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Ecosystems and Networks Integrated with Genes and Molecular Assemblies (Final Scientific/Technical Report)

The ENIGMA science focus area (SFA) is a multi-disciplinary, multi-institutional research effort focused on addressing foundational knowledge gaps in environmental microbial communities by studying groundwater and sediment microbiomes in the shallow subsurface at the contaminated Oak Ridge Field Research Site (FRC). We seek to discover and characterize the reciprocal interactions between the microbial communities and the geochemical and geophysical parameters of the shallow subsurface within the contamination plume. The goal of the Fields lab is to help manage and conduct laboratory experiments informed by field observations using ecological and physiological approaches to study microbial populations in situ as well as ex situ (in the laboratory). In particular, we aim to study and characterize the impact of hydrological constraints on free-living and biofilm biomass and activity with increasing spatial and temporal resolution under static and flow conditions. We also aim to help characterize novel microbial groups that are present and active under relevant field conditions, including the development of molecular techniques for in situ detection as well as metabolic interactions that underlie pertinent physiology and ecology.

59 BASIC BIOLOGICAL SCIENCES↗

Groundwater characterization and monitoring at a complex industrial waste site using electrical resistivity imaging

A contaminated industrial waste site in Washington State (USA) containing buried, metallic-waste storage tanks, pipes, and wells, was evaluated to determine the feasibility of monitoring groundwater remediation activities associated with an underlying perched aquifer system using electrical resistivity tomography. The perched aquifer, located ~65 m below ground surface and ~10 m above the regional water table, contains high concentrations of nitrate, uranium, and other contaminants of concern from past tank leaks and intentional releases of wastes to surface disposal sites. The extent of the perched water aquifer is not well known, and the effectiveness of groundwater extraction for contaminant removal is uncertain, so supplemental characterization and monitoring technologies are being evaluated. Numerical simulations of subsurface flow and contaminant transport were performed with a highly resolved model of the hydrogeologic system and waste site infrastructure, and these simulations were used as the physical basis for electrical resistivity tomography modeling. The modeling explicitly accounted for metallic infrastructure at the site. The effectiveness of using surface electrodes versus surface and horizontal subsurface electrodes, for imaging groundwater extraction from the perched water aquifer, was investigated. Although directional drilling is a mature technology, its use for electrode emplacement in the deep subsurface under a complex industrial waste site via horizontal wells has not yet been demonstrated. Results from this study indicate that using horizontal subsurface electrode arrays could significantly improve the ability of electrical resistivity tomography to image deep subsurface features and monitor remediation activities under complex industrial waste sites.

54 ENVIRONMENTAL SCIENCES↗

Geophysical Methods for Stratigraphic Identification

The goal of this work is to identify geophysical methods that can be used to delineate (in 3D) a large-scale paleochannel that has been inferred to exist between the 200 West and 200 East Areas of the Hanford Site’s Central Plateau . This paleochannel is of particular importance because it will significantly impact flow and contaminant transport from 200 West to 200 East. Its high permeability can both accelerate contaminant transport and lower contaminant concentrations through spreading. Information about the spatial extent and structure of such features is needed to inform subsurface flow and contaminant transport models that support remedy decisions at Hanford.

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Evaluating Remediation Options for a Perched-Water Unit at the Hanford Site - 20378

At the U.S. Department of Energy's Hanford Site, liquid-phase waste was discharged using surface disposal features such as ponds, trenches, and cribs. These practices distributed contaminants in the subsurface, some of which are currently in the vadose zone above the groundwater. At the 200-DV-1 operable unit (OU) at the Hanford Site, a key feature is a perched-water zone. This perched-water zone contains several million liters of water contaminated with high concentrations of uranium, technetium-99 (Tc-99), and nitrate that serves as a continuing source of contamination to the underlying aquifer. Currently, a pumping system is used to remove contaminant mass from the perched-water zone. However, water extraction will become more challenging as the perched unit dewaters. As a result, residual contaminants remaining after pumping is no longer effective needs to be addressed with post-extraction mitigation approaches, appropriate monitoring, and selection of suitable remediation endpoints. Thus, a remedy evaluation needs to include the unique conditions of this perched-water zone. As part of the initial evaluation, a set of technologies have been preliminarily identified as potentially applicable to the perched-water zone, including in situ remediation technologies to sequester uranium and Tc-99 and to degrade nitrate. While there is sufficient information available for direct consideration of some of the reviewed technologies in a feasibility study, five in situ remediation technologies were identified as needing additional information on their effectiveness under the geochemical and contaminant conditions of the perched-water zone. (authors)

