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At least 559 records · Page 31Linked to original sources
USGS2005

Experimental evaluation of factors affecting temporal variability of water samples obtained from long-screened wells

As a well is pumped through time, concentrations of specific constituents in the water discharging from the well may change as a result of their transport within the well and the aquifer. A series of experiments conducted at a research site on Cape Cod, Massachusetts, examined the effects of transport on the chemistry of water samples obtained from a long-screened well. Analyses of time series of constituent concentrations in water pumped from the long-screened well showed persistent temporal trends during the first experiment. Iron concentrations decreased over a five-hour test (15 casing volumes), whereas the calcium and magnesium concentrations increased. In contrast, the time series of constituent concentrations of water discharging from the same well showed less change with time during a later experiment. Numerical simulations were undertaken to test the relative importance of several possible factors affecting the temporal variations of these constituents. During the process of quantitatively explaining the changes in concentrations over time observed in the two experiments, different system conceptualizations were used, including (1) flow and transport in the aquifer without wellbore transport, (2) flow and transport in the aquifer with advective flow and transport in the wellbore, and (3) flow and transport in the aquifer with advective flow and transport in the wellbore and a thin layer (skin) of water surrounding the well with constituent concentrations that had been altered by the presence of the well. The conjectured skin of wellbore water, which could have invaded the aquifer because of nearby sampling or dispersion and diffusion near the wellbore, in conjunction with flow and transport in the aquifer and advective transport within the wellbore, produced a reasonable match between the simulated and observed concentrations. The data analysis confirms the known fact that long-screened wells provide mechanisms for the redistribution of chemical constituents in the aquifer. The analysis provides new insight into the mechanisms responsible for the observed changes in concentrations during the sampling of long-screened wells. The analysis quantifies the effects of the various conceptual models of flow and transport in and around wells on the interpretation and meaning of chemical analyses of water withdrawn from long-screened wells.A series of experiments was conducted at a research site on Cape Cod, Massachusetts, to examine the effects of transport on the chemistry of water samples obtained from a long-screened well. A time-series analysis of the constituents concentration in pumped water revealed a persistent temporal trend during the first experiment. Iron concentrations decreased over a five-hour test, while calcium and magnesium concentrations increased. Numerical simulations were undertaken to test the relative importance of several possible factors affecting the temporal variations of the constituents to quantify the effects of the various conceptual models of flow and transport in and around the wells.

Ground Water↗
USGS2011

Effects of turbidity, light level, and cover on predation of white sturgeon larvae by prickly sculpins

White sturgeon Acipenser transmontanus occur in rivers of the western United States and southwestern Canada, but some populations are in decline because of recruitment failure. Many river systems in this area have been altered as a result of development that has caused major environmental changes. Our goal was to examine how three changes - lower turbidity levels, higher light levels, and altered substrates - might affect predation by prickly sculpin Cottus asper on white sturgeon larvae. We experimentally investigated predation at various turbidity levels and found that significantly more white sturgeon yolk sac larvae were eaten at lower turbidity levels. The effects of light level (1-4 and 7-15 1x), the presence or absence of rocks as cover, and prey size (14-17 mm and 20-24 mm total length) on the outcome of predator-prey interactions were also examined. Significantly fewer white sturgeon were eaten during trials that combined the lowest light level, cover, and the smallest larvae. Our results suggest that altered river conditions caused by impoundment and other factors have increased predation on white sturgeon larvae. ?? Copyright by the American Fisheries Society 2005.

Transactions of the American Fisheries Society↗
USGS2012

Effects of earthworms on slopewash, surface runoff, and fine-litter transport on a humid-tropical forested hillslope in eastern Puerto Rico: Chapter G in Water quality and landscape processes of four watersheds in eastern Puerto Rico

Rainfall, slopewash (the erosion of soil particles), surface runoff, and fine-litter transport were measured in tropical wet forest on a hillslope in the Luquillo Experimental Forest, Puerto Rico, from February 1998 until April 2000. Slopewash data were collected using Gerlach troughs at eight plots, each 2 square meters in area. Earthworms were excluded by electroshocking from four randomly selected plots. The other four (control) plots were undisturbed. During the experiment, earthworm population in the electroshocked plots was reduced by 91 percent. At the end of the experiment, the electroshocked plots had 13 percent of earthworms by count and 6 percent by biomass as compared with the control plots. Rainfall during the sampling period (793 days) was 9,143 millimeters. Mean and maximum rainfall by sampling period (mean of 16 days) were 189 and 563 millimeters, respectively. Surface runoff averaged 0.6 millimeters and 1.2 millimeters by sampling period for the control and experimental plots, equal to 0.25 and 0.48 percent of mean rainfall, respectively. Disturbance of the soil environment by removal of earthworms doubled runoff and increased the transport (erosion) of soil and organic material by a factor of 4.4. When earthworms were removed, the erosion of mineral soil (soil mass left after ashing) and the transport of fine litter were increased by a factor of 5.3 and 3.4, respectively. It is assumed that increased runoff is a function of reduced soil porosity, resulting from decreased burrowing and reworking of the soil in the absence of earthworms. The background, or undisturbed, downslope transport of soil, as determined from the control plots, was 51 kilograms per hectare and the "disturbance" rate, determined from the experimental plots, was 261 kilograms per hectare. The background rate for downslope transport of fine litter was 71 kilograms per hectare and the disturbance rate was 246 kilograms per hectare. Data from this study indicate that the reduction in soil macrofauna population, in this case, earthworms, plays a key role in increasing runoff and soil erosion and, therefore, has important implications for forest and water management.

Luquillo Experimental Forest↗
USGS2013

Field measurement of basal forces generated by erosive debris flows

It has been proposed that debris flows cut bedrock valleys in steeplands worldwide, but field measurements needed to constrain mechanistic models of this process remain sparse due to the difficulty of instrumenting natural flows. Here we present and analyze measurements made using an automated sensor network, erosion bolts, and a 15.24 cm by 15.24 cm force plate installed in the bedrock channel floor of a steep catchment. These measurements allow us to quantify the distribution of basal forces from natural debris‒flow events that incised bedrock. Over the 4 year monitoring period, 11 debris‒flow events scoured the bedrock channel floor. No clear water flows were observed. Measurements of erosion bolts at the beginning and end of the study indicated that the bedrock channel floor was lowered by 36 to 64 mm. The basal force during these erosive debris‒flow events had a large‒magnitude (up to 21 kN, which was approximately 50 times larger than the concurrent time‒averaged mean force), high‒frequency (greater than 1 Hz) fluctuating component. We interpret these fluctuations as flow particles impacting the bed. The resulting variability in force magnitude increased linearly with the time‒averaged mean basal force. Probability density functions of basal normal forces were consistent with a generalized Pareto distribution, rather than the exponential distribution that is commonly found in experimental and simulated monodispersed granular flows and which has a lower probability of large forces. When the bed sediment thickness covering the force plate was greater than ~ 20 times the median bed sediment grain size, no significant fluctuations about the time‒averaged mean force were measured, indicating that a thin layer of sediment (~ 5 cm in the monitored cases) can effectively shield the subjacent bed from erosive impacts. Coarse‒grained granular surges and water‒rich, intersurge flow had very similar basal force distributions despite differences in appearance and bulk‒flow density. These results demonstrate that debris flows can have strong control on rates of steepland evolution and contribute to a foundation needed for modeling debris‒flow incision stochastically.

Journal of Geophysical Research F: Earth Surface↗
USGS2011

The molecular mechanism of Mo isotope fractionation during adsorption to birnessite

Fractionation of Mo isotopes during adsorption to manganese oxides is a primary control on the global ocean Mo isotope budget. Previous attempts to explain what drives the surprisingly large isotope effect δ97/95Modissolved-δ97/95Moadsorbed=1.8‰ have not successfully resolved the fractionation mechanism. New evidence from extended X-ray absorption fine structure analysis and density functional theory suggests that Mo forms a polymolybdate complex on the surfaces of experimental and natural samples. Mo in this polynuclear structure is in distorted octahedral coordination, while Mo remaining in solution is predominantly in tetrahedral coordination as MoO42- . Our results indicate that the difference in coordination environment between dissolved Mo and adsorbed Mo is the cause of isotope fractionation. The molecular mechanism of metal isotope fractionation in this system should enable us to explain and possibly predict metal isotope effects in other systems where transition metals adsorb to mineral surfaces.

