Geology topics

Douglas B. Kent

Publications and source records attributed to Douglas B. Kent.

At least 19 recordsLinked to original sources

USGS2024

Prioritizing US Geological Survey science on salinization and salinity in candidate and selected priority river basins

The US Geological Survey (USGS) is selecting and prioritizing basins, known as Integrated Water Science basins, for monitoring and intensive study. Previous efforts to aid in this selection process include a scientifically defensible and quantitative assessment of basins facing human-caused water resource challenges (Van Metre et al. in Environmental Monitoring and Assessment , 192(7), 458 2020). In the present work, we explore this ranking process based on water quality considerations, specifically salinity and salinization. We selected top candidate basins to study salinity and salinization issues in 18 hydrologic regions that include 163 candidate basins. Our prioritization is based on quantitative assessment of sources of salinity, drivers of change, and receptors that must respond to those sources and drivers. Source terms represented in the prioritization include geology, depth to brackish groundwater, stream conductivity, chloride in precipitation, urban and agricultural land use, application of road salt as a deicer, and irrigation. Drivers represented in prioritization include changes in chemical weathering as a result of changes in rainwater chemistry. Receptors include measures of water stress, measurements of stream ecological health, and socioeconomic factors. In addition, we present research activities for the USGS on salinity and salinization that can be pursued in these basins including assessment of sources, pathways, and loadings; predicting and understanding changes in sources, peaks, and trends; understanding the components of salinity and mobilization of contaminants; understanding the relationship between salinization and changing ecosystems; and developing knowledge on the causes and distribution of groundwater salinity, brackish water resources, and challenges related to desalination.

Enviornmental Monitoring and Assessment↗

USGS2024

Spatial, seasonal, and diel controls of nitrogen-carbon-oxygen cycling during lake-water infiltration to an aquifer

Many freshwater lakes are groundwater flow-through systems. Although lakes commonly are considered to be sinks for nitrogen inputs, relatively little is known about carbon and nitrogen export from lakes to groundwater. The current study focused on lake-bottom biogeochemical processes accompanying the transport of nitrogen, dissolved oxygen (O 2 ), and dissolved organic carbon (DOC) during lake-water recharge from a groundwater flow-through lake. Lake-water and porewater (15–100 cm below lakebed) samples were collected along transects within the lake downwelling zone. Infiltrating porewater O 2 and DOC concentrations decreased with depth while nitrate (NO 3 − ) concentrations increased, indicating nitrification of organic matter within the profiles. The depth of NO 3 − production and transport was seasonally dependent. In winter, NO 3 − and O 2 were exported beyond 100-cm depth; whereas in summer, shallow nitrification zones were underlain by deeper NO 3 − reduction zones, and diel patterns of O 2 and NO 3 − penetration depths were observed. Microbial community compositions and stable isotope profiles (δ 15 N[NO 3 − ], δ 18 O[NO 3 − ], δ 18 O[O 2 ]) were consistent with apparent C–N–O reaction stoichiometries indicating O 2 reduction and nitrification in shallower porewater, followed by varying NO 3 − reduction at depth. Maximum porewater NO 3 − concentrations (∼10–20 μM) were limited by infiltrating O 2 concentrations and C/N ratios of reacting organic matter. Lake-water level variations caused changes in shoreline position and porewater velocities, while variations in lake-water temperature, DOC, and O 2 contributed to changes in reaction rates and depth of O 2 and NO 3 − penetration into the lakebed. The quality of groundwater recharged by lake water reflected temporally and spatially varying physical and biogeochemical processes in the sediment porewater.

Journal of Geophysical Research: Biogeosciences↗

USGS2024

Prioritizing water availability study settings to address geogenic contaminants and related societal factors

