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At least 307 records · Page 17

Geophysical signatures of soil AFFF contamination from spectral induced polarization and low field nuclear magnetic resonance methods

Few field methods are available for characterizing source zones contaminated with aqueous film forming foam (AFFF). Non-invasive geophysical characterization of AFFF source zone contamination in situ could assist with the delineation and characterization of these sites, allowing for more informed sampling regimes aimed at quantifying subsurface poly- and perfluoroalkyl substances (PFAS) contamination. In this study, we present initial results from the investigation of the sensitivity of two existing surface and borehole-deployable geophysical technologies, spectral induced polarization (SIP), and low field nuclear magnetic resonance (NMR), to soils impacted with AFFF. To investigate the sensitivity of these methods to AFFF-impacted soil, bench-scale column experiments were conducted on samples consisting of natural and synthetic soils and groundwater. While our findings do not show strong evidence of NMR sensitivity to soil PFAS contamination, we do find evidence that SIP has sufficient sensitivity to detect PFAS sorption to soils. This finding is based on evidence that AFFF constituents associated with the pore surface produce a measurable polarization response in both freshly contaminated synthetic soils and in soils historically impacted with AFFF.

54 ENVIRONMENTAL SCIENCES↗

Quantum chemically calculated Abraham parameters for quantifying and predicting polymer hydrophobicity

The leakage and accumulation of plastic in the environment is a significant and growing problem with numerous detrimental impacts and has led to a push toward the design and development of more environmentally benign materials. To this end, we have developed a quantum chemistry-based model for predicting the mobility of polymer materials from molecular structure. Hydrophobicity is used as a surrogate for mobility given that hydrophobic interactions drive much of the partitioning of contaminants in and out of various environmentally relevant compartments. To model polymer hydrophobicity, we adjusted a previously developed Quantum Chemically Calculated Abraham Parameter model to calculate Abraham parameters of small molecules from molecular structure information. The resulting model predicted the octanol-water partition coefficient (K OW ) of polymer repeating units with a root mean square error (RMSE) of 0.48 (log scale). Additionally, the hydrophobicity of high molecular weight polymer materials was captured through solubility parameters and Nile red staining experiments from the literature and predicted with RMSEs of 1.21 (J/cc) 0.5 and 3.42 nm, respectively. Finally, to test the environmental applicability of the model, the relative adsorption capacity of three polymers was predicted and used to unify sorption isotherms across multiple sorbates and polymer sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Boundary-layer transition effects on airplane stability and control

Surface contamination of laminar-flow airfoils can significantly modify the location of transition from laminar-to-turbulent boundary-layer flow. The contamination can be the result of insect debris, environmental effects such as ice crystals and moisture due to mist or rain, surface damage, or other contamination adhering to the surface. Location and mode of transition have a dominant effect on the lift-and-drag characteristics of a lifting surface. The influences of laminar boundary-layer flow behavior on airplane stability and control are examined through theoretical results and experimental (wind-tunnel and free-flight) data. For certain airfoils with a relatively steep pressure recovery it is shown that loss of laminar flow near the leading edge can result in premature separation of the turbulent boundary layer and, consequently, in loss of lift and control effectiveness. Aerodynamic modifications which minimize boundary-layer transition effects on airplane stability and control are also discussed.

Van Dam, C. P.↗

Uranium(VI) attenuation in a carbonate-bearing oxic alluvial aquifer

Uranium minerals are commonly found in soils and sediment across the United States at an average concentration of 2–4 mg/kg. Uranium occurs in the environment primarily in two forms, the oxidized, mostly soluble uranium(VI) form, or the reduced, sparingly soluble reduced uranium(IV) form. Here we describe subsurface geochemical conditions that result in low uranium concentrations in an alluvial aquifer with naturally occurring uranium in soils and sediments in the presence of complexing ligands under oxidizing conditions. Groundwater was saturated with respect to calcite and contained calcium (78–90 mg/L) with elevated levels of carbonate alkalinity (291–416 mg/L as HCO 3 -). X-ray adsorption near edge structure (XANES) spectroscopy identified that sediment-associated uranium was oxidized as a uranium(VI) form (85%). Calcite was the predominant mineral by mass in the ultrafine fraction in uranium-bearing sediments (>16 mg/kg). Furthermore, groundwater geochemical modeling indicated calcite and/or a calcium-uranyl-carbonate mineral such as liebigite in equilibrium with groundwater. The δ 13 C (0.57‰ ± 0.15‰) was indicative of abiotic carbonate deposition. Thus, solid-phase uranium(VI) associated with carbonate is likely maintaining uranium(VI) groundwater levels below the maximum contaminant level (MCL; 30 µg/L), presenting a deposition mechanism for uranium attenuation rather than solely a means of mobilization.

54 ENVIRONMENTAL SCIENCES↗

The Present Habitability Potential of Gale Crater: What We Have Learned So Far From Mars Science Laboratory

The Mars Science Laboratory mission has comprehensively interrogated the surface environment of Mars as it explores Gale Crater. Both chemical and physical attributes of the present environment have been measured over the course of the mission, enabling us to compare the present state of the martian surface with the environmental requirements of prokaryotic microbes. While this approach does not exclude the possibility of martian life that may have evolved to adapt to the present conditions, it is advantageous in that it allows us to evaluate environmental requirements of known life and also provide insight into the likelihood of forward contamination by Earth organisms with the comparison of their environmental requirements with the measured attributes of the environment at Gale Crater. We have already modeled a paleoenvironment with high habitability potential (HP) based upon chemistry, mineralogy and other geological evidence such as sedimentary structures and larger scale geomorphology [1]. In this report, we turn our attention to the present HP of the Yellowknife Bay area, including the importance of the physical environmental metrics such as atmospheric pressure, air and ground temperature, ionizing radiation, wind speed and direction, slope, etc.

Conrad, P. G.↗

Rapid Electrochemical Detection and Identification of Microbiological and Chemical Contaminants for Manned Spaceflight Project

Microbial control in the spacecraft environment is a daunting task, especially in the presence of human crew members. Currently, assessing the potential crew health risk associated with a microbial contamination event requires return of representative environmental samples that are analyzed in a ground-based laboratory. It is therefore not currently possible to quickly identify microbes during spaceflight. This project addresses the unmet need for spaceflight-compatible microbial identification technology. The electrochemical detection and identification platform is expected to provide a sensitive, specific, and rapid sample-to-answer capability for in-flight microbial monitoring that can distinguish between related microorganisms (pathogens and non-pathogens) as well as chemical contaminants. This will dramatically enhance our ability to monitor the spacecraft environment and the health risk to the crew. Further, the project is expected to eliminate the need for sample return while significantly reducing crew time required for detection of multiple targets. Initial work will focus on the optimization of bacterial detection and identification. The platform is designed to release nucleic acids (DNA and RNA) from microorganisms without the use of harmful chemicals. Bacterial DNA or RNA is captured by bacteria-specific probe molecules that are bound to a microelectrode, and that capture event can generate a small change in the electrical current (Lam, et al. 2012. Anal. Chem. 84(1): 21-5.). This current is measured, and a determination is made whether a given microbe is present in the sample analyzed. Chemical detection can be accomplished by directly applying a sample to the microelectrode and measuring the resulting current change. This rapid microbial and chemical detection device is designed to be a low-cost, low-power platform anticipated to be operated independently of an external power source, characteristics optimal for manned spaceflight and areas where power and computing resources are scarce.

Pierson, Duane↗

Environmental monitors in the Midcourse Space Experiments (MSX)

The Midcourse Space Experiment (MSX) is an SDