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At least 19 records

Spatiotemporal Changes in Trace Metal Bioavailability in the Sediment Pore water of a Constructed Wetland Using Passive Pore water Samplers

Sediments in aquatic systems often act as a major sink for contaminants. Diffusive gradient in thin films (DGTs) and in situ equilibrium dialysis samplers (peepers) are two major in situ pore water sampling devices that overcome the problems associated with conventional pore water sampling methods. In the present study, DGTs and peepers were used to study the spatial and seasonal effects (cool months, October–February; warm months, May–September) on metal bioavailability in the H‐02 constructed wetland and the sink versus source role of the sediments by calculating the metal resupply capacity. Data showed similar seasonal trends in metal concentrations using passive samplers, peepers, and DGTs. Pooled Cu and Zn concentrations measured using DGTs were lower in warm months (1.67 ± 1.50 and 2.62 ± 0.68 μg L –1 , respectively, p < 0.001) versus in cool months (2.12 ± 0.65 and 5.58 ± 1.33 μg L –1 , respectively, p < 0.001; mean ± 95% confidence interval). Sulfate (SO 4 2− ) concentrations were significantly (p = 0.0139) lower in warm months (averaged at 0.22 ± 0.05 mg L –1 ) compared to in cool months (0.16 ± 0.05 mg L –1 ). The increase in SO 4 2− concentration is an indicator of the lower activity of sulfate‐reducing bacteria, which need SO 4 2− during anaerobic respiration, in which SO 4 2− is reduced to sulfide (S 2– ) that forms insoluble salts with Cu and Zn, which could partially explain the higher bioavailability of these metals in the cool season. Metal resupply capacity of the sediments was mostly <0.2 for Cu and Zn. Taken together, the H0‐2 wetland sediments mostly acted as a sink to both Cu and Zn over the course of the present study. Environ Toxicol Chem 2023;42:2726–2736. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

54 ENVIRONMENTAL SCIENCES↗

Modeling Stress-Induced Pore Water Pressures in The Vadose Zone Beneath a Composite-Lined Landfill - 20029

A finite-element model was developed to evaluate mechanisms contributing to positive pore pressures measured with sealed pressure transducers in the geological buffer beneath the Environmental Management Waste Management Facility, a composite-lined mixed waste disposal facility operated by the US Department of Energy. The geological buffer is a 3-m-thick engineered fine-textured layer directly beneath the Environmental Management Waste Management Facility's composite liner, and above the groundwater table. The model accounts for changes in pore water pressure resulting from (i) loading imposed by waste placed on the overlying liner, (ii) moistening of the geological buffer due to equilibration with the underlying geological materials, and (iii) fluctuations in the elevation of the underlying groundwater table. Pore water pressures predicted by the model are in good agreement with pore water pressures measured in the field. The predictions confirm that positive pore water pressures recorded by the sealed pressure transducers in the geological buffer are excess pore water pressures induced by the vertical normal stress imposed by waste placed on the liner, and are not due to a rise in the groundwater table. Simulations also showed that two additional years of filling would further increase the pore water pressure without any change in elevation of the groundwater table. The geological buffer remained unsaturated during the simulation, with a B-coefficient (parameter indicative of the degree of saturation) similar to that computed from the field-measured pore water pressures and waste filling records. Larger increases in pore water pressure were observed when the geological buffer was assumed to have higher initial saturation, as was observed in the field data. Incorporating seasonal fluctuations in the groundwater table beneath the geological buffer in the model resulted in predictions of small seasonal oscillation in the pore water pressure at the measurement location, similar to seasonal oscillations observed in the field. Predictions made with the model indicate that the dissipation of the excess pore water pressures will occur over decades due to the low hydraulic conductivity of the geological buffer material. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Uncertainty propagation in pore water chemical composition calculation using surrogate models