Water availability for human and ecological uses depends on both water quantity and water quality. The U.S. Geological Survey (USGS) is developing strategies for prioritizing regional-scale and watershed basin-scale studies of water availability across the nation. Previous USGS ranking processes for basin-scale studies incorporated primarily water quantity factors but are now considering additional water quality factors. This study presents a ranking based on the potential impacts of geogenic constituents on water quality and consideration of societal factors related to water quality. High-concentration geogenic constituents, including trace elements and radionuclides, are among the most prevalent contaminants limiting water availability in the USA and globally. Geogenic constituents commonly occur in groundwater because of subsurface water–rock interactions, and their distributions are controlled by complex geochemical processes. Geogenic constituent mobility can also be affected by human activities (e.g., mining, energy production, irrigation, and pumping). Societal factors and relations to drinking water sources and water quality information are often overlooked when evaluating research priorities. Sociodemographic characteristics, data gaps resulting from historical data-collection disparities, and infrastructure condition/age are examples of factors to consider regarding environmental justice. This paper presents approaches for ranking and prioritizing potential basin-scale study areas across the contiguous USA by considering a suite of conventional physical and geochemical variables related to geogenic constituents, with and without considering variables related to societal factors. Simultaneous consideration of societal and conventional factors could provide decision makers with more diverse, interdisciplinary tools to increase equity and reduce bias in prioritizing focused research areas and future water availability studies.

Environmental Monitoring and Assessment↗

USGS2024

Illegal dumping of oil and gas wastewater alters arid soil microbial communities

The Permian Basin, underlying southeast New Mexico and west Texas, is one of the most productive oil and gas (OG) provinces in the United States. Oil and gas production yields large volumes of wastewater with complex chemistries, and the environmental health risks posed by these OG wastewaters on sensitive desert ecosystems are poorly understood. Starting in November 2017, 39 illegal dumps, as defined by federal and state regulations, of OG wastewater were identified in southeastern New Mexico, releasing ~600,000 L of fluid onto dryland soils. To evaluate the impacts of these releases, we analyzed changes in soil geochemistry and microbial community composition by comparing soils from within OG wastewater dump-affected samples to unaffected zones. We observed significant changes in soil geochemistry for all dump-affected compared with control samples, reflecting the residual salts and hydrocarbons from the OG-wastewater release (e.g., enriched in sodium, chloride, and bromide). Microbial community structure significantly ( P < 0.01) differed between dump and control zones, with soils from dump areas having significantly ( P < 0.01) lower alpha diversity and differences in phylogenetic composition. Dump-affected soil samples showed an increase in halophilic and halotolerant taxa, including members of the Marinobacteraceae, Halomonadaceae, and Halobacteroidaceae, suggesting that the high salinity of the dumped OG wastewater was exerting a strong selective pressure on microbial community structure. Taxa with high similarity to known hydrocarbon-degrading organisms were also detected in the dump-affected soil samples. Overall, this study demonstrates the potential for OG wastewater exposure to change the geochemistry and microbial community dynamics of arid soils.

Applied and Environmental Microbiology↗

USGS2023

Ammonia and aquatic ecosystems – A review of global sources, biogeochemical cycling, and effects on fish

The purpose of this review is to better understand the full life cycle and influence of ammonia from an aquatic biology perspective. While ammonia has toxic properties in water and air, it also plays a central role in the biogeochemical nitrogen (N) cycle and regulates mechanisms of normal and abnormal fish physiology. Additionally, as the second most synthesized chemical on Earth, ammonia contributes economic value to many sectors, particularly fertilizers, energy storage, explosives, refrigerants, and plastics. But, with so many uses, industrial N 2 -fixation effectively doubles natural reactive N concentrations in the environment. The consequence is global, with excess fixed nitrogen driving degradation of soils, water, and air; intensifying eutrophication, biodiversity loss, and climate change; and creating health risks for humans, wildlife, and fisheries. Thus, the need for ammonia research in aquatic systems is growing. In response, we prepared this review to better understand the complexities and connectedness of environmental ammonia. Even the term “ammonia” has multiple meanings. So, we have clarified the nomenclature, identified units of measurement, and summarized methods to measure ammonia in water. We then discuss ammonia in the context of the N-cycle, review its role in fish physiology and mechanisms of toxicity, and integrate the effects of human N-fixation, which continuously expands ammonia's sources and uses. Ammonia is being developed as a carbon-free energy carrier with potential to increase reactive nitrogen in the environment. With this in mind, we review the global impacts of excess reactive nitrogen and consider the current monitoring and regulatory frameworks for ammonia. The presented synthesis illustrates the complex and interactive dynamics of ammonia as a plant nutrient, energy molecule, feedstock, waste product, contaminant, N-cycle participant, regulator of animal physiology, toxicant, and agent of environmental change. Few molecules are as influential as ammonia in the management and resilience of Earth's resources.

