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At least 1,747 records · Page 97Linked to original sources
USGS2008

Effects of methylmercury exposure on glutathione metabolism, oxidative stress, and chromosomal damage in captive-reared common loon (Gavia immer) chicks

We quantified the level of dietary mercury (Hg), delivered as methylmercury chloride (CH3HgCl), associated with negative effects on organ and plasma biochemistries related to glutathione (GSH) metabolism and oxidative stress, and chromosomal damage in captive-reared common loon (Gavia immer) chicks reared from hatch to 105 days. Mercury-associated effects related to oxidative stress and altered glutathione metabolism occurred at 1.2 :g Hg/g and 0.4 :g Hg/g, an ecologically relevant dietary mercury level, but not at 0.08 :g Hg/g. Among the variables that contributed most to dissimilarities in tissue chemistries between control and treatment groups were increased levels of oxidized glutathione (GSSG), GSH peroxidase, and the ratio of GSSG to GSH in brain tissue; increased levels of hepatic GSH; and decreased levels of hepatic glucose-6-phosphate dehydrogenase (G-6-PDH). Our results also suggest that chronic exposure to environmentally relevant dietary Hg levels did not result in statistically significant somatic chromosomal damage in common loon chicks. Oxidative stress and altered glutathione metabolism were evident in common loon chicks exposed to >0.4 :g Hg as CH3HgCl per gram wet food intake.

Environmental Pollution↗
USGS2019

Decreased atmospheric nitrogen deposition in eastern North America: Predicted responses of forest ecosystems

Historical increases in emissions and atmospheric deposition of oxidized and reduced nitrogen (N) provided the impetus for extensive, global-scale research investigating the effects of excess N in terrestrial and aquatic ecosystems, with several regions within the Eastern Deciduous Forest of the United States found to be susceptible to negative effects of excess N. The Clean Air Act and associated rules have led to decreases in emissions and deposition of oxidized N, especially in eastern U.S., representing a research challenge and opportunity for ecosystem ecologists and biogeochemists. The purpose of this paper is to predict changes in the structure and function of North American forest ecosystems in a future of decreased N deposition. Hysteresis is a property of a system wherein output is not a strict function of corresponding input, incorporating lag, delay, or history dependence, particularly when the response to decreasing input is different from the response to increasing input. We suggest a conceptual hysteretic model predicting varying lag times in recovery of soil acidification, plant biodiversity, soil microbial communities, forest carbon (C) and N cycling, and surface water chemistry toward pre-N impact conditions. Nearly all of these can potentially respond strongly to reductions in N deposition. Most responses are expected to show some degree of hysteresis, with the greatest delays in response occurring in processes most tightly linked to “slow pools” of N in wood and soil organic matter. Because experimental studies of declines in N loads in forests of North America are lacking and because of the expected hysteresis, it is difficult to generalize from experimental results to patterns expected from declining N deposition. These will likely be long-term phenomena, difficult to distinguish from other, concurrent environmental changes, including elevated atmospheric CO 2 , climate change, reductions in acidity, invasions of new species, and long-term vegetation responses to past disturbance.

Environmental Pollution↗
USGS2021

Regional target loads of atmospheric nitrogen and sulfur deposition for the protection of stream and watershed soil resources of the Adirondack Mountains, USA

