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At least 271 records · Page 15Linked to original sources
USGS2021

Trends and current status of aluminum chemistry in Adirondack headwater streams 30 Years after the Clean Air Act Amendments of 1990

Mobilization of toxic forms of aluminum (Ali) have been one of the most harmful effects of acidic deposition on aquatic ecosystems. Large decreases in acidic deposition levels have resulted in decreases in Ali concentrations in surface waters starting in the 1990s. However, recent studies indicate that fish communities are still being impaired by elevated Ali concentrations in streams, suggesting the need for a present-day assessment of the recovery status of Al chemistry in impacted regions such as the Adirondack region of New York, United States. Therefore, the recovery status of Al was assessed from long-term high-frequency monitoring of three Adirondack streams up through 2019, and multiple resampling of 127 headwater streams throughout the Adirondack region between 2004/2005 and 2018/2019. Results indicated that concentrations of Ali have continued to decrease throughout the Adirondack region, but that harmful conditions still exist in a substantial number of streams during spring snowmelt. In the western Adirondack region, 35 percent of streams during spring snowmelt, (typically the most acidic period), and 10 percent of streams during summer were still experiencing harmful concentrations of Ali ( >1.0 μmol L −1 ) in 2018/2019. In the less-impacted east-central Adirondack region, 10 percent of streams during snowmelt, and 4 percent of streams during summer were experiencing harmful Ali concentrations in 2018. Temporal decreases in Ali concentrations were due in part to a shift in speciation from Ali to non-toxic organically complexed Al as dissolved organic carbon concentrations increased, which was also a response to decreasing acidic deposition. Increased availability of calcium resulting from acid-neutralization processes such as weathering also contributed to the decrease in Ali over the past 5–8 years. The current low levels of acidic deposition may have begun to enhance recovery by increasing the effectiveness of ambient acid neutralization processes.

New York↗
USGS2014

Relationships between water and gas chemistry in mature coalbed methane reservoirs of the Black Warrior Basin

Water and gas chemistry in coalbed methane reservoirs of the Black Warrior Basin reflects a complex interplay among burial processes, basin hydrodynamics, thermogenesis, and late-stage microbial methanogenesis. These factors are all important considerations for developing production and water management strategies. Produced water ranges from nearly potable sodium-bicarbonate water to hypersaline sodium-chloride brine. The hydrodynamic framework of the basin is dominated by structurally controlled fresh-water plumes that formed by meteoric recharge along the southeastern margin of the basin. The produced water contains significant quantities of hydrocarbons and nitrogen compounds, and the produced gas appears to be of mixed thermogenic-biogenic origin. Late-stage microbial methanogenesis began following unroofing of the basin, and stable isotopes in the produced gas and in mineral cements indicate that late-stage methanogenesis occurred along a CO 2 -reduction metabolic pathway. Hydrocarbons, as well as small amounts of nitrate in the formation water, probably helped nourish the microbial consortia, which were apparently active in fresh to hypersaline water. The produced water contains NH 4 + and NH 3 , which correlate strongly with brine concentration and are interpreted to be derived from silicate minerals. Denitrification reactions may have generated some N 2 , which is the only major impurity in the coalbed gas. Carbon dioxide is a minor component of the produced gas, but significant quantities are dissolved in the formation water. Degradation of organic compounds, augmented by deionization of NH 4 + , may have been the principal sources of hydrogen facilitating late-stage CO 2 reduction.

Alabama↗
USGS2022

Porewater chemistry of Louisiana marshes with contrasting salinities and its implications for coastal acidification

Dissolved inorganic carbon (DIC) and total alkalinity (TA) are fundamental components of carbonate systems that control pH and buffering capacity of the receiving water body. Three coastal marshes with contrasting salinities in Barataria Basin, Louisiana, USA, were sampled to understand seasonal changes in porewater carbonate chemistry and its impact on surrounding water bodies. Each marsh was sampled five times between December 2018 and October 2019. Porewater DIC and TA increased with depth irrespective of marsh type and ranged from 4.47 to 31.61 mmol/kg and from 1.78 to 28.56 mmol/kg, respectively. The salt marsh had higher porewater DIC and TA compared to the lower salinity intermediate and brackish marshes, probably due to sulfate reduction in the salt marsh. However, it is likely that denitrification is the dominant anaerobic process in these marshes because of low porewater TA/DIC ratios in all three marshes. Porewater TA and DIC concentrations were generally higher during warmer months than colder months. However, the marsh flooding regime had a profound influence on TA and DIC concentrations by changing the redox potential of the marsh soil. Porewater TA/DIC ratios in all three marshes were generally less than 1, while surface water TA/DIC ratios were around 1, suggesting that export of DIC and TA from coastal marshes have the potential to contribute to coastal acidification.

