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Chemistry and origin of minor and trace elements in selected vitrinite concentrates from bituminous and anthracitic coals

Organic and inorganic affinities were determined by comparing the elemental concentrations in the vitrinite concentrates to the concentrations in the companion whole coals. The ratios of these concentrations for 33 selected elements are shown in Figure 1. Ratios greater than 1 indicate organic affinity, and ratios less than 1 indicate inorganic affinity. Br and W generally showed organic affinity in all samples in this study. In the nine samples from the eastern United States (Fig. 1A-C) less than one-fourth of the trace elements show organic affinity compared to nearly one-half for the three English and Australian samples (Fig. 1D). The elements that generally show organic affinity in the non-U.S.A. samples studied include As, Cs, Hf, and Ni, which have generally inorganic affinities in the U.S.A. samples, and Cr, Sb, Se, and U, which have mixed (both organic and inorganic) affinities, in the U.S.A. coals studied, has an inorganic affinity in the English coals studied. B shows organic affinity in the samples from the Illinois basin (Fig. 1C). For the samples studied, Ba shows organic affinity in the Appalachian basin bituminous coals (Fig. 1B), inorganic affinity in the Illinois basin coals, and overall mixed affinities. In all the samples studied, Cu, Mn, Na, Sr, Ta, V, and Zn show mixed affinities, and A1, Co, Eu, Fe, Ga, K, La, Mg, Sc, Si, Th, Ti, and Ub have generally inorganic affinity.

International Journal of Coal Geology

Biogeochemistry of a treeline watershed, northwestern Alaska

Since 1950, mean annual temperatures in northwestern Alaska have increased. Change in forest floor and soil temperature or moisture could alter N mineralization rates, production of dissolved organic carbon (DOC) and organic nitrogen (DON), and their export to the aquatic ecosystem. In 1990, we began study of nutrient cycles in the 800-ha Asik watershed, located at treeline in the Noatak National Preserve, northwestern Alaska. This paper summarizes relationships between topographic aspect, soil temperature and moisture, inorganic and organic N pools, C pools, CO 2 efflux, growing season net N mineralization rates, and stream water chemistry. Forest floor (O2) C/N ratios, C pools, temperature, and moisture were greater on south aspects. More rapid melt of the soil active layer (zone of annual freeze–thaw) and permafrost accounted for the higher moisture. The O2 C and N content were correlated with moisture, inorganic N pools, CO 2 efflux, and inversely with temperature. Inorganic N pools were correlated with temperature and CO 2 efflux. Net N mineralization rates were positive in early summer, and correlated with O2 moisture, temperature, and C and N pools. Net nitrification rates were inversely correlated with moisture, total C and N. The CO 2 efflux increased with temperature and moisture, and was greater on south aspects. Stream ion concentrations declined and DOC increased with discharge. Stream inorganic nitrogen (DIN) output exceeded input by 70%. Alpine stream water nitrate (NO − 3 ) and DOC concentrations indicated substantial contributions to the watershed DIN and DOC budgets.

Alaska

Estimating the impact of seep methane oxidation on ocean pH and dissolved inorganic radiocarbon along the U.S. mid‐Atlantic Bight

Ongoing ocean warming can release methane (CH 4 ) currently stored in ocean sediments as free gas and gas hydrates. Once dissolved in ocean waters, this CH 4 can be oxidized to carbon dioxide (CO 2 ). While it has been hypothesized that the CO 2 produced from aerobic CH 4 oxidation could enhance ocean acidification, a previous study conducted in Hudson Canyon shows that CH 4 oxidation has a small short‐term influence on ocean pH and dissolved inorganic radiocarbon. Here we expand upon that investigation to assess the impact of widespread CH 4 seepage on CO 2 chemistry and possible accumulation of this carbon injection along 234 km of the U.S. Mid‐Atlantic Bight. Consistent with the estimates from Hudson Canyon, we demonstrate that a small fraction of ancient CH 4 ‐derived carbon is being assimilated into the dissolved inorganic radiocarbon (mean fraction of 0.5 ± 0.4 %). The areas with the highest fractions of ancient carbon coincide with elevated CH 4 concentration and active gas seepage. This suggests that aerobic CH 4 oxidation has a greater influence on the dissolved inorganic pool in areas where CH 4 concentrations are locally elevated, instead of displaying a cumulative effect downcurrent from widespread groupings of CH 4 seeps. An upper limit approximation of the input rate of ancient‐derived DIC into the waters overlying the northern U. S Mid‐Atlantic Bight further suggests that oxidation of ancient CH 4 ‐derived carbon is not negligible on the global scale and could contribute to deep‐water acidification over longer time scales.

