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USGS2022

Small anthropogenic landforms from past charcoal production control moisture dynamics and chemistry in northcentral Appalachian soils

Throughout the northeastern United States (U.S.) and Europe, relict charcoal hearths (RCHs) are regularly being discovered in proximity to furnaces once used for the extraction of metal from ore or quick-lime production; charcoal produced in hearths was used as a furnace fuel. Given previous research has shown that topographic and subsurface disturbance can be great when a hearth is constructed, we hypothesize that hearth construction alters surface hydrology and soil chemistry in environments in and near hearths. We used a landscape classification process to identify 6,758 hearths near furnaces at Greenwood and Pine Grove Furnace State Park, central and southcentral Pennsylvania, U.S. Two types of digital elevation model wetness indexes were used to quantify surface hydrology effects in and around hearths. Modeled wetness conditions were compared to field soil volumetric water content in RCHs near Greenwood Furnace State Park. Modeled wetness indexes indicate that RCH interiors are significantly wetter than RCH rim areas; RCHs are acting as a landscape moisture sink. Results also indicate that RCHs on slopes result in downslope drier conditions below RCHs. Field measured volumetric water content indicates that as distance from the center of the hearth increases, soil moisture significantly decreases. Geomorphic position was found to not be related to RCH wetness. Soil from RCHs, compared to nearby native soils, has significantly higher total C, a lower Mehlich 3 extractable acidity, higher Ca and P. No trend was evident with RCH soil chemistry and geomorphic position. The high frequency of RCH occurrence, in proximity to the furnace’s RCHs supported, suggests that RCHs today could locally be an important niche for understory flora and fauna. Further research could explore how RCHs might be affecting surrounding plant populations and how within RCH patterns, especially on hillslopes, might represent a distinctly different scale of physical and chemical variability.

Pennsylvania↗

USGS2005

Effects of iron on arsenic speciation and redox chemistry in acid mine water

Concern about arsenic is increasing throughout the world, including areas of the United States. Elevated levels of arsenic above current drinking-water regulations in ground and surface water can be the result of purely natural phenomena, but often are due to anthropogenic activities, such as mining and agriculture. The current study correlates arsenic speciation in acid mine drainage and mining-influenced water with the important water-chemistry properties Eh, pH, and iron(III) concentration. The results show that arsenic speciation is generally in equilibrium with iron chemistry in low pH AMD, which is often not the case in other natural-water matrices. High pH mine waters and groundwater do not always hold to the redox predictions as well as low pH AMD samples. The oxidation and precipitation of oxyhydroxides deplete iron from some systems, and also affect arsenite and arsenate concentrations through sorption processes. ?? 2004 Elsevier B.V. All rights reserved.

Journal of Geochemical Exploration↗

USGS2011

Modeling hot spring chemistries with applications to martian silica formation

Many recent studies have implicated hydrothermal systems as the origin of martian minerals across a wide range of martian sites. Particular support for hydrothermal systems include silica (SiO 2 ) deposits, in some cases >90% silica, in the Gusev Crater region, especially in the Columbia Hills and at Home Plate. We have developed a model called CHEMCHAU that can be used up to 100 °C to simulate hot springs associated with hydrothermal systems. The model was partially derived from FREZCHEM, which is a colder temperature model parameterized for broad ranges of temperature (<−70 to 25 °C), pressure (1–1000 bars), and chemical composition. We demonstrate the validity of Pitzer parameters, volumetric parameters, and equilibrium constants in the CHEMCHAU model for the Na–K–Mg–Ca–H–Cl–ClO 4 –SO 4 –OH–HCO 3 –CO 3 –CO 2 –O 2 –CH 4 –Si–H 2 O system up to 100 °C and apply the model to hot springs and silica deposits. A theoretical simulation of silica and calcite equilibrium shows how calcite is least soluble with high pH and high temperatures, while silica behaves oppositely. Such influences imply that differences in temperature and pH on Mars could lead to very distinct mineral assemblages. Using measured solution chemistries of Yellowstone hot springs and Icelandic hot springs, we simulate salts formed during the evaporation of two low pH cases (high and low temperatures) and a high temperature, alkaline (high pH) sodic water. Simulation of an acid-sulfate case leads to precipitation of Fe and Al minerals along with silica. Consistency with martian mineral assemblages suggests that hot, acidic sulfate solutions are plausibility progenitors of minerals in the past on Mars. In the alkaline pH (8.45) simulation, formation of silica at high temperatures (355 K) led to precipitation of anhydrous minerals (CaSO 4 , Na 2 SO 4 ) that was also the case for the high temperature (353 K) low pH case where anhydrous minerals (NaCl, CaSO 4 ) also precipitated. Thus we predict that secondary minerals associated with massive silica deposits are plausible indicators on Mars of precipitation environments and aqueous chemistry. Theoretical model calculations are in reasonable agreement with independent experimental silica concentrations, which strengthens the validity of the new CHEMCHAU model.