Science of the Total Environment↗

USGS2022

Using biological responses to monitor freshwater post-spill conditions over 3 years in Blacktail Creek, North Dakota, USA

A pipeline carrying unconventional oil and gas (OG) wastewater spilled approximately 11 million liters of wastewater into Blacktail Creek, North Dakota, USA. Flow of the mix of stream water and wastewater down the channel resulted in storage of contaminants in the hyporheic zone and along the banks, providing a long-term source of wastewater constituents to the stream. A multi-level investigation was used to assess the potential effects of oil and brine spills on aquatic life. In this study, we used a combination of experiments using a native fish species, Fathead Minnow ( Pimephales promelas ), field sampling of the microbial community structure, and measures of estrogenicity. The fish investigation included in situ experiments and experiments with collected site water. Estrogenicity was measured in collected site water samples, and microbial community analyses were conducted on collected sediments. During the initial post-spill investigation, February 2015, performing in situ fish bioassays was impossible because of ice conditions. However, microbial community (e.g., the presence of members of the Halomonadaceae, a family that is indicative of elevated salinity) and estrogenicity differences were compared to reference sites and point to early biological effects of the spill. We noted water column effects on in situ fish survival 6 months post-spill during June 2015. At that time, total dissolved ammonium (sum of ammonium and ammonia, TAN) was 4.41 mg NH 4 /L with an associated NH 3 of 1.09 mg/L, a concentration greater than the water quality criteria established to protect aquatic life. Biological measurements in the sediment defined early and long-lasting effects of the spill on aquatic resources. The microbial community structure was affected during all sampling events. Therefore, sediment may act as a sink for constituents spilled and as such provide an indication of continued and cumulative effects post-spill. However, lack of later water column effects may reflect pulse hyporheic flow of ammonia from shallow ground water. Combining fish toxicological, microbial community structure and estrogenicity information provides a complete ecological investigation that defines potential influences of contaminants at organismal, population, and community levels. In general, in situ bioassays have implications for the individual survival and changes at the population level, microbial community structure defines potential changes at the community level, and estrogenicity measurements define changes at the individual and molecular level. By understanding effects at these various levels of biological organization, natural resource managers can interpret how a course of action, especially for remediation/restoration, might affect a larger group of organisms in the system. The current work also reviews potential effects of additional constituents defined during chemistry investigations on aquatic resources.

North Dakota↗

USGS2021

Integrated science for the study of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in the environment—A strategic science vision for the U.S. Geological Survey

Concerns related to perfluoroalkyl and polyfluoroalkyl substances (PFAS) in sources of drinking water and in natural and engineered environments have captured national attention over the last few decades. This report provides an overview of the science gaps that exist in the fields of study related to PFAS that are relevant to the U.S. Geological Survey mission and identifies opportunities where the U.S. Geological Survey can help address these gaps on the basis of the agency’s capabilities and expertise. The integrated science activities envisioned in this document can be designed to address science needs at local, regional, and national scales and varying timeframes as stakeholders are engaged and their needs evolve. This document is intended as an information resource for U.S. Geological Survey scientists who are prioritizing and planning research related to PFAS and may be useful for developing partnerships and collaborations with other scientists, agencies, and stakeholders.

Circular↗

USGS2021

Geochemical and geophysical indicators of oil and gas wastewater can trace potential exposure pathways following releases to surface waters

Releases of oil and gas (OG) wastewaters can have complex effects on stream-water quality and downstream organisms, due to sediment-water interactions and groundwater/surface water exchange. Previously, elevated concentrations of sodium (Na), chloride (Cl), barium (Ba), strontium (Sr), and lithium (Li), and trace hydrocarbons were determined to be key markers of OG wastewater releases when combined with Sr and radium (Ra) isotopic compositions. Here, we assessed the persistence of an OG wastewater spill in a creek in North Dakota using a combination of geochemical measurements and modeling, hydrologic analysis, and geophysical investigations. OG wastewater comprised 0.1 to 0.3% of the stream-water compositions at downstream sites in February and June 2015 but could not be quantified in 2016 and 2017. However, OG-wastewater markers persisted in sediments and pore water for 2.5 years after the spill and up to 7.2-km downstream from the spill site. Concentrations of OG wastewater constituents were highly variable depending on the hydrologic conditions. Electromagnetic measurements indicated substantially higher electrical conductivity under the bank adjacent to a seep 7.2 km downstream from the spill site. Geomorphic investigations revealed mobilization of sediment is an important contaminant transport process. Labile Ba, Ra, Sr, and ammonium (NH 4 ) concentrations extracted from sediments indicated sediments are a long-term reservoir of these constituents, both in the creek and on the floodplain. Using the drivers of ecological effects identified at this intensively studied site we identified 41 watersheds across the North Dakota landscape that may be subject to similar episodic inputs from OG wastewater spills. Effects of contaminants released to the environment during OG waste management activities remain poorly understood; however, analyses of Ra and Sr isotopic compositions, as well as trace inorganic and organic compound concentrations at these sites in pore-water provide insights into potentials for animal and human exposures well outside source-remediation zones.