Louisiana↗
USGS2014

Does water chemistry affect the dietary uptake and toxicity of silver nanoparticles by the freshwater snail Lymnaea stagnalis ?

Silver nanoparticles (AgNPs) are widely used in many applications and likely released into the aquatic environment. There is increasing evidence that Ag is efficiently delivered to aquatic organisms from AgNPs after aqueous and dietary exposures. Accumulation of AgNPs through the diet can damage digestion and adversely affect growth. It is well recognized that aspects of water quality, such as hardness, affect the bioavailability and toxicity of waterborne Ag. However, the influence of water chemistry on the bioavailability and toxicity of dietborne AgNPs to aquatic invertebrates is largely unknown. Here we characterize for the first time the effects of water hardness and humic acids on the bioaccumulation and toxicity of AgNPs coated with polyvinyl pyrrolidone (PVP) to the freshwater snail Lymnaea stagnalis after dietary exposures. Our results indicate that bioaccumulation and toxicity of Ag from PVP-AgNPs ingested with food are not affected by water hardness and by humic acids, although both could affect interactions with the biological membrane and trigger nanoparticle transformations. Snails efficiently assimilated Ag from the PVP-AgNPs mixed with diatoms (Ag assimilation efficiencies ranged from 82 to 93%). Rate constants of Ag uptake from food were similar across the entire range of water hardness and humic acid concentrations. These results suggest that correcting regulations for water quality could be irrelevant and ineffective where dietary exposure is important.

Environmental Pollution↗
USGS2018

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

Multiply isotopically substituted molecules (‘clumped’ isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature–time conditions corresponding to ‘low,’ ‘mature,’ and ‘over-mature’ stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions (‘high’ to ‘over-mature’ stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ 18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where ‘secondary’ cracking of retained oil in shale or wet gas hydrocarbons (C 2-5 , especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.

Geochimica et Cosmochimica Acta↗
USGS2023

Four decades of regional wet deposition, local bulk deposition, and stream-water chemistry show the influence of nearby land use on forested streams in Central Appalachia☆

Hydrologic monitoring began on two headwater streams (<1 km 2 ) on the University of Kentucky's Robinson Forest in 1971. We evaluated stream-water (1974–2013) and bulk-deposition (wet + dust) (1984–2013) chemistry in the context of regional wet-deposition patterns that showed decreases in both sulfate and nitrate concentrations as well as proximal surface-mine expansion. Decadal time steps (1974–83, 1984–93, 1994–2003, 2004–2013) were used to quantify change. Comparison of the first two decades showed similarly decreased sulfate (minimum flow-adjusted annual-mean concentration of ≈13.5 mg/L in 1982 to 8.8 mg/L in 1992) and increased pH (6.6–6.8) in both streams, reflecting contemporaneous changes in both bulk and wet deposition. In contrast, concentrations of nitrate (0.14 to >0.25 mg/L) and base cations increased between these two decades, coinciding with expansion of surface mining between 1985 and 1995. In 2004, stream-water pH (6.7 in 2004), sulfate (9.2 mg/L), and nitrate (>0.11 mg/L) were similar to 1982, despite wet-deposition concentrations being lower. Base-cation concentrations were higher in the stream adjacent to ongoing surface mining relative to the stream situated near the middle of the experimental forest. However, pH decreased to approximately 5.7 by 2013 for both streams, which, combined with a shift in dominant cations from calcium to magnesium and potassium, indicates that the soil-buffering capacity of this landscape has been exceeded. Ratios of bulk deposition and stream-water concentrations indicate enrichment of sulfate (1.7–25.2) and cations (0.5–64.8), but not nitrogen (0.1–5.6), indicating that the Forest is not nitrogen saturated and that ongoing changes in water-quality are sulfate driven. When concentrations were adjusted to account for changes in streamflow (climate) over the 4 decades, external influences (land management/regulation) explained most change. The amount and direction of change differed among constituents, both between consecutive decades and between the first and last decades, reflecting the influence of localized surface mining even as regional wet deposition continued to improve due to the Clean Air Act. The implication is that localized stressors have the potential to out-pace the benefits of national environmental policies for communities that depend on local water-resources in similar environments.