Acidic deposition contributes to a range of environmental impacts across forested landscapes, including acidification of soil and drainage water, toxic aluminum mobilization, depletion of available soil nutrient cations, and impacts to forest and aquatic species health and biodiversity. In response to decreasing levels of acidic deposition, soils and drainage waters in some regions of North America have become gradually less acidic. Thresholds of atmospheric deposition at which adverse ecological effects are manifested are called critical loads (CLs) and/or target loads (TLs). Target loads are developed based on approaches that account for spatial and temporal aspects of acidification and recovery. Exceedance represents the extent to which current or projected future levels of acidic deposition exceed the level expected to cause ecological harm. We report TLs of sulfur (S) and nitrogen (N) deposition and the potential for ecosystem recovery of watershed soils and streams in the Adirondack region of New York State, resources that have been less thoroughly investigated than lakes. Regional TLs were calculated by statistical extrapolation of hindcast and forecast simulations of 25 watersheds using the process-based model PnET-BGC coupled with empirical observations of stream hydrology and established sensitivity of sugar maple ( Acer saccharum ) to soil base saturation and brook trout ( Salvelinus fontinalis ) to stream acid neutralizing capacity (ANC). Historical impacts and the expected recovery timeline of regional soil and stream chemistry and fish community condition within the Adirondack Park were evaluated. Analysis suggests that many low-order Adirondack streams and associated watershed soils have low TLs (<40 meq/m 2 /yr of N+S deposition) to achieve specified benchmarks for recovery of soil base saturation or stream ANC. Acid-sensitive headwater and low-order streams and watershed soils in the region are expected to experience continued adverse effects from N and S deposition well into the future even under aggressive emissions reductions. Watershed soils and streams in the western Adirondack Park are particularly vulnerable to acidic deposition and currently in exceedance of TLs. The methods used for linking statistical and process-based models to consider chemical and biological response under varying flow conditions at the regional scale in this study can be applied to other areas of concern.

New York↗
USGS2024

Widespread chemical dilution of streams continues as long-term effects of acidic deposition slowly reverse

Studies of recovery from acidic deposition have focused on reversal of acidification and its associated effects, but as recovery proceeds slowly, chemical dilution of surface waters is emerging as a key factor in the recovery process that has significant chemical and biological implications. This investigation uses long-term chemical records from 130 streams in the Adirondack region of New York, USA, to evaluate the role of ongoing decreases in conductance, an index of dilution, in the recovery of these streams. Stream chemistry data spanning up to 40 years (1980s–2022) showed that acid-neutralizing capacity has increased in 92% of randomly selected streams, but that harmful levels of acidification still occur in 37% of these streams. Conductance and Ca 2+ concentrations decreased in 79% of streams, and SO 4 2− concentrations in streams continued to show strong decreases but remained several times higher than concentrations in precipitation. These changes were ongoing through 2022 even though acidic deposition levels were approaching those estimated for pre-industrialization. Further dilution is continuing through ongoing decreases in stream SO 4 2− . Nevertheless, Ca 2+ continued to be leached from soils by SO 4 2− , organic acids and NO 3 − , limiting the replenishment of available soil Ca 2+ , a prerequisite to stem further dilution of stream water.

Environmental Pollution↗
USGS2005

Systematics of halogen elements and their radioisotopes in thermal springs of the Cascade Range, Central Oregon, Western USA

This study quantifies the cycling of halogen elements through the Cascadia subduction zone based on the chemistry of thermal springs in the Central Oregon Cascade Range and of a mineral spring in the forearc (Willamette Valley). Considerations based on mass balances, element ratios, and 36 Cl/Cl and 129 I/I ratios suggest that halogens discharged through the thermal springs in the Cascade Range are probably derived from magma degassing. Our results indicate that < 35% of the subducted Cl and < 20% of the subducted Br and I could be transported through arc volcanism and the thermal springs, a considerably lower percentage than estimated for other volcanic arcs along the Pacific Rim. A likely explanation for this difference is that a large fraction of the halogens is released from the slab at shallow depths into the serpentinized sub-forearc mantle because of the relatively high temperatures in the subducting Juan de Fuca plate. The small fraction of halogens subducted to depth probably also indicates a low rate of water transport, which is consistent with the observation that the Cascade Range sub-arc mantle is relatively dry and has a low degree of volcanic vigor, compared with other arcs.

