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At least 271 records · Page 15Linked to original sources
USGS2009

The δ 15 N and δ 18 O values of N 2 O produced during the co-oxidation of ammonia by methanotrophic bacteria

In order to determine if the δ 15 N and δ 18 O values of N 2 O produced during co-oxidation of NH 4 + by methanotrophic (methane oxidizing) bacteria can be isotopically distinguished from N 2 O produced either by autotrophic nitrifying or denitrifying bacteria, we conducted laboratory incubation experiments with pure cultures of methanotrophic bacteria that were provided NH 4 Cl as an oxidation substrate. The N 2 O produced during NH 4 + oxidation by methanotrophic bacteria showed nitrogen isotope fractionation between NH 4 + and N 2 O ( ε N 2 O–NH 4 + ) of − 48 and − 55‰ for Methylomonas methanica and Methylosinus trichosporium , OB3b respectively. These large fractionations are similar to those previously measured for autotrophic nitrifying bacteria and consistent with N 2 O formation by multiple rate limiting steps that include NH 4 + oxidation by the methane monooxygenase enzyme and reduction of NO 2 − to N 2 O. Consequently, N 2 O formed by NH 4 + oxidation via methanotrophic or autotrophic nitrifying bacteria might generally be characterized by lower δ 15 N N 2 O values than that formed by denitrificaiton, although this also depends on the variability of δ 15 N of available nitrogen sources (e.g., NH 4 + , NO 3 − , NO 2 − ). Additional incubations with M. trichosporium OB3b at high and low CH 4 conditions in waters of different δ 18 O values revealed that 19–27% of the oxygen in N 2 O was derived from O 2 with the remainder from water. The biochemical mechanisms that could explain this amount of O 2 incorporation are discussed. The δ 18 O of N 2 O formed under high CH 4 conditions was ~ + 15‰ more positive than that formed under lower CH 4 conditions. This enrichment resulted in part from the incorporation of O 2 into N 2 O that was enriched in 18 O due to an isotope fractionation effect of − 16.1 ± 2.0‰ and − 17.5 ± 5.4‰ associated with O 2 consumption during the high and low methane concentration incubations, respectively. Therefore, N 2 O formed by NH 4 + oxidation via methanotrophic or autotrophic nitrifying bacteria can have very positive δ 18 O N 2 O values if the O 2 incorporated is previously enriched in 18 O from high rates of respiration. Nitrous oxide was collected from various depths in soils overlying a coal-bed methane seep where methanotrophic bacteria are naturally enriched. In one sampling when soil methane concentrations were very high, the δ 18 O VSMOW values of the N 2 O were highly enriched (+ 50‰), consistent with our laboratory experiments. Thus, soils overlying methane seeps could provide an 18 O-enriched source of atmospheric N 2 O.

Chemical Geology↗
USGS2010

Phosphorus and iron cycling in deep saprolite, Luquillo Mountains, Puerto Rico

Rapid weathering and erosion rates in mountainous tropical watersheds lead to highly variable soil and saprolite thicknesses which in turn impact nutrient fluxes and biological populations. In the Luquillo Mountains of Puerto Rico, a 5-m thick saprolite contains high microorganism densities at the surface and at depth overlying bedrock. We test the hypotheses that the organisms at depth are limited by the availability of two nutrients, P and Fe. Many tropical soils are P-limited, rather than N-limited, and dissolution of apatite is the dominant source of P. We document patterns of apatite weathering and of bioavailable Fe derived from the weathering of primary minerals hornblende and biotite in cores augered to 7.5 m on a ridgetop as compared to spheroidally weathering bedrock sampled in a nearby roadcut. Iron isotopic compositions of 0.5 N HCl extracts of soil and saprolite range from about δ 56 Fe = 0 to − 0.1‰ throughout the saprolite except at the surface and at 5 m depth where δ 56 Fe = − 0.26 to − 0.64‰. The enrichment of light isotopes in HCl-extractable Fe in the soil and at the saprolite–bedrock interface is consistent with active Fe cycling and consistent with the locations of high cell densities and Fe(II)-oxidizing bacteria, identified previously. To evaluate the potential P-limitation of Fe-cycling bacteria in the profile, solid-state concentrations of P were measured as a function of depth in the soil, saprolite, and weathering bedrock. Weathering apatite crystals were examined in thin sections and an apatite dissolution rate of 6.8 × 10 − 14 mol m − 2 s − 1 was calculated. While surface communities depend on recycled nutrients and atmospheric inputs, deep communities survive primarily on nutrients released by the weathering bedrock and thus are tightly coupled to processes related to saprolite formation including mineral weathering. While low available P may limit microbial activity within the middle saprolite, fluxes of P from apatite weathering should be sufficient to support robust growth of microorganisms in the deep saprolite.

