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At least 397 records · Page 22Linked to original sources

Riparian control of stream-water chemistry: Implications for hydrochemical basin models

End-member mixing analysis has been used to determine the hydrological structure for basin hydrochemical models at several catchments. Implicit in this use is the assumption that controlling end members have been identified, and that these end members represent distinct landscape locations. At the Panola Mountain Research Watershed, the choice of controlling end members was supported when a large change in the calcium and sulphate concentration of one of the end members was reflected in the stream water. More extensive sampling of groundwater and soil water indicated, however, that the geographic extent of the contributing end members was limited to the riparian zone. Hillslope solutions were chemically distinct from the riparian solutions and did not appear to make a large contribution to streamflow. The dominant control of the riparian zone on stream-water chemistry suggests that hydrological flow paths cannot be inferred from stream-water chemical dynamics.

IAHS-AISH Publication↗

Effect of storm trajectories on snowfall chemistry in Rocky Mountain National Park, Colorado

Snowfall samples from snowstorms lasting 1 to 4 days were collected near the Bear Lake snow telemetry (SnoTel) site in Rocky Mountain National Park, Colorado (ROMO), during the 1998-99 snowfall season to determine if storms moving in from different directions affect the chemistry of precipitation in the park. Storm pathways to Bear Lake during snowfall events were estimated using the HYSPLIT4 backward-trajectory model developed by the National Oceanic and Atmospheric Administration. Deposition of acidic ions of nitrate and sulfate in snowfall during the study varied substantially (two- to threefold) depending on storm trajectory because air masses traversing the park originated from different surrounding areas, including some having large sources of emissions of nitrate and sulfate. Concentrations of nitrate and sulfate in samples were lowest when storms reached ROMO from north and east of the park and were elevated when air masses traveled from the west where a number of power plants are located. Concentrations were highest in storms reaching ROMO from the south, a region with urban areas including Metropolitan Denver.

Conference Paper↗

Use of stream chemistry for monitoring acidic deposition effects in the Adirondack region of New York

Acid-neutralizing capacity (ANC) and pH were measured weekly from October 1991 through September 2001 in three streams in the western Adirondack Mountain region of New York to identify trends in stream chemistry that might be related to changes in acidic deposition. A decreasing trend in atmospheric deposition of SO42- was observed within the region over the 10-yr period, although most of the decrease occurred between 1991 and 1995. Both ANC and pH were inversely related to flow in all streams; therefore, a trend analysis was conducted on (i) the measured values of ANC and pH and (ii) the residuals of the concentration-discharge relations. In Buck Creek, ANC increased significantly (p < 0.05) over the 10 yr, but the residuals of ANC showed no trend (p > 0.10). In Bald Mountain Brook, ANC and residuals of ANC increased significantly (p < 0.01), although the trend was diatonic-a distinct decrease from 1991 to 1996 was followed by a distinct increase from 1996 to 2001. In Fly Pond outlet, ANC and residuals of ANC increased over the study period (p < 0.01), although the trend of the residuals resulted largely from an abrupt increase in 1997. In general, the trends observed in the three streams are similar to results presented for Adirondack lakes in a previous study, and are consistent with the declining trend in atmospheric deposition for this region, although the observed trends in ANC and pH in streams could not be directly attributed to the trends in acidic deposition.

Conference Paper↗

Acid precipitation studies in Colorado and Wyoming: interim report of surveys of montane amphibians and water chemistry