Journal of Geophysical Research- Biogeosciences

Crassulacean acid metabolism in Isoetes bolanderi in high elevation oligotrophic lakes

Isoetes bolanderi dominates the littoral flora of Siesta (elevation 2,440 m) and Ellery (2,905 m) lakes in the Sierra Nevada Range of California, USA. Both lakes are sparsely vegetated and I. bolanderi maintained aboveground oven dry weight of 30–50 m −22 through most of the 1981 summer growing season. Plants at the higher elevation Ellery Lake were half as large as plants at Siesta Lake and had substantially more biomass in corms. Titratable acidity levels in Isoetes leaves showed a diurnal fluctuation <50 μeq g 1 fresh weight early in the season at the highest elevation site but this increased to ∼300 μeq g 1 FW by mid-summer; starch and chlorophyll levels likewise increased in the leaves over this time. Throughout the season the magnitude of the diurnal acid change was comparable in Isoetes from both lakes but the dynamics of daytime deacidification were not. Averaged over the season, total daytime deacidification at Ellery Lake was 65% complete by noon whereas at Siesta Lake it was only 22% complete by noon. It is suggested that this may be related to the fact that Siesta Lake was more acidic and thus more carbon was in the form of free CO 2 . In both lakes water chemistry showed no consistent diurnal fluctuation in pH or free CO 2 though total inorganic carbon levels were at the extreme low end for aquatic habitats. The studies reported here suggest that under extremely low inorganic carbon levels there may be selection for nighttime CO 2 assimilation. Consistent with this hypothesis is the observation that emergent I. bolanderi plants, resulting from fluctuating water levels, initiated leaves with stomata (unlike adjacent submerged plants) and, although these leaves had substantially higher chlorophyll levels, they showed an order of magnitude less acid fluctuation than submerged leaves.

California

In situ arsenic removal in an alkaline clastic aquifer

In situ removal of As from ground water used for water supply has been accomplished elsewhere in circum-neutral ground water containing high dissolved Fe(II) concentrations. The objective of this study was to evaluate in situ As ground-water treatment approaches in alkaline ground-water (pH > 8) that contains low dissolved Fe (<a few tens of μg/L). The low dissolved Fe content limits development of significant Fe-oxide and the high-pH limits As adsorption onto Fe-oxide. The chemistries of ground water in the two aquifers studied are similar except for the inorganic As species. Although total inorganic As concentrations were similar, one aquifer has dominantly aqueous As(III) and the other has mostly As(V). Dissolved O 2 , Fe(II), and HCl were added to water and injected into the two aquifers to form Fe-oxide and lower the pH to remove As. Cycles of injection and withdrawal involved varying Fe(II) concentrations in the injectate. The As concentrations in water withdrawn from the two aquifers were as low as 1 and 6 μg/L, with greater As removal from the aquifer containing As(V). However, Fe and Mn concentrations increased to levels greater than US drinking water standards during some of the withdrawal periods. A balance between As removal and maintenance of low Fe and Mn concentrations may be a design consideration if this approach is used for public-supply systems. The ability to lower As concentrations in situ in high-pH ground water should have broad applicability because similar high-As ground water is present in many parts of the world.

Applied Geochemistry

Ground-Water Temperature, Noble Gas, and Carbon Isotope Data from the Espanola Basin, New Mexico