Icarus↗

USGS2023

Species and physiographic factors drive Indian cucumber root and Canada mayflower plant chemistry: Implications for white-tailed deer forage quality

Nutrition is fundamental to white-tailed deer ( Odocoileus virginianus ) management given its relationship to habitat carrying capacity and population productivity. Ecological Sites (ESs) are a United States federal landscape management unit of specific land potential due to unique soils, topography, climate, parent material, and perhaps deer forage nutritional value. We present results of a study that extends the use of ESs to inform white-tailed deer management by evaluating indicator plant chemistry in two spring forb species, Indian cucumber root ( Medeola virginiana) and Canada mayflower ( Maianthemum canadense ), across the northcentral Appalachians. We sampled spring forbs and underlying soils across two ESs: Dry, upland, oak–maple–hemlock hardwood forest (OMH) and Deep soil, high slope, northern hardwood forests (NHF). Plant elemental content, soil pH, and site aspect, slope and elevation were measured. Our results show that forb chemistry differs between species and within a species geographically. Indian cucumber root, as compared to Canada mayflower, has significantly higher Mg, Na, Cu, Fe, and Zn, and lower Mn. Canada mayflower in the NHF ES, versus OMH ES, was found to have significantly higher K, Mn, and B. Indian cucumber root in the NHF ES, versus the OMH ES, was found to have significantly higher Mg, Al, Fe, and Ca:P ratio but lower K. Linear discriminant analysis shows that plant tissue Mn was the best discriminator between species, and between ESs, Canada mayflower plant tissue Mn and Indian cucumber plant tissue P, K, Ca, Mg and Mn were best discriminators. Given that nutrition determines habitat carrying capacity, differences in forage nutrition between ESs may have different potentials to support deer. Forage nutrition is an important aspect of deer habitat conditions and carrying capacity, thus ESs are likely to support deer populations with different growth potential, which means that even if the same plant species occur in different ESs their nutritional value to deer may differ.

Journal of Environmental Management↗

USGS2011

Groundwater chemistry near an impoundment for produced water, Powder River Basin, Wyoming, USA

The Powder River Basin is one of the largest producers of coal-bed natural gas (CBNG) in the United States. An important environmental concern in the Basin is the fate of the large amounts of groundwater extracted during CBNG production. Most of this produced water is disposed of in unlined surface impoundments. A 6-year study of groundwater flow and water chemistry at one impoundment, Skewed Reservoir, has produced the most detailed data set for any impoundment in the Basin. Data were collected from a network of 21 observation wells and three suction lysimeters. A groundwater mound formed atop bedrock within initially unsaturated, unconsolidated deposits underlying the reservoir. Heterogeneity in physical and chemical properties of sediments resulted in complex groundwater flow paths and highly variable groundwater chemistry. Sulfate, bicarbonate, sodium, and magnesium were the dominant ions in all areas, but substantial variability existed in relative concentrations; pH varied from less than 3 to more than 9, and total dissolved solids concentrations ranged from less than 5000 to greater than 100,000 mg/L. Selenium was a useful tracer of reservoir water; selenium concentrations exceeded 300 μg/L in samples obtained from 18 of the 24 sampling points. Groundwater travel time from the reservoir to a nearby alluvial aquifer (a linear distance of 177 m) was calculated at 474 days on the basis of selenium concentrations. The produced water is not the primary source of solutes in the groundwater. Naturally occurring salts and minerals within the unsaturated zone, dissolved and mobilized by infiltrating impoundment water, account for most of the solute mass in groundwater. Gypsum dissolution, cation-exchange, and pyrite oxidation appear to be important reactions. The complex geochemistry and groundwater flow paths at the study site underscore the difficulty in assessing effects of surface impoundments on water resources within the Powder River Basin.

