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At least 289 records · Page 16Linked to original sources
USGS2000

Formation of ferromanganese crusts on northwest intertropical Pacific seamounts: Electron photomicrography and microprobe chemistry

Seven ferromanganese crusts from the northwest intertropical Pacific seamounts were analyzed for photomicroscopic growth structures, microprobe chemistry, and ages based on Co-chronometer growth rate. The crusts on the Marshall Islands seamounts are thick and ale divided into phosphatized lower older and nonphosphatized upper younger growth generations: the older crust consists of compact laminations and columns impregnated with carbonate fluoapatite (CFA), whereas the younger crust is characterized by porous botryoids and columns of ??-MnO2 and Fe oxyhydroxide. The crusts on the Federated States of Micronesia (FSM) and Palau Islands seamounts are thin and are often incorporated with inorganic opal-A in the uppermost part, comprising the younger generation. Some crusts show scours and fractures. Although the growth of crusts has been often interrupted by mass failure of slope sediments, the crusts on the Marshall Islands seamounts are estimated to have grown at rate of about 3 mm/Ma since the middle Eocene and to have been phosphatized in the late Oligocene during the host seamounts were located beneath the equatorial zone of high productivity. Prolonged infiltration of the oxygen minimum zone (OMZ) water into shallower water older crusts redistributed crust composition by precipitating CFA, enriching subsequent amounts of Mn and Ni, and removing some Co. The younger crust has formed at slower rate (about 2 mm/Ma) under the stronger influence of bottom-water circulation in the north of the equatorial zone, concentrating abundant Co. In the uppermost part of some crusts, siliceous skeletons transform with burial to inorganic opal-A and Si-rich Fe oxyhydroxide, suggesting that biosilica diagenesis can enhance crust growth. (C) 2000 Elsevier Science B.V.

Marine Geology↗
USGS2009

Chemistry of dissolved organic matter in rivers, lakes, and reservoirs

Recent investigations provide new insight on the structural chemistry of dissolved organic matter (DOM) in freshwater environments and the role of these structures in contaminant binding. Molecular models of DOM derived from allochthonous and autochthonous sources show that short-chain, branched, and alicyclic structures are terminated by carboxyl or methyl groups in DOM from both sources. Allochthonous DOM, however, had aromatic structures indicative of tannin and lignin residues, whereas the autochthonous DOM was characterized by aliphatic alicyclic structures indicative of lipid hydrocarbons as the source. DOM isolated from different morphoclimatic regions had minor structural differences.

Book chapter↗
USGS2009

Mercury cycling in stream ecosystems. 1. Water column chemistry and transport

We studied total mercury (THg) and methylmercury (MeHg) in eight streams, located in Oregon, Wisconsin, and Florida, that span large ranges in climate, landscape characteristics, atmospheric Hg deposition, and water chemistry. While atmospheric deposition was the source of Hg at each site, basin characteristics appeared to mediate this source by providing controls on methylation and fluvial THg and MeHg transport. Instantaneous concentrations of filtered total mercury (FTHg) and filtered methylmercury (FMeHg) exhibited strong positive correlations with both dissolved organic carbon (DOC) concentrations and streamflow for most streams, whereas mean FTHg and FMeHg concentrations were correlated with wetland density of the basins. For all streams combined, whole water concentrations (sum of filtered and particulate forms) of THg and MeHg correlated strongly with DOC and suspended sediment concentrations in the water column.

Environmental Science & Technology↗
USGS1999

Long‐term trends in stream water and precipitation chemistry at five headwater basins in the northeastern United States

