organisms. ?? 2009 US Government.

Archives of Environmental Contamination and Toxico

Study of multicomponent mixtures in solution with a vertical-axis transmission-type filter-fluorometer

Fluorescence intensity, sensitivity, and the effect of diverse ions are discussed in relation to chemical equilibrium and the general equation for fluorescence. High sensitivity is the common denominator in eliminating or reducing all types of interference and the general equation is the key for quickly selecting conditions that give maximum sensitivity. With a transmission-type fluorometer, experimental fluorescence intensities adhere to the general equation over a very wide range of light absorption. If the instrument has a vertical axis, solution depth can be adjusted so that the data fall on that portion of the theoretical curve which is essentially a straight line. When the fluorescence wavelength selected for measurement is not absorbed by the solution, the general equation reduces to a much simpler expression, and then, under proper circumstances, fluorescence values can be used for calculations as confidently and as easily as absorbance values.

Analytical Chemistry

Simulations of ground-water flow and particle pathline analysis in the zone of contribution of a public-supply well in Modesto, eastern San Joaquin Valley, California

Shallow ground water in the eastern San Joaquin Valley is affected by high nitrate and uranium concentrations and frequent detections of pesticides and volatile organic compounds (VOC), as a result of ground-water development and intensive agricultural and urban land use. A single public-supply well was selected for intensive study to evaluate the dominant processes affecting the vulnerability of public-supply wells in the Modesto area. A network of 23 monitoring wells was installed, and water and sediment samples were collected within the approximate zone of contribution of the public-supply well, to support a detailed analysis of physical and chemical conditions and processes affecting the water chemistry in the well. A three-dimensional, steady-state local ground-water-flow and transport model was developed to evaluate the age of ground water reaching the well and to evaluate the vulnerability of the well to nonpoint source input of nitrate and uranium. Particle tracking was used to compute pathlines and advective travel times in the ground-water flow model. The simulated ages of particles reaching the public-supply well ranged from 9 to 30,000 years, with a median of 54 years. The age of the ground water contributed to the public-supply well increased with depth below the water table. Measured nitrate concentrations, derived primarily from agricultural fertilizer, were highest (17 milligrams per liter) in shallow ground water and decreased with depth to background concentrations of less than 2 milligrams per liter in the deepest wells. Because the movement of water is predominantly downward as a result of ground-water development, and because geochemical conditions are generally oxic, high nitrate concentrations in shallow ground water are expected to continue moving downward without significant attenuation. Simulated long-term nitrate concentrations indicate that concentrations have peaked and will decrease in the public-supply well during the next 100 years because of the low nitrate concentrations in recharge beneath the urban area and the increasing proportion of urban-derived ground water reaching the well. The apparent lag time between peak input concentrations and peak concentrations in the well is about 20 to 30 years. Measured uranium concentrations were also highest (45 micrograms per liter) in shallow ground water, and decreased with depth to background concentrations of about 0.5 microgram per liter. Naturally-occurring uranium adsorbed to aquifer sediments is mobilized by oxygen-rich, high-alkalinity water. Alkalinity increased in shallow ground water in response to agricultural development. As ground-water pumping increased in the 1940s and 1950s, this alkaline water moved downward through the ground-water flow system, mobilizing the uranium adsorbed to aquifer sediments. Ground water with high alkalinity and high uranium concentrations is expected to continue to move deeper in the system, resulting in increased uranium concentrations with depth in ground water. Because alkalinity (and correspondingly uranium) concentrations were high in shallow ground water beneath both the urban and the agricultural land, long-term uranium concentrations in the public-supply well are expected to increase as the proportion of uranium-affected water contributed to the well increases. Assuming that the alkalinity near the water table remains the same, the simulation of long-term alkalinity in the public-supply well indicates that uranium concentrations in the public-supply well will likely approach the maximum contaminant level; however, the time to reach this level is more than 100 years because of the significant proportion of old, unaffected water at depth that is contributed to the public-supply well.

California