Ground-water samples were collected from 56 locations throughout the Espanola Basin and analyzed for general chemistry (major ions and trace elements), carbon isotopes (delta 13C and 14C activity) in dissolved inorganic carbon, noble gases (He, Ne, Ar, Kr, Xe, and 3He/4He ratio), and tritium. Temperature profiles were measured at six locations in the southeastern part of the basin. Temperature profiles suggest that ground water generally becomes warmer with distance from the mountains and that most ground-water flow occurs at depths <250 m below ground surface. The two dominant water types in the basin are Ca/CO3+HCO3 and Na/CO3+HCO3, followed by mixed-cation/CO3+HCO3. Waters generally evolve from Ca/CO3+HCO3 to Na/CO3+HCO3 with increasing residence time through Ca-Na cation exchange with clay minerals. Basin ground water can be divided into four hydrochemical zones based on chemical and isotopic composition: West, Southeast, Northeast, and Central Deep. Hydrochemical zone boundaries are roughly correlated with contacts between geologic units or lithosome transitions within the Tesuque Formation. Geochemical mass-transfer modeling was performed using NETPATH and 14C ages were adjusted accordingly. Isotopic input parameters were varied within reasonable limits to assess uncertainty in the adjusted 14C ages. For each sample, a preferred adjusted age was selected from multiple possible adjusted ages based primarily on the fit between measured and modeled delta 13C values. The range of possible age adjustments for most samples is about 6,000 years or less, indicating that the preferred adjusted age for most samples has a total range of uncertainty of <6,000 years. Preferred adjusted ages range from 0 to 35,400 years. First-order trends in the age distribution include older ages generally occurring farther from rivers on the east side of the basin and farther from the mountains, consistent with both mountain-front recharge and recharge on the basin floor in the form of stream-loss and arroyo recharge. Ages also increase with depth in the Southeast zone, the only area where discrete-depth samples could be collected. Recharge temperatures derived from noble gas concentrations were used in conjunction with an empirically derived local relationship between recharge temperature and elevation to constrain recharge elevation and to estimate fractions of mountain-block recharge (MBR) in sampled waters of Holocene age. Noble gas recharge temperatures indicate that ground water in the Southeast zone contains a significant fraction of MBR, commonly 20-50 percent or more. The same is apparently true for the Northeast zone, though only two data points could be used to evaluate the MBR fraction in this area. Recharge temperatures indicate that the upper 30 m of the regional aquifer on the Pajarito Plateau typically contain little or no MBR. Tritium concentrations and apparent 3H/3He ages indicate that water in the mountain block is dominantly <50 years old, and water in the basin-fill is dominantly >50 years old, consistent with the 14C ages. Terrigenic He (Heterr) concentrations in ground water are high (log Delta Heterr of 2 to 5) throughout much of the basin. High Heterr concentrations are probably caused by in situ production in the Tesuque Formation from locally high concentrations of U-bearing minerals (Northeast zone only), or by upward diffusive/advective transport of crustal- and mantle-sourced He possibly enhanced by basement piercing faults, or by both. The 3He/4He ratio of Heterr (Rterr) is commonly high (Rterr/Ra of 0.3-2.0, where Ra is the 3He/4He ratio in air) suggesting that Espanola Basin ground water commonly contains mantle-sourced He. The 3He/4He ratio of Heterr is generally the highest in the western and southern parts of the basin, closest to the western border fault system and the Quaternary to Miocene volcanics of the Jemez Mountains and Cerros del Rio.

Scientific Investigations Report

Spectrographic analysis of coal and coal ash

Coal can be analyzed on the spectrograph for per cent ash and composition of ash in a matter of a few minutes, using the total energy method. The composition of the ash so determined can be used to calculate ash softening temperatures. This analysis can be made in sufficiently short a time to control tipple and washing operations for preparation of coal to meet specifications. This spectrographic method can be readily adapted to the analysis of rocks, minerals, and inorganic chemicals of all kinds.

Analytical Chemistry

The relation of harvesting intensity to changes in soil, soil water, and stream chemistry in a northern hardwood forest, Catskill Mountains, USA

Previous studies have shown that clearcutting of northern hardwood forests mobilizes base cations, inorganic monomeric aluminum (Al im ), and nitrate (NO 3 - - N) from soils to surface waters, but the effects of partial harvests on NO 3 - - N have been less frequently studied. In this study we describe the effects of a series of partial harvests of varying proportions of basal area removal (22%, 28% and 68%) on Al im , calcium (Ca 2+ ), and NO 3 - - N concentrations in soil extracts, soil water, and surface water in the Catskill Mountains of New York, USA. Increases in NO 3 - - N concentrations relative to pre-harvest values were observed within a few months after harvest in soils, soil water, and stream water for all three harvests. Increases in Al im and Ca 2+ concentrations were also evident in soil water and stream water over the same time period for all three harvests. The increases in Al im , Ca 2+ , and NO 3 - - N concentrations in the 68% harvest were statistically significant as measured by comparing the 18-month pre-harvest period with the 18-month post-harvest period, with fewer significant responses in the two harvests of lowest intensity. All three solutes returned to pre-harvest concentrations in soil water and stream water in the two lowest intensity harvests in 2&ndash;3 years compared to a full 3 years in the 68% harvest. When the results of this study were combined with those of a previous nearby clearcut and 40% harvest, the post-harvest increases in NO 3 - - N concentrations in stream water and soil water suggest a harvesting level above which the relation between concentration and harvest intensity changes; there was a greater change in concentration per unit change in harvest intensity when basal area removal was greater than 40%. These results indicate that the deleterious effects on aquatic ecosystems previously demonstrated for intensive harvests in northern hardwood forests of northeastern North America that receive high levels of atmospheric N deposition can be greatly diminished as harvesting intensity decreases below 40?8%. These results await confirmation through additional incremental forest harvest studies at other locations throughout the world that receive high levels of atmospheric N deposition.