North Dakota↗

USGS2019

Seasonal and spatial variation in the location and reactivity of a nitrate-contaminated groundwater discharge zone in a lakebed

Groundwater discharge delivering anthropogenic N from surrounding watersheds can impact lake nutrient budgets. However, upgradient groundwater processes and changing dynamics in N biogeochemistry at the groundwater-lake interface are complex and difficult to resolve. In this study, hydrograph variations in a groundwater flow-through lake altered discharge patterns of a wastewater-derived, groundwater contaminant plume, thereby affecting biogeochemical processes controlling N transport. Groundwater geochemistry 15 cm under the lakebed along transects perpendicular to shore varied from oxic to anoxic with increasing nitrate concentrations (10-75 M) and corresponding gradients in nitrite and nitrous oxide. Porewater depth profiles of nitrate concentrations and stable isotope compositions largely reflected upgradient groundwater N sources and N-cycle processes, with minor additional nitrate reduction in the shallowest lakebed sediments. Potential denitrification rates determined in laboratory microcosms were 10-100 fold higher in near-surface sediments (0-5 cm) than in deeper sediments (5-30 cm) and were correlated with sediment carbon content and abundance of denitrification genes (nirS, nosZI, and nosZII). Potential anammox-driven N2 production was highest in deeper anoxic sediments. Injection of bromide and nitrite in the lake sediments indicated a vertical porewater velocity of 4-5 cm hr-1, with highest nitrite consumption rates above 10 cm. However, short residence times in the shallow sediments allowed only a small fraction of the contaminant nitrate to be removed before discharging into the lake. Results demonstrate the importance of resolving local versus upgradient biogeochemical processes affecting contaminant distribution in discharge areas, and transient migration of local gradients and processes in response to changing lake levels and groundwater flow paths.

Journal of Geophysical Research: Biogeosciences↗

USGS2019

Reactive transport modeling to understand attenuation of arsenic concentrations in anoxic groundwater during Fe(II) oxidation by nitrate

A previously published field-experimental investigation showed that injection of nitrate in anoxic groundwater that contained aqueous and sediment-bound Fe(II) diminished concentrations of As(V) and As(III) to below drinking-water limits. In the current study, reactive transport modeling confirmed that the observed attenuation was consistent with oxidation of Fe(II) by nitrate, leading to precipitation of hydrous ferric oxide, which, in turn, sorbed both As(V) and As(III). After calibration with site-specific observations, reactive transport modeling could aid in designing effective treatment to remove arsenic using injection of nitrate to oxidize Fe(II).

Book chapter↗

USGS2018

When oil and water mix: Understanding the environmental impacts of shale development

Development of shale gas and tight oil, or unconventional oil and gas (UOG), has dramatically increased domestic energy production in the U.S. UOG resources are typically developed through the use of hydraulic fracturing, which creates high-permeability flow paths into large volumes of tight rocks to provide a means for hydrocarbons to move to a wellbore. This process uses significant volumes of water, sand, and chemicals, raising concerns about risks to the environment and to human health. Researchers in various disciplines have been working to make UOG development more efficient, and to better understand the risks to air quality, water quality, landscapes, human health, and ecosystems. Risks to air include releases of methane, carbon dioxide, volatile organic compounds, and particulate matter. Water-resource risks include excessive withdrawals, stray gas in drinking-water aquifers, and surface spills of fluids or chemicals. Landscapes can be significantly altered by the infrastructure installed to support large drilling platforms and associated equipment. Exposure routes, fate and transport, and toxicology of chemicals used in the hydraulic fracturing process are poorly understood, as are the potential effects on terrestrial and aquatic ecosystems and human health. This is made all the more difficult by an adaptable and evolving industry that frequently changes methods and constantly introduces new chemicals. Geoscientists responding to questions about the risks of UOG should refer to recent, rigorous scientific research.