Kentucky↗
USGS2010

Source and fate of inorganic solutes in the Gibbon River, Yellowstone National Park, Wyoming, USA: I. Low-flow discharge and major solute chemistry

The Gibbon River in Yellowstone National Park (YNP) is an important natural resource and habitat for fisheries and wildlife. However, the Gibbon River differs from most other mountain rivers because its chemistry is affected by several geothermal sources including Norris Geyser Basin, Chocolate Pots, Gibbon Geyser Basin, Beryl Spring, and Terrace Spring. Norris Geyser Basin is one of the most dynamic geothermal areas in YNP, and the water discharging from Norris is much more acidic (pH 3) than other geothermal basins in the upper-Madison drainage (Gibbon and Firehole Rivers). Water samples and discharge data were obtained from the Gibbon River and its major tributaries near Norris Geyser Basin under the low-flow conditions of September 2006. Surface inflows from Norris Geyser Basin were sampled to identify point sources and to quantify solute loading to the Gibbon River. The source and fate of the major solutes (Ca, Mg, Na, K, SiO 2 , Cl, F, HCO 3 , SO 4 , NO 3 , and NH 4 ) in the Gibbon River were determined in this study and these results may provide an important link in understanding the health of the ecosystem and the behavior of many trace solutes. Norris Geyser Basin is the primary source of Na, K, Cl, SO 4 , and N loads (35–58%) in the Gibbon River. The largest source of HCO 3 and F is in the lower Gibbon River reach. Most of the Ca and Mg originate in the Gibbon River upstream from Norris Geyser Basin. All the major solutes behave conservatively except for NH 4 , which decreased substantially downstream from Gibbon Geyser Basin, and SiO 2 , small amounts of which precipitated on mixing of thermal drainage with the river. As much as 9–14% of the river discharge at the gage is from thermal flows during this period.

Wyoming↗
USGS2004

Population ecology and shell chemistry of a phytal ostracode species (Loxoconcha matagordensis) in the Chesapeake Bay watershed

Population ecology and shell chemistry were studied in the phytal ostracode Loxoconcha matagordensis (Swain 1955) collected from Zostera marina seagrass beds in the Chesapeake Bay to provide seasonal constraints on shell secretion time for paleothermometry. Population density and age structure were defined by two main breeding cycles that occurred between 01 to 15 June and 02 to 16 August 2001. The time interval between breeding cycles was ???2 months and total juvenile standing crop increased almost three-fold between the first and second breeding cycles. Dark brown over-wintered adults comprised the majority of the population between March and April 2001, while newly secreted translucent adults were predominant between June and September. Seasonal shell Mg/Ca and Sr/Ca ratios were positively correlated with water temperature at both sites, with the strongest correlations occurring between June and September from newly secreted shells at Dameron Marsh. Old, dark brown shells contained 10% to 23% and 1% to 6% less Mg/Ca and Sr/Ca, respectively, than new shells. Because a fossil assemblage of L. matagordensis will contain ???30% old shells (dark-brown), these results suggest that fossil Mg/Ca ratios yield an integrated late spring to summer temperature signal. Shell Mg/Ca and Sr/Ca ratios of specimens of L. matagordensis collected from living Zostera were positively correlated, suggesting that temperature may influence both elemental ratios. Mg/Ca and Sr/Ca ratios of fossil shells of the related species Loxoconcha sp. A obtained from four sediment cores were also studied and exhibited a weaker correlation between the two elemental ratios. ?? 2004 Elsevier B.V. All rights reserved.