Oregon↗
USGS2013

Crustal-scale recycling in caldera complexes and rift zones along the Yellowstone hotspot track: O and Hf isotopic evidence in diverse zircons from voluminous rhyolites of the Picabo volcanic field, Idaho

Rhyolites of the Picabo volcanic field (10.4–6.6 Ma) in eastern Idaho are preserved as thick ignimbrites and lavas along the margins of the Snake River Plain (SRP), and within a deep (>3 km) borehole near the central axis of the Yellowstone hotspot track. In this study we present new O and Hf isotope data and U–Pb geochronology for individual zircons, O isotope data for major phenocrysts (quartz, plagioclase, and pyroxene), whole rock Sr and Nd isotope ratios, and whole rock geochemistry for a suite of Picabo rhyolites. We synthesize our new datasets with published Ar–Ar geochronology to establish the eruptive framework of the Picabo volcanic field, and interpret its petrogenetic history in the context of other well-studied caldera complexes in the SRP. Caldera complex evolution at Picabo began with eruption of the 10.44±0.27 Ma (U–Pb) Tuff of Arbon Valley (TAV), a chemically zoned and normal-δ 18 O (δ 18 O magma=7.9‰) unit with high, zoned 87 Sr/ 86 Sr i (0.71488–0.72520), and low-ε Nd (0) (−18) and ε Hf (0) (−28). The TAV and an associated post caldera lava flow possess the lowest ε Nd (0) (−23), indicating ∼40–60% derivation from the Archean upper crust. Normal-δ 18 O rhyolites were followed by a series of lower-δ 18 O eruptions with more typical (lower crustal) Sr–Nd–Hf isotope ratios and whole rock chemistry. The voluminous 8.25±0.26 Ma West Pocatello rhyolite has the lowest δ 18 O value (δ 18 O melt =3.3‰), and we correlate it to a 1,000 m thick intracaldera tuff present in the INEL-1 borehole (with published zircon ages 8.04–8.35 Ma, and similarly low-δ 18 O zircon values). The significant (4–5‰) decrease in magmatic-δ 18 O values in Picabo rhyolites is accompanied by an increase in zircon δ 18 O heterogeneity from ∼1‰ variation in the TAV to >5‰ variation in the late-stage low-δ 18 O rhyolites, a trend similar to what is characteristic of Heise and Yellowstone, and which indicates remelting of variably hydrothermally altered tuffs followed by rapid batch assembly prior to eruption. However, due to the greater abundance of low-δ 18 O rhyolites at Picabo, the eruptive framework may reflect an intertwined history of caldera collapse and coeval Basin and Range rifting and hydrothermal alteration. We speculate that the source rocks with pre-existing low-δ 18 O alteration may be related to: (1) deeply buried and unexposed older deposits of Picabo-age or Twin Falls-age low-δ 18 O volcanics; and/or (2) regionally-abundant late Eocene Challis volcanics, which were hydrothermally altered near the surface prior to or during peak Picabo magmatism. Basin and Range extension, specifically the formation of metamorphic core complexes exposed in the region, could have facilitated the generation of low-δ 18 O magmas by exhuming heated rocks and creating the large water-rock ratios necessary for shallow hydrothermal alteration of tectonically (rift zones) and volcanically (calderas) buried volcanic rocks. These interpretations highlight the major processes by which supereruptive volumes of magma are generated in the SRP, mechanisms applicable to producing rhyolites worldwide that are facilitated by plume driven volcanism and extensional tectonics.

Idaho↗
USGS2018

Carboniferous climate teleconnections archived in coupled bioapatite δ18OPO4 and 87Sr/86Sr records from the epicontinental Donets Basin, Ukraine