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Mixed heavy metal stress induces global iron starvation response

Abstract Multiple heavy metal contamination is an increasingly common global problem. Heavy metals have the potential to disrupt microbially mediated biogeochemical cycling. However, systems-level studies on the effects of combinations of heavy metals on bacteria are lacking. For this study, we focused on the Oak Ridge Reservation (ORR; Oak Ridge, TN, USA) subsurface which is contaminated with several heavy metals and high concentrations of nitrate. Using a native Bacillus cereus isolate that represents a dominant species at this site, we assessed the combined impact of eight metal contaminants, all at site-relevant concentrations, on cell processes through an integrated multi-omics approach that included discovery proteomics, targeted metabolomics, and targeted gene-expression profiling. The combination of eight metals impacted cell physiology in a manner that could not have been predicted from summing phenotypic responses to the individual metals. Exposure to the metal mixture elicited a global iron starvation response not observed during individual metal exposures. This disruption of iron homeostasis resulted in decreased activity of the iron-cofactor-containing nitrate and nitrite reductases, both of which are important in biological nitrate removal at the site. We propose that the combinatorial effects of simultaneous exposure to multiple heavy metals is an underappreciated yet significant form of cell stress in the environment with the potential to disrupt global nutrient cycles and to impede bioremediation efforts at mixed waste sites. Our work underscores the need to shift from single- to multi-metal studies for assessing and predicting the impacts of complex contaminants on microbial systems.

59 BASIC BIOLOGICAL SCIENCES↗

Spectral Induced Polarization-Biogeochemical Relationships for Remediation Amendment Monitoring

Geophysical tools such as electrical resistivity (ER) can indirectly monitor subsurface changes in response to remedial injections. These methods exhibit relatively low spatial resolution compared to sediment core characterization but are advantageous due to the ability to collect measurements non-intrusively over time across large volumes of the subsurface. Moreover, along with confirmatory groundwater or core sampling, geophysical methods can be used during active biogeochemical remedies to monitor short-term contaminant transformations and mobility, as well as part of an overall strategy for long-term monitoring of subsurface contaminated sites. The use of alternating current spectral induced polarization (SIP) provides significantly more information than conventional geophysical methods like direct current ER. SIP allows for monitoring changes in both solution and surface conductivity by separation of real and imaginary conductivity, respectively, as well as surface capacitance. In principle, SIP can measure indicators of remedy progression such as precipitation reactions that sequester contaminants, potentially providing a better indication of amendment delivery and reactivity as compared to conventional ER methods. However, multiple processes and material properties have overlapping (interacting) electrical responses across a range of frequencies. Hence, the purpose of this scoping study was to evaluate if SIP can be used to monitor (a) amendment delivery and (b) precipitation and reactivity of amendments under consideration at Hanford. SIP measurements were collected in fully saturated columns packed with sand and Hanford formation sediments containing (a) amendments that were highly conductive with significant capacitance (zero valent iron – ZVI, sulfur modified iron – SMI) and (b) amendments that exhibited low electrical conductivity with a small capacitance (calcite, apatite, bismuth). The sand was a quartz material with homogenous particle size that exhibited a relatively low surface conductivity. It was used as a control for comparison with the sediments from the Hanford Site, which have a greater surface conductivity because of their complex mineralogy and heterogeneous particle size distribution and may have complex interactions with amendments. The amendment mass fraction was varied to represent the different stages and subsurface locations associated with the delivery of a remedy. The primary objective was to identify the solution and solid surface changes associated with the delivery amendments and their secondary reactions within the subsurface. The figure below summarizes results for the amendments tested through this project. The SIP phase shift or imaginary conductivity change for the high conductivity amendments was more than 10 times that of the low conductivity amendments, highlighting the relative ease of detection of ZVI and SMI independent of the background signal from sand or Hanford sediments. The ZVI phase shift and imaginary conductivity changes occur primarily at high frequency (> 100 Hz) whereas SMI changes were at low frequency (0.01 to 10 Hz). SIP signals of SMI also increased over time and the maximum shifted to lower frequencies. The low conductivity amendments (calcite, abiotic and biotic apatite, bismuth subnitrate) exhibited relatively small phase and imaginary conductivity changes when added to sediments. The changes were above minimum detection limits (0.5 mrad for phase shift, 0.03 µS/cm for imaginary conductivity) for the highest concentration except for the commercial bismuth material. The lowest amendment concentration that can be detected is likely sediment specific, as minerals in sediments (clays, magnetite, Fe-oxides) have some capacitance and, therefore, exhibit a variable phase shift.

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Anaerobic benzene oxidation in Geotalea daltonii involves activation by methylation and is regulated by the transition state regulator AbrB

ABSTRACT Benzene is a widespread groundwater contaminant that persists under anoxic conditions. The aim of this study was to more accurately investigate anaerobic microbial degradation pathways to predict benzene fate and transport. Preliminary genomic analysis of Geotalea daltonii strain FRC-32, isolated from contaminated groundwater, revealed the presence of putative aromatic-degrading genes. G. daltonii was subsequently shown to conserve energy for growth on benzene as the sole electron donor and fumarate or nitrate as the electron acceptor. The hbs gene, encoding for 3-hydroxybenzylsuccinate synthase (Hbs), a homolog of the radical-forming, toluene-activating benzylsuccinate synthase (Bss), was upregulated during benzene oxidation in G. daltonii , while the bss gene was upregulated during toluene oxidation. Addition of benzene to the G. daltonii whole-cell lysate resulted in toluene formation, indicating that methylation of benzene was occurring. Complementation of σ 54 - (deficient) E. coli transformed with the bss operon restored its ability to grow in the presence of toluene, revealing bss to be regulated by σ 54 . Binding sites for σ 70 and the transition state regulator AbrB were identified in the promoter region of the σ 54 -encoding gene rpoN, and binding was confirmed. Induced expression of abrB during benzene and toluene degradation caused G. daltonii cultures to transition to the death phase. Our results suggested that G. daltonii can anaerobically oxidize benzene by methylation, which is regulated by σ 54 and AbrB. Our findings further indicated that the benzene, toluene, and benzoate degradation pathways converge into a single metabolic pathway, representing a uniquely efficient approach to anaerobic aromatic degradation in G. daltonii . IMPORTANCE The contamination of anaerobic subsurface environments including groundwater with toxic aromatic hydrocarbons, specifically benzene, toluene, ethylbenzene, and xylene, has become a global issue. Subsurface groundwater is largely anoxic, and further study is needed to understand the natural attenuation of these compounds. This study elucidated a metabolic pathway utilized by the bacterium Geotalea daltonii capable of anaerobically degrading the recalcitrant molecule benzene using a unique activation mechanism involving methylation. The identification of aromatic-degrading genes and AbrB as a regulator of the anaerobic benzene and toluene degradation pathways provides insights into the mechanisms employed by G. daltonii to modulate metabolic pathways as necessary to thrive in anoxic contaminated groundwater. Our findings contribute to the understanding of novel anaerobic benzene degradation pathways that could potentially be harnessed to develop improved strategies for bioremediation of groundwater contaminants.

Bullows, James E.↗

Ubiquity and Causes of Soil Water Preferential Flow Across 17 Ecoregions

Abstract Preferential flow (PF) in soil causes the rapid transport of water, nutrients, and contaminants into the subsurface, influencing groundwater recharge and streamflow. Data scarcity has hindered the quantification of PF occurrence and the identification of its drivers across diverse ecoregions. We address this gap by analyzing high‐frequency, multi‐depth soil moisture data across 17 ecoregions in the USA, using ∼1,500 sensors at 40 sites. We discovered that PF is widespread, with sites experiencing PF in up to 60% of rainfall events ≥2 mm. Multiple approaches consistently show that PF is more likely to occur with increased peak rainfall intensity, finer textured material, low soil moisture variability, humid climate, and higher net primary productivity. This suggests that PF patterns could shift with projected climate changes, increasing uncertainty in predictions of groundwater recharge, water quality, and streamflow generation. Plain Language Summary Water can bypass part of the soil's matrix through a process called preferential flow (PF). This quick transport of water through the soil brings with it nutrients and contaminants and eventually makes it to groundwater and streams. To ensure ample amounts of good quality groundwater and surface water we need to understand when and where PF occurs. We inferred when PF occurred at 40 different sites across 17 ecoregions in the USA using soil moisture and rainfall data. We found that PF happened at all sites and in up to 60% of rainfall events ≥2 mm. Preferential flow was most likely at sites with high rainfall intensities, high clay content in soils, low variability in soil moisture, and high vegetation productivity. As rainfall intensities are predicted to increase due to climate change and vegetation becomes more productive, PF occurrence becomes more important for predicting groundwater recharge, water quality, and streamflow generation. Key Points Preferential flow (PF) is ubiquitous across the USA and occurs in up to 60% of all rainfall events ≥2 mm Rainfall intensity, soil texture, and antecedent soil moisture emerge as critical in generating PF across diverse ecoregions Two different PF detection approaches show similar relationships between key drivers and occurrence of PF

Li, Bonan↗

Cytochrome Nanowire XRD

Microbial metabolism plays an important role in the global cycling of carbon, nutrients, and metals. Recent discovery of microorganisms sharing energy using direct electrical connections might represent a prominent strategy by which anaerobic microorganisms interact with the diversity of environments. The purpose of the proposed research is to apply these newly developed principles of electron exchange in microbial communities to the study of biogeochemical cycling in climate and subsurface systems. Previous studies revealed that soil bacteria Geobacter sulfurreducens produce conductive pili nanofilaments that facilitate long-range electron transport to extracellular electron acceptors and other cells. This discovery has already transformed our understanding of the function of microbial communities in diverse environments, making basic contributions to microbial ecology and helping to improve practical applications such as increasing current output of microbial fuel cells and enhancing the conversion of organic waste to methane. Microbial electron exchange via pili may also contribute to methane production in terrestrial environments that are major sources of atmospheric methane. However, the mechanism of electron transport through pili is not well understood. Initial studies have suggested that pili exhibit metallic-like conductivity similar to conducting polymer polyaniline. However, these studies were limited to electrical measurements. X-ray diffraction studies have suggested that aromatic amino acids tyrosine and phenylalanine are closely packed in pili. But these studies used homology modeling to predict the pilus assembly and information about the number of monomers in each pilus assembly unit and their organization are still lacking. The central hypothesis of this proposal is aromatics in pili enable intermolecular electron delocalization due to pi-stacking that can give rise to metallic-like conductivity. By analyzing pili structure using infrared scattering-scanning near field optical microscope (IR s-SNOM) and combining with solution NMR, Focused Ion Beam (FIB and computational capabilities, this work will provide comprehensive understanding of the conduction mechanism from a structure-function perspective. The specific aims are: 1) With infrared scattering scanning near field optical microscope (IR s-SNOM), image the organization and density of pilin monomers and pH-induced conformational changes in a pilus filament. 2) With solution NMR, resolve pH-induced structural changes in the pilin monomer. 3) Using Focused Ion Beam (FIB), draw electrodes on single pili to measure their conductivity. 4) With computational modeling using the NWChem, simulate the effect of environment on the electronic properties of pili as a function of pH. The proposed work will gain the nanoscale insight into the structure of the pili, as the basis for understanding interspecies electrical communications. The improved understanding will be harnessed to accelerate bioenergy production and bioremediation using pili as well as for predictive modeling of carbon cycling in diverse environments to reach the central goals of DOE-BER to develop sustainable energy sources, regulate the contaminants in the subsurface and understand the effects of greenhouse gas emissions on biosphere. The proposed studies will provide design principles for engineering of electrical interactions among these communities by manipulating the amino acid composition of pili. Moreover, these studies will identify the forces that maintain the function of these communities in the face of environmental perturbation. Therefore, these studies will help to address the need "to incorporate process understanding of biogeochemical cycling into a scalable hierarchy of predictive capabilities" specified in EMSL's Science Themes.

59 BASIC BIOLOGICAL SCIENCES↗

Physical and Hydraulic Properties of RCRA Borehole Samples from the Hanford Site : Final Report, Fiscal Years 2023-2024

Sediment from 44 core samples collected from Resource Conservation and Recovery Act (RCRA) boreholes drilled in the 200 East and 200 West areas of the Hanford Site were characterized for physical and hydraulic properties (Table S.1). Characterization data included gravimetric water contents and matric potentials, grain-size distributions, saturated hydraulic conductivity, water retention characteristics, and unsaturated hydraulic conductivity. These properties provide site-specific data and parameters that can be used in subsurface flow and contaminant transport models to assess the transport and fate of contaminants in the vadose zone and underlying aquifer systems. The analyzed core samples come from specific areas and depth intervals at the Hanford Site that were targeted for sampling to address data gaps identified by site contractors (Khaleel 2020). X-ray computed tomography (XCT) was used to evaluate the general textural characteristics of the samples and to determine which samples to use for further physical and hydraulic property characterization. Subsequent sample selection was determined by consensus after review of the XCT images by Pacific Northwest National Laboratory, Central Plateau Cleanup Company, and INTERA staff.