Marine Micropaleontology↗
USGS2016

Sediment chemistry and toxicity in Barnegat Bay, New Jersey: Pre- and post-Hurricane Sandy, 2012–13

Hurricane Sandy made landfall in Barnegat Bay, October, 29, 2012, damaging shorelines and infrastructure. Estuarine sediment chemistry and toxicity were investigated before and after to evaluate potential environmental health impacts and to establish post-event baseline sediment-quality conditions. Trace element concentrations increased throughout Barnegat Bay up to two orders of magnitude, especially north of Barnegat Inlet, consistent with northward redistribution of silt. Loss of organic compounds, clay, and organic carbon is consistent with sediment winnowing and transport through the inlets and sediment transportmodeling results. The number of sites exceeding sediment quality guidance levels for trace elements tripled post-Sandy. Sediment toxicity post-Sandy was mostly unaffected relative to pre-Sandy conditions, but at the site with the greatest relative increase for trace elements, survival rate of the test amphipod decreased (indicating degradation). This study would not have been possible without comprehensive baseline data enabling the evaluation of storm-derived changes in sediment quality.

New Jersey↗
USGS2014

The chemistry of hydrothermal magnetite: a review

Magnetite (Fe 3 O 4 ) is a well-recognized petrogenetic indicator and is a common accessory mineral in many ore deposits and their host rocks. Recent years have seen an increased interest in the use of hydrothermal magnetite for provenance studies and as a pathfinder for mineral exploration. A number of studies have investigated how specific formation conditions are reflected in the composition of the respective magnetite. Two fundamental questions underlie these efforts — (i) How can the composition of igneous and, more importantly, hydrothermal magnetite be used to discriminate mineralized areas from barren host rocks, and (ii) how can this assist exploration geologists to target ore deposits at greater and greater distances from the main mineralization? Similar to igneous magnetite, the most important factors that govern compositional variations in hydrothermal magnetite are (A) temperature, (B) fluid composition — element availability, (C) oxygen and sulfur fugacity, (D) silicate and sulfide activity, (E) host rock buffering, (F) re-equilibration processes, and (G) intrinsic crystallographic controls such as ionic radius and charge balance. We discuss how specific formation conditions are reflected in the composition of magnetite and review studies that investigate the chemistry of hydrothermal and igneous magnetite from various mineral deposits and their host rocks. Furthermore, we discuss the redox-related alteration of magnetite (martitization and mushketovitization) and mineral inclusions in magnetite and their effect on chemical analyses. Our database includes published and previously unpublished magnetite minor and trace element data for magnetite from (1) banded iron formations (BIF) and related high-grade iron ore deposits in Western Australia, India, and Brazil, (2) Ag–Pb–Zn veins of the Coeur d'Alene district, United States, (3) porphyry Cu–(Au)–(Mo) deposits and associated (4) calcic and magnesian skarn deposits in the southwestern United States and Indonesia, and (5) plutonic igneous rocks from the Henderson Climax-type Mo deposit, United States, and the un-mineralized Inner Zone Batholith granodiorite, Japan. These five settings represent a diverse suite of geological settings and cover a wide range of formation conditions. The main discriminator elements for magnetite are Mg, Al, Ti, V, Cr, Mn, Co, Ni, Zn, and Ga. These elements are commonly present at detectable levels (10 to > 1000 ppm) and display systematic variations. We propose a combination of Ni/(Cr + Mn) vs. Ti + V, Al + Mn vs. Ti + V, Ti/V and Sn/Ga discriminant plots and upper threshold concentrations to discriminate hydrothermal from igneous magnetite and to fingerprint different hydrothermal ore deposits. The overall trends in upper threshold values for the different settings can be summarized as follows: (I) BIF (hydrothermal) — low Al, Ti, V, Cr, Mn, Co, Ni, Zn, Ga and Sn; (II) Ag–Pb–Zn veins (hydrothermal) — high Mn and low Ga and Sn; (III) Mg-skarn (hydrothermal) — high Mg and Mn and low Al, Ti, Cr, Co, Ni and Ga; (IV) skarn (hydrothermal) — high Mg, Al, Cr, Mn, Co, Ni and Zn and low Sn; (V) porphyry (hydrothermal) — high Ti and V and low Sn; (VI) porphyry (igneous) — high Ti, V and Cr and low Mg; and (VII) Climax-Mo (igneous) — high Al, Ga and Sn and low Mg and Cr.