Acid deposition may be detrimental or stressful to native populations of wildlife. Because many species of amphibians breed in shallow ponds created by spring rains or melting snow, they may be particularly vulnerable to the effects of acidification. From 1986 to 1988, we surveyed 105 locations in the central Rocky Mountains where amphibians had been recorded previously, and we found that two species of amphibians had experiences major losses. We found the northern leopard frog ( Rana pipiens ) at only 4 of 33 (12%) historically known localities, and the boreal toad ( Bufo boreas ) was present at 10 of 59 (17%) known localities. Three other species have not suffered region-wide declines. Tiger salamanders ( Ambystoma tigrinum ) and wood frogs ( Rana sylvatica ) were present at 45% and 69% of known localities respectively, and were observed at several localities were they had not been recorded previously. Chorus frogs ( Pseudacris triseriata ) suffered a catastrophic decline in population size in one population monitored since 1961, but regionally, this species was observed in 36 of 56 (64%) known localities and in another 19 localities where there were no previous records. Complete water chemistry was recorded for 41 localities, and pH was measured at 110 sites in total. Acid neutralizing capacity, pH, specific conductivity, and cation concentrations were negatively correlated with elevation. However, in mountain ponds and lakes, pH was rarely less than 6.0 during the amphibian breeding season. We tested the tolerance of embryos of the four species of frogs to low pH. The LC 50 pH was 4.8 for chorus frogs, 4.4-4.7 for leopard frogs, 4.4-4.5 for boreal toads, and 4.2-4.3 for wood frogs. Survival of wood frog embryos declined when exposed to aluminum concentrations of 100 µg/L or greater, but boreal toad embryos survived exposure to aluminum concentrations of 400 µg/L. Acid deposition does not appear to be a major factor in the decline of leopard frogs and boreal toads. However, we have not yet investigated effects of sublethal pH on growth and development of tadpoles. Pollution remains suspect, but other factors, including natural fluctuations in population size, may account for the observed declines.

Colorado;Wyoming↗

Water quality assessment of the Eastern Iowa Basins: Basic water chemistry of rivers and streams, 1996-98

The U.S. Geological Survey began data-collection activities in the Eastern Iowa Basins study unit of the National Water-Quality Assessment Program in September 1995 with the purpose of determining the status and trends in water quality of water from the Wapsipinicon, Cedar, Iowa, and Skunk River basins. From March 1996 through September 1998, monthly surface-water samples were collected from 11 sites on the study's rivers and streams representing three distinct physiographic regions, the Des Moines Lobe, the Iowan Surface, the Southern Iowa Drift Plain, and one subregion, the Iowan Karst. These water samples were analyzed for basic water chemistry, including, but not limited to the following cations: sodium, potassium, magnesium, calcium, and silica; anions: chloride, fluoride, sulfate, and bicarbonate; and two metals - iron and maganese. Although none of the concentrations of the constituents exceeded health advisories or drinking-water regulations, extremely high or low concentrations could potentially affect aquatic life. Calcium, magnesium, and potassium are essential elements for both plant and animal life; manganese is an essential element in plant metabolism; and silica is important in the growth of diatom algae. Calcium had the largest median concentration of 61 milligrams per liter (mg/L) of the cations, and the largest maximum concentration of 100 mg/L. Bicarbonate had the largest median concentration of 210 mg/L of the anions, and the largest maximum concentration of 400 mg/L. Basic water-quality differences related to physiographic differences and seasonality were evident in streams and rivers in the Eastern Iowa Basins. Of the three major landforms, water samples from sites within the Des Moines Lobe, the youngest landform in the study area, had significantly higher median concentrations of calcium (85 mg/L), magnesium (28 mg/L), sulfate (28 mg/L), fluoride (0.31 mg/L), and silica (16 mg/L). The Des Moines Lobe region is calcium magnesium bicarbonate-rich due to the Paleozoic source rocks (limestones and shales) in the bedrock. Water samples from sites within the Southern Iowa Drift Plain had higher median concentrations of sodium (12 mg/L), potassium (3.2 mg/L), and chloride (21 mg/L). Concentrations also varied according to the time of year. Grouping the data into four seasonal periods, water samples collected during the months of October, November, and December, had higher median concentrations of calcium, magnesium, and chloride, then samples collected during other quarters of the year. Water quality in the streams during this low-flow period (October through December) is representative of that in the contributing aquifers.

Iowa↗

Spatial differences in hydrologic characteristics and water chemistry of a temperate coastal plain peatland: The Great Dismal Swamp, USA

Spatial differences in hydrologic processes and geochemistry across forested peatlands control the response of the wetland-community species and resiliency to natural and anthropogenic disturbances. Knowing these controls is essential to effectively managing peatlands as resilient wetland habitats. The Great Dismal Swamp is a 45,325 hectare peatland in the Atlantic Coastal Plain of Virginia and North Carolina, USA, managed by the U.S. Fish and Wildlife Service. The existing forest-species distribution is a product of timber harvesting, hydrologic alteration by canal and road construction, and wildfires. Since 2009, studies of hydrologic and geochemical controls have expanded knowledge of groundwater flow paths, water chemistry, response to precipitation events, and characteristics of the peat. Dominant hydrologic and geochemical controls include (1) the gradual slope in land surface, (2) vertical differences in the hydraulic characteristics of the peat, (3) the proximity of lateral groundwater and small stream inflows from uplands, (4) the presence of an extensive canal and road network, and (5) small, adjustable-height dams on the canals. Although upland sources provide some surface water and lateral groundwater inflow to western parts of the swamp, direct groundwater recharge by precipitation is the major source of water throughout the swamp and the only source in many areas. Additionally, the proximity and type of upland water sources affect water levels and nutrient concentrations in canal water and groundwater. Where streams are a dominant upland source, variations in groundwater levels and nutrient concentrations are greater than where recharge by precipitation is the primary water source. Where upland groundwater is a dominant source, water levels are more stable. Because the species distribution of forest communities in the Swamp is strongly influenced by these controls, swamp managers are beginning to incorporate this knowledge into forest, water, and fire management plans.

North Carolina, Virginia↗

Using high-frequency sampling to detect effects of atmospheric pollutants on stream chemistry

We combined information from long-term (weekly over many years) and short-term (high-frequency during rainfall and snowmelt events) stream water sampling efforts to understand how atmospheric deposition affects stream chemistry. Water samples were collected at the Sleepers River Research Watershed, VT, a temperate upland forest site that receives elevated atmospheric deposition of pollutants such as nitrogen (N) and mercury (Hg). Our use of high-frequency sampling documents responses of nutrients and mercury in streamflow to atmospheric deposition inputs to the watershed.

Conference Paper↗

Effects of a causeway on the chemistry of the brine in Great Salt Lake, Utah

During 1958-59, the Southern Pacific Co. constructed a permeable rockfill causeway to carry its railroad tracks across Great Salt Lake. The causeway divides the lake into two parts and interrupts the formerly free movement of brine about the lake. The causeway has caused significant changes in the chemistry of the lake, including a dilution of the brine in the south part of the lake and a concentration of the brine in the north part.

Utah↗

Hematology and clinical chemistry of sea otters vaptured in Prince William Sound, Alaska following the Exxon Valdez Oil Spill

Hematologic and serum chemical analyses were performed on sea otter blood samples collected from 31 adult males, 63 adult females, and 42 pups captured in western Prince William Sound (oiled area), and 12 adult males, 40 adult females, and 15 pups captured in eastern Prince William Sound (unoiled area) in 1989 and 1990. Hematologic differences between eastern and western adult males were minimal. Both hematocrits and hemoglobins were higher in western than eastern otters but the biological significance of this is equivocal. Western males had higher absolute eosinophil counts, suggesting possible systemic hypersensitivity reactions. Western males had higher serum protein and serum globulin levels than eastern males, suggesting greater antigenic stimulation (more inflammatory and/or infectious conditions). There were no differences in hematologic parameters between eastern and western female otters. Some chemistry changes were present, but the degree of difference was small. Total protein and serum globulin levels were slightly higher in western females, a finding also seen in adult males. Mean levels of liver enzymes for western females were somewhat higher than for the eastern otters, suggesting the possibility of subclinical liver disease. As a group, western pup hematocrits, hemoglobins, and red cell counts were significantly lower than those of eastern pups. From a biological perspective, these reductions were minimal but supported by individual animal data. The red cell data suggest a mild anemia in western pups; however, the degree of anemia was minimal, so that biological significance was equivocal. Other hematologic and clinical chemical differences between eastern and western pups were not striking and were also of equivocal biological significance.