Puerto Rico↗
USGS2010

Controls on biochemical oxygen demand in the upper Klamath River, Oregon

A series of 30-day biochemical oxygen demand (BOD) experiments were conducted on water column samples from a reach of the upper Klamath River that experiences hypoxia and anoxia in summer. Samples were incubated with added nitrification inhibitor to measure carbonaceous BOD (CBOD), untreated to measure total BOD, which included demand from nitrogenous BOD (NBOD), and coarse-filtered to examine the effect of removing large particulate matter. All BOD data were fit well with a two-group model, so named because it considered contributions from both labile and refractory pools of carbon: BOD t = a 1 (1 − e − a 0 t ) + a 2 t . Site-average labile first-order decay rates a 0 ranged from 0.15 to 0.22/day for CBOD and 0.11 to 0.29/day for BOD. Site-average values of refractory zero-order decay rates a 2 ranged from 0.13 to 0.25 mg/L/day for CBOD and 0.01 to 0.45 mg/L/day for BOD; the zero-order CBOD decay rate increased from early- to mid-summer. Values of ultimate CBOD for the labile component a 1 ranged from 5.5 to 28.8 mg/L for CBOD, and 7.6 to 30.8 mg/L for BOD. Two upstream sites had higher CBOD compared to those downstream. Maximum measured total BOD 5 and BOD 30 during the study were 26.5 and 55.4 mg/L; minimums were 4.2 and 13.6 mg/L. For most samples, the oxygen demand from the three components considered here were: labile CBOD > NBOD > refractory CBOD, though the relative importance of refractory CBOD to oxygen demand increased over time. Coarse-filtering reduced CBOD for samples with high particulate carbon and high biovolumes of Aphanizomenon flos-aquae . There was a strong positive correlation between BOD, CBOD, and the labile component of CBOD to particulate C and N, with weaker positive correlation to field pH, field dissolved oxygen, and total N. The refractory component of CBOD was not correlated to particulate matter, instead showing weak but statistically significant correlation to dissolved organic carbon, UV absorbance at 254 nm, and total N. Particulate organic matter, especially the alga A. flos-aquae , is an important component of oxygen demand in this reach of the Klamath River, though refractory dissolved organic matter would continue to exert an oxygen demand over longer time periods and as water travels downstream.

Oregon↗
USGS2010

Effects of temperature on silicate weathering: Solute fluxes and chemical weathering in a temperate rain forest watershed, Jamieson Creek, British Columbia

Chemical weathering of silicate minerals has long been known as a sink for atmospheric CO 2 , and feedbacks between weathering and climate are believed to affect global climate. While warmer temperatures are believed to increase rates of weathering, weathering in cool climates can be accelerated by increased mineral exposure due to mechanical weathering by ice. In this study, chemical weathering of silicate minerals is investigated in a small temperate watershed. The Jamieson Creek watershed is covered by mature coniferous forest and receives high annual precipitation (4000 mm), mostly in the form of rainfall, and is underlain by quartz diorite bedrock and glacial till. Analysis of pore water concentration gradients indicates that weathering in hydraulically unsaturated ablation till is dominated by dissolution of plagioclase and hornblende. However, a watershed scale solute mass balance indicates high relative fluxes of K and Ca, indicating preferential leaching of these solutes possibly from the relatively unweathered lodgement till. Weathering rates for plagioclase and hornblende calculated from a watershed scale solute mass balance are similar in magnitude to rates determined using pore water concentration gradients. When compared to the Rio Icacos basin in Puerto Rico, a pristine tropical watershed with similar annual precipitation and bedrock, but with dissimilar regolith properties, fluxes of weathering products in stream discharge from the warmer site are 1.8 to 16.2-fold higher, respectively, and regolith profile-averaged plagioclase weathering rates are 3.8 to 9.0-fold higher. This suggests that the Arrhenius effect, which predicts a 3.5- to 9-fold increase in the dissolution rate of plagioclase as temperature is increased from 3.4° to 22 °C, may explain the greater weathering fluxes and rates at the Rio Icacos site. However, more modest differences in K and Ca fluxes between the two sites are attributed to accelerated leaching of those solutes from glacial till at Jamieson Creek. Our findings suggest that under conditions of high rainfall and favorable topography, weathering rates of silicate minerals in warm tropical systems will tend to be higher than in cool temperate systems, even if the temperate system is has been perturbed by an episode of glaciation that deposits regolith high in fresh mineral surface area.