Ore Geology Reviews↗
USGS2005

Ecology and shell chemistry of Loxoconcha matagordensis

Studies of the seasonal ecology and shell chemistry of the ostracode Loxoconcha matagordensis and related species of Loxoconcha from regions off eastern North America reveal that shell size and trace elemental (Mg/Ca ratio) composition are useful in paleothermometry using fossil populations. Seasonal sampling of populations from Chesapeake Bay, augmented by samples from Florida Bay, indicate that shell size is inversely proportional to water temperature and that Mg/Ca ratios are positively correlated with the water temperature in which the adult carapace was secreted. Microprobe analyses of sectioned valves reveal intra-shell variability in Mg/Ca ratios but this does not strongly influence the utility of whole shell Mg/Ca analyses for paleoclimate application.

Palaeogeography, Palaeoclimatology, Palaeoecology↗
USGS2017

Using large databases of groundwater chemistry in the northern Midwest USA: The effects of geologic and anthropogenic factors

Regional geochemical databases for the northern Midwest USA are being compiled to examine the various geogenic and anthropogenic factors that control the chemistry of groundwater. At the regional scale, variations are seen that are attributable to agricultural and urban effects, or to geologic factors. Examples of the former include enrichments of nitrate in groundwater, while examples of the latter mainly highlight geochemical differences between carbonate rocks and all other rock types in the region. This paper examines a few of these regional effects and the spatial scales at which they can be observed.

Article↗
USGS2009

Storm clouds on Saturn: Lightning-induced chemistry and associated materials consistent with Cassini/VIMS spectra

Thunderstorm activity on Saturn is associated with optically detectable clouds that are atypically dark throughout the near-infrared. As observed by Cassini/VIMS, these clouds are ~20% less reflective than typical neighboring clouds throughout the spectral range from 0.8 ??m to at least 4.1 ??m. We propose that active thunderstorms originating in the 10-20 bar water-condensation region vertically transport dark materials at depth to the ~1 bar level where they can be observed. These materials in part may be produced by chemical processes associated with lightning, likely within the water clouds near the ~10 bar freezing level of water, as detected by the electrostatic discharge of lightning flashes observed by Cassini/RPWS (e.g., Fischer et al. 2008, Space Sci. Rev., 137, 271-285). We review lightning-induced pyrolytic chemistry involving a variety of Saturnian constituents, including hydrogen, methane, ammonia, hydrogen sulfide, phosphine, and water. We find that the lack of absorption in the 1-2 ??m spectral region by lightning-generated sulfuric and phosphorous condensates renders these constituents as minor players in determining the color of the dark storm clouds. Relatively small particulates of elemental carbon, formed by lightning-induced dissociation of methane and subsequently upwelled from depth - perhaps embedded within and on the surface of spectrally bright condensates such as ammonium hydrosulfide or ammonia - may be a dominant optical material within the dark thunderstorm-related clouds of Saturn. ?? 2009 Elsevier Ltd. All rights reserved.

Planetary and Space Science↗
USGS2019

Effects of ferric sulfate and polyaluminum chloride coagulation enhanced treatment wetlands on Typha growth, soil and water chemistry

Land surface subsidence is a concern in many deltas worldwide as it contributes to water quality degradation, loss of fertile land and increased potential for levee failure. As a possible solution to these concerns, on-site coagulation enhanced treatment wetlands(CETWs), coagulation water treatment followed by wetland passage serving as a settling basin, were implemented in a field-scale study located on a subsided island of the Sacramento-San Joaquin Delta in northern California under three treatments; coagulation with polyaluminum chloride (PAC), coagulation with ferric sulfate and an untreated control. Because CETWs offer a relatively novel solution for water quality improvement and subsidence reversal due to its low-infrastructure requirements and in-situ nature, effects from these systems remain uncharted and they may have adverse effects on plant biomass production that also contribute to sediment accretion. This study focuses on the effect CETWs had on the growth of Typha spp .; the dominant vegetation in the wetlands. Plant growth parameters and nutrient content were measured in conjunction with soil, pore waterand surface water chemistry. Soil analysis indicated there was no intermixing of newly formed flocs and original soil material. Where there was significant deposition of floc, PAC treatment reduced phosphate concentrations and ferric sulfate treatment increased total Fe concentrations in surrounding water compared to the control. Results indicated coagulation treatments had no negative effects on Typha leaf nutrient content, Typha growth or allometric parameters. Additionally, no signs of plant toxicity such as necrosis, wilting or chlorosis were observed in any of the treatments. Overall, this study suggests that CETWs are viable treatment option for water quality improvement and sediment accretion while having no negative impact on the growth of Typha plants.