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A New Approach to Predict Hydrogeological Parameters Using Shear Waves from the Multichannel Analysis of Surface Waves Method

For near-surface contaminant characterization, the accurate prediction of hydrogeological parameters in anisotropic and heterogeneous environments has been a challenge since the last decades. However, recent advances in near-surface geophysics have facilitated the use of geophysical data for hydrogeological characterization in the last few years. A pseudo 3-D high resolution P-wave shallow seismic reflection survey was performed at the P Reactor Area, Savannah River Site, South Carolina in order to delineate and predict migration pathways of a large contaminant plume including trichloroethylene. This contaminant plume originates from the northwest section of the reactor facility that is located within the Upper Atlantic Coastal Plain. The data were collected with 40 Hz geophones, an accelerated weight-drop as seismic source and 1 m receiver spacing with near- and far-offsets of 0.5 and 119.5 m, respectively. In such areas with near-surface contaminants, a detailed subsurface characterization of the vadose zone hydraulic parameters is very important. Indeed, an inexpensive method of deriving such parameters by the use of seismic reflection surveys is beneficial, and our approach uses the relationship between seismic velocity and hydrogeological parameters together with empirical observations relating porosity to permeability and hydraulic conductivity. Shear wave velocity ( V s ) profiles were estimated from surface wave dispersion analysis of the seismic reflection data and were subsequently used to derive hydraulic parameters such as porosity, permeability, and hydraulic conductivity. Additional geophysical data including core samples, vertical seismic profiling, surface electrical resistivity tomography, natural gamma and electrical resistivity logs allowed for a robust assessment of the validity and geological significance of the estimated V s and hydrogeological models. The results demonstrate the usefulness of this approach for the upper 15 m of shallow unconsolidated sediments even though the survey design parameters were not optimal for surface wave analysis due to the higher than desired frequency geophones.

Engineering↗

Methods for Delivery and Distribution of Amendments for Subsurface Remediation: A Critical Review

The ability to reliably deliver and widely distribute remedial amendments through the subsurface environment is of paramount importance to achieve clean-up objectives for contaminated sediments and groundwater for protection of sensitive environmental habitats and natural resources. A wide range of amendment types, delivery techniques, and subsurface access methods are available. However, the applicability of these approaches is dependent on a multitude of site-specific factors and conditions. In this review, an overview of amendment types (i.e., liquid, gas, and solids) and access/distribution methods is provided, along with discussion of the maturity level (low, medium, or high), advantages, and limitations that relate to the potential effectiveness of each approach in the context of site-specific factors (subsurface geology, geochemistry, contaminant properties, etc.). Each amendment type and delivery approach are further evaluated for applicability to the following subsurface target zones: saturated, unsaturated, and perched water, with specific focus on high and low permeability variants of each zone. The review highlights a critical need for field-tested approaches targeting unsaturated and perched water zones, as well as low-permeability regions within all subsurface regions. The intent of this review is to provide critical information and insight into how amendments can be delivered, emplaced, and/or distributed effectively in the subsurface environment to effectively manage subsurface contamination.