Reconstructions of paleo-seawater chemistry are largely inferred from biogenic records of epicontinental seas. Recent studies provide considerable evidence for large-scale spatial and temporal variability in the environmental dynamics of these semi-restricted seas that leads to the decoupling of epicontinental isotopic records from those of the open ocean. We present conodont apatite δ 18 O PO4 and 87 Sr/ 86 Sr records spanning 24 Myr of the late Mississippian through Pennsylvanian derived from the U–Pb calibrated cyclothemic succession of the Donets Basin, eastern Ukraine. On a 2 to 6 Myr-scale, systematic fluctuations in bioapatite δ 18 O PO4 and 87 Sr/ 86 Sr broadly follow major shifts in the Donets onlap–offlap history and inferred regional climate, but are distinct from contemporaneous more open-water δ 18 O PO4 and global seawater Sr isotope trends. A −1 to −6‰ offset in Donets δ 18 O PO4 values from those of more open-water conodonts and greater temporal variability in δ 18 O PO4 and 87 Sr/ 86 Sr records are interpreted to primarily record climatically driven changes in local environmental processes in the Donets sea. Systematic isotopic shifts associated with Myr-scale sea-level fluctuations, however, indicate an extrabasinal driver. We propose a mechanistic link to glacioeustasy through a teleconnection between high-latitude ice changes and atmospheric p CO 2 and regional monsoonal circulation in the Donets region. Inferred large-magnitude changes in Donets seawater salinity and temperature, not archived in the more open-water or global contemporaneous records, indicate a modification of the global climate signal in the epicontinental sea through amplification or dampening of the climate signal by local and regional environmental processes. This finding of global climate change filtered through local processes has implications for the use of conodont δ 18 O PO4 and 87 Sr/ 86 Sr values as proxies of paleo-seawater composition, mean temperature, and glacioeustasy.

Donets Basin↗
USGS2020

Beyond sticks and stones: Integrating physical and ecological conditions into watershed restoration assessments using a food web modeling approach

Watershed assessments have become common for prioritizing restoration in river networks. These assessments primarily focus on geomorphic conditions of rivers but less frequently incorporate non-geomorphic abiotic factors such as water chemistry and temperature, and biotic factors such as the structure of food webs. Using a dynamic food web model that integrates physical and ecological environmental conditions of rivers, we simulated how juvenile salmon ( Oncorhynchus spp.) biomass responded to restoration at twelve sites distributed across the Methow River (Washington, USA), ranging from headwater tributaries to mainstem reaches. We explored responses to three common river restoration strategies: (1) physical habitat modification, (2) nutrient supplementation, and (3) increased riparian vegetation cover. We also simulated how different food web configurations that exist in salmon-bearing streams, such as the presence of ‘non-target’ fishes and ‘armored’ predation resistant invertebrates, could mediate restoration outcomes. Some locations in the river network experienced relatively large increases in modeled fish biomass with restoration, whereas other locations were almost entirely unresponsive. Spatial variation in restoration outcomes was primarily controlled by non-geomorphic environmental conditions, such as nutrient availability, water temperature, and stream canopy cover. Restoration responses also varied significantly with different food web configurations, suggesting that as the structure of food webs varies across river networks, so too could the outcome of restoration. These findings illustrate that ecological responses to restoration may exhibit substantial spatial variation within river networks, resulting from heterogeneity in environmental conditions that are commonly overlooked—but which can and should be considered—in restoration planning and prioritization.

Washington↗
USGS2014

Three-year growth response of young Douglas-fir to nitrogen, calcium, phosphorus, and blended fertilizers in Oregon and Washington

Studies of nutrient limitation in Douglas-fir forests of the Pacific Northwest focus predominantly on nitrogen, yet many stands demonstrate negligible or even negative growth response to nitrogen fertilization. To understand what nutrients other than nitrogen may limit forest productivity in this region, we tested six fertilizer treatments for their ability to increase stem volume growth response of dominant and co-dominant trees in young Douglas-fir plantations across a range of foliar and soil chemistry in western Oregon and Washington. We evaluated responses to single applications of urea, lime, calcium chloride, or monosodium phosphate at 16 sites, and to two site-specific nutrients blends at 12 of these sites. Across sites, the average stem volume growth increased marginally with urea, lime, and phosphorus fertilization. Fertilization responses generally aligned with plant and soil indicators of nutrient limitation. Response to nitrogen addition was greatest on soils with low total nitrogen and high exchangeable calcium concentrations. Responses to lime and calcium chloride additions were greatest at sites with low foliar calcium and low soil pH. Response to phosphorus addition was greatest on sites with low foliar phosphorus and high soil pH. Blended fertilizers yielded only marginal growth increases at one site, with no consistent effect across sites. Overall, our results highlight that calcium and phosphorus can be important growth limiting nutrients on specific sites in nitrogen-rich Douglas-fir forests of the Pacific Northwest.