GSA Today↗

USGS2017

Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε 15 N/ε 18 O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several weeks. Additionally, Fe(II)-oxidizing, nitrate-reducing microbial enrichment cultures were obtained from aquifer sediments. Growth experiments with the cultures sequentially produced nitrite and nitrous oxide from nitrate while simultaneously oxidizing Fe(II). Field and culture results suggest that nitrogen oxide reduction and Fe(II) oxidation in the aquifer are a complex interaction of coupled biotic and abiotic reactions. Overall, the results of this study demonstrate that anoxic nitrate-dependent iron oxidation can occur in groundwater; that it could control iron speciation; and that the process can impact the mobility of other chemical species (e.g., phosphate and arsenic) not directly involved in the oxidation–reduction reaction.

Massachusetts↗

USGS2017

Extent and persistence of secondary water quality impacts after enhanced reductive bioremediation

Electron donor (ED) addition can be very effective in stimulating enhanced reductive bioremediation (ERB) of a wide variety of groundwater contaminants. However, ERB can result in Secondary Water Quality Impacts (SWQIs) including decreased levels of dissolved oxygen (O 2 ), nitrate (NO 3- ), and sulfate (SO 4 2- ), and elevated levels of dissolved manganese (Mn 2+ ), dissolved iron (Fe 2+ ), methane (CH 4 ), sulfide (S 2- ), organic carbon, and naturally occurring hazardous compounds (e.g., arsenic). Fortunately, this ‘plume’ of impacted groundwater is usually confined within the original contaminant plume and is unlikely to adversely impact potable water supplies. This report summarizes available information on processes controlling the production and natural attenuation of SWQI parameters and can be used as a guide in understanding the magnitude, areal extent, and duration of SWQIs in ERB treatment zones and the natural attenuation of SWQI parameters as the dissolved solutes migrate downgradient with ambient groundwater flow. This information was compiled from a wide variety of sources including a survey and statistical analysis of SWQIs from 47 ERB sites, geochemical model simulations, field studies at sites where organic-rich materials have entered the subsurface (e.g., wastewater, landfill leachate, and hydrocarbon plumes), and basic information on physical, chemical, and biological processes in the subsurface. This information is then integrated to provide a general conceptual model of the major processes controlling SWQI production and attenuation.

Technical Report↗

USGS2016

Wastewater disposal from unconventional oil and gas development degrades stream quality at a West Virginia injection facility

The development of unconventional oil and gas (UOG) resources has rapidly increased in recent years; however, the environmental impacts and risks are poorly understood. A single well can generate millions of liters of wastewater, representing a mixture of formation brine and injected hydraulic fracturing fluids. One of the most common methods for wastewater disposal is underground injection; we are assessing potential risks of this method through an intensive, interdisciplinary study at an injection disposal facility in West Virginia. In June 2014, waters collected downstream from the site had elevated specific conductance (416 μS/cm) and Na, Cl, Ba, Br, Sr, and Li concentrations, compared to upstream, background waters (conductivity, 74 μS/cm). Elevated TDS, a marker of UOG wastewater, provided an early indication of impacts in the stream. Wastewater inputs are also evident by changes in 87Sr/86Sr in streamwater adjacent to the disposal facility. Sediments downstream from the facility were enriched in Ra and had high bioavailable Fe(III) concentrations relative to upstream sediments. Microbial communities in downstream sediments had lower diversity and shifts in composition. Although the hydrologic pathways were not able to be assessed, these data provide evidence demonstrating that activities at the disposal facility are impacting a nearby stream and altering the biogeochemistry of nearby ecosystems.

Environmental Science & Technology↗

USGS2016

Hydrologic controls on nitrogen cycling processes and functional gene abundance in sediments of a groundwater flow-through lake