Wyoming↗

USGS2022

Olivine and glass chemistry record cycles of plumbing system recovery after summit collapse events at Kīlauea Volcano, Hawai‘i

The eruptive activity of Kīlauea Volcano (Hawai‘i) in the past 2500 years has alternated between centuries-long periods dominated either by explosive or effusive eruptions. The onset of explosive periods appears to be marked by caldera collapse events at the volcano's summit accompanied by draining of Kīlauea's magmatic plumbing system. Here we leverage >1800 olivine forsterite (Fo) contents, >900 glass MgO contents, and estimated magma supply rates from the past six centuries to describe the relationships between summit collapse and the composition of erupted material. On a first order basis, the major element chemistry of the centuries-long eruptive periods largely originates from fundamental differences between fractional crystallization of shallowly stored magmas during high-supply effusive-dominated periods versus little evolution of mafic recharge magmas during low-supply explosive-dominated periods. The modern effusive period (1820s-present) is dominated by relatively evolved olivine forsterite contents (Fo81–82) for Kīlauea, which is interpreted to reflect a buffered crustal reservoir system in which shallow storage and fractional crystallization control the composition of magmas. In contrast, olivine crystals from the explosive Keanakāko‘i Tephra (1500 - early 1800s C.E.) are dominated by higher olivine forsterite contents (Fo89) which are interpreted to reflect more primitive compositions, are correlated with glass MgO compositions extending to high values (e.g.,11.0 wt%), and show signs of magma mixing (zoned olivine, bimodal Fo populations). These signatures reflect a disrupted reservoir system in which high-MgO recharge melts mix with melts left over from draining of the shallow (<5 km) magma plumbing. Superimposed on these explosive-effusive periods are three decades- to centuries long periods of progressively evolving olivine and glass compositions. Eruptions that occur after caldera collapse in ~1500C.E. and smaller scale crater collapse events in 1790 (inferred) and 1924 have heterogeneous olivine populations dominated by ≥Fo88 and typically high MgO glasses. These compositions reflect inefficient mixing of stored and primitive recharge magmas after the disruption of the shallow plumbing system. After these collapses, olivine Fo and glass MgO subsequently evolve to <Fo82 and <7.0 wt% compositions, reflecting the recovery of the crustal plumbing system to an end-member system state characterized by efficient mixing of recharge and stored magmas that serve to buffer the shallow magma reservoirs. These evolved signatures suggest that a mature and buffered reservoir system may be a key condition for significant disruptions of volcanic plumbing systems. Plumbing system recovery is slower following large-scale caldera collapse (hundreds of years) compared to recovery following smaller crater collapse (tens of years), which may be modulated by differences in magma supply rates. Following the 2018 crater collapse olivine populations have high-Fo but glasses are low MgO, suggesting that this collapse might have disrupted shallow magma pathways but not strongly impacted the reservoir(s). Ultimately, olivine and glass major element chemistry record the impacts of caldera and smaller but significant summit crater collapse events at Kīlauea and could be used to provide a framework for better characterizing long-term volcano evolution in Hawai‘i and shield volcanoes elsewhere.

Hawaii↗

USGS2017

Influence of sediment chemistry and sediment toxicity on macroinvertebrate communities across 99 wadable streams of the Midwestern USA