British Columbia↗
USGS2010

Mechanisms for chemostatic behavior in catchments: implications for CO 2 consumption by mineral weathering

Concentrations of weathering products in streams often show relatively little variation compared to changes in discharge, both at event and annual scales. In this study, several hypothesized mechanisms for this “chemostatic behavior” were evaluated, and the potential for those mechanisms to influence relations between climate, weathering fluxes, and CO 2 consumption via mineral weathering was assessed. Data from Loch Vale, an alpine catchment in the Colorado Rocky Mountains, indicates that cation exchange and seasonal precipitation and dissolution of amorphous or poorly crystalline aluminosilicates are important processes that help regulate solute concentrations in the stream; however, those processes have no direct effect on CO 2 consumption in catchments. Hydrograph separation analyses indicate that old water stored in the subsurface over the winter accounts for about one-quarter of annual streamflow, and almost one-half of annual fluxes of Na and SiO 2 in the stream; thus, flushing of old water by new water (snowmelt) is an important component of chemostatic behavior. Hydrologic flushing of subsurface materials further induces chemostatic behavior by reducing mineral saturation indices and increasing reactive mineral surface area, which stimulate mineral weathering rates. CO 2 consumption by carbonic acid mediated mineral weathering was quantified using mass-balance calculations; results indicated that silicate mineral weathering was responsible for approximately two-thirds of annual CO 2 consumption, and carbonate weathering was responsible for the remaining one-third. CO 2 consumption was strongly dependent on annual precipitation and temperature; these relations were captured in a simple statistical model that accounted for 71% of the annual variation in CO 2 consumption via mineral weathering in Loch Vale.

Colorado↗
USGS2010

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (?? 18 O H2O ) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O 2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ?? 18 O SO4-H2O , of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ?? SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O 2 into sulfate. ?? 34 S SO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ?? 34 S SO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

Chemical Geology↗
USGS2010

Kinetics of selenium release in mine waste from the Meade Peak Phosphatic Shale, Phosphoria Formation, Wooley Valley, Idaho, USA

Phosphorite from the Meade Peak Phosphatic Shale member of the Permian Phosphoria Formation has been mined in southeastern Idaho since 1906. Dumps of waste rock from mining operations contain high concentrations of Se which readily leach into nearby streams and wetlands. While the most common mineralogical residence of Se in the phosphatic shale is elemental Se, Se(0), Se is also an integral component of sulfide phases (pyrite, sphalerite and vaesite–pyrite ss ) in the waste rock. It may also be present as adsorbed selenate and/or selenite, and FeSe 2 and organo-selenides. Se release from the waste rock has been observed in field and laboratory experiments. Release rates calculated from waste rock dump and column leachate solutions describe the net, overall Se release from all of the possible sources of Se listed above. In field studies, Se concentration in seepage water (pH 7.4–7.8) from the Wooley Valley Unit 4 dump ranges from 3600 µg/L in May to 10 µg/L by Sept. Surface water flow, Q , from the seep also declines over the summer, from 2 L/s in May to 0.03 L/s in Sept. Se flux ([Se] ⁎ Q ) reaches a steady-state of < 150 mg/day in 1–4 months, depending upon the volume of Q . Se release (mg/L) follows a first order reaction with a rate constant, k , = 1.35 – 6.35e−3 h − 1 (11.8–55.6 yr − 1 ). Laboratory experiments were performed with the waste shale in packed bed reactors; residence time varied from 0.09 to 400 h and outlet pH ∼ 7.5. Here, Se concentration increased with increasing residence time and release was modeled with a first order reaction with k = 2.19e−3 h − 1 (19.2 yr − 1 ). Rate constants reported here fall within an order of magnitude of reported rate constants for oxidation of Se(0) formed by bacterial precipitation. This similarity among rate constants from both field and laboratory studies combined with the direct observation of Se(0) in waste shales of the Phosphoria Formation suggests that oxidation of Se(0) may control steady-state Se concentration in water draining the Wooley Valley waste dump.