Muller, Katherine A.↗

Evaluation of Zero-Net-Rate Pumping Tests

Accurately estimating the distribution of aquifer properties is key to understanding contaminant movement in the subsurface. The distribution of aquifer properties is typically addressed using slug or constant-rate well tests, and the pros and cons of these tests are well known. Slug tests are appealing because they avoid removing contaminated water, but their results are affected by well skin and the small volume of displaced water limits the volume of aquifer that can be evaluated. Constant-rate well tests have the disadvantage of requiring disposal of potentially contaminated water, but they can generate properties that are more representative than slug tests, and they can be used to estimate well efficiency and storativity, which are difficult to characterize using slug tests. Periodic pumping tests are appealing because they have many of the advantages and few of the disadvantages of slug and constant-rate well tests. Periodic pumping tests involve cycling the pumping rate with a regular period and measuring the resulting response in monitoring wells. Some of these tests involve imposing a periodic rate on a constant mean rate. However, other tests involve moving water out and back into the well at rates that are balanced so the net rate after each period is zero. Some zero-net-rate (ZNR) well tests use rates that follow a sinusoidal pattern, whereas others use a square wave pattern that switches between a constant rate of pumping and a constant rate of injection to achieve a zero-net rate. ZNR well tests appear to be a useful compromise between slug and constant rate tests, but methods for conducting and analyzing the results from these tests have received limited evaluation. Periodic pumping tests are typically evaluated through recorded pressure responses to a disturbance source. Recent work has demonstrated that the strain field in the vadose zone shows a response to disturbances in the underlying aquifer. Various instrument designs are available that can record vertical and horizontal strain to very precise resolutions (10-9 ε). Measuring the strain in the vadose zone can present lower costs than measuring pressure in a monitoring well, so using strain could improve the resolution of ZNR tests, as well as make these tests potentially cheaper. A ZNR periodic pumping system was constructed and used to perform tests in the Clemson, South Carolina area. The system was designed to pump and inject with a periodic square-wave, so pumping occurs at a constant rate for half the period and is followed by injection at the same rate for half the period resulting in no net gain or loss of water from the aquifer. The system is designed to generate flow rates from 1 to 3.5 gallons per minute (gpm) with a capacity of 875-gallon per half period. Pressure and strain monitoring points are located in the vicinity of the pumping well. A series of 10 ZNR periodic pumping tests were conducted at the field site, with periods ranging from 2 to 540 minutes. Pressure data were collected and recorded in four monitoring wells in various locations around the pumping well. In addition, vertical and horizontal strain and tilt data were recorded in various locations around the pumping well. Traditional aquifer tests, including slug tests and constant-rate pumping tests were conducted at the field site to provide a baseline of aquifer parameter estimates that are compared the results of ZNR tests. Pressure data measured at monitoring wells during ZNR tests were analyzed utilizing an analytical solution (Streltsova, 1988) that assumes a confined aquifer and estimates hydraulic diffusivity and transmissivity using the time lag and amplitude of the pressure signal. The storativity can be separated out from the hydraulic diffusivity using the transmissivity estimate. The time-lag and amplitude of the pressure signals were estimated using a Fourier transform. The time-lag of the primary period of the pressure increases as a linear function of distance from the pumping well, and it increases as the square root of the period of the ZNR test over a range of periods spanning two orders of magnitudes. The first few harmonics follow similar trends, but the higher frequency harmonics diverge from this trend. Strain and tilt data from various instruments in the vadose and saturated zones are periodic during ZNR tests. The time lags of the strain components increase roughly linearly with distance from the well. Many of the time lags of the strain data from the vadose zone are similar to the time lags observed in the pressure data from a similar distance and pumping period. Theoretical experiments were performed to understand how pressure and strain responds to ZNR periodic pumping. The time-lags of the simulated pressure responses match the field data trends. The results were used to validate the Streltsova (1988) solution for periodic pumping to estimate hydraulic diffusivity. Hydraulic diffusivity was estimated to be 1.8 x 10-2 m2s-1 < Dh < 9.0 x 10-2 m2s-1 using pressure data from all the wells during ZNR tests. Transmissivity was estimated to be 0.8 x 10-4 m2s-1 < T < 4.3 x 10-4 m2s-1. Assuming Storativity = T/Dh gives 1.1 x 10-3 < S < 19 x10-3. Transmissivity is used to estimate the hydraulic conductivity, K, by dividing by the assumed aquifer thickness. Two constant-rate pumping tests were conducted and analyzed using two conceptual models: The Hantush (1961) solution was used to analyze data assuming confined conditions and the Neuman (1974) solution was used to analyze data assuming unconfined conditions. The Hantush (1961) solution estimated transmissivity to be 1.6 x 10-4 m2s-1 < T < 1.8 x 10-4 m2s-1 when using data from all the wells. Storativity was estimated to be 4.4 x 10-3 < S < 8.2 x 10-3. Assuming Dh = T/S gives 0.22 x 10-2 m2s-1 < Dh < 3.6 x 10-2 m2s-1. The Neuman (1974) solution estimated transmissivity to be 0.80 x 10-4 m2s-1 < T < 0.84 x 10-4 m2s-1. Total storativity (S + Sy) was estimated to be 22 x 10-3 < S < 110 x 10-3. Storativity excluding the Sy term was estimated to be 2.2 x 10-3 < S < 2.5 x 10-3. Assuming Dh = T/S gives 0.073 x 10-2 m2s-1 < S < 0.36 x 10-2 m2s-1. Two slug tests were performed on the pumping well, PW-2. The Bouwer and Rice (1976) solution for slug tests was used to analyze the data. This solution works for both confined and unconfined conditions, so both conceptual models were covered through the analysis. Hydraulic conductivity was estimated to be 1.95 x 10-6 ms-1 < K < 2.49 x 10-6 ms-1. Statistical comparison show generally no significant difference in the estimates of Dh, K, or S made using ZNR and conventional pumping tests.. However, the total storage estimated by the Neuman (1974) solution for unconfined settings is larger than that estimate using the Streltsove analysis applied to the ZNR tests. This is likely because the Neuman solution considers delayed yield from storage that the water table, whereas the Streltsova (1988) solution assumes confined conditions. The analysis also indicates that there is a statistically significant difference between parameters estimated with conventional slug tests and those measured with either constant-rate pumping tests or ZNR tests. Hydraulic diffusivity is estimated from the time-lag and the distance from the well. The time-lags of the strain data from the vadose zone are similar to the lags of the pressure data from a similar distance. This indicates that hydraulic diffusivities estimated from the strain data measured in the vadose zone would be similar to the estimates from the pressure data measured in the aquifer. There appear to be sign reversals in some of the strain data that were corrected to estimate the time lag. The dissolved oxygen (CO) concentration was measured during several ZNR tests to evaluate the feasibility of using the procedure to increase contaminant degradation kinetics that are related to DO. The results indicate that DO can be increased during the cycling of ZNR tests in some cases.