Geochimica et Cosmochimica Acta↗
USGS2015

Temperature profile around a basaltic sill intruded into wet sediments

The transfer of heat into wet sediments from magmatic intrusions or lava flows is not well constrained from field data. Such field constraints on numerical models of heat transfer could significantly improve our understanding of water–lava interactions. We use experimentally calibrated pollen darkening to measure the temperature profile around a basaltic sill emplaced into wet lakebed sediments. It is well known that, upon heating, initially transparent palynomorphs darken progressively through golden, brown, and black shades before being destroyed; however, this approach to measuring temperature has not been applied to volcanological questions. We collected sediment samples from established Miocene fossil localities at Clarkia, Idaho. Fossils in the sediments include pollen from numerous tree and shrub species. We experimentally calibrated changes in the color of Clarkia sediment pollen and used this calibration to determine sediment temperatures around a Miocene basaltic sill emplaced in the sediments. Results indicated a flat temperature profile above and below the sill, with T > 325 °C within 1 cm of the basalt-sediment contact, near 300 °C at 1–2 cm from the contact, and ~ 250 °C at 1 m from the sill contact. This profile suggests that heat transport in the sediments was hydrothermally rather than conductively controlled. This information will be used to test numerical models of heat transfer in wet sediments on Earth and Mars.

Journal of Volcanology and Geothermal Research↗
USGS2002

In‐stream sorption of fulvic acid in an acidic stream: A stream‐scale transport experiment

The variation of concentration and composition of dissolved organic carbon (DOC) in stream waters cannot be explained solely on the basis of soil processes in contributing subcatchments. To investigate in‐stream processes that control DOC, we injected DOC‐enriched water into a reach of the Snake River (Summit County, Colorado) that has abundant iron oxyhydroxides coating the streambed. The injected water was obtained from the Suwannee River (Georgia), which is highly enriched in fulvic acid. The fulvic acid from this water is the standard reference for aquatic fulvic acid for the International Humic Substances Society and has been well characterized. During the experimental injection, significant removal of sorbable fulvic acid occurred within the first 141 m of stream reach. We coinjected a conservative tracer (lithium chloride) and analyzed the results with the one‐dimensional transport with inflow and storage (OTIS) stream solute transport model to quantify the physical transport mechanisms. The downstream transport of fulvic acid as indicated by absorbance was then simulated using OTIS with a first‐order kinetic sorption rate constant applied to the sorbable fulvic acid. The “sorbable” fraction of injected fulvic acid was irreversibly sorbed by streambed sediments at rates (kinetic rate constants) of the order of 10 −4 –10 −3 s −1 . In the injected Suwannee River water, sorbable and nonsorbable fulvic acid had distinct chemical characteristics identified in 13 C‐NMR spectra. The 13 C‐NMR spectra indicate that during the experiment, the sorbable “signal” of greater aromaticity and carboxyl content decreased downstream; that is, these components were preferentially removed. This study illustrates that interactions between the water and the reactive surfaces will modify significantly the concentration and composition of DOC observed in streams with abundant chemically reactive surfaces on the streambed and in the hyporheic zone.

Water Resources Research↗
USGS2019

Brood size affects future reproduction in a long-lived bird with precocial young

Estimation of trade-offs between current reproduction and future survival and fecundity of long-lived vertebrates is essential to understanding factors that shape optimal reproductive investment. Black brant geese (Branta bernicla nigricans) fledge more goslings, on average, when their broods are experimentally enlarged to be greater than the most common clutch size of four eggs. Thus, we hypothesized that the lesser frequency of brant clutches exceeding four eggs results, at least partially, from a future reduction in survival, breeding probability, or clutch size for females tending larger broods. We used an eight-year mark-recapture dataset (Barker robust design) with five years of clutch and brood manipulations to estimate long-term consequences of reproductive decisions in brant. We did not find evidence of a trade-off between reproductive effort and true survival or future initiation date and clutch size. Rather, future breeding probability was maximized (0.92 ± 0.03 [se]) for manipulated females tending broods of four goslings and lower for females tending smaller (one gosling; 0.63 ± 0.09 [se]) or larger broods (seven goslings; 0.52 ± 0.15 [se]). Our results suggest that demographic trade-offs for female brant tending large broods may reduce the fitness value of clutches larger than four and, therefore, contribute to the paucity of larger clutches. The lack of a trade-off between reproductive effort and survival provides evidence that survival, to which fitness is most sensitive in long-lived animals, is buffered against temporal variation in brant.