Idaho↗
USGS2010

Timing and duration of garnet granulite metamorphism in magmatic arc crust, Fiordland, New Zealand

Pembroke Granulite from Fiordland, New Zealand provides a window into the mid- to lower crust of magmatic arcs. Garnet Sm-Nd and zircon U-Pb ages constrain the timing and duration of high-P partial melting that produced trondhjemitic high Sr/Y magma. Trace element zoning in large, euhedral garnet is compatible with little post growth modification and supports the interpretation that garnet Sm-Nd ages of 126.1??2.0 and 122.6??2.0. Ma date crystal growth. Integration of the garnet ages with U-Pb zircon ages elucidates a history of intrusion(?) and a protracted period of high-temperature metamorphism and partial melting. The oldest zircon ages of 163 to 150. Ma reflect inheritance or intrusion and a cluster of zircon ages ca. 134. Ma date orthopyroxene-bearing mineral assemblages that may be magmatic or metamorphic in origin. Zircon and garnet ages from unmelted gneiss and garnet reaction zones record garnet granulite facies metamorphism at 128 to 126. Ma. Peritectic garnet and additional zircon ages from trondhjemite veins and garnet reaction zones indicate that garnet growth and partial melting lasted until ca. 123. Ma. Two single fraction garnet ages and young zircon ages suggest continued high-temperature re-equilibration until ca. 95. Ma. Phase diagram sections constrain orthopyroxene assemblages to <0.6 GPa @ 650??C, peak garnet granulite facies metamorphic conditions to 680-815??C @ 1.1-1.4. GPa, and a P-T path with a P increase of???0.5. GPa. These sections are compatible with water contents???0.28wt.%, local dehydration during garnet granulite metamorphism, and <0.3. GPa P increases during garnet growth. Results demonstrate the utility of integrated U-Pb zircon and Sm-Nd garnet ages, and phase diagram sections for understanding the nature, duration, and conditions of deep crustal metamorphism and melting. Geochronologic and thermobarometric data for garnet granulite indicate that thickening of arc crust, which caused high-pressure metamorphism in northern Fiordland, must have occurred prior to 126. Ma, that loading occurred at a rate of ca. 0.06. GPa/m.y., and that garnet granulite metamorphism lasted 3-7m.y. Locally-derived partial melts formed and crystallized in considerably less than 10 and perhaps as little as 3m.y. ?? 2010 Elsevier B.V.

Chemical Geology↗
USGS2010

Dissolution-reprecipitation of igneous zircon in mid-ocean ridge gabbro, Atlantis Bank, Southwest Indian Ridge

Zircons recovered from oceanic gabbro exposed on Atlantis Bank, Southwest Indian Ridge, typically display oscillatory and sector zoning consistent with igneous crystallization from mafic magmas. In one rock (of twenty investigated), weak-oscillatory-zonation patterns are overprinted by secondary textural features characterized by mottled, convoluted and wavy internal zonation patterns that are frequently associated with secondary micron- to submicron-scale micro-porosity. These zircons are hosted in a felsic vein that intruded an oxide gabbro, both of which are cross-cut by monomineralic amphibole- and quartz-rich veinlets. Zircons with weak-oscillatory-zonation patterns record a weighted-average 206 Pb/ 238 U age of 12.76 ± 0.20 Ma (mswd = 1.5), and have high trace element concentrations [e.g., ΣREEs (∼ 0.4–2.2 wt.%), Y (∼ 0.6–2.8 wt.%), P (∼ 0.4–0.9 wt.%)], and Th/U (0.1–0.5). These zircons are anomalously old (≥1 Myr) relative to the magnetic age for this portion of oceanic crust (11.75 Ma). In contrast, zircons with non-igneous, secondary textures have a younger weighted-average 206 Pb/ 238 U age of 12.00 ± 0.16 Ma (mswd = 1.7), and have lower trace element concentrations [e.g., ΣREEs (∼ 0.2–0.8 wt.%), Y (∼ 0.3–1.0 wt.%), P (∼ 0.1–0.3 wt.%)], and slightly lower Th/U (0.1–0.3). The weighted-average age of these zircons is similar to the magnetic anomaly age, and other 206 Pb/ 238 U ages of nearby rocks. We do not observe a correlation between crystallographic misorientation, internal texture, or trace element chemistry. We suggest that the decrease in trace element concentrations associated with the development of non-igneous alteration textures is attributed to the purging of non-essential structural constituent cations from the zircon crystal lattice at amphibolite-facies conditions. The mechanism of alteration/re-equilibration was likely an interface-coupled dissolution–reprecipitation processes that affected pre-existing, anomalously old zircons during shallow-level magmatic construction of Atlantis Bank at ∼ 12.0 Ma.