Oregon, Washington↗
USGS2004

Mineral dissolution in the Cape Cod aquifer, Massachusetts, USA: I . Reaction stoichiometry and impact of accessory feldspar and glauconite on strontium isotopes, solute concentrations, and REY distribution

To compare relative reaction rates of mineral dissolution in a mineralogically simple groundwater aquifer, we studied the controls on solute concentrations, Sr isotopes, and rare earth element and yttrium (REY) systematics in the Cape Cod aquifer. This aquifer comprises mostly carbonate-free Pleistocene sediments that are about 90% quartz with minor K-feldspar, plagioclase, glauconite, and Fe-oxides. Silica concentrations and pH in the groundwater increase systematically with increasing depth, while Sr isotopic ratios decrease. No clear relationship between 87 Sr/ 86 Sr and Sr concentration is observed. At all depths, the 87 Sr/ 86 Sr ratio of the groundwater is considerably lower than the Sr isotopic ratio of the bulk sediment or its K-feldspar component, but similar to that of a plagioclase-rich accessory separate obtained from the sediment. The Si- 87 Sr/ 86 Sr-depth relationships are consistent with dissolution of accessory plagioclase. In addition, solutes such as Sr, Ca, and particularly K show concentration spikes superimposed on their respective general trends. The K-Sr- 87 Sr/ 86 Sr systematics suggests that accessory glauconite is another major solute source to Cape Cod groundwater. Although the authigenic glauconite in the Cape Cod sediment is rich in Rb, it is low in in-grown radiogenic 87 Sr because of its young Pleistocene age. The low 87 Sr/ 86 Sr ratios are consistent with equilibration of glauconite with seawater. The impact of glauconite is inferred to vary due to its variable abundance in the sediments. In the Cape Cod groundwater, the variation of REY concentrations with sampling depth resembles that of K and Rb, but differs from that of Ca and Sr. Shale-normalized REY patterns are light REY depleted, show negative Ce anomalies and super-chondritic Y/Ho ratios, but no Eu anomalies. REY input from feldspar, therefore, is insignificant compared to input from a K-Rb-bearing phase, inferred to be glauconite. These results emphasize that interpretation of groundwater chemistry, even in relatively simple aquifers, may be complicated by solute contributions from “exotic” accessory minerals such as glauconite. To detect such peculiarities, groundwater studies should combine the study of elemental concentration and isotopic composition of several solutes that show different geochemical behavior.

Massachusetts↗
USGS2005

Control of Fe(III) site occupancy on the rate and extent of microbial reduction of Fe(III) in nontronite

A quantitative study was performed to understand how Fe(III) site occupancy controls Fe(III) bioreduction in nontronite by Shewanella putrefaciens CN32. NAu-1 and NAu-2 were nontronites and contained Fe(III) in different structural sites with 16 and 23% total iron (w/w), respectively, with almost all iron as Fe(III). Mo??ssbauer spectroscopy showed that Fe(III) was present in the octahedral site in NAu-1 (with a small amount of goethite), but in both the tetrahedral and the octahedral sites in NAu-2. Mo??ssbauer data further showed that the octahedral Fe(III) in NAu-2 existed in at least two environments- trans (M1) and cis (M2) sites. The microbial Fe(III) reduction in NAu-1 and NAu-2 was studied in batch cultures at a nontronite concentration of 5 mg/mL in bicarbonate buffer with lactate as the electron donor. The unreduced and bioreduced nontronites were characterized by X-ray diffraction (XRD), Mo??ssbauer spectroscopy, and transmission electron microscopy (TEM). In the presence of an electron shuttle, anthraquinone-2,6-disulfonate (AQDS), the extent of bioreduction was 11%-16% for NAu-1 but 28%-32% for NAu-2. The extent of reduction in the absence of AQDS was only 5%-7% for NAu-1 but 14%-18% for NAu-2. The control experiments with heat killed cells and without cells did not show any appreciable reduction (<2%). The extent of reduction in experiments performed with a dialysis membrane to separate cells from clays (without AQDS) was 2%-3% for NAu-1 but 5%-7% for NAu-2, suggesting that cells probably released an electron shuttling compound and/or Fe(III) chelator. The reduction rate was also faster in NAu-2 than that in NAu-1. Mo??ssbauer data of the bioreduced nontronite materials indicated that the Fe(III) reduction in NAu-1 was mostly from the presence of goethite, whereas the reduction in NAu-2 was due to the presence of the tetrahedral and trans-octahedral Fe(III) in the structure. The measured aqueous Fe(II) was negligible. As a result of bioreduction, the average nontronite particle thickness remained nearly the same (from 2.1 to 2.5 nm) for NAu-1, but decreased significantly from 6 to 3.5 nm for NAu-2 with a concomitant change in crystal size distribution. The decrease in crystal size suggests reductive dissolution of nontronite NAu-2, which was supported by aqueous solution chemistry (i.e., aqueous Si). These data suggest that the more extensive Fe(III) bioreduction in NAu-2 was due to the presence of the tetrahedral and the trans-octahedral Fe(III), which was presumed to be more reducible. The biogenic Fe(II) was not associated with biogenic solids or in the aqueous solution. We infer that it may be either adsorbed onto surfaces of nontronite particles/bacteria or in the structure of nontronite. Furthermore, we have demonstrated that natural nontronite clays were capable of supporting cell growth even in medium without added nutrients, possibly due to presence of naturally existing nutrients in the nontronite clays. These results suggest that crystal chemical environment of Fe(III) is an important determinant in controlling the rate and extent of microbial reduction of Fe(III) in nontronite. Copyright ?? 2005 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗
USGS2008

Experimental investigation on thermochemical sulfate reduction by H2S initiation

Hydrogen sulfide (H 2 S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 °C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO 4 in the presence of variable H 2 S partial pressures at three different pH conditions. The experimental results showed that the in - situ pH of the aqueous solution (herein, in - situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in - situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H 2 S occurred under acidic conditions (at pH ∼3–3.5). However, sulfate reduction at pH ∼5.0 was undetectable even at high initial H 2 S concentrations. To investigate whether the reaction of H 2 S (aq) and HSO 4 - "> HSO4- occurs at pH ∼3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO 4 and variable H 2 S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO 4 reduction was not measurable in the absence of paraffin even with high H 2 S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H 2 S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H 2 S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc. 82 , 1911–1916). Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H 2 S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 °C and a 0.1-°C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H 2 S pressure. Thus, we propose that the LSC produced from H 2 S reaction with HC are most likely the reactive intermediates for H 2 S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content.

Geochimica et Cosmochimica Acta↗
USGS2008

Theoretical study on the reactivity of sulfate species with hydrocarbons

The abiotic, thermochemically controlled reduction of sulfate to hydrogen sulfide coupled with the oxidation of hydrocarbons, is termed thermochemical sulfate reduction (TSR), and is an important alteration process that affects petroleum accumulations in nature. Although TSR is commonly observed in high-temperature carbonate reservoirs, it has proven difficult to simulate in the laboratory under conditions resembling nature. The present study was designed to evaluate the relative reactivities of various sulfate species in order to provide greater insight into the mechanism of TSR and potentially to fill the gap between laboratory experimental data and geological observations. Accordingly, quantum mechanics density functional theory (DFT) was used to determine the activation energy required to reach a potential transition state for various aqueous systems involving simple hydrocarbons and different sulfate species. The entire reaction process that results in the reduction of sulfate to sulfide is far too complex to be modeled entirely; therefore, we examined what is believed to be the rate limiting step, namely, the reduction of sulfate S(VI) to sulfite S(IV). The results of the study show that water-solvated sulfate anions SO 4 2- are very stable due to their symmetrical molecular structure and spherical electronic distributions. Consequently, in the absence of catalysis, the reactivity of SO 4 2- is expected to be extremely low. However, both the protonation of sulfate to form bisulfate anions ( HSO 4 - ) and the formation of metal-sulfate contact ion-pairs could effectively destabilize the sulfate molecular structure, thereby making it more reactive. Previous reports of experimental simulations of TSR generally have involved the use of acidic solutions that contain elevated concentrations of " HSO 4 - relative to SO 4 2- . However, in formation waters typically encountered in petroleum reservoirs, the concentration of HSO 4 - is likely to be significantly lower than the levels used in the laboratory, with most of the dissolved sulfate occurring as SO 4 2- , aqueous calcium sulfate ([CaSO 4 ] (aq) ), and aqueous magnesium sulfate ([MgSO 4 ] (aq) ). Our calculations indicate that TSR reactions that occur in natural environments are most likely to involve bisulfate ions ( HSO 4 - ) and/or magnesium sulfate contact ion-pairs ([MgSO 4 ] CIP ) rather than ‘free’ sulfate ions ( SO 4 2- ) or solvated sulfate ion-pairs, and that water chemistry likely plays a significant role in controlling the rate of TSR.