Alaska↗

Evaluating physical habitat and water chemistry data from statewide stream monitoring programs to establish least-impacted conditions in Washington State

Various GIS-generated land-use predictor variables, physical habitat metrics, and water chemistry variables from 75 reference streams and 351 randomly sampled sites throughout Washington State were evaluated for effectiveness at discriminating reference from random sites within level III ecoregions. A combination of multivariate clustering and ordination techniques were used. We describe average observed conditions for a subset of predictor variables as well as proposing statistical criteria for establishing reference conditions for stream habitat in Washington. Using these criteria, we determined whether any of the random sites met expectations for reference condition and whether any of the established reference sites failed to meet expectations for reference condition. Establishing these criteria will set a benchmark from which future data will be compared.

Washington↗

Mineralogical characterization of weathered outcrops as a tool for constraining water chemistry predictions during project planning

Weathered samples from naturally exposed outcrops of troctolite associated with a magmatic Ni-Cu sulphide deposit were characterized by synchrotron-based micro-X-ray fluorescence mapping (µ-XRF) and X-ray absorption spectroscopy (XAS), as well as by lab-based X-ray diffraction, electron microscopy, Raman spectroscopy and wet chemical methods. Metal mobility in weathered samples was assessed using a sequential leach procedure. Results are interpreted in the context of predictions for future mine water chemistry and used to refine the conceptual model for metal mobility following weathering of waste rock at a potential future mine site.

Conference Paper↗

Sedex hydrothermal systems triggered upheavals to marine chemistry and mass extinctions: Applications for ore genesis research and mineral exploration

New USGS research reveals that the discharge of metal-rich brine that formed sedex deposits on ancient seafloors had profound effects on global ocean chemistry and biologic evolution. For example, brine expulsion caused short-duration positive excursions (“spikes”) in the global marine Sr isotope record. While these spikes are unexplained by conventional oceanic models, our chronostratigraphic correlations of major sedex events, combined with mass balance evidence and oceanographic modeling, confirm that the flux of radiogenic Sr from sedex brines during ore formation was sufficient to cause these once enigmatic 87Sr/86Sr spikes. Recognition that the timing of peak 87 Sr/ 86 Sr spikes correlates exactly with global δ 13 C (and δ 18 O) spikes, climate change, deposition of metal-rich black shales and ironstones, metal-induced malformation (teratology) of marine organisms, and mass extinctions, establishes a causal relationship between sedex deposits and these dramatic events in earth history. The relationships among these features are not fully understood. However, our new model demonstrates that the flux of key biolimiting nutrients and metals contained in sedex brines exceeds that of the total modern riverine flux to the ocean. Undoubtably, these immense nutrient fluxes spurred ocean eutrophication, which, ultimately, through a series of positive feedback mechanisms, may be a previously unrecognized trigger of global ocean anoxic events (OAEs) that produced these chemical and biological perturbations. A derivative result from this integrative research is the recognition that OAEs resulted in the formation of “bathtub rim” deposits at redox boundaries along continental margins that concentrated various redox sensitive critical minerals. For example, we have identified midcontinent phosphorite deposits that contains heavy REE grades and tonnages that rival any REE deposit in the world. The recognition that sedex-forming fluid expulsion events are recorded in the global marine isotopic, geologic, and biological records, defines a new approach to the study of and exploration for sedex deposits. Traditional ore genesis research, coupled with chronostratigraphic correlation and high-resolution 87 Sr/ 86 Sr isotope chemostratigraphy can be used to answer long-standing questions about geologic processes responsible for formation of these extraordinary deposits. This approach allows us to constrain, for the first time, the age, duration, and fluxes of fluids and metals vented into the ocean by these giant hydrothermal systems. Accordingly, the fact that large mineralizing events are recorded in the marine sedimentary record opens the tantalizing prospect that we have the ability to conduct effective resource assessments and define prospective basins anywhere in the world. This innovative approach allows for identification of favorable stratigraphic ages and basins and remote evaluation of the size (and, thus, the mineral potential) of undiscovered mineral deposits. This methodology could be applied on regional basin-wide assessments, to evaluate sedimentary basin prospectivity, resource favorability of specific horizons therein, and to the evaluation of the potential of early-stage prospects.