New York

Assessment of selected inorganic constituents in streams in the Central Arizona Basins study area, Arizona and northern Mexico, through 1998

Stream properties and water-chemistry constituent concentrations from data collected by the National Water-Quality Assessment and other U.S. Geological Survey water-quality programs were analyzed to (1) assess water quality, (2) determine natural and human factors affecting water quality, and (3) compute stream loads for the surface-water resources in the Central Arizona Basins study area. Stream temperature, pH, dissolved-oxygen concentration and percent saturation, and dissolved-solids, suspended-sediment, and nutrient concentration data collected at 41 stream-water quality monitoring stations through water year 1998 were used in this assessment. Water-quality standards applicable to the stream properties and water-chemistry constituent concentration data for the stations investigated in this study generally were met, although there were some exceedences. In a few samples from the White River, the Black River, and the Salt River below Stewart Mountain Dam, the pH in reaches designated as a domestic drinking water source was higher than the State of Arizona standard. More than half of the samples from the Salt River below Stewart Mountain Dam and almost all of the samples from the stations on the Central Arizona Project Canal—two of the three most important surface-water sources used for drinking water in the Central Arizona Basins study area—exceeded the U.S. Environmental Protection Agency drinking water Secondary Maximum Contaminant Level for dissolved solids. Two reach-specific standards for nutrients established by the State of Arizona were exceeded many times: (1) the annual mean concentration of total phosphorus was exceeded during several years at stations on the main stems of the Salt and Verde Rivers, and (2) the annual mean concentration of total nitrogen was exceeded during several years at the Salt River near Roosevelt and at the Salt River below Stewart Mountain Dam. Stream properties and water-chemistry constituent concentrations were related to streamflow, season, water management, stream permanence, and land and water use. Dissolved-oxygen percent saturation, pH, and nutrient concentrations were dependent on stream regulation, stream permanence, and upstream disposal of wastewater. Seasonality and correlation with streamflow were dependant on stream regulation, stream permanence, and upstream disposal of wastewater. Temporal trends in streamflow, stream properties, and water-chemistry constituent concentrations were common in streams in the Central Arizona Basins study area. Temporal trends in the streamflow of unregulated perennial reaches in the Central Highlands tended to be higher from 1900 through the 1930s, lower from the 1940s through the 1970s, and high again after the 1970s. This is similar to the pattern observed for the mean annual precipitation for the Southwestern United States and indicates long-term trends in flow of streams draining the Central Highlands were driven by long-term trends in climate. Streamflow increased over the period of record at stations on effluent-dependent reaches as a result of the increase in the urban population and associated wastewater returns to the Salt and Gila Rivers in the Phoenix metropolitan area and the Santa Cruz River in the Tucson metropolitan area. Concentrations of dissolved solids decreased in the Salt River below Stewart Mountain Dam and in the Verde River below Bartlett Dam. This decrease represents an improvement in the water quality and resulted from a concurrent increase in the amount of runoff entering the reservoirs. Stream loads of water-chemistry constituents were compared at different locations along the streams with one another, and stream loads were compared to upstream inputs of the constituent from natural and anthropogenic sources to determine the relative importance of different sources and to determine the fate of the water-chemistry constituent. Of the dissolved solids transported into the Basin and Range Lowlands each year from the Central Arizona Project Canal and from streams draining the Central Highlands, about 1.2 billion kilograms accumulated in the soil, unsaturated zone, and aquifers in agricultural and urban areas as a result of irrigating crops and urban vegetation. Stream loads of phosphorus decreased from the 91st Avenue Wastewater-Treatment Plant downstream to the Gila River at Gillespie Dam, probably as a result of adsorption of phosphorus to the streambed sediments. In this same reach, stream loads of nitrogen increased, most likely because of inputs from fertilizers. The annual mass of nitrogen and phosphorus input to developed basins from quantifiable sources was much larger than the mass input to basins that had little or no municipal or agricul-tural development. These computed inputs exclude the mass of nitrogen and phosphorus from sources such as geologic formations and soils that could not be quantified. The quantifiable annual inputs of nitrogen and phosphorus for the upper Salt River Basin and the upper Verde River Basin were similar to those for the West Clear Creek Basin. This similarity suggests that the small amount of municipal and agricultural development in the upper Salt River and the upper Verde River Basins did not greatly change the basin input flux. For basins with minimal urban and agricultural development, the largest quantifiable source of nitrogen was precipitation, and the largest source of phosphorus was human bodily waste treated by sewer and septic systems. This was in contrast to developed basins, for which fertilizer was the largest quantifiable source of both nutrients. For most basins examined, quantifiable inputs of nitrogen and phosphorus from nonpoint sources were greater than inputs from point sources. This relation emphasizes the importance of land- and water-management policies that protect surface-water resources from nonpoint sources of nutrients as well as from point sources. The amount of nitrogen and phosphorus transpor-ted out of basins was a small fraction of the total for the quantifiable inputs. This result indicated that most of the nutrients input to basins were not transported out of the basins in surface water, but rather were transported to the subsurface (the soil, unsaturated zone, or aquifer), released to the atmosphere (such as volatilized ammonia), or incorporated into the biomass.