Chemical Geology↗
USGS2010

The age of the Steens reversal and the Columbia River Basalt Group

The Columbia River Basalt Group (CRBG) eruptions have a well-defined relative magnetostratigraphy but have not been definitively correlated to the geomagnetic polarity time scale. 40 Ar/ 39 Ar ages are presented from lavas erupted in the R 0 through N 1 magnetozones of the CRBG and in the transition between R 0 and N 0 . Four ages from transitionally magnetized lava flows at Steens Mountain, Catlow Peak, and Poker Jim Ridge with a weighted mean age 16.58 ± 0.10 Ma 1 and the more precise age 16.654 ± 0.025 Ma of the normally magnetized Oregon Canyon tuff at the top of the Catlow Peak section show that the oldest CRBG magnetozone ( R 0 ) correlates with the C5Cr chron. Bayesian statistical analysis applied to data from four flows at Catlow Peak (using the mean age of the Steens reversal) gives a best and preferred age of the Steens reversal of 16.73 + 0.13/−0.08 Ma (95% confidence). Depending on the geomagnetic polarity time scale model, the eruption rate from N 0 through R 2 (0.34–0.45 Ma in the middle and the bulk of the CRBG emplacement) averaged 0.30–0.41 km 3 /a and peaked at a rate 1 1/2 to 4 1/2 times higher during R 2.

Chemical Geology↗
USGS2010

Controls on rind thickness on basaltic andesite clasts weathering in Guadeloupe

A clast of low porosity basaltic andesite collected from the B horizon of a soil developed on a late Quaternary volcaniclastic debris flow in the Bras David watershed on Basse-Terre Island, Guadeloupe, exhibits weathering like that observed in many weathered clasts of similar composition in other tropical locations. Specifically, elemental profiles measured across the core-rind interface document that primary minerals and glass weather to Fe oxyhydroxides, gibbsite and minor kaolinite in the rind. The earliest reaction identified in the core is oxidation of Fe in pyroxene but the earliest reaction that creates significant porosity is plagioclase dissolution. Elemental loss varies in the order Ca???Na>K???Mg>Si>Al>Fe???P??Ti, consistent with the relative reactivity of phases in the clast from plagioclase???pyroxene???glass>apatite>ilmenite. The rind surrounds a core of unaltered material that is more spherical than the original clast. The distance from the core-rind boundary to a visually prominent rind layer, L, was measured as a proxy for the rind thickness at 36 locations on a slab cut vertically through the nominal center of the clast. This distance averaged 24.4??3.1mm. Maximum and minimum values for L, 35.8 and 20.6mm, were observed where curvature of the core-rind boundary is greatest (0.12mm-1) and smallest (0.018mm-1) respectively. Extrapolating from other rinds in other locations, the rate of rind formation is estimated to vary by a factor of about 2 (from ~4 to 7??10-14ms-1) from low to high curvature. The observation of a higher rate of rind formation for a higher curvature interface is consistent with a diffusion-limited model for weathering rind formation. The diffusion-limited model predicts that, like rind thickness, values of the thickness of the reaction front (h) for a given reaction, defined as the zone over which a parent mineral such as plagioclase completely weathers to rind material, should also increase with curvature. Values of h were quantified as a function of interface curvature using bulk chemical analysis (500<h<2000??m). Values of h were also quantified by measuring loss of matrix glass and increase in porosity as a function of curvature. In contrast to rind thickness, h shows no consistent increase with curvature. This contradiction is attributed to the mm-scale roughness of the interface which is related to phenocryst grain size. Therefore, the overall rind formation rate is strongly affected by curvature measured at the scale of the clast, while mineral reaction rates documented by reaction front thickness are strongly affected by curvature at the scale of phenocrysts. Similarly, the weathering advance rate (ms-1) for the entire Bras David watershed can be extrapolated from the clast weathering rate if roughness at the watershed scale equals values of approximately 400-800. ?? 2010 Elsevier B.V.