Geological Society of Nevada Newsletter↗

Crystal chemistry and structure refinement of five hydrated calcium borates

The crystal structures of the five known members of the series Ca 2 B 6 O 11 ·xH 2 O (x = 1, 5, 5, 7, 9, and 13) have been refined by full-matrix least-squares techniques, yielding bond distances and angles with standard errors of less than 0·01 Å and 0·5°, respectively. The results illustrate the crystal chemical principles that govern the structures of hydrated borate compounds. The importance of hydrogen bonding in the ferroelectric transition of colemanite is confirmed by more accurate proton assignments.

Journal of Inorganic and Nuclear Chemistry↗

Sources of aerosol nitrate to the Gulf of Aqaba: Evidence from δ15N and δ18O of nitrate and trace metal chemistry

The nitrogen (N) and oxygen (O) isotopic composition (δ 15 N and δ 18 O) of water soluble aerosol nitrate was measured in aerosol samples collected in Eilat, Israel, from August 2003 to November 2004. During this period δ 15 N values ranged from − 6.9‰ to + 1.9‰ and δ 18 O from + 65.1‰ to + 84.9‰ and exhibited strong seasonal variability with higher average δ 15 N values observed in the summer and higher δ 18 O values in the winter. Nitrate isotopic composition was compared with bulk chemical composition and extractable ion and trace metals on co-collected samples linking nitrate isotopic composition to various sources of aerosols to this region. Atmospheric processes impacting the isotopic signatures of nitrate were also considered. Based on back trajectory analyses, the majority of NO 3 − came from air masses originating over the Mediterranean Sea (34%), Western Europe (20%) and the local Negev desert (19%), which contain a larger anthropogenic imprint compared to southern and eastern air masses which are dominated by mineral dust. The potential role of reactive mineral dust aerosols as a regulator of NO 3 − isotopic composition is considered; however, based on factor analysis, neither δ 15 N nor δ 18 O were associated with mineral dust components (such as Fe or Al), but rather with anthropogenic indicators such as Cu, Cd, P and Pb. Seasonality in primary NO x cycling reactions driven by seasonal changes in solar radiation, relative humidity and temperature also influence the observed isotopic signatures. The isotope data, together with trace element analysis, suggests that seasonal variations in both δ 15 N NO3 and δ 18 O NO3 are related to both NO x source and transport processes as well as NO x chemical reactions in the atmosphere. The flux-weighted δ 15 N of aerosol NO 3 − in this area averaged − 2.6‰ making aerosol deposition a substantial contributor of low δ 15 N nitrogen to the oligotrophic waters of the Gulf of Aqaba. Thus, while the flux of atmospheric N to oligotrophic marine systems is smaller than the upward flux of NO 3 − from deep water, it nonetheless represents an important source of new N having a low δ 15 N. Further, if this low δ 15 N signature is not considered, it could interfere with N-fixation estimates based on isotopic composition of dissolved nitrate or particulate organic nitrogen. Thus, atmospheric deposition should be constrained for accurate estimates of marine N-fixation when based on δ 15 N in the ocean. Indeed, in the Gulf of Aqaba, low upper water δ 15 N NO3 values could be related to inputs of atmospheric NO 3 − as well as N-fixation.