Central Arizona Basins study area

Estimating 14C groundwater ages in a methanogenic aquifer

This paper addresses the problem of 14 C age dating of groundwaters in a confined regional aquifer affected by methanogenesis. Increasing CH 4 concentrations along the groundwater flow system and 13 C and 14 C isotopic data for dissolved inorganic carbon, dissolved organic carbon, and CH 4 clearly show the effect of methanogenesis on groundwater chemistry. Inverse reaction path modeling using NETPATH indicates the predominant geochemical reactions controlling the chemical evolution of groundwater in the aquifer are incongruent dissolution of dolomite, ion exchange, methanogenesis, and oxidation of sedimentary organic matter. Modeling of groundwater 14 C ages using NETPATH indicates that a significant part of groundwater in the Alliston aquifer is less than 13,000 years old; however, older groundwater in the range of 15,000–23,000 years is also present in the aquifer. This paper demonstrates that 14C ages calculated using NETPATH, incorporating the effects of methanogenesis on the carbon pools, provide reasonable groundwater ages that were not possible by other isotopic methods.

Water Resources Research

Soil and soil solution chemistry under red spruce stands across the northeastern united states

Red spruce ecosystems in the northeastern United States are of interest because this species is undergoing regional decline. Their underlying soils have been examined closely at only a few sites, and information available on red spruce soils throughout this region is limited.This study was conducted to examine soil and soil solution chemistry at red spruce sites in the northeastern US that encompass the range of soil conditions in which red spruce grow. Soils and soil solutions from Oa and B horizons were obtained over a 2-year period from 12 undisturbed red spruce forests (elevations of 80-975 m) in New York, Vermont, New Hampshire, and Maine. All sites had extremely acid Spodosols (Oa soil pH range 2.56 to 3.11 in 0.01 M CaCl2), with generally low concentrations of base cations and high concentrations of Al on soil exchange sites. There was considerable range in exchange chemistry across the sites, however, with exchangeable Ca in Oa horizons ranging from 2.1 to 21.6 cmolckg-1 and exchangeable Al from 3.6 to 18.3 cmolckg-1. Solution chemistry had high concentrations of DOC in the Oa horizons (1160-15200 ??mol L-1), with higher concentrations in the fall than in the spring, which was probably a reflection of fresh litter inputs. Despite high concentrations of DOC in all solutions, inorganic Al was found in some Oa solutions at concentrations as high as 26 ??mol L-1. Ratios of Ca2+ to inorganic Al concentraturns were less than 1.0 in the Oa horizon of one site, and were well below 1.0 in B horizons of all sites. That soil chemistry was related to soil solution chemistry was demonstrated by solution Al concentrations in the forest floor having significant relationships with pyrophosphate extractable Al, although it was not related in the B horizon. Soil exchangeable Ca/Al ratios in the Oa horizon explained 75% of the variation in solution Ca2+/inorganic Al ratios when mean values were used for each site. Our studies have expanded the range of soil chemical conditions measured for red spruce soils. By characterizing the regional variability, these results will enable site intensive process studies to be better applied to regional problems such as spruce decline.