Stream water data from five headwater basins in the northeastern United States covering water years 1968–1996 and precipitation data from eight nearby precipitation monitoring sites covering water years 1984‐1996 were analyzed for temporal trends in chemistry using the nonparametric seasonal Kendall test. Concentrations of SO 4 declined at three of five streams during 1968–1996 ( p < 0.1), and all of the streams exhibited downward trends in SO 4 over the second half of the period (1984–1996). Concentrations of SO 4 in precipitation declined at seven of eight sites from 1984 to 1996, and the magnitudes of the declines (−0.7 to −2.0 µeq L −1 yr −1 ) generally were similar to those of stream water SO 4 . These results indicate that changes in precipitation SO 4 were of sufficient magnitude to account for changes in stream water SO 4 . Concentrations of Ca + Mg declined at three of five streams and five of eight precipitation sites from 1984 to 1996. Precipitation acidity decreased at five of eight sites during the same period, but alkalinity increased in only one stream. In most cases the decreases in stream water SO 4 were similar in magnitude to declines in stream water Ca + Mg, which is consistent with the theory of leaching by mobile acid anions in soils. In precipitation the magnitudes of SO 4 declines were similar to those of hydrogen, and declines in Ca +Mg were much smaller. This indicates that recent decreases in SO 4 deposition are now being reflected in reduced precipitation acidity. The lack of widespread increases in stream water alkalinity, despite the prevalence of downward trends in stream water SO 4 , suggests that at most sites, increases in stream water p H and acid‐neutralizing capacity may be delayed until higher soil base‐saturation levels are achieved.

Water Resources Research↗
USGS2000

Stream chemistry modeling of two watersheds in the Front Range, Colorado

We investigated the hydrologic, geochemical, and biogeochemical controls on stream chemical composition on the Green Lakes Valley and Andrews Creek watersheds using the alpine hydrochemical model (AHM). Both sites had comparable data sets from 1994 and 1996, including high‐resolution spatial data and high‐frequency time series of hydrology, geochemistry, and meteorology. The model of each watershed consisted of three terrestrial subunits (soil, talus, and rock), with the routing between the subunits determined by spatial land cover data. Using 1994 data for model calibration and 1996 data for evaluation, AHM captured the dominant processes and successfully simulated daily stream chemical composition on both watersheds. These results confirm our procedure of using spatial and site‐specific field and laboratory data to generate an initial catchment model and then calibrating the model to calculate effective parameters for unmeasured processes. A net source of nitrogen was identified in the Andrews Creek watershed during the spring snowmelt period, whereas nitrogen was immobilized in the Green Lakes Valley. This difference was most likely due to the larger and more dominant area of talus in the Andrews Creek watershed. Our results also indicate that routing of snowmelt through either soil or talus material is sufficient for retention of H + and release of base cations but that N retention is more important on areas mapped as soil. Owing to the larger ionic pulse and larger fraction of surface runoff the Green Lakes Valley was more sensitive to a doubling of wet deposition chemistry than the Andrews Creek watershed.

Colorado↗
USGS2002

Weathering reactions and hyporheic exchange controls on stream water chemistry in a glacial meltwater stream in the McMurdo Dry Valleys

In the McMurdo Dry Valleys, Antarctica, dilute glacial meltwater flows down well‐established streambeds to closed basin lakes during the austral summer. During the 6–12 week flow season, a hyporheic zone develops in the saturated sediment adjacent to the streams. Longer Dry Valley streams have higher concentrations of major ions than shorter streams. The longitudinal increases in Si and K suggest that primary weathering contributes to the downstream solute increase. The hypothesis that weathering reactions in the hyporheic zone control stream chemistry was tested by modeling the downstream increase in solute concentration in von Guerard Stream in Taylor Valley. The average rates of solute supplied from these sources over the 5.2 km length of the stream were 6.1 × 10 −9 mol Si L −1 m −1 and 3.7 × 10 −9 mol K L −1 m −1 , yielding annual dissolved Si loads of 0.02–1.30 mol Si m −2 of watershed land surface. Silicate minerals in streambed sediment were analyzed to determine the representative surface area of minerals in the hyporheic zone subject to primary weathering. Two strategies were evaluated to compute sediment surface area normalized weathering rates. The first applies a best linear fit to synoptic data in order to calculate a constant downstream solute concentration gradient, dC / dx (constant weathering rate contribution, CRC method); the second uses a transient storage model to simulate dC / dx , representing both hyporheic exchange and chemical weathering (hydrologic exchange, HE method). Geometric surface area normalized dissolution rates of the silicate minerals in the stream ranged from 0.6 × 10 −12 mol Si m −2 s −1 to 4.5 × 10 −12 mol Si m −2 s −1 and 0.4 × 10 −12 mol K m −2 s −1 to 1.9 × 10 −12 mol K m −2 s −1 . These values are an order of magnitude lower than geometric surface area normalized weathering rates determined in laboratory studies and are an order of magnitude greater than geometric surface area normalized weathering rates determined in a warmer, wetter setting in temperate basins, despite the cold temperatures, lack of precipitation and lack of organic material. These results suggest that the continuous saturation and rapid flushing of the sediment due to hyporheic exchange facilitates weathering in Dry Valley streams.