Chemical Geology↗
USGS2010

In situ sulfur isotope analysis of sulfide minerals by SIMS: Precision and accuracy, with application to thermometry of ~3.5Ga Pilbara cherts

Secondary ion mass spectrometry (SIMS) measurement of sulfur isotope ratios is a potentially powerful technique for in situ studies in many areas of Earth and planetary science. Tests were performed to evaluate the accuracy and precision of sulfur isotope analysis by SIMS in a set of seven well-characterized, isotopically homogeneous natural sulfide standards. The spot-to-spot and grain-to-grain precision for δ34S is ± 0.3‰ for chalcopyrite and pyrrhotite, and ± 0.2‰ for pyrite (2SD) using a 1.6 nA primary beam that was focused to 10 µm diameter with a Gaussian-beam density distribution. Likewise, multiple δ34S measurements within single grains of sphalerite are within ± 0.3‰. However, between individual sphalerite grains, δ34S varies by up to 3.4‰ and the grain-to-grain precision is poor (± 1.7‰, n = 20). Measured values of δ34S correspond with analysis pit microstructures, ranging from smooth surfaces for grains with high δ34S values, to pronounced ripples and terraces in analysis pits from grains featuring low δ34S values. Electron backscatter diffraction (EBSD) shows that individual sphalerite grains are single crystals, whereas crystal orientation varies from grain-to-grain. The 3.4‰ variation in measured δ34S between individual grains of sphalerite is attributed to changes in instrumental bias caused by different crystal orientations with respect to the incident primary Cs+ beam. High δ34S values in sphalerite correlate to when the Cs+ beam is parallel to the set of directions < uuw>, from [111] to [110], which are preferred directions for channeling and focusing in diamond-centered cubic crystals. Crystal orientation effects on instrumental bias were further detected in galena. However, as a result of the perfect cleavage along {100} crushed chips of galena are typically cube-shaped and likely to be preferentially oriented, thus crystal orientation effects on instrumental bias may be obscured. Test were made to improve the analytical precision of δ34S in sphalerite, and the best results were achieved by either reducing the depth of the analysis pits using a Köhler illuminated primary beam, or by lowering the total impact energy from 20 keV to 13 keV. The resulting grain-to-grain precision in δ34S improves from ± 1.7‰ to better than 0.6‰ (2SD) in both procedures. With careful use of appropriate analytical conditions, the accuracy of SIMS analysis for δ34S approaches ± 0.3‰ (2SD) for chalcopyrite, pyrite and pyrrhotite and ± 0.6‰ for sphalerite. Measurements of δ34S in sub-20 µm grains of pyrite and sphalerite in ∼ 3.5 Ga cherts from the Pilbara craton, Western Australia show that this analytical technique is suitable for in situ sulfur isotope thermometry with ± 50 °C accuracy in appropriate samples, however, sulfides are not isotopically equilibrated in analyzed samples.

Chemical Geology↗
USGS2010

River solute fluxes reflecting active hydrothermal chemical weathering of the Yellowstone Plateau Volcanic Field, USA

In the past few decades numerous studies have quantified the load of dissolved solids in large rivers to determine chemical weathering rates in orogenic belts and volcanic areas, mainly motivated by the notion that over timescales greater than ~100kyr, silicate hydrolysis may be the dominant sink for atmospheric CO2, thus creating a feedback between climate and weathering. Here, we report the results of a detailed study during water year 2007 (October 1, 2006 to September 30, 2007) in the major rivers of the Yellowstone Plateau Volcanic Field (YPVF) which hosts Earth's largest "restless" caldera and over 10,000 thermal features. The chemical compositions of rivers that drain thermal areas in the YPVF differ significantly from the compositions of rivers that drain non-thermal areas. There are large seasonal variations in river chemistry and solute flux, which increases with increasing water discharge. The river chemistry and discharge data collected periodically over an entire year allow us to constrain the annual solute fluxes and to distinguish between low-temperature weathering and hydrothermal flux components. The TDS flux from Yellowstone Caldera in water year 2007 was 93t/km2/year. Extensive magma degassing and hydrothermal interaction with rocks accounts for at least 82% of this TDS flux, 83% of the cation flux and 72% of the HCO3- flux. The low-temperature chemical weathering rate (17t/km2/year), calculated on the assumption that all the Cl- is of thermal origin, could include a component from low-temperature hydrolysis reactions induced by CO2 ascending from depth rather than by atmospheric CO2. Although this uncertainty remains, the calculated low-temperature weathering rate of the young rhyolitic rocks in the Yellowstone Caldera is comparable to the world average of large watersheds that drain also more soluble carbonates and evaporates but is slightly lower than calculated rates in other, less-silicic volcanic regions. Long-term average fluxes at Yellowstone are likely ~20% higher than those in the abnormally dry water year 2007, but the protocol used in this study can be easily adaptable to track future changes in low-temperature weathering and hydrothermal flux components, which could provide better monitoring of magmatic unrest. ?? 2010.