Science of the Total Environment↗
USGS2005

Influence of water chemistry and travel distance on bacteriophage PRD-1 transport in a sandy aquifer

Experiments were conducted to evaluate the impact of groundwater chemistry and travel distance on the transport and fate behavior of PRD-1, a bacteriophage employed as a surrogate tracer for pathogenic enteric viruses. The experiments were conducted in the unconfined aquifer at the United States Geological Survey Cape Cod Toxic-Substances Hydrology Research Site in Falmouth, Massachusetts. The transport behavior of bromide (Br − ) and PRD-1 were evaluated in a sewage-effluent contaminated zone and a shallower uncontaminated zone at this site. Several multilevel sampling devices located along a 13-m transect were used to collect vertically discrete samples to examine longitudinal and vertical variability of PRD-1 retardation and attenuation. The concentration of viable bacteriophage in the aqueous phase decreased greatly during the first few meters of transport. This decrease is attributed to a combination of colloid filtration (attachment) and inactivation. The removal was greater (10 −12 relative recovery) and occurred within the first meter for the uncontaminated zone, whereas it was lesser (10 −9 relative recovery) and occurred over 4 m in the contaminated zone. The lesser removal observed for the contaminated zone is attributed to the influence of sorbed and dissolved organic matter, phosphate, and other anions, which are present in higher concentrations in the contaminated zone, on PRD-1 attachment. After the initial decrease, the aqueous PRD-1 concentrations remained essentially constant in both zones for the remainder of the tests (total travel distances of 13 m), irrespective of variations in geochemical properties within and between the two zones. The viable, mobile PRD-1 particles traveled at nearly the rate of bromide, which was used as a non-reactive tracer. The results of this study indicate that a small fraction of viable virus particles may persist in the aqueous phase and travel significant distances in the subsurface environment.

Water Research↗
USGS2010

Effects of altered groundwater chemistry upon the pH-dependency and magnitude of bacterial attachment during transport within an organically contaminated sandy aquifer

The effects of a dilute (ionic strength = 5 × 10 −3 M) plume of treated sewage, with elevated levels (3.9 mg/L) of dissolved organic carbon (DOC), upon the pH-dependency and magnitude of bacterial transport through an iron-laden, quartz sand aquifer (Cape Cod, MA) were evaluated using sets of replicate, static minicolumns. Compared with uncontaminated groundwater, the plume chemistry diminished bacterial attachment under mildly acidic (pH 5.0–6.5) in-situ conditions, in spite of the 5-fold increase in ionic strength and substantively enhanced attachment under more alkaline conditions. The effects of the hydrophobic neutral and total fractions of the plume DOC; modest concentrations of fulvic and humic acids (1.5 mg/L); linear alkyl benzene sulfonate (LAS) (25 mg/L); Imbentin (200 μg/L), a model nonionic surfactant; sulfate (28 mg/L); and calcium (20 mg/L) varied sharply in response to relatively small changes in pH, although the plume constituents collectively decreased the pH-dependency of bacterial attachment. LAS and other hydrophobic neutrals (collectively representing only ∼3% of the plume DOC) had a disproportionately large effect upon bacterial attachment, as did the elevated concentrations of sulfate within the plume. The findings further suggest that the roles of organic plume constituents in transport or bacteria through acidic aquifer sediments can be very different than would be predicted from column studies performed at circumneutral pH and that the inorganic constituents within the plume cannot be ignored.