Performance assessment in deep geological nuclear waste repository systems necessitates an extended knowledge of the pore water chemical conditions prevailing in host-rock formations. In the last two decades, important progress has been made in the experimental characterization and thermodynamic modeling of pore water speciation, but the influence of experimental artifacts and uncertainties of thermodynamic input parameters are seldom evaluated. In this respect, we conducted an uncertainty propagation study in a reference geochemical model describing the pore water chemistry of the Callovian-Oxfordian clay formation. Nineteen model input parameters were perturbed, including those associated to experimental characterization (leached anions, exchanged cations, cation exchange selectivity coefficients) and those associated to generic thermodynamic databases (solubilities). A set of 13 quantities of interest were studied by the use of polynomial chaos expansions built non-intrusively with a least-squares forward stepwise regression approach. Training and validation sets of simulations were carried out using the geochemical speciation code PHREEQC. The statistical results explored the marginal distribution of each quantity of interest, their bivariate correlations as well as their global sensitivity indices. The influence of the assumed distributions for input parameters uncertainties was evaluated by considering two parametric domain sizes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Environmental controls on observed spatial variability of soil pore water geochemistry in small headwater catchments underlain with permafrost

Abstract. Soil pore water (SPW) chemistry can vary substantially across multiple scales in Arctic permafrost landscapes. The magnitude of these variations and their relationship to scale are critical considerations for understanding current controls on geochemical cycling and for predicting future changes. These aspects are especially important for Arctic change modeling where accurate representation of sub-grid variability may be necessary to predict watershed-scale behaviors. Our research goal is to characterize intra- and inter-watershed soil water geochemical variations at two contrasting locations in the Seward Peninsula of Alaska, USA. We then attempt to identify the key factors controlling concentrations of important pore water solutes in these systems. The SPW geochemistry of 18 locations spanning two small Arctic catchments was examined for spatial variability and its dominant environmental controls. The primary environmental controls considered were vegetation, soil moisture and/or redox condition, water–soil interactions and hydrologic transport, and mineral solubility. The sampling locations varied in terms of vegetation type and canopy height, presence or absence of near-surface permafrost, soil moisture, and hillslope position. Vegetation was found to have a significant impact on SPW NO3- concentrations, associated with the localized presence of nitrogen-fixing alders and mineralization and nitrification of leaf litter from tall willow shrubs. The elevated NO3- concentrations were, however, frequently equipoised by increased microbial denitrification in regions with sufficient moisture to support it. Vegetation also had an observable impact on soil-moisture-sensitive constituents, but the effect was less significant. The redox conditions in both catchments were generally limited by Fe reduction, seemingly well-buffered by a cache of amorphous Fe hydroxides, with the most reducing conditions found at sampling locations with the highest soil moisture content. Non-redox-sensitive cations were affected by a wide variety of water–soil interactions that affect mineral solubility and transport. Identification of the dominant controls on current SPW hydrogeochemistry allows for qualitative prediction of future geochemical trends in small Arctic catchments that are likely to experience warming and permafrost thaw. As source areas for geochemical fluxes to the broader Arctic hydrologic system, geochemical processes occurring in these environments are particularly important to understand and predict with regards to such environmental changes.

Conroy, Nathan Alec (ORCID:0000000305973373)↗

Influence of Pore Water on the Fracture of Silica Sand at Particle Scale

The fracture of particles has a significant influence on the engineering behavior of granular materials. There are no reported conclusive answers in the literature to explain the influence of pore water on the fracture of sand, gravel, railroad ballast rock, aggregates, rockfill, and so on. Here, in this paper, two novel techniques were adopted to investigate the influence of pore water on the fracture of natural silica sand at the particle scale. The three-dimensional (3D) synchrotron microcomputed tomography (SMT) imaging technique was used to acquire and analyze multiple 3D images of specimens composed of wetted silica sand that were subjected to confined one-dimensional (1D) compression loading up to the fracture stage. A few representative particles were identified and digitally separated from the liquid water and gas phases. The 3D SMT images offer clear experimental evidence of the phase transition of water from liquid to gas within the opening cracks. In addition, a computational fluid dynamics numerical simulation framework for water flow into an opening crack was adopted and the results show that the fast opening of the crack induced cavitation, water phase transition, and water hammer effects. The results of the numerical simulations agree with the confined 1D compression experiments where the onset of the bubbles (gas phase) within the crack is mainly generated during the secondary cavitation stage, and the generated bubble near the crack mouth opening resulted from the primary cavitation, which was directly caused by the crack expansion. The results reported in this paper present a new cavitation phenomenon that occurs during particle fracture, which offers a physics-based explanation of why water-wetted sand fractures at smaller stresses than dry and can pave the way for more in-depth future studies on the fracture of water-wetted sand.