Geochimica et Cosmochimica Acta↗
USGS2009

Structural characterization of terrestrial microbial Mn oxides from Pinal Creek, AZ

The microbial catalysis of Mn(II) oxidation is believed to be a dominant source of abundant sorption- and redox-active Mn oxides in marine, freshwater, and subsurface aquatic environments. In spite of their importance, environmental oxides of known biogenic origin have generally not been characterized in detail from a structural perspective. Hyporheic zone Mn oxide grain coatings at Pinal Creek, Arizona, a metals-contaminated stream, have been identified as being dominantly microbial in origin and are well studied from bulk chemistry and contaminant hydrology perspectives. This site thus presents an excellent opportunity to study the structures of terrestrial microbial Mn oxides in detail. XRD and EXAFS measurements performed in this study indicate that the hydrated Pinal Creek Mn oxide grain coatings are layer-type Mn oxides with dominantly hexagonal or pseudo-hexagonal layer symmetry. XRD and TEM measurements suggest the oxides to be nanoparticulate plates with average dimensions on the order of 11 nm thick × 35 nm diameter, but with individual particles exhibiting thickness as small as a single layer and sheets as wide as 500 nm. The hydrated oxides exhibit a 10-Å basal-plane spacing and turbostratic disorder. EXAFS analyses suggest the oxides contain layer Mn(IV) site vacancy defects, and layer Mn(III) is inferred to be present, as deduced from Jahn–Teller distortion of the local structure. The physical geometry and structural details of the coatings suggest formation within microbial biofilms. The biogenic Mn oxides are stable with respect to transformation into thermodynamically more stable phases over a time scale of at least 5 months. The nanoparticulate layered structural motif, also observed in pure culture laboratory studies, appears to be characteristic of biogenic Mn oxides and may explain the common occurrence of this mineral habit in soils and sediments.

Geochimica et Cosmochimica Acta↗
USGS2009

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation, and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka Marine Terrace Chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized [White A. F., Schulz M. S., Vivit D. V., Blum A., Stonestrom D. A. and Anderson S. P. (2008) Chemical weathering of a Marine Terrace Chronosequence, Santa Cruz, California. I: interpreting the long-term controls on chemical weathering based on spatial and temporal element and mineral distributions. Geochim. Cosmochim. Acta 72 (1), 36-68] and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisserand [Hellmann R. and Tisserand D. (2006) Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar. Geochim. Cosmochim. Acta 70 (2), 364-383] or the aluminum inhibition model proposed by Oelkers et al. [Oelkers E. H., Schott J. and Devidal J. L. (1994) The effect of aluminum, pH, and chemical affinity on the rates of aluminosilicate dissolution reactions. Geochim. Cosmochim. Acta 58 (9), 2011-2024], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site. Additionally, observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO 2 (aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws. ?? 2009 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗
USGS2009

The stable carbon isotope biogeochemistry of acetate and other dissolved carbon species in deep subseafloor sediments at the northern Cascadia Margin