American Naturalist↗
USGS2019

Measuring settling velocity in a strongly tidal estuary

Predicting sediment transport in estuarine systems requires understanding sediment settling velocity, its range of fluctuations, and the shortcomings of the tools to measure it. Previous studies have used Laser In-Situ Scattering and Transmissometry (LISST) instruments to measure particle size and Acoustic Doppler Velocimeters (ADV) to return estimates of settling velocity. We deployed both instruments over a 4-week period in summer 2016 in San Pablo Bay, CA, and observed conflicting results from the two instruments. The LISST indicated the settling velocity decreased with increasing bed shear stress, while the ADV showed that settling velocity increased. Comparing the experimental conditions from this study with previous research reveals that the ADV method requires steady state conditions that were not achieved. Although the ADV method uses easily measured quantities to return the settling velocity, it relies on assumptions that are not always valid in estuarine settings.

California↗
USGS2009

Atomic weights of the elements 1999

The biennial review of atomic-weight, Ar(E), determinations and other cognate data have resulted in changes for the standard atomic weights of the following elements: Presented are updated tables of the standard atomic weights and their uncertainties estimated by combining experimental uncertainties and terrestrial variabilities. In addition, this report again contains an updated table of relative atomic-mass values and half-lives of selected radioisotopes. Changes in the evaluated isotopic abundance values from those published in 1997 are so minor that an updated list will not be published for the year 1999. Many elements have a different isotopic composition in some nonterrestrial materials. Some recent data on parent nuclides that might affect isotopic abundances or atomic-weight values are included in this report for the information of the interested scientific community.

Pure and Applied Chemistry↗
USGS1986

Potential for nitrosamine formation in seven fishery chemicals

In recent years, nitrosamines have been reported as possible causes of cancer, mutations, or birth defects. Inasmuch as these compounds may be formed by the interaction of certain amines with nitrite in the aquatic environment, we evaluated seven fishery chemicals for their potential to form nitrosamines: the experimental fish toxicant digeranylethanolamine (GD‐174); the four therapeutants Terramycin, erythromycin, Hyamine 1622, and Hyamine 3500; and the two tracer dyes rhodamine B and rhodamine WT. The results indicate that the controlled use of the seven fishery chemicals in natural environments will not lead to the formation of nitrosamines.

Progressive Fish-Culturist↗
USGS2022

Loss of street tree canopy increases stormwater runoff

Urban forests have largely been overlooked for the role they play in reducing stormwater runoff volume by using hydrologic processes such as interception (rainfall intercepted by tree canopy), evapotranspiration (the transfer of water from vegetation into the atmosphere) and infiltration (percolation of rainwater into the Earth’s soil). Early research into the effects of trees on urban stormwater runoff used simple estimates based on assumptions of canopy coverage and design storm criteria. In a review of available literature on how capable urban trees are at reducing runoff, the Center for Watershed Protection (2017) found only six studies; three of them used measured data from a single plot, and the other three used models. When identifying gaps in research on the role of trees in stormwater management, Kuehler and others (2017) highlighted the need for studies that scale the local effects of urban trees to the larger sewershed catchment area, allowing a more holistic understanding of the urban tree canopy effects on hydrology. For these reasons, the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, U.S. Forest Service, and the University of Wisconsin, quantified the effect of removing urban street trees and their canopy on stormwater generation in a medium-density residential area. Using a paired-catchment experimental design, rainfall-runoff relations were characterized in two medium-density residential catchments in Fond du Lac, Wisconsin, during May through September in 2018–20. Results of the study are detailed in Selbig and others (2022). During the calibration phase, hydrograph metrics from paired runoff events were used to develop the relation between the control and test catchments with street trees in place. The ability to measure changes to the rainfall-runoff response after removal of tree canopy was made possible by an aggressive tree removal program by the city as a response to rapid infestation from the Agrilus planipennis (emerald ash borer). In March 2020, a total of 31 street trees were removed at the onset of the treatment period, resulting in a loss of 2,990 square meters of canopy over streets, driveways, sidewalks, and grassed areas.