Simultaneous assessment of sediment chemistry, sediment toxicity, and macroinvertebrate communities can provide multiple lines of evidence when investigating relations between sediment contaminants and ecological degradation. These three measures were evaluated at 99 wadable stream sites across 11 states in the Midwestern United States during the summer of 2013 to assess sediment pollution across a large agricultural landscape. This evaluation considers an extensive suite of sediment chemistry totaling 274 analytes (polycyclic aromatic hydrocarbons, organochlorine compounds, polychlorinated biphenyls, polybrominated diphenyl ethers, trace elements, and current-use pesticides) and a mixture assessment based on the ratios of detected compounds to available effects-based benchmarks. The sediments were tested for toxicity with the amphipod Hyalella azteca (28-d exposure), the midge Chironomus dilutus (10-d), and, at a few sites, with the freshwater mussel Lampsilis siliquoidea (28-d). Sediment concentrations, normalized to organic carbon content, infrequently exceeded benchmarks for aquatic health, which was generally consistent with low rates of observed toxicity. However, the benchmark-based mixture score and the pyrethroid insecticide bifenthrin were significantly related to observed sediment toxicity. The sediment mixture score and bifenthrin were also significant predictors of the upper limits of several univariate measures of the macroinvertebrate community (EPT percent, MMI (Macroinvertebrate Multimetric Index) Score, Ephemeroptera and Trichoptera richness) using quantile regression. Multivariate pattern matching (Mantel-like tests) of macroinvertebrate species per site to identified contaminant metrics and sediment toxicity also indicate that the sediment mixture score and bifenthrin have weak, albeit significant, influence on the observed invertebrate community composition. Together, these three lines of evidence (toxicity tests, univariate metrics, and multivariate community analysis) suggest that elevated contaminant concentrations in sediments, in particular bifenthrin, is limiting macroinvertebrate communities in several of these Midwest streams.

Science of the Total Environment↗

USGS2003

Modeling aqueous ferrous iron chemistry at low temperatures with application to Mars

Major uncertainties exist with respect to the aqueous geochemical evolution of the Martian surface. Considering the prevailing cryogenic climates and the abundance of salts and iron minerals on Mars, any attempt at comprehensive modeling of Martian aqueous chemistry should include iron chemistry and be valid at low temperatures and high solution concentrations. The objectives of this paper were to (1) estimate ferrous iron Pitzer-equation parameters and iron mineral solubility products at low temperatures (from < 0 ??C to 25 ??C), (2) incorporate these parameters and solubility products into the FREZCHEM model, and (3) use the model to simulate the surficial aqueous geochemical evolution of Mars. Ferrous iron Pitzer-equation parameters were derived in this work or taken from the literature. Six new iron minerals [FeCl2??4H2O, FeCl2??6H2O, FeSO4??H2O, FeSO4??7H2O, FeCO3, and Fe(OH)3] were added to the FREZCHEM model bringing the total solid phases to 56. Agreement between model predictions and experimental data are fair to excellent for the ferrous systems: Fe-Cl, Fe-SO4, Fe-HCO3, H-Fe-Cl, and H-Fe-SO4. We quantified a conceptual model for the aqueous geochemical evolution of the Martian surface. The five stages of the conceptual model are: (1) carbonic acid weathering of primary ferromagnesian minerals to form an initial magnesium-iron-bicarbonate-rich solution; (2) evaporation and precipitation of carbonates, including siderite (FeCO3), with evolution of the brine to a concentrated NaCl solution; (3) ferrous/ferric iron oxidation; (4) either evaporation or freezing of the brine to dryness; and (5) surface acidification. What began as a dilute Mg-Fe-HCO3 dominated leachate representing ferromagnesian weathering evolved into an Earth-like seawater composition dominated by NaCl, and finally into a hypersaline Mg-Na-SO4-Cl brine. Weathering appears to have taken place initially under conditions that allowed solution of ferrous iron [low O2(g)], but later caused oxidation of iron [high O2(g)]. Surface acidification and/or sediment burial can account for the minor amounts of Martian surface carbonates. This model rests on a large number of assumptions and is therefore speculative. Nevertheless, the model is consistent with current understanding concerning surficial salts and minerals based on Martian meteorites, Mars lander data, and remotely-sensed spectral analyses. ?? 2003 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

USGS1997

Effects of carbon dioxide variations in the unsaturated zone on water chemistry in a glacial-outwash aquifer

The research site at Otis Air Base, Cape Cod, Massachusetts, has been developed for hydrogeological and geochemical studies of sewage-effluent contaminated groundwater since 1982. Research of hydrologic properties, transport, and chemical and biological processes is ongoing, but the origin of background water chemistry has not been determined. The principal geochemical process giving rise to the observed background water chemistry is CO2-controlled hydrolysis of Na feldspar. Geochemical modeling demonstrated that CO2 sources could vary over the project area. Analyses of unsaturated zone gases showed variations in CO2 which were dependent on land use and vegetative cover in the area of groundwater recharge. Measurements of CO2 in unsaturated-zone gases showed that concentrations of total inorganic C in recharge water should range from about 0.035 to 1.0 mmoles/L in the vicinity of Otis Air Base. Flux of CO2 from the unsaturated zone varied for a principal land uses, ranging from 86 gC/m2/yr for low vegetated areas to 1630 gC/m2/yr for a golf course. Carbon dioxide flux from woodlands was 220 gC/m2/yr, lower than reported fluxes of 500 to 600 gC/m2/yr for woodlands in a similar climate. Carbon dioxide flux from grassy areas was 540 gC/m2/yr, higher than reported fluxes of 230 to 490 gC/m2/yr for grasslands in a similar climate.