The fate and transport of inorganic nitrogen (N) is a critically important issue for human and aquatic ecosystem health because discharging N-contaminated groundwater can foul drinking water and cause algal blooms. Factors controlling N-processing were examined in sediments at three sites with contrasting hydrologic regimes at a lake on Cape Cod, MA. These factors included water chemistry, seepage rates and direction of groundwater flow, and the abundance and potential rates of activity of N-cycling microbial communities. Genes coding for denitrification, anaerobic ammonium oxidation (anammox), and nitrification were identified at all sites regardless of flow direction or groundwater dissolved oxygen concentrations. Flow direction was, however, a controlling factor in the potential for N-attenuation via denitrification in the sediments. Potential rates of denitrification varied from 6 to 4500 pmol N/g/h from the inflow to the outflow side of the lake, owing to fundamental differences in the supply of labile organic matter. The results of laboratory incubations suggested that when anoxia and limiting labile organic matter prevailed, the potential existed for concomitant anammox and denitrification. Where oxic lake water was downwelling, potential rates of nitrification at shallow depths were substantial (1640 pmol N/g/h). Rates of anammox, denitrification, and nitrification may be linked to rates of organic N-mineralization, serving to increase N-mobility and transport downgradient.

Massachusetts↗

USGS2013

Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments

Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

Colorado↗

USGS2013

Kinetics of homogeneous and surface-catalyzed mercury(II) reduction by iron(II)

Production of elemental mercury, Hg(0), via Hg(II) reduction is an important pathway that should be considered when studying Hg fate in environment. We conducted a kinetic study of abiotic homogeneous and surface-catalyzed Hg(0) production by Fe(II) under dark anoxic conditions. Hg(0) production rate, from initial 50 pM Hg(II) concentration, increased with increasing pH (5.5–8.1) and aqueous Fe(II) concentration (0.1–1 mM). The homogeneous rate was best described by the expression, r hom = k hom [FeOH + ] [Hg(OH) 2 ]; k hom = 7.19 × 10 +3 L (mol min) −1 . Compared to the homogeneous case, goethite (α-FeOOH) and hematite (α-Fe 2 O 3 ) increased and γ-alumina (γ-Al 2 O 3 ) decreased the Hg(0) production rate. Heterogeneous Hg(0) production rates were well described by a model incorporating equilibrium Fe(II) adsorption, rate-limited Hg(II) reduction by dissolved and adsorbed Fe(II), and rate-limited Hg(II) adsorption. Equilibrium Fe(II) adsorption was described using a surface complexation model calibrated with previously published experimental data. The Hg(0) production rate was well described by the expression r het = k het [>SOFe (II) ] [Hg(OH) 2 ], where >SOFe (II) is the total adsorbed Fe(II) concentration; k het values were 5.36 × 10 +3 , 4.69 × 10 +3 , and 1.08 × 10 +2 L (mol min) −1 for hematite, goethite, and γ-alumina, respectively. Hg(0) production coupled to reduction by Fe(II) may be an important process to consider in ecosystem Hg studies.

Environmental Science & Technology↗

USGS2013

Characterizing particle-scale equilibrium adsorption and kinetics of uranium(VI) desorption from U-contaminated sediments

Rates of U(VI) release from individual dry-sieved size fractions of a field-aggregated, field-contaminated composite sediment from the seasonally saturated lower vadose zone of the Hanford 300-Area were examined in flow-through reactors to maintain quasi-constant chemical conditions. The principal source of variability in equilibrium U(VI) adsorption properties of the various size fractions was the impact of variable chemistry on adsorption. This source of variability was represented using surface complexation models (SCMs) with different stoichiometric coefficients with respect to hydrogen ion and carbonate concentrations for the different size fractions. A reactive transport model incorporating equilibrium expressions for cation exchange and calcite dissolution, along with rate expressions for aerobic respiration and silica dissolution, described the temporal evolution of solute concentrations observed during the flow-through reactor experiments. Kinetic U(VI) desorption was well described using a multirate SCM with an assumed lognormal distribution for the mass-transfer rate coefficients. The estimated mean and standard deviation of the rate coefficients were the same for all <2 mm size fractions but differed for the 2–8 mm size fraction. Micropore volumes, assessed using t-plots to analyze N2 desorption data, were also the same for all dry-sieved <2 mm size fractions, indicating a link between micropore volumes and mass-transfer rate properties. Pore volumes for dry-sieved size fractions exceeded values for the corresponding wet-sieved fractions. We hypothesize that repeated field wetting and drying cycles lead to the formation of aggregates and/or coatings containing (micro)pore networks which provided an additional mass-transfer resistance over that associated with individual particles. The 2–8 mm fraction exhibited a larger average and standard deviation in the distribution of mass-transfer rate coefficients, possibly caused by the abundance of microporous basaltic rock fragments.

Water Resources Research↗