Gulf of Aqaba, Eliat↗

Crystal chemistry of thallium in marine ferromanganese deposits

Our understanding of the up to 7 orders of magnitude partitioning of thallium (Tl) between seawater and ferromanganese (FeMn) deposits rests upon two foundations: (1) being able to quantify the Tl(I)/Tl(III) ratio that reflects the extent of the oxidative scavenging of Tl by vernadite (δ-MnO 2 ), the principle manganate mineral in oxic and suboxic environments, and (2) being able to determine the sorption sites and bonding environments of the Tl(I) and Tl(III) complexes on vernadite. We investigated these foundations by determining the oxidation state and chemical form of Tl in FeMn crusts and nodules from the global oceans at a Tl concentration ranging from several hundred ppm (mg/kg) down to the low ppm level. Seventeen hydrogenetic crusts and eleven nodules from the Pacific, Atlantic, Arctic, and Indian Oceans and Baltic Sea were characterized by chemical analysis, X-ray diffraction, Raman spectroscopy, Mn K-edge X-ray absorption near-edge structure (XANES) spectroscopy, Tl L 3 -edge high energy-resolution XANES (HR-XANES) spectroscopy, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The Tl concentration increases linearly from 1.5 to 319 ppm with the Mn/Fe ratio in Fe-vernadite from hydrogenetic crusts, whereas the percentage of Tl(III) to total Tl varies between 62 and 100% independent of both the Mn/Fe and Mn(III)/Mn(IV) ratios. The data, complemented by molecular modeling of the Tl(III) coordination and by XANES calculations, suggest that the enrichment of Tl in Fe-vernadite is driven by (1) the oxidative uptake of octahedrally coordinated Tl(III) above the vacant Mn(IV) sites and on the layer edges of the vernadite layers, and (2) the sorption of Tl(I) on the crystallographic site of Ba at the surface of the vernadite layers, which is an analogue to the surface site of K. Thus, Tl has a high affinity for vernadite regardless of its oxidation state, and the lack of correlation between Tl(III) and the Mn/Fe ratio in FeMn crusts is explained by the affinity of Tl(I) for the Ba site. The Tl concentration varies between 2 and 112 ppm in surface and buried nodules independent of the Mn/Fe ratio, and the percentage of Tl(III) varies between 0 and 100%. Nodules subjected to sediment diagenesis with replacement of layered vernadite by tunneled todorokite are depleted in Tl and have more reduced thallium. Knowledge of the complex interplay of mineralogy, surface chemical processes, and crystallographic siting is required to understand the variability of Tl concentrations, redox state, and acquisition processes by marine FeMn deposits.

ACS Earth and Space Chemistry↗

Chlorfenapyr and mallard ducks: Overview, study design, macroscopic effects, and analytical chemistry

The first commercial pesticide derived from a class of compounds known as halogenated pyrroles was registered for use in the United States in 2001. Chlorfenapyr degrades slowly in soil, sediment, and water and is highly toxic to birds. Information on biochemical or histological endpoints in birds is lacking; therefore, a two‐year study was conducted to provide information needed to develop diagnostic criteria for chlorfenapyr toxicosis. In the first year, male mallard ducks were fed concentrations of 0, 2, 5, or 10 ppm technical chlorfenapyr or 5 ppm of a formulated product in their diet during a 10‐week chronic exposure study. Survival, body weight, feed consumption (removal), behavior, and molt progression were monitored. Feed and liver were analyzed for chlorfenapyr and two metabolites. Five of 10 ducks in the 10‐ppm group died, and neurotoxic effects were observed in the 5‐and 10‐ppm groups. Feed removal increased for ducks receiving chlorfenapyr and body weights of 5‐ and 10‐ppm ducks were reduced. Loss of body fat, muscle atrophy, and bile retention were suggestive of metabolic disruption or a decreased ability to digest and absorb nutrients. Liver and kidney weights and liver and kidney weight/body weight ratios exhibited a positive response to concentrations of chlorfenapyr in the diet. Emaciation and elevated organ weight/body weight ratios are candidates for a suite of indicators of chronic chlorfenapyr exposure. Liver is the preferred tissue for chemical confirmation of exposure.

Environmental Toxicology and Chemistry↗