Applied Geochemistry↗

USGS2002

Comparison of snowpack and winter wet-deposition chemistry in the Rocky Mountains, USA: Implications for winter dry deposition

Depth-integrated snowpack chemistry was measured just prior to maximum snowpack depth during the winters of 1992-1999 at 12 sites co-located with National Atmospheric Deposition Program/National Trend Network (NADP/NTN) sites in the central and southern Rocky Mountains, USA. Winter volume-weighted mean wet-deposition concentrations were calculated for the NADP/NTN sites, and the data were compared to snowpack concentrations using the paired t-test and the Wilcoxon signed-rank test. No statistically significant differences were indicated in concentrations of SO42- or NO3- (p>0.1). Small, but statistically significant differences (p???0.03) were indicated for all other solutes analyzed. Differences were largest for Ca2+ concentrations, which on average were 2.3??eql-1 (43%) higher in the snowpack than in winter NADP/NTN samples. Eolian carbonate dust appeared to influence snowpack chemistry through both wet and dry deposition, and the effect increased from north to south. Dry deposition of eolian carbonates was estimated to have neutralized an average of 6.9??eql-1 and a maximum of 12??eql-1 of snowpack acidity at the southernmost sites. The good agreement between snowpack and winter NADP/NTN SO42- and NO3- concentrations indicates that for those solutes the two data sets can be combined to increase data density in high-elevation areas, where few NADP/NTN sites exist. This combination of data sets will allow for better estimates of atmospheric deposition of SO42- and NO3- across the Rocky Mountain region.

Atmospheric Environment↗

USGS2000

Comparison of precipitation chemistry in the Central Rocky Mountains, Colorado, USA

Volume-weighted mean concentrations of nitrate (NO3-), ammonium (NH4+), and sulfate (SO42-) in precipitation were compared at high-elevation sites in Colorado from 1992 to 1997 to evaluate emission source areas to the east and west of the Rocky Mountains. Precipitation chemistry was measured by two sampling methods, the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) and snowpack surveys at maximum accumulation. Concentrations of NO3- and SO42- in winter precipitation were greater on the western slope of the Rockies, and concentrations of NO3- and NH4+ in summer precipitation were greater on the eastern slope. Summer concentrations in general were almost twice as high as winter concentrations. Seasonal weather patterns in combination with emission source areas help to explain these differences. This comparison shows that high-elevation ecosystems in Colorado are influenced by air pollution emission sources located on both sides of the Continental Divide. It also suggests that sources of nitrogen and sulfur located east of the Divide have a greater influence on precipitation chemistry in the Colorado Rockies. Copyright (C) 2000.

Atmospheric Environment↗

USGS2006

Effects of hurricanes Katrina and Rita on the chemistry of bottom sediments in Lake Pontchartrain, Louisiana, USA

The effects of Hurricanes Katrina and Rita and the subsequent unwatering of New Orleans, Louisiana, on the sediment chemistry of Lake Pontchartrain were evaluated by chemical analysis of samples of street mud and suspended and bottom sediments. The highest concentrations of urban-related elements and compounds (e.g., Pb, Zn, polycyclic aromatic hydrocarbons, and chlordane) in bottom sediments exceeded median concentrations in U.S. urban lakes and sediment-quality guidelines. The extent of the elevated concentrations was limited, however, to within a few hundred meters of the mouth of the 17th Street Canal, similar to results of historical assessments. Chemical and radionuclide analysis of pre- and post-Hurricane Rita samples indicates that remobilization of near-shore sediment by lake currents and storms is an ongoing process. The effects of Hurricanes Katrina and Rita on the sediment chemistry of Lake Pontchartrain are limited spatially and are most likely transitory.