Chemical Geology↗
USGS2011

Diel cycles in dissolved barium, lead, iron, vanadium, and nitrite in a stream draining a former zinc smelter site near Hegeler, Illinois

Diel variations in the concentrations of a number of constituents have the potential to substantially affect the appropriate sampling regimen in acidic streams. Samples taken once during the course of the day cannot adequately reflect diel variations in water quality and may result in an inaccurate understanding of biogeochemical processes, ecological conditions, and of the threat posed by the water to human health and the associated wildlife. Surface water and groundwater affected by acid drainage were sampled every 60 to 90 min over a 48-hour period at a former zinc smelter known as the Hegeler Zinc Superfund Site, near Hegeler, Illinois. Diel variations related to water quality in the aquifer were not observed in groundwater. Diel variations were observed in the temperature, pH, and concentration of dissolved oxygen, nitrite, barium, iron, lead, vanadium, and possibly uranium in surface water. Temperature, dissolved oxygen, nitrite, barium, lead, and uranium generally attained maximum values during the afternoon and minimum values during the night. Iron, vanadium, and pH generally attained minimum values during the afternoon and maximum values during the night. Concentrations of dissolved oxygen were affected by the intensity of photosynthetic activity and respiration, which are dependent upon insolation. Nitrite, an intermediary in many nitrogen reactions, may have been formed by the oxidation of ammonium by dissolved oxygen and converted to other nitrogen species as part of the decomposition of organic matter. The timing of the pH cycles was distinctly different from the cycles found in Midwestern alkaline streams and likely was the result of the photoreduction of Fe 3+ to Fe 2+ and variations in the intensity of precipitation of hydrous ferric oxide minerals. Diel cycles of iron and vanadium also were primarily the result of variations in the intensity of precipitation of hydrous ferric oxide minerals. The diel variation in the concentrations of lead, uranium, and barium may have been affected by competition with Fe + 2 for sorption sites on hydrous ferric oxide minerals.

Illinois↗
USGS2011

Biological and geochemical controls on diel dissolved inorganic carbon cycling in a low-order agricultural stream: Implications for reach scales and beyond

Movement of dissolved inorganic carbon (DIC) through the hydrologic cycle is an important component of global carbon budgets, but there is considerable uncertainty about the controls of DIC transmission from landscapes to streams, and through river networks to the oceans. In this study, diel measurements of DIC, d13C-DIC, dissolved oxygen (O2), d18O-O2, alkalinity, pH, and other parameters were used to assess the relative magnitudes of biological and geochemical controls on DIC cycling and flux in a nutrient-rich, net autotrophic stream. Rates of photosynthesis (P), respiration (R), groundwater discharge, air–water exchange of CO2, and carbonate precipitation/dissolution were quantified through a time-stepping chemical/isotope (12C and 13C, 16O and 18O) mass balance model. Groundwater was the major source of DIC to the stream. Primary production and carbonate precipitation were equally important sinks for DIC removed from the water column. The stream was always super-saturated with respect to carbonate minerals, but carbonate precipitation occurred mainly during the day when P increased pH. We estimated more than half (possibly 90%) of the carbonate precipitated during the day was retained in the reach under steady baseflow conditions. The amount of DIC removed from the overlying water through carbonate precipitation was similar to the amount of DIC generated from R. Air–water exchange of CO2 was always from the stream to the atmosphere, but was the smallest component of the DIC budget. Overall, the in-stream DIC reactions reduced the amount of CO2 evasion and the downstream flux of groundwater-derived DIC by about half relative to a hypothetical scenario with groundwater discharge only. Other streams with similar characteristics are widely distributed in the major river basins of North America. Data from USGS water quality monitoring networks from the 1960s to the 1990s indicated that 40% of 652 stream monitoring stations in the contiguous USA were at or above the equilibrium saturation state for calcite, and 77% of all stations exhibited apparent increases in saturation state from the 1960/70s to the 1980/90s. Diel processes including partially irreversible carbonate precipitation may affect net carbon fluxes from many such watersheds.