Ocean drilling has revealed the existence of vast microbial populations in the deep subseafloor, but to date little is known about their metabolic activities. To better understand the biogeochemical processes in the deep biosphere, we investigate the stable carbon isotope chemistry of acetate and other carbon-bearing metabolites in sediment pore-waters. Acetate is a key metabolite in the cycling of carbon in anoxic sediments. Its stable carbon isotopic composition provides information on the metabolic processes dominating acetate turnover in situ. This study reports our findings for a methane-rich site at the northern Cascadia Margin (NE Pacific) where Expedition 311 of the Integrated Ocean Drilling Program (IODP) sampled the upper 190 m of sediment. At Site U1329, δ 13 C values of acetate span a wide range from −46.0‰ to −11.0‰ vs. VPDB and change systematically with sediment depth. In contrast, δ 13 C values of both the bulk dissolved organic carbon (DOC) (−21.6 ± 1.3‰ vs. VPDB) and the low-molecular-weight compound lactate (−20.9 ± 1.8‰ vs. VPDB) show little variability. These species are interpreted to represent the carbon isotopic composition of fermentation products. Relative to DOC, acetate is up to 23.1‰ depleted and up to 9.1‰ enriched in 13 C. Broadly, 13 C-depletions of acetate relative to DOC indicate flux of carbon from acetogenesis into the acetate pool while 13 C-enrichments of pore-water acetate relative to DOC suggest consumption of acetate by acetoclastic methanogenesis. Isotopic relationships between acetate and lactate or DOC provide new information on the carbon flow and the presence and activity of specific functional microbial communities in distinct biogeochemical horizons of the sediment. In particular, they suggest that acetogenic CO 2 -reduction can coexist with methanogenic CO 2 -reduction, a notion contrary to the hypothesis that hydrogen levels are controlled by the thermodynamically most favorable electron-accepting process. Further, the isotopic relationship suggests a relative increase in acetate flow to acetoclastic methanogenesis with depth although its contribution to total methanogenesis is probably small. Our study demonstrates how the stable carbon isotope biogeochemistry of acetate can be used to identify pathways of microbial carbon turnover in subsurface environments. Our observations also raise new questions regarding the factors controlling acetate turnover in marine sediments.

Geochimica et Cosmochimica Acta↗
USGS2011

Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ 13 C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane.

Geochimica et Cosmochimica Acta↗
USGS2011

Fluoride geochemistry of thermal waters in Yellowstone National Park: I. Aqueous fluoride speciation

Thermal water samples from Yellowstone National Park (YNP) have a wide range of pH (1–10), temperature, and high concentrations of fluoride (up to 50 mg/l). High fluoride concentrations are found in waters with field pH higher than 6 (except those in Crater Hills) and temperatures higher than 50 °C based on data from more than 750 water samples covering most thermal areas in YNP from 1975 to 2008. In this study, more than 140 water samples from YNP collected in 2006–2009 were analyzed for free-fluoride activity by ion-selective electrode (ISE) method as an independent check on the reliability of fluoride speciation calculations. The free to total fluoride concentration ratio ranged from <1% at low pH values to >99% at high pH. The wide range in fluoride activity can be explained by strong complexing with H + and Al 3+ under acidic conditions and lack of complexing under basic conditions. Differences between the free-fluoride activities calculated with the WATEQ4F code and those measured by ISE were within 0.3–30% for more than 90% of samples at or above 10 −6 molar, providing corroboration for chemical speciation models for a wide range of pH and chemistry of YNP thermal waters. Calculated speciation results show that free fluoride, F − , and major complexes ( HF ( aq ) 0 "> HF(aq)0 , AlF 2+ , AlF 2 + "> AlF2+ and AlF 3 0 "> AlF30 ) account for more than 95% of total fluoride. Occasionally, some complex species like AlF 4 - "> AlF4- , FeF 2+ , FeF 2 + "> FeF2+ , MgF + and BF 2 ( OH ) 2 - "> BF2(OH)2- may comprise 1–10% when the concentrations of the appropriate components are high. According to the simulation results by PHREEQC and calculated results, the ratio of main fluoride species to total fluoride varies as a function of pH and the concentrations and ratios of F and Al.

Yellowstone National Park↗