Smith-Jones, Austin↗

Unclassified Source Term and Radionuclide Data for the Groundwater Flow and Contaminant Transport Model for Corrective Action Units 101 and 102: Central and Western Pahute Mesa, Nye County, Nevada, Revision 1

This report documents the evaluation of information and data available on the unclassified source term and radionuclide (RN) contamination for Central and Western Pahute Mesa (PM): Corrective Action Units (CAUs) 101 and 102. The Central and Western PM CAUs constitute two areas of the Nevada National Security Site (NNSS) used for underground nuclear testing (Figure 1-1). Eighty-five underground nuclear tests were conducted at the PM CAUs between 1965 and 1992 (NNSA/NFO, 2015b). Underground nuclear tests deposit radioactive elements in the subsurface, resulting in groundwater contamination in the vicinity of the underground test locations. At the PM CAUs, the testing resulted in more than 2.68 × 10 7 curies (Ci) of radioactivity (decay-corrected to September 30, 2012) remaining underground (Finnegan et al., 2016). Of the 85 underground nuclear tests conducted at the PM CAUs, three were shallow tests detonated within 200 meters (m) of the surface and referred to as the “near-surface tests”; the remaining 82 were detonated deeper than 200 m below ground surface (bgs) and are referred to as the “deep underground tests” in this document.

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Reducing Cost of Chlorinated Volatile Organic Compound Remediation by Transitioning from Active to Passive Soil Vapor Extraction - 20157

Areas of high chlorinated volatile organic compound (cVOC) contamination at the Savannah River Site (SRS) have been undergoing remediation via soil vapor extraction, sometimes coupled with thermal treatments to enhance extraction rates. These active systems are effective in removing large amounts of contaminant mass from the subsurface and mitigating the impacts to groundwater. However, as extraction rates decline, costs must be evaluated with respect to the benefit of continued active operation. A decision framework for identifying conditions when a transition to a more passive remediation is appropriate has been developed with state and federal regulatory agencies. Two remediation areas have recently been transitioned from active soil vapor extraction (ASVE) to passive soil vapor extraction (PSVE) at the SRS. Performance evaluation goals including plume stabilization, overall mass removal trends, environmental sustainability and costs were considered in transitioning from active remediation to passive technologies at both sites. At the Dynamic Underground Stripping (DUS) project at the M-Area Settling Basin, ASVE was combined with steam injection to extract cVOCs during active operations. Steam injection occurred from September 2005 to September 2009. DUS utilized 63 steam injection wells, 34 active vapor extraction wells, and 3 active soil vapor extraction units (SVEUs). Two active SVEUs had 60 horsepower blowers; the third had a 25-horsepower blower. Mass removal was closely tracked during DUS operations; over 181,437 kilograms (400,000 pounds) of cVOCs were removed while active steam injection occurred. After steaming was stopped, ASVE continued. The 34 active wells were evaluated in 2012. The ASVE wells were grouped into categories of high, medium, and low extraction rates. High producing wells remained connected to a single active SVEU. Low producing wells were abandoned, and the medium producing wells were transitioned to PSVE (Microblowers{sup TM}). Microblowers{sup TM} utilize a dedicated blower per well and are solar powered. This passive technology provides energy, maintenance, and operation costs savings while still providing an efficient reduction in cVOC migration to groundwater. In 2018, the remaining ASVE wells were evaluated again. The purpose of this testing was to identify which wells removed the most mass. An optimal well configuration was determined. The criteria to discontinue ASVE was removal of less than 18 kilograms (40 pounds) per week of cVOCs. After 3 months of shutdown (rebound conditions), 2.7 kilograms (5.9 pounds) of cVOCs per week were being removed. Data from the rebound test justified ending ASVE and transitioning wells with higher extraction rates to PSVE. Wells that had depleted the cVOC mass within their zone of influence were abandoned. Performance data from existing PSVE wells justified ending PSVE at wells with depleted extraction rates. Currently the system has 16 PSVE wells operating. Another ASVE system was being used to treat cVOC contaminated soil at the A-Area Miscellaneous Rubble Pile (AMRP) at SRS. System operation began in 2004, with 7 ASVE wells connected to a 60- horsepower blower. Mass removal rates and contaminant concentrations remained consistently low over the ASVE lifespan at AMRP. This indicated that mass removal was diffusion limited. With this data, the 7 ASVE wells were transitioned to PSVE in 2017. Twelve pressure monitoring points were also transitioned to PSVE wells. AMRP currently has 19 PSVE wells operating. Both transitions from active to passive remediation had concurrence from the United States Environmental Protection Agency and the South Carolina Department of Health and Environmental Control. These transitions ensure that only the necessary amount of energy is being exerted to remediate the environment. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Hyperbolic Reformulation Approach to Enable Efficient Simulation of Groundwater Flow and Reactive Transport