Soil Science

Increases in dissolved organic carbon accelerate loss of toxic Al in Adirondack lakes recovering from acidification

Increasing pH and decreasing Al in surface waters recovering from acidification have been accompanied by increasing concentrations of dissolved organic carbon (DOC) and associated organic acids that partially offset pH increases and complicate assessments of recovery from acidification. To better understand the processes of recovery, monthly chemistry from 42 lakes in the Adirondack region, NY, collected from 1994 to 2011, were used to (1) evaluate long-term changes in DOC and associated strongly acidic organic acids and (2) use the base-cation surplus (BCS) as a chemical index to assess the effects of increasing DOC concentrations on the Al chemistry of these lakes. Over the study period, the BCS increased (p < 0.01) and concentrations of toxic inorganic monomeric Al (IMAl) decreased (p < 0.01). The decreases in IMAl were greater than expected from the increases in the BCS. Higher DOC concentrations that increased organic complexation of Al resulted in a decrease in the IMAl fraction of total monomeric Al from 57% in 1994 to 23% in 2011. Increasing DOC concentrations have accelerated recovery in terms of decreasing toxic Al beyond that directly accomplished by reducing atmospheric deposition of strong mineral acids.

Environmental Science & Technology

Transient groundwater chemistry near a river: Effects on U(VI) transport in laboratory column experiments

In the 300 Area of a U(VI)-contaminated aquifer at Hanford, Washington, USA, inorganic carbon and major cations, which have large impacts on U(VI) transport, change on an hourly and seasonal basis near the Columbia River. Batch and column experiments were conducted to investigate the factors controlling U(VI) adsorption/desorption by changing chemical conditions over time. Low alkalinity and low Ca concentrations (Columbia River water) enhanced adsorption and reduced aqueous concentrations. Conversely, high alkalinity and high Ca concentrations (Hanford groundwater) reduced adsorption and increased aqueous concentrations of U(VI). An equilibrium surface complexation model calibrated using laboratory batch experiments accounted for the decrease in U(VI) adsorption observed with increasing (bi)carbonate concentrations and other aqueous chemical conditions. In the column experiment, alternating pulses of river and groundwater caused swings in aqueous U(VI) concentration. A multispecies multirate surface complexation reactive transport model simulated most of the major U(VI) changes in two column experiments. The modeling results also indicated that U(VI) transport in the studied sediment could be simulated by using a single kinetic rate without loss of accuracy in the simulations. Moreover, the capability of the model to predict U(VI) transport in Hanford groundwater under transient chemical conditions depends significantly on the knowledge of real-time change of local groundwater chemistry.

Washington

Questa baseline and pre-mining ground-water quality investigation. 20. Water chemistry of the Red River and selected seeps, tributaries, and precipitation, Taos County, New Mexico, 2000-2004