cavitation↗

East River Pore Water FTICR-MS Data associated with "Geomorphic and Hydrogeochemical Controls on Fine-Scale Hyporheic Microbiome Assembly and Function"

Pore water samples were collected from distributed locations around Meander A in East River (Crested Butte, CO, USA) during the summer of 2018. This dataset consists of the characterization of dissolved organic matter using 12 Tesla Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS; in .xml format) analyzed through the Environmental Molecular Sciences Laboratory (EMSL; https://www.pnnl.gov/environmental-molecular-sciences-laboratory).This study aimed to understand organic matter assemblages differ within a streambed with differing geomorphology and the interplay between streambed organic matter and microbiome function. Any published work that utilizes data presented in this dataset should cite the dataset using the DOI number. If using the dataset, please acknowledge the U.S. Department of Energy (DOE) Office of Science (BER) Subsurface Biogeochemical Research (SBR) program, the Environmental Molecular Sciences Laboratory (EMSL), and Worldwide Hydrobiogeochemical Observation Network for Dynamic River Systems (WHONDRS). The publication DOI will be added to this abstract when available.

54 ENVIRONMENTAL SCIENCES↗

East River Surface and Pore Water FTICR-MS Data Associated with “Implications of sample treatment on characterization of the riverine environmental metabolome”

Surface and pore water samples were collected from distributed locations around Meander A in East River (Crested Butte, CO, USA) during the summer of 2018. This dataset consists of the characterization of dissolved organic matter using 12 Tesla Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS; in .xml format) analyzed through the Environmental Molecular Sciences Laboratory (EMSL; https://www.pnnl.gov/environmental-molecular-sciences-laboratory) using two different sample pre-treatment methods (solid phase extraction, no solid phase extraction) and two electrospray ionization methods (ESI-positive, ESI-negative) to identify the impacts of these choices on the final dataset. This study aimed to understand how the different sample processing methods influence the resulting FTICR-MS dataset. Any published work that utilizes data presented in this dataset should cite the dataset using the DOI number. If using the dataset, please acknowledge the U.S. Department of Energy (DOE) Office of Science (BER) Subsurface Biogeochemical Research (SBR) program, the Environmental Molecular Sciences Laboratory (EMSL), and Worldwide Hydrobiogeochemical Observation Network for Dynamic River Systems (WHONDRS). The publication DOI will be added to this abstract when available.

54 ENVIRONMENTAL SCIENCES↗

In-situ neutron radiography of pore-water movement in portland cement mortar under subzero temperature exposure: Insights from D 2 O-H 2 O systems

Neutron radiography was employed in this study to monitor real-time pore water movement in portland cement mortar exposed to subzero temperatures, providing novel insights into freeze-thaw (F-T) damage mechanisms. Deuterated water (D 2 O) was used to hydrate the cement in the mortar specimens, and the pore structure was saturated with water (H 2 O), allowing for a contrast that enabled detailed tracking of water movement predominantly in the pore structure. Furthermore, the mortar sample was placed on a chiller plate set to subzero temperatures, thereby providing a one-dimensional temperature gradient vertically in the sample. Neutron radiography revealed that unfrozen water migrated upward as the freezing front advanced, which can create hydraulic pressure within the mortar microstructure and may contribute to the initiation and propagation of microcracks during F-T cycles. Additional characterization of the concrete made with D 2 O showed a marked contrast to the samples made with H 2 O, including delayed hydration, diminished compressive strength, and greater porosity. Therefore, while mortar made with D 2 O allowed for greater neutron contrast to the pores filled with H 2 O, further study is required to produce mortars with similar properties to those made with H 2 O. In addition, further refinement is needed to the radiography experiment to allow for greater control of temperatures and potential quantification of the water concentration.

Air-void system↗

Data Report: Pore Water Geochemistry at Green Canyon 955, deepwater Gulf of Mexico

Two holes were drilled in Green Canyon Block 955 (GC 955) in the deepwater Gulf of Mexico: Hole GC 955 H002 (H002) and Hole GC 955 H005 (H005). Here we present the solute concentrations and oxygen and hydrogen isotope ratios of pore water extracted from sediment whole-round samples collected from these holes. The analytical methods, degree of sample contamination, and the method for contamination correction are discussed as are the general trends in the geochemical data.