Wisconsin↗
USGS2012

Calibration and intercomparison of acetic acid measurements using proton transfer reaction mass spectrometry (PTR-MS)

Acetic acid is one of the most abundant organic acids in the ambient atmosphere, with maximum mixing ratios reaching into the tens of parts per billion by volume (ppbv) range. The identities and associated magnitudes of the major sources and sinks for acetic acid are poorly characterized, due in part to the limitation in available measurement techniques. This paper demonstrates that Proton Transfer Reaction Mass Spectrometry (PTR-MS) can reliably quantify acetic acid vapor in ambient air. Three different PTR-MS configurations were calibrated at low ppbv mixing ratios using permeation tubes, which yielded calibration factors between 7.0 and 10.9 normalized counts per second per ppbv (ncps ppbv −1 ) at a drift tube field strength of 132 townsend (Td). Detection limits ranged from 0.06 to 0.32 ppbv with dwell times of 5 s. These calibration factors showed negligible humidity dependence. Using the experimentally determined calibration factors, PTR-MS measurements of acetic acid during the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) campaign were validated against results obtained using Mist Chambers coupled with Ion Chromatography (MC/IC). An orthogonal least squares linear regression of paired data yielded a slope of 1.14 ± 0.06 (2σ), an intercept of 0.049 ± 20 (2σ) ppbv, and an R 2 of 0.78. The median mixing ratio of acetic acid on Appledore Island, ME during the ICARTT campaign was 0.530 ± 0.025 ppbv with a minimum of 0.075 ± 0.004 ppbv, and a maximum of 3.555 ± 0.171 ppbv.

Atmospheric Measurement Techniques↗
USGS2006

Parasitic Cowbirds have increased immunity to West Nile and other mosquitoborne encephalitis viruses

The rapid geographic spread of West Nile Virus [WNV, Flaviviridae, Flavivirus] across the United States has stimulated interest in comparative host infection studies of avian species to delineate competent reservoir hosts critical for viral amplification. Striking taxonomic differences in avian susceptibility have been noted, offering the opportunity to strategically select species on the basis of life history traits to examine aspects of pathogen virulence or host immunity. We hypothesized that avian brood parasites would show increased resistance to pathogens compared to related taxa, because they have been exposed in their evolutionary history to a wide array of infectious organisms from their different parenting species. The Brown-headed Cowbird (Molothrus ater) is a generalist brood parasite that parasitizes 200+ North American species. Elevated exposure to other species? parasites may have created an unusual degree of pathogen resistance. We compared the relative susceptibility of adult cowbirds to three closely-related non-parasitic species, Red-winged blackbirds, Tricolored blackbirds and Brewer?s blackbirds, to invading NY99 strain of WNV that is highly virulent for many passeriform birds. Previously we had experimentally infected these species with two North American mosquitoborne encephalitis viruses, western equine encephalomyelitis virus [WEEV, Togaviridae, Alphavirus] and St. Louis encephalitis virus [SLEV, Flaviviridae, Flavivirus]. Our results showed that cowbirds exhibited significantly lower viremia responses against all three viruses as well as after co-infection with both WEEV and WNV than did the three related, non-parasitic species. These data supported our hypothesis and indicated that cowbirds were more resistant to infection to both native and introduced viruses.

Book chapter↗
USGS2014

Gear and seasonal bias associated with abundance and size structure estimates for lentic freshwater fishes

All freshwater fish sampling methods are biased toward particular species, sizes, and sexes and are further influenced by season, habitat, and fish behavior changes over time. However, little is known about gear-specific biases for many common fish species because few multiple-gear comparison studies exist that have incorporated seasonal dynamics. We sampled six lakes and impoundments representing a diversity of trophic and physical conditions in Iowa, USA, using multiple gear types (i.e., standard modified fyke net, mini-modified fyke net, sinking experimental gill net, bag seine, benthic trawl, boat-mounted electrofisher used diurnally and nocturnally) to determine the influence of sampling methodology and season on fisheries assessments. Specifically, we describe the influence of season on catch per unit effort, proportional size distribution, and the number of samples required to obtain 125 stock-length individuals for 12 species of recreational and ecological importance. Mean catch per unit effort generally peaked in the spring and fall as a result of increased sampling effectiveness in shallow areas and seasonal changes in habitat use (e.g., movement offshore during summer). Mean proportional size distribution decreased from spring to fall for white bass Morone chrysops , largemouth bass Micropterus salmoides , bluegill Lepomis macrochirus , and black crappie Pomoxis nigromaculatus , suggesting selectivity for large and presumably sexually mature individuals in the spring and summer. Overall, the mean number of samples required to sample 125 stock-length individuals was minimized in the fall with sinking experimental gill nets, a boat-mounted electrofisher used at night, and standard modified nets for 11 of the 12 species evaluated. Our results provide fisheries scientists with relative comparisons between several recommended standard sampling methods and illustrate the effects of seasonal variation on estimates of population indices that will be critical to the future development of standardized sampling methods for freshwater fish in lentic ecosystems.

Iowa↗
USGS2012

The response of soil organic carbon of a rich fen peatland in interior Alaska to projected climate change

It is important to understand the fate of carbon in boreal peatland soils in response to climate change because a substantial change in release of this carbon as CO 2 and CH 4 could influence the climate system. The goal of this research was to synthesize the results of a field water table manipulation experiment conducted in a boreal rich fen into a process-based model to understand how soil organic carbon (SOC) of the rich fen might respond to projected climate change. This model, the peatland version of the dynamic organic soil Terrestrial Ecosystem Model (peatland DOS-TEM), was calibrated with data collected during 2005–2011 from the control treatment of a boreal rich fen in the Alaska Peatland Experiment (APEX). The performance of the model was validated with the experimental data measured from the raised and lowered water-table treatments of APEX during the same period. The model was then applied to simulate future SOC dynamics of the rich fen control site under various CO 2 emission scenarios. The results across these emissions scenarios suggest that the rate of SOC sequestration in the rich fen will increase between year 2012 and 2061 because the effects of warming increase heterotrophic respiration less than they increase carbon inputs via production. However, after 2061, the rate of SOC sequestration will be weakened and, as a result, the rich fen will likely become a carbon source to the atmosphere between 2062 and 2099. During this period, the effects of projected warming increase respiration so that it is greater than carbon inputs via production. Although changes in precipitation alone had relatively little effect on the dynamics of SOC, changes in precipitation did interact with warming to influence SOC dynamics for some climate scenarios.

Alaska↗
USGS2024

Effects of trap funnel and finger design on Sea Lamprey entrance and retention

Traps are used to catch adult sea lampreys during their upstream migration to estimate their abundance in streams and, in turn, provide a measure of the Sea Lamprey Control Program’s effectiveness. During 2015 and 2016, we experimentally compared two components of sea lamprey trap design: trap entrance funnel type and the presence of retention devices, using side-by-side instream test chambers as well as laboratory flumes. We modeled how likelihoods of entrance and retention were influenced by funnel type, retention fingers, water temperature, and lamprey sex. Likelihood of entrance was highest with bottom-oriented funnels and no retention fingers. As water temperature increased, the likelihood of entrance generally increased, but funnel type and retention fingers determined the magnitude of the increase. Likelihood of retention was highest with bottom-oriented funnels and retention fingers and was also influenced by water temperature. Overall, the likelihood of capture (result of entrance + retention) was highest for bottom-oriented funnels and varied by water temperature and lamprey sex but not retention fingers. Further testing on other components of trap design is needed. This type of controlled experimental design can help guide future work to improve trap exploitation rates.

Water↗
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↗