Water Resources Research↗
USGS2003

Diagnostic tools for mixing models of stream water chemistry

Mixing models provide a useful null hypothesis against which to evaluate processes controlling stream water chemical data. Because conservative mixing of end‐members with constant concentration is a linear process, a number of simple mathematical and multivariate statistical methods can be applied to this problem. Although mixing models have been most typically used in the context of mixing soil and groundwater end‐members, an extension of the mathematics of mixing models is presented that assesses the “fit” of a multivariate data set to a lower dimensional mixing subspace without the need for explicitly identified end‐members. Diagnostic tools are developed to determine the approximate rank of the data set and to assess lack of fit of the data. This permits identification of processes that violate the assumptions of the mixing model and can suggest the dominant processes controlling stream water chemical variation. These same diagnostic tools can be used to assess the fit of the chemistry of one site into the mixing subspace of a different site, thereby permitting an assessment of the consistency of controlling end‐members across sites. This technique is applied to a number of sites at the Panola Mountain Research Watershed located near Atlanta, Georgia.

Water Resources Research↗
USGS2008

Infiltration from an impoundment for coal‐bed natural gas, Powder River Basin, Wyoming: Evolution of water and sediment chemistry

Development of coal‐bed natural gas (CBNG) in the Powder River Basin, Wyoming, has increased substantially in recent years. Among environmental concerns associated with this development is the fate of groundwater removed with the gas. A preferred water‐management option is storage in surface impoundments. As of January 2007, permits for more than 4000 impoundments had been issued within Wyoming. A study was conducted on changes in water and sediment chemistry as water from an impoundment infiltrated the subsurface. Sediment cores were collected prior to operation of the impoundment and after its closure and reclamation. Suction lysimeters were used to collect water samples from beneath the impoundment. Large amounts of chloride (12,300 kg) and nitrate (13,500 kg as N), most of which accumulated naturally in the sediments over thousands of years, were released into groundwater by infiltrating water. Nitrate was more readily flushed from the sediments than chloride. If sediments at other impoundment locations contain similar amounts of chloride and nitrate, impoundments already permitted could release over 48 × 10 6 kg of chloride and 52 × 10 6 kg of nitrate into groundwater in the basin. A solute plume with total dissolved solid (TDS) concentrations at times exceeding 100,000 mg/L was created in the subsurface. TDS concentrations in the plume were substantially greater than those in the CBNG water (about 2300 mg/L) and in the ambient shallow groundwater (about 8000 mg/L). Sulfate, sodium, and magnesium are the dominant ions in the plume. The elevated concentrations are attributed to cation‐exchange‐enhanced gypsum dissolution. As gypsum dissolves, calcium goes into solution and is exchanged for sodium and magnesium on clays. Removal of calcium from solution allows further gypsum dissolution.