03 NATURAL GAS↗

The effects of pressure, temperature, and pore water on velocities in Westerly granite

A description is presented of an experimental assembly which has been developed to conduct concurrent measurements of compressional and shear wave velocities in rocks at high temperatures and confining pressures and with independent control of the pore pressure. The apparatus was used in studies of the joint effects of temperature, external confining pressure, and internal pore water on sonic velocities in Westerly granite. It was found that at a given temperature, confining pressure has a larger accelerating effect on compressional waves in dry rock, whereas at a given confining pressure, temperature has a larger retarding effect on shear waves.

Spencer, J. W., Jr.↗

Microanalysis of dissolved iron and phosphate in pore waters of hypersaline sediment

Diurnal fluctuations of reduced iron concentrations, expected to occur in reduced sediments in the photic zone, were studied. Iron concentration was compared to O2-H2S, a microcanalysis of sulfate reduction was performed, as well as an examination of diurnal concentration of dissolved phosphate and changes in interstitial CO2. The iron profiles suggest a strong correlation between iron remobilization and processes occurring in the light. Phosphate profiles suggest the removal of phosphate is strongly correlated with precipitation of oxidized iron in the upper 2 mm to 5 mm of the sediments. Pore water CO2 concentrations and carbon isotope ratios are presented. These data are from the analyses of minisediment cores collected from the 42 per mil salt pond and incubated in the laboratory under light and dark conditions.

Haddad, R.↗

Influence of gradation on shear behavior and pore water response of sand

Here, this paper examines the influence of particle size distribution (PSD) on the shearing behavior of sand using axisymmetric triaxial compression (ATC) testing in conjunction with 3D imaging using synchrotron micro-computed tomography (SMT). Angular sand was sieved to obtain a narrow gradation (uniform) and a wide gradation (non-uniform) with uniformity coefficients (C u ) of 1.2 and 3.0, respectively. Experiments were conducted under drained conditions and a constant effective cell pressure (σ$^{'}_3$) of 50 kPa at low and high back pressures (BP). Results of paired ATC-SMT were analyzed in terms of global constitutive behavior, strain localization, and localized flow characteristics. A new particle tracking algorithm is developed to expose strain localization. Relative particle translation gradient (RPTG) results revealed that gradation affects how early the shear band develops and a tendency for narrow gradation to exhibit varying degrees of diffused shear band at high axial strain (ε 1 ) even though a clear single shear band was observed at the peak strength. Geometric tortuosity (τ) is used as a quantitative parameter to assess flow changes and the efficiency of the flow path. Representative elementary volumes (REVs) inside and outside the shear band were analyzed and the results showed a variation in flow path characteristics where wide gradation specimens had preferential flow paths.

Computed tomography↗

Simulation and analysis of slip flow of water at hydrophobic silica surfaces of nanometer slit pores

Water flow in nanopores is controlled fundamentally by pore wettability and interfacial water features. In the research herein reported, Molecular dynamics (MD) was used to simulate water flow in nanometer slit pores of silica surfaces with variable wetting characteristics. Compared to Couette flow, the simulated slit-pores of the talc (001) and octadecyltrichlorosilane (OTS) monolayer surfaces exhibited water flow enhancement and a positive slip length at the interface, whereas water flow velocity at the quartz (001) and amorphous silica surfaces was zero, adhering to the no slip condition. More intensive interactions between the interfacial water and hydrophilic silica surfaces were confirmed by MD simulation and sum-frequency vibrational spectroscopy (SFVS) results. A water exclusion zone of approximately 3 Å was found at the hydrophobic silica surfaces by quantitative MD interfacial water analysis and validated by SFVS. This exclusion zone dimension was similar in magnitude to the slip length (4–5 Å) as determined from simulated water flow in hydrophobic silica slit pores. The simulated slip lengths at the hydrophobic surfaces (0.2–1 nm) were significantly less than the experimental slip lengths (>40 nm) reported in the literature. In the case of the experimental results, this difference appears to be due to nanobubbles expected to be present at hydrophobic surfaces.