As part of a multi-year project to infer the pre-mining ground-water quality at Molycorp's Questa mine site, surface-water samples of the Red River, some of its tributaries, seeps, and snow samples were collected for analysis of inorganic solutes and of water and sulfate stable isotopes in selected samples. The primary aim of this study was to document diel, storm event, and seasonal variations in water chemistry for the Red River and similar variations in water chemistry for Straight Creek, a natural analog site similar in topography, hydrology, and geology to the mine site for inferring pre-mining water-quality conditions. Red River water samples collected between 2000 and 2004 show that the largest variations in water chemistry occur during late summer rainstorms, often monsoonal in nature. Within hours, discharge of the Red River increased from 8 to 102 cubic feet per second and pH decreased from 7.80 to 4.83. The highest concentrations of metals (iron, aluminum, zinc, manganese) and sulfate also occur during such events. Low-pH and high-solute concentrations during rainstorm runoff are derived primarily from alteration 'scar' areas of naturally high mineralization combined with steep topography that exposes continually altered rock because erosion is too rapid for vegetative growth. The year 2002 was one of the driest on record, and Red River discharge reflected the low seasonal snow pack. No snowmelt peak appeared in the hydrograph record, and a late summer storm produced the highest flow for the year. Snowmelt was closer to normal during 2003 and demonstrated the dilution effect of snowmelt on water chemistry. Two diel sampling events were conducted for the Red River, one during low flow and the other during high flow, at two locations, at the Red River gaging station and just upstream from Molycorp's mill site. No discernible diel trends were observed except for dissolved zinc and manganese at the upstream site during low flow. Straight Creek drainage water was sampled periodically from 2001 to 2004 at the down stream end of surface drainage near the point at which it disappeared into the debris fan. This water has a minimal range in pH (2.7 to 3.2) but a substantial concentration range in many solutes; for example, sulfate concentrations varied from 525 to 2,660 mg/L. Many elements covary with sulfate suggesting that dilution is the primary control of the range in solute concentrations. A transect of water samples higher in the scar area were collected in October of 2003. They had a lower range in pH (2.44 to 3.05) and higher solute concentrations than those collected periodically from lower in the catchment. Water isotopes for the upper transect samples indicated slight evaporation, and in part, may account for the higher solute concentrations. Drainage waters also were collected from Hottentot, Junebug, Hansen, Little Hansen, and Goat Hill Gulch drainages. Most constituents from other scar drainage waters showed ranges of concentration similar to those of the Straight Creek waters. An exception was water collected from Goat Hill Gulch, which has some of the highest concentrations of any surface-water sample collected but also contained waste-rock leachates.

New Mexico

Intertidal salt marshes as an important source of inorganic carbon to the coastal ocean

Dynamic tidal export of dissolved inorganic carbon (DIC) to the coastal ocean from highly productive intertidal marshes and its effects on seawater carbonate chemistry are thoroughly evaluated. The study uses a comprehensive approach by combining tidal water sampling of CO 2 parameters across seasons, continuous in situ measurements of biogeochemically-relevant parameters and water fluxes, with high-resolution modeling in an intertidal salt marsh of the U.S. northeast region. Salt marshes can acidify and alkalize tidal water by injecting CO 2 (DIC) and total alkalinity (TA). DIC and TA generation may also be decoupled due to differential effects of marsh aerobic and anaerobic respiration on DIC and TA. As marsh DIC is added to tidal water, the buffering capacity first decreases to a minimum and then increases quickly. Large additions of marsh DIC can result in higher buffering capacity in ebbing tide than incoming tide. Alkalization of tidal water, which mostly occurs in the summer due to anaerobic respiration, can further modify buffering capacity. Marsh exports of DIC and alkalinity may have complex implications for the future, more acidified ocean. Marsh DIC export exhibits high variability over tidal and seasonal cycles, which is modulated by both marsh DIC generation and by water fluxes. The marsh DIC export of 414 g C m −2 yr −1 , based on high-resolution measurements and modeling, is more than twice the previous estimates. It is a major term in the marsh carbon budget and translates to one of the largest carbon fluxes along the U.S. East Coast.

Massachusetts

Water-quality assessment of the Trinity River Basin, Texas— Ground-water quality of the Trinity, Carrizo-Wilcox, and Gulf Coast aquifers, February-August 1994