Environmental Science & Technology↗

USGS2000

Relations of habitat-specific algal assemblages to land use and water chemistry in the Willamette Basin, Oregon

Benthic algal assemblages, water chemistry, and habitat were characterized at 25 stream sites in the Willamette Basin, Oregon, during low flow in 1994. Seventy-three algal samples yielded 420 taxa - Mostly diatoms, blue-green algae, and green algae. Algal assemblages from depositional samples were strongly dominated by diatoms (76% mean relative abundance), whereas erosional samples were dominated by blue-green algae (68% mean relative abundance). Canonical correspondence analysis (CCA) of semiquantitative and qualitative (presence/absence) data sets identified four environmental variables (maximum specific conductance, % open canopy, pH, and drainage area) that were significant in describing patterns of algal taxa among sites. Based on CCA, four groups of sites were identified: Streams in forested basins that supported oligotrophic taxa, such as Diatoma mesodon; small streams in agricultural and urban basins that contained a variety of eutrophic and nitrogen-heterotrophic algal taxa; larger rivers draining areas of mixed land use that supported planktonic, eutrophic, and nitrogen-heterotrophic algal taxa; and streams with severely degraded or absent riparian vegetation (> 75% open canopy) that were dominated by other planktonic, eutrophic, and nitrogen-heterotrophic algal taxa. Patterns in water chemistry were consistent with the algal autecological interpretations and clearly demonstrated relationships between land use, water quality, and algal distribution patterns.

Conference Paper↗

USGS2001

Changes in the chemistry of precipitation in the United States, 1981-1998

Regulatory measures in the United States, such as Title IV of the Clean Air Act Amendments of 1990, have primarily restricted sulfur dioxide emissions as a way to control acidic deposition. These restrictions, coupled with increasing concentrations of NH4+ in wet deposition in some regions of the U.S. and continued high emissions of nitrogen oxides have generated a significant shift in the chemistry of precipitation as measured at National Atmospheric Deposition Program/National Trends Network sites. Trends in precipitation chemistry at NADP/NTN sites were evaluated for statistical significance for the period 1981-1998 using a Seasonal Mann-Kendall Test, a robust non-parametric test for detection of monotonic trends. SO42- declines were detected at 100 of the 147 sites examined while no sites exhibited increasing SO42- trends. On average, SO42- declined 35% over the period 1981-1998 with downward SO42- trends being most pronounced in the northeastern United States. In contrast, no consistent trends in NO3- concentrations were observed in precipitation in any major region of the United States. Although the majority of sites did not exhibit significant trends in NH4+ concentration, 30 sites exhibited upward trends. For Ca2+ concentration in precipitation, 64 sites exhibited a significant decreasing trend and no sites exhibited an upward trend.

Water, Air, & Soil Pollution↗

USGS2011

River chemistry as a monitor of Yosemite Park mountain hydroclimates

High-frequency, high-altitude measurements of water chemistry provide insights into processes relating to the hydrology, climate, and geochemistry of mountain catchments. When such observations are combined with stream stage, temperature, snow, weather, and other surface hydroclimate measurements, they are particularly useful in allowing connections between climate, river discharge, river chemistry, and ecosystems to be discerned. Climate is the major source of variability in U.S. and global water resources. For example, large-scale variations in the global atmosphere and the Pacific Ocean are responsible for much of the variability in river discharge in Hawaii, Alaska, the U.S. Pacific Northwest, and the U.S. Southwest [ Cayan and Peterson , 1989], and thus are closely linked to water and energy resources of the western United States [ Cayan et al ., 2003].

Eos, Earth and Space Science News↗

USGS2007

Modeling englacial radar attenuation at Siple Dome, West Antarctica, using ice chemistry and temperature data