42 ENGINEERING↗

Spatial and temporal metagenomics of river compartments reveals viral community dynamics in an urban impacted stream

Although river ecosystems constitute a small fraction of Earth’s total area, they are critical modulators of microbially and virally orchestrated global biogeochemical cycles. However, most studies either use data that is not spatially resolved or is collected at timepoints that do not reflect the short life cycles of microorganisms. To address this gap, we assessed how viral and microbial communities change over a 48-hour period by sampling surface water and pore water compartments of the wastewater-impacted River Erpe in Germany. We sampled every 3 hours resulting in 32 samples for which we obtained metagenomes along with geochemical and metabolite measurements. From our metagenomes, we identified 6,500 viral and 1,033 microbial metagenome assembled genomes (MAGs) and found distinct community membership and abundance associated with each river compartment (e.g., Competibacteraceae in surfacewater and Sulfurimonadaceae in pore water). We show that 17% of our viral MAGs clustered to viruses from other ecosystems like wastewater treatment plants and rivers. Our results also indicated that 70% of the viral community was persistent in surface waters, whereas only 13% were persistent in the pore waters taken from the hyporheic zone. Finally, we predicted linkages between 73 viral genomes and 38 microbial genomes. These putatively linked hosts included members of the Competibacteraceae, which we suggest are potential contributors to river carbon and nitrogen cycling via denitrification and nitrogen fixation. Together, these findings demonstrate that members of the surface water microbiome from this urban river are stable over multiple diurnal cycles. These temporal insights raise important considerations for ecosystem models attempting to constrain dynamics of river biogeochemical cycles.

54 ENVIRONMENTAL SCIENCES↗

Simulations of the IR and Raman spectra of water confined in amorphous silica slit pores

Water in nano-scale confining environments is a key element in many biological, material, and geological systems. The structure and dynamics of the liquid can be dramatically modified under these conditions. Probing these changes can be challenging, but vibrational spectroscopy has emerged as a powerful tool for investigating their behavior. A critical, evolving component of this approach is a detailed understanding of the connection between spectroscopic features and molecular-level details. In this paper, this issue is addressed by using molecular dynamics simulations to simulate the linear infrared (IR) and Raman spectra for isotopically dilute HOD in D 2 O confined in hydroxylated amorphous silica slit pores. The effect of slit-pore width and hydroxyl density on the silica surface on the vibrational spectra is also investigated. The primary effect of confinement is a blueshift in the frequency of OH groups donating a hydrogen bond to the silica surface. This appears as a slight shift in the total (measurable) spectra but is clearly seen in the distance-based IR and Raman spectra. Analysis indicates that these changes upon confinement are associated with the weaker hydrogen-bond accepting properties of silica oxygens compared to water molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying Subsurface Flow and Solute Transport in a Snowmelt‐Recharged Hillslope With Multiyear Water Balance

Abstract Quantifying flow and transport from hillslopes is vital for understanding water quantity and quality in rivers, but remains obscure because of limited subsurface measurements. Using measured hydraulic conductivity K profiles and water balance over a single year to calibrate a transmissivity feedback model for a hillslope in the East River watershed (Colorado) proved unsatisfactory for predicting flow over the subsequent years. Well‐constrained field‐scale K were obtained by optimizing subsurface flux predictions over years having large differences in recharge, and by including estimates of interannual transfer of excess snowmelt recharge. Water and solute exports during high snowmelt recharge occur predominantly via shallow groundwater flow through weathered rock and soil because of their enlarged transmissivities under saturated conditions. Conversely, these shallow pathways are less active in snow drought years when the water table remains deeper within the weathering zone. Hillslope soil water monitoring showed that rainfall does not infiltrate deeply during summer and fall months, and revealed water losses consistent with model ET predictions. By combining water table‐dependent fluxes with pore water chemistry in different zones, time‐dependent rates of solute exports become predictable. As an example, calibrated K were combined with dissolved nitrogen concentrations in pore waters to show the snowmelt‐dependence of reactive nitrogen exported from the hillslope, further supporting the recent finding that the weathering zone is the dominant source of reactive nitrogen at this site. Subsurface export predictions can now be obtained for wide ranges of recharge based on measurements of water table elevation and profiles of pore water chemistry.

54 ENVIRONMENTAL SCIENCES↗