Chemical Geology↗
USGS2011

Potential effects of alpha-recoil on uranium-series dating of calcrete

Evaluation of paleosol ages in the vicinity of Yucca Mountain, Nevada, at the time the site of a proposed high-level nuclear waste repository, is important for fault-displacement hazard assessment. Uranium-series isotope data were obtained for surface and subsurface calcrete samples from trenches and boreholes in Midway Valley, Nevada, adjacent to Yucca Mountain. 230 Th/U ages of 33 surface samples range from 1.3 to 423 thousand years (ka) and the back-calculated 234 U/ 238 U initial activity ratios (AR) are relatively constant with a mean value of 1.54 ± 0.15 (1σ), which is consistent with the closed-system behavior. Subsurface calcrete samples are too old to be dated by the 230 Th/U method. U-Pb data for post-pedogenic botryoidal opal from a subsurface calcrete sample show that these subsurface calcrete samples are older than ~ 1.65 million years (Ma), old enough to have attained secular equilibrium had their U-Th systems remained closed. However, subsurface calcrete samples show U-series disequilibrium indicating open-system behavior of 238 U daughter isotopes, in contrast with the surface calcrete, where open-system behavior is not evident. Data for 21 subsurface calcrete samples yielded calculable 234 U/ 238 U model ages ranging from 130 to 1875 ka (assuming an initial AR of 1.54 ± 0.15, the mean value calculated for the surface calcrete samples). A simple model describing continuous α-recoil loss predicts that the 234 U/ 238 U and 230 Th/ 238 U ARs reach steady-state values ~ 2 Ma after calcrete formation. Potential effects of open-system behavior on 230 Th/U ages and initial 234 U/ 238 U ARs for younger surface calcrete were estimated using data for old subsurface calcrete samples with the 234 U loss and assuming that the total time of water-rock interaction is the only difference between these soils. The difference between the conventional closed-system and open-system ages may exceed errors of the calculated conventional ages for samples older than ~ 250 ka, but is negligible for younger soils.

Chemical Geology↗
USGS2011

A mass-balance model to separate and quantify colloidal and solute redistributions in soil

Studies of weathering and pedogenesis have long used calculations based upon low solubility index elements to determine mass gains and losses in open systems. One of the questions currently unanswered in these settings is the degree to which mass is transferred in solution (solutes) versus suspension (colloids). Here we show that differential mobility of the low solubility, high field strength (HFS) elements Ti and Zr can trace colloidal redistribution, and we present a model for distinguishing between mass transfer in suspension and solution. The model is tested on a well-differentiated granitic catena located in Kruger National Park, South Africa. Ti and Zr ratios from parent material, soil and colloidal material are substituted into a mixing equation to quantify colloidal movement. The results show zones of both colloid removal and augmentation along the catena. Colloidal losses of 110kgm-2 (-5% relative to parent material) are calculated for one eluviated soil profile. A downslope illuviated profile has gained 169kgm-2 (10%) colloidal material. Elemental losses by mobilization in true solution are ubiquitous across the catena, even in zones of colloidal accumulation, and range from 1418kgm-2 (-46%) for an eluviated profile to 195kgm-2 (-23%) at the bottom of the catena. Quantification of simultaneous mass transfers in solution and suspension provide greater specificity on processes within soils and across hillslopes. Additionally, because colloids include both HFS and other elements, the ability to quantify their redistribution has implications for standard calculations of soil mass balances using such index elements. ?? 2011.

Chemical Geology↗
USGS2011

Using Lagrangian sampling to study water quality during downstream transport in the San Luis Drain, California, USA

To investigate the mechanism for diel (24h) changes commonly observed at fixed sampling locations and how these diel changes relate to downstream transport in hypereutrophic surface waters, we studied a parcel of agricultural drainage water as it traveled for 84h in a concrete-lined channel having no additional water inputs or outputs. Algal fluorescence, dissolved oxygen, temperature, pH, conductivity, and turbidity were measured every 30min. Grab samples were collected every 2h for water quality analyses, including nutrients, suspended sediment, and chlorophyll/pheophytin. Strong diel patterns were observed for dissolved oxygen, pH, and temperature within the parcel of water. In contrast, algal pigments and nitrate did not exhibit diel patterns within the parcel of water, but did exhibit strong diel patterns for samples collected at a fixed sampling location. The diel patterns observed at fixed sampling locations for these constituents can be attributed to algal growth during the day and downstream transport (washout) of algae at night. Algal pigments showed a rapid daytime increase during the first 48h followed by a general decrease for the remainder of the study, possibly due to sedimentation and photobleaching. Algal growth (primarily diatoms) was apparent each day during the study, as measured by increasing dissolved oxygen concentrations, despite low phosphate concentrations (<0.01mgL-1).

California↗