Water Resources Research↗
USGS2011

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↗
USGS2012

Temporal variations of geyser water chemistry in the Upper Geyser Basin, Yellowstone National Park, USA

Geysers are rare features that reflect a delicate balance between an abundant supply of water and heat and a unique geometry of fractures and porous rocks. Between April 2007 and September 2008, we sampled Old Faithful, Daisy, Grand, Oblong, and Aurum geysers in Yellowstone National Park's Upper Geyser Basin and characterized temporal variations in major element chemistry and water isotopes (δ 18 O, δD, 3 H). We compare these temporal variations with temporal trends of Geyser Eruption Intervals (GEI). SiO 2 concentrations and geothermometry indicate that the geysers are fed by waters ascending from a reservoir with temperatures of ∼190 to 210°C. The studied geysers display small and complex chemical and isotopic seasonal variations, and geysers with smaller volume display larger seasonal variations than geysers with larger volumes. Aurum and Oblong Geysers contain detectable tritium concentrations, suggesting that erupted water contains some modern meteoric water. We propose that seasonal GEI variations result from varying degrees of evaporation, meteoric water recharge, water table fluctuations, and possible hydraulic interaction with the adjacent Firehole River. We demonstrate that the concentrations of major dissolved species in Old Faithful Geyser have remained nearly constant since 1884 despite large changes in Old Faithful's eruption intervals, suggesting that no major changes have occurred in the hydrothermal system of the Upper Geyser Basin for >120 years. Our data set provides a baseline for monitoring future changes in geyser activity that might result from varying climate, earthquakes, and changes in heat flow from the underlying magmatic system.

Wyoming↗
USGS2019

Carbon chemistry of intact versus chronically drained peatlands in the southeastern USA

The Great Dismal Swamp (GDS) is a large temperate swamp in Virginia/North Carolina with peat soils historically resistant to microbial decomposition. However, this peatland has been subject to ~200 years of disturbance during which extensive drainage, fire suppression, and wide-spread logging have increased decomposition and dramatically decreased the distribution of Atlantic white cedar (AWC). The purpose of this study was to determine the impact of long-term drainage and AWC loss on the carbon chemistry of GDS peats. Peat cores were collected from three drained GDS vegetation communities (pocosin, AWC, and red maple-black gum) and compared to cores collected from an intact, undrained AWC peatland at the Alligator River National Wildlife Refuge (AR) in North Carolina, USA. The AR peats had higher lignin content in the deeper peat intervals, and lignin content and % organic carbon were largely invariant with depth compared to the GDS peats. The concentrations of syringyl group phenols were greater in the surface layers of GDS peats, likely reflecting the selective removal of AWC and transition from gymnosperms to angiosperms. Acid to aldehyde ratios for vanillyl and syringyl group phenols indicated that the GDS peats were more decomposed, particularly at depth, and that this occurred under aerobic conditions. Moreover, solid state 13C NMR confirmed a coincident loss of carbohydrates and increase in recalcitrant byproducts of carbohydrate degradation with depth. These data indicate that long-term drainage has accelerated the decomposition of peat at the GDS, reducing the capacity and stability of the carbon sink.

Virginia, North Carolina↗
USGS2010

Modeling the effects of variable groundwater chemistry on adsorption of molybdate

Laboratory experiments were used to identify and quantify processes having a significant effect on molybdate (MoO 4 2− ) adsorption in a shallow alluvial aquifer on Cape Cod, assachusetts. Aqueous chemistry in the aquifer changes as a result of treated sewage effluent mixing with groundwater. Molybdate adsorption decreased as p H, ionic strength, and the concentration of competing anions increased. A diffuse-layer surface complexation model was used to simulate adsorption of MoO 4 2− , phosphate (PO 4 3− ), and sulfate (SO 4 2− ) on aquifer sediment. Equilibrium constants for the model were calculated by calibration to data from batch experiments. The model was then used in a one-dimensional solute transport program to successfully simulate initial breakthrough of MoO 4 2− from column experiments. A shortcoming of the solute transport program was the inability to account for kinetics of physical and chemical processes. This resulted in a failure of the model to predict the slow rate of desorption of MoO 4 2− from the columns. The mobility of MoO 4 2− ncreased with ionic strength and with the formation of aqueous complexes with calcium, magnesium, and sodium. Failure to account for MoO 4 2− speciation and ionic strength in the model resulted in overpredicting MoO 4 2− adsorption. Qualitatively, the laboratory data predicted the observed behavior of MoO 4 2− in the aquifer, where retardation of MoO 4 2− was greatest in uncontaminated roundwater having low p H, low ionic strength, and low concentrations of PO 4 3− and SO 4 2− .