Water Research↗
USGS1998

Chemistry, isotopic composition, and origin of a methane-hydrogen sulfide hydrate at the Cascadia subduction zone

Although the presence of extensive gas hydrate on the Cascadia margin, offshore from the western U.S. and Canada, has been inferred from marine seismic records and pore water chemistry, solid gas hydrate has only been found at one location. At Ocean Drilling Program (ODP) Site 892, offshore from central Oregon, gas hydrate was recovered close to the sediment-water interface at 2–19 m below the seafloor (mbsf) at 670 m water depth. The gas hydrate occurs as elongated platy crystals or crystal aggregates, mostly disseminated irregularly, with higher concentrations occurring in discrete zones, thin layers, and/or veinlets parallel or oblique to the bedding. A 2- to 3-cm thick massive gas hydrate layer, parallel to bedding, was recovered at ∼ 17 mbsf. Gas from a sample of this layer was composed of both CH 4 and H 2 S. This sample is the first mixed-gas hydrate of CH 4 H 2 S documented in ODP; it also contains ethane and minor amounts of CO 2 . Measured temperatures of the recovered core ranged from 2 to −1.8°C and are 6 to 8 degrees lower than in-situ temperatures. These temperature anomalies were caused by the partial dissociation of the CH 4 H 2 S hydrate during recovery without a pressure core sampler.During this dissociation, toxic levels of H 2 S (δ 34 S, +27.4‰) were released. The δ 13 C values of the CH 4 in the gas hydrate, −64.5 to −67.5‰ (PDB) , together with δD values of −197 to −199‰ (SMOW) indicate a primarily microbial source for the CH 4 . The δ 18 O value of the hydrate H 2 O is +2.9‰ (SMOW) , comparable with the experimental fractionation factor for sea-ice. The unusual composition (CH 4 H 2 S) and depth distribution (2–19 mbsf) of this gas hydrate indicate mixing between a methane-rich fluid with a pore fluid enriched in sulfide; at this site the former is advecting along an inclined fault into the active sulfate reduction zone. The facts that the CH 4 H 2 S hydrate is primarily confined to the present day active sulfate reduction zone (2–19 mbsf), and that from here down to the BSR depth (19–68 mbsf) the gas hydrate inferred to exist is a ≥99% CH 4 hydrate, suggest that the mixing of CH 4 and H 2 S is a geologically young process. Because the existence of a mixed CH 4 H 2 S hydrate is indicative of moderate to intense advection of a methane-rich fluid into a near surface active sulfate reduction zone, tectonically active (faulted) margins with organic-rich sediments and moderate to high sedimentation rates are the most likely regions of occurrence. The extension of such a mixed hydrate below the sulfate reduction zone should reflect the time-span of methane advection into the sulfate reduction zone.

Earth and Planetary Science Letters↗
USGS2001

Seasonal and event-scale variations in solute chemistry for four Sierra Nevada catchments

Hydrobiogeochemical processes controlling stream water chemistry were examined in four small (<5 km2) catchments having contrasting bedrock lithologies in the western Sierra Nevada foothills of California. The Mediterranean climate with its cool/wet and hot/dry cycle produces strong seasonal patterns in hydrological, biological and geochemical processes. Stream water solutes fall into three general groups according to seasonal fluctuation in concentration: Strong, rainy season minimum-dry season maximum (Cl-, SO42-, base cations); weak, rainy season minimum-dry season maximum (Si); and rainy season maximum-dry season minimum (NO3- and K+). Solute dynamics in soil solutions and stream water suggest that mixing of drainage waters from bedrock and soil sources regulate stream water solute concentrations. Patterns are further altered by the leaching of solutes accumulated in the soil over the summer period of desiccation and the temporal discoupling of nutrient cycles that occurs due to differences in the timing between vegetation growth (late spring) and leaching (early winter). Solute concentrations are remarkably similar between watersheds with varying bedrock types, with the exception of nitrate, sulfate and bicarbonate. Three watersheds have nitrogen-bearing metasedimentary bedrock that contributes to elevated nitrate concentrations in stream waters. Watersheds whose bedrock includes mineralized veins of sulfide and carbonate minerals similarly have greater sulfate and bicarbonate concentrations in stream water. Hydrobiogeochemical processes are highly dynamic at the seasonal and storm-event temporal scales and spatially complex at the watershed scale making management of stream water chemical composition, such as nitrate concentrations, very challenging. ?? 2001 Elsevier Science B.V.

Journal of Hydrology↗