The radar reflectivity of an ice-sheet bed is a primary measurement for discriminating between thawed and frozen beds. Uncertainty in englacial radar attenuation and its spatial variation introduces corresponding uncertainty in estimates of basal reflectivity. Radar attenuation is proportional to ice conductivity, which depends on the concentrations of acid and sea-salt chloride and the temperature of the ice. We synthesize published conductivity measurements to specify an ice-conductivity model and find that some of the dielectric properties of ice at radar frequencies are not yet well constrained. Using depth profiles of ice-core chemistry and borehole temperature and an average of the experimental values for the dielectric properties, we calculate an attenuation rate profile for Siple Dome, West Antarctica. The depth-averaged modeled attenuation rate at Siple Dome (20.0 ?? 5.7 dB km-1) is somewhat lower than the value derived from radar profiles (25.3 ?? 1.1 dB km-1). Pending more experimental data on the dielectric properties of ice, we can match the modeled and radar-derived attenuation rates by an adjustment to the value for the pure ice conductivity that is within the range of reported values. Alternatively, using the pure ice dielectric properties derived from the most extensive single data set, the modeled depth-averaged attenuation rate is 24.0 ?? 2.2 dB km-1. This work shows how to calculate englacial radar attenuation using ice chemistry and temperature data and establishes a basis for mapping spatial variations in radar attenuation across an ice sheet. Copyright 2007 by the American Geophysical Union.

Journal of Geophysical Research F: Earth Surface↗

USGS2024

Uranium redox and deposition transitions embedded in deep-time geochemical models and mineral chemistry networks

Uranium (U) is an important global energy resource and a redox sensitive trace element that reflects changing environmental conditions and geochemical cycling. The redox evolution of U mineral chemistry can be interrogated to understand the formation and distribution of U deposits and the redox processes involved in U geochemistry throughout Earth history. In this study, geochemical modeling using thermodynamic data, and mineral chemistry network analysis are used to investigate U geochemistry and deposition through time. The number of U 6+ mineral localities surpasses the number of U 4+ mineral localities in the Paleoproterozoic. Moreover, the number of sedimentary U 6+ mineral localities increases earlier in the Phanerozoic than the number of U 4+ sedimentary mineral localities, likely due to the necessity of sufficient sedimentary organic matter to reduce U 6+ –U 4+ . Indeed, modeling calculations indicate that increased oxidative weathering due to surface oxygenation limited U 4+ uraninite (UO 2 ) formation from weathered granite and basalt. Louvain network community detection shows that U 6+ forms minerals with many more shared elements and redox states than U 4+ . The range of weighted Mineral Element Electronegativity Coefficient of Variation (wMEE CV ) values of U 6+ minerals increases through time, particularly during the Phanerozoic. Conversely, the range of wMEE CV values of U 4+ minerals is consistent through time due to the relative abundance of uraninite, coffinite, and brannerite. The late oxidation and formation of U 6+ minerals compared to S 6+ minerals illustrates the importance of the development of land plants, organic matter deposition, and redox-controlled U deposition from ground water in continental sediments during this time-period.

Geochemistry, Geophysics, Geosystems↗

USGS2010

Processes controlling the chemistry of two snowmelt‐dominated streams in the Rocky Mountains

Time‐intensive discharge and chemical data for two alpine streams in the Loch Vale watershed, Colorado, were used to identify sources of runoff, flow paths, and important biogeochemical processes during the 1992 snowmelt runoff season. In spite of the paucity of soil cover the chemical composition of the streams is regulated much as in typical forested watersheds. Soils and other shallow groundwater matrices such as boulder fields appear to be more important in controlling surface‐water chemistry than their abundance would indicate. The chemical composition of the major source waters (usually thought of as end‐members whose chemical composition is relatively constant over time) changes at the same time that their mixing ratio in streams changes, confounding use of end‐member mixing models to describe stream‐water chemistry. Changes in the chemical composition of these source waters are caused by the ionic pulse of solutes from the snowpack and the small size of the shallow groundwater reservoir compared to the volume of snowmelt passing through it. The brief hydrologic residence time in the shallow groundwater indicates that concentrations of most dissolved constituents of stream water were controlled by fast geochemical processes that occurred on timescales of hours to days, rather than slower processes such as weathering of primary minerals. Differences in the timing of snowmelt‐related processes between different areas of the watershed also affect the stream‐water chemical composition. Cirque lakes affect discharge and chemical composition of one of the streams; seasonal control on stream‐water NO 3 and SiO 2 concentrations by diatom uptake in the lakes was inferred. Elution of acidic waters from the snowpack, along with dilution of base cations originating in shallow groundwater, caused episodes of decreased acid‐neutralizing capacity in the streams, but the streams did not become acidic.

Colorado↗