Water Resources Research↗
USGS2012

Applications of mineral surface chemistry to environmental problems

Environmental surface chemistry involves processes that occur at the interface between the regolith, hydrosphere and atmosphere. The more limited scope of the present review addresses natural and anthropogenically-induced inorganic geochemical reactions between solutes in surface and ground waters and soil and aquifer substrates. Important surficial reactions include sorption, ion exchange, dissolution, precipitation and heterogeneous oxidation/reduction processes occurring at the solid/aqueous interface. Recent research advances in this field have addressed, both directly and indirectly, societal issues related to water quality, pollution, biogeochemical cycling, nutrient budgets and chemical weathering related to long term global climate change. This review will include recent advances in the fundamental and theoretical understanding of these surficial processes, breakthroughs in experimental and instrumental surface characterization, and development of methodologies for field applications.

Reviews of Geophysics↗
USGS2010

The chemistry of iron, aluminum, and dissolved organic material in three acidic, metal-enriched, mountain streams, as controlled by watershed and in-stream processes

Several studies were conducted in three acidic, metal-enriched, mountain streams, and the results are discussed together in this paper to provide a synthesis of watershed and in-stream processes controlling Fe, Al, and DOC (dissolved organic carbon) concentrations. One of the streams, the Snake River, is naturally acidic; the other two, Peru Creek and St. Kevin Gulch, receive acid mine drainage. Analysis of stream water chemistry data for the acidic headwaters of the Snake River shows that some trace metal solutes (Al, Mn, Zn) are correlated with major ions, indicating that watershed processes control their concentrations. Once in the stream, biogeochemical processes can control transport if they occur over time scales comparable to those for hydrologic transport. Examples of the following in-stream reactions are presented: (1) photoreduction and dissolution of hydrous iron oxides in response to an experimental decrease in stream p H, (2) precipitation of Al at three stream confluences, and (3) sorption of dissolved organic material by hydrous iron and aluminum oxides in a stream confluence. The extent of these reactions is evaluated using conservative tracers and a transport model that includes storage in the substream zone.

Water Resources Research↗
USGS2011

Diel biogeochemical processes and their effect on the aqueous chemistry of streams: A review

This review summarizes biogeochemical processes that operate on diel, or 24-h, time scales in streams and the changes in aqueous chemistry that are associated with these processes. Some biogeochemical processes, such as those producing diel cycles of dissolved O 2 and pH, were the first to be studied, whereas processes producing diel concentration cycles of a broader spectrum of chemical species including dissolved gases, dissolved inorganic and organic carbon, trace elements, nutrients, stable isotopes, and suspended particles have received attention only more recently. Diel biogeochemical cycles are interrelated because the cyclical variations produced by one biogeochemical process commonly affect another. Thus, understanding biogeochemical cycling is essential not only for guiding collection and interpretation of water-quality data but also for geochemical and ecological studies of streams. Expanded knowledge of diel biogeochemical cycling will improve understanding of how natural aquatic environments function and thus lead to better predictions of how stream ecosystems might react to changing conditions of contaminant loading, eutrophication, climate change, drought, industrialization, development, and other factors.

Chemical Geology↗
USGS2023

Carbonate chemistry and carbon sequestration driven by inorganic carbon outwelling from mangroves and saltmarshes

Mangroves and saltmarshes are biogeochemical hotspots storing carbon in sediments and in the ocean following lateral carbon export (outwelling). Coastal seawater pH is modified by both uptake of anthropogenic carbon dioxide and natural biogeochemical processes, e.g., wetland inputs. Here, we investigate how mangroves and saltmarshes influence coastal carbonate chemistry and quantify the contribution of alkalinity and dissolved inorganic carbon (DIC) outwelling to blue carbon budgets. Observations from 45 mangroves and 16 saltmarshes worldwide revealed that >70% of intertidal wetlands export more DIC than alkalinity, potentially decreasing the pH of coastal waters. Porewater-derived DIC outwelling (81 ± 47 mmol m −2 d −1 in mangroves and 57 ± 104 mmol m −2 d −1 in saltmarshes) was the major term in blue carbon budgets. However, substantial amounts of fixed carbon remain unaccounted for. Concurrently, alkalinity outwelling was similar or higher than sediment carbon burial and is therefore a significant but often overlooked carbon sequestration mechanism.