Ground-water samples were collected from wells in the outcrops of the Trinity, Carrizo-Wilcox, and Gulf Coast aquifers during February-August 1994 to determine the quality of ground water in the three major aquifers in the Trinity River Basin study unit, Texas. These samples were collected and analyzed for selected properties, nutrients, major inorganic constituents, trace elements, pesticides, dissolved organic carbon, total phenols, methylene blue active substances, and volatile organic compounds as part of the U.S. Geological Survey National Water-Quality Assessment Program. Quality-control practices included the collection and analysis of blank, duplicate, and spiked samples. Samples were collected from 12 shallow wells (150 feet or less) and from 12 deep wells (greater than 150 feet) in the Trinity aquifer, 11 shallow wells and 12 deep wells in the Carrizo-Wilcox aquifer, and 14 shallow wells and 10 deep wells in the Gulf Coast aquifer. The three aquifers had similar water chemistries-calcium was the dominant cation and bicarbonate the dominant anion. Statistical tests relating well depths to concentrations of nutrients and major inorganic constituents indicated correlations between well depth and concentrations of ammonia nitrogen, nitrite plus nitrate nitrogen, bicarbonate, sodium, and dissolved solids in the Carrizo-Wilcox aquifer and between well depth and concentrations of sulfate in the Gulf Coast aquifer. The tests indicated no significant correlations for the Trinity aquifer. Concentrations of dissolved solids were larger than the secondary maximum contaminant level of 500 milligrams per liter established for drinking water by the U.S. Environmental Protection Agency in 12 wells in the Trinity aquifer, 4 wells in the Carrizo-Wilcox aquifer, and 6 wells in the Gulf Coast aquifer. Iron concentrations were larger than the secondary maximum contaminant level of 300 micrograms per liter in at least 3 samples from each aquifer, and manganese concentrations were larger than the secondary maximum contaminant level of 50 micrograms per liter in at least 2 samples from each aquifer. The pesticides atrazine, deethylatrazine, and pp'-DDE were detected in at least one sample from each aquifer. Diazinon was detected in 11 Trinity aquifer samples and 4 Carrizo-Wilcox aquifer samples. Each aquifer had one detection of a volatile organic compound-benzene in the Trinity aquifer, trichlorofluoromethane in the Carrizo-Wilcox aquifer, and trichloromethane in the Gulf Coast aquifer.

Texas

Wetlands serve as natural sources for improvement of stream ecosystem health in regions affected by acid deposition

For over 40 years, acid deposition has been recognized as a serious international environmental problem, but efforts to restore acidified streams and biota have had limited success. The need to better understand the effects of different sources of acidity on streams has become more pressing with the recent increases in surface water organic acids, or 'brownification' associated with climate change and decreased inorganic acid deposition. Here, we carried out a large scale multi-seasonal investigation in the Adirondacks, one of the most acid-impacted regions in the United States, to assess how acid stream producers respond to local and watershed influences and whether these influences can be used in acidification remediation. We explored the pathways of wetland control on aluminum chemistry and diatom taxonomic and functional composition. We demonstrate that streams with larger watershed wetlands have higher organic content, lower concentrations of acidic anions, and lower ratios of inorganic to organic monomeric aluminum, all beneficial for diatom biodiversity and guilds producing high biomass. Although brownification has been viewed as a form of pollution, our results indicate that it may be a stimulating force for biofilm producers with potentially positive consequences for higher trophic levels. Our research also reveals that the mechanism of watershed control of local stream diatom biodiversity through wetland export of organic matter is universal in running waters, operating not only in hard streams, as previously reported, but also in acid streams. Our findings that the negative impacts of acid deposition on Adirondack stream chemistry and biota can be mitigated by wetlands have important implications for biodiversity conservation and stream ecosystem management. Future acidification research should focus on the potential for wetlands to improve stream ecosystem health in acid-impacted regions and their direct use in stream restoration, for example, through stream rechanneling or wetland construction in appropriate hydrologic settings.

Global Change Biology

Tracking solutes and water from subsurface drip irrigation application of coalbed methane-produced waters, Powder River Basin, Wyoming

One method to beneficially use water produced from coalbed methane (CBM) extraction is subsurface drip irrigation (SDI) of croplands. In SDI systems, treated CBM water (injectate) is supplied to the soil at depth, with the purpose of preventing the buildup of detrimental salts near the surface. The technology is expanding within the Powder River Basin, but little research has been published on its environmental impacts. This article reports on initial results from tracking water and solutes from the injected CBM-produced waters at an SDI system in Johnson County, Wyoming. In the first year of SDI operation, soil moisture significantly increased in the SDI areas, but well water levels increased only modestly, suggesting that most of the water added was stored in the vadose zone or lost to evapotranspiration. The injectate has lower concentrations of most inorganic constituents relative to ambient groundwater at the site but exhibits a high sodium adsorption ratio. Changes in groundwater chemistry during the same period of SDI operation were small; the increase in groundwater-specific conductance relative to pre-SDI conditions was observed in a single well. Conversely, groundwater samples collected beneath another SDI field showed decreased concentrations of several constituents since the SDI operation. Groundwater-specific conductance at the 12 other wells showed no significant changes. Major controls on and compositional variability of groundwater, surface water, and soil water chemistry are discussed in detail. Findings from this research provide an understanding of water and salt dynamics associated with SDI systems using CBM-produced water.

Wyoming