We apply Cattaneo's relaxation approach to the one-dimensional coupled Boussinesq groundwater flow and advection-diffusion-reaction equations, commonly used in engineering applications to simulate contaminant transport in the subsurface. The diffusion-type governing equations are reformulated as a hyperbolic system, augmented by an equation that can be interpreted as a momentum balance. The hyperbolization enables an efficient unified computation of the primary variable and its gradients, for example piezometric head and unit discharge in the Boussinesq equation. An augmented Roe scheme is used to solve the hyperbolic system. The hyperbolized system of equations is studied in a set of steady state and transient test cases with idealized geometry. These test cases confirm the equivalence of the hyperbolic system to its original formulation. The larger time step size of the hyperbolic equation is verified theoretically by means of a stability analysis and numerically in the test cases. Finally, a reach-scale application of flow and transport across a river meander is considered. This application case shows that the performance of the hyperbolic relaxation approach holds for more realistic groundwater flow and transport problems, relevant to water resources management.

54 ENVIRONMENTAL SCIENCES↗

ORT: a workflow linking genome-scale metabolic models with reactive transport codes

Abstract Motivation Nutrient and contaminant behavior in the subsurface are governed by multiple coupled hydrobiogeochemical processes which occur across different temporal and spatial scales. Accurate description of macroscopic system behavior requires accounting for the effects of microscopic and especially microbial processes. Microbial processes mediate precipitation and dissolution and change aqueous geochemistry, all of which impacts macroscopic system behavior. As ‘omics data describing microbial processes is increasingly affordable and available, novel methods for using this data quickly and effectively for improved ecosystem models are needed. Results We propose a workflow (‘Omics to Reactive Transport—ORT) for utilizing metagenomic and environmental data to describe the effect of microbiological processes in macroscopic reactive transport models. This workflow utilizes and couples two open-source software packages: KBase (a software platform for systems biology) and PFLOTRAN (a reactive transport modeling code). We describe the architecture of ORT and demonstrate an implementation using metagenomic and geochemical data from a river system. Our demonstration uses microbiological drivers of nitrification and denitrification to predict nitrogen cycling patterns which agree with those provided with generalized stoichiometries. While our example uses data from a single measurement, our workflow can be applied to spatiotemporal metagenomic datasets to allow for iterative coupling between KBase and PFLOTRAN. Availability and implementation Interactive models available at https://pflotranmodeling.paf.subsurfaceinsights.com/pflotran-simple-model/. Microbiological data available at NCBI via BioProject ID PRJNA576070. ORT Python code available at https://github.com/subsurfaceinsights/ort-kbase-to-pflotran. KBase narrative available at https://narrative.kbase.us/narrative/71260 or static narrative (no login required) at https://kbase.us/n/71260/258. Supplementary information Supplementary data are available at Bioinformatics online.

54 ENVIRONMENTAL SCIENCES↗

Investigation of the distribution of laser-induced damage precursors in etched grating sidewalls fabricated using inductively coupled plasma reactive-ion etching

Inductively coupled plasma reactive-ion etching for grating fabrication is explored with emphasis on the type and distribution of process-induced defects that can act as precursors to laser-induced damage initiation. To provide flexibility in the ability to perform a variety of material characterization methods, grating-like features with large pitch were fabricated in silica monolayers. The results indicate that the etch process introduces surface fluorine and subsurface carbon-containing contamination, which reduces the laser-induced damage threshold. The local relative concentrations of the laser-damage precursors introduced during the etch step of the manufacturing process were investigated using angle-resolved damage testing, taking advantage of the shift of the location of the peak electric-field intensity incident on the grating sidewall. The results suggest an increased level of etch-related defects near the base of the sidewall, with directly fluorinated silicon identified as the primary defect.

Dent, R. [Univ. of Rochester, NY (United States). ↗