Nature↗
USGS2004

The influence of groundwater chemistry on arsenic concentrations and speciation in a quartz sand and gravel aquifer

We examined the chemical reactions influencing dissolved concentrations, speciation, and transport of naturally occurring arsenic (As) in a shallow, sand and gravel aquifer with distinct geochemical zones resulting from land disposal of dilute sewage effluent. The principal geochemical zones were: (1) the uncontaminated zone above the sewage plume [350 μ M dissolved oxygen (DO), p H 5.9]; (2) the suboxic zone (5 μ M DO, p H 6.2, elevated concentrations of sewage-derived phosphate and nitrate); and (3) the anoxic zone [dissolved iron(II) 100–300 μ M, p H 6.5–6.9, elevated concentrations of sewage-derived phosphate]. Sediments are comprised of greater than 90% quartz but the surfaces of quartz and other mineral grains are coated with nanometer-size iron (Fe) and aluminum (Al) oxides and/or silicates, which control the adsorption properties of the sediments. Uncontaminated groundwater with added phosphate (620 μ M) was pumped into the uncontaminated zone while samples were collected 0.3 m above the injection point. Concentrations of As(V) increased from below detection (0.005 μ M) to a maximum of 0.07 μ M during breakthrough of phosphate at the sampling port; As(III) concentrations remained below detection. These results are consistent with the hypothesis that naturally occurring As(V) adsorbed to constituents of the coatings on grain surfaces was desorbed by phosphate in the injected groundwater. Also consistent with this hypothesis, vertical profiles of groundwater chemistry measured prior to the tracer test showed that dissolved As(V) concentrations increased along with dissolved phosphate from below detection in the uncontaminated zone to approximately 0.07 and 70 μ M, respectively, in the suboxic zone. Concentrations of As(III) were below detection in both zones. The anoxic zone had approximately 0.07 μ M As(V) but also had As(III) concentrations of 0.07–0.14 μ M, suggesting that release of As bound to sediment grains occurred by desorption by phosphate, reductive dissolution of Fe oxides, and reduction of As(V) to As(III), which adsorbs only weakly to the Fe-oxide-depleted material in the coatings. Results of reductive extractions of the sediments suggest that As associated with the coatings was relatively uniformly distributed at approximately 1 nmol/g of sediment (equivalent to 0.075 ppm As) and comprised 20%-50% of the total As in the sediments, determined from oxidative extractions. Quartz sand aquifers provide high-quality drinking water but can become contaminated when naturally occurring arsenic bound to Fe and Al oxides or silicates on sediment surfaces is released by desorption and dissolution of Fe oxides in response to changing chemical conditions.

Geochemical Transactions↗
USGS2005

Assessing background ground water chemistry beneath a new unsewered subdivision

Previous site-specific studies designed to assess the impacts of unsewered subdivisions on ground water quality have relied on upgradient monitoring wells or very limited background data to characterize conditions prior to development. In this study, an extensive monitoring program was designed to document ground water conditions prior to construction of a rural subdivision in south-central Wisconsin. Previous agricultural land use has impacted ground water quality; concentrations of chloride, nitrate-nitrogen, and atrazine ranged from below the level of detection to 296 mg/L, 36 mg/L, and 0.8 ??g/L, respectively, and were highly variable from well to well and through time. Seasonal variations in recharge, surface topography, aquifer heterogeneities, surficial loading patterns, and well casing depth explain observed variations in ground water chemistry. This variability would not have been detected if background conditions were determined from only a few monitoring wells or inferred from wells located upgradient of the subdivision site. This project demonstrates the importance of characterizing both ground water quality and chemical variability prior to land-use change to detect any changes once homes are constructed. Copyright ?? 2005 National Ground Water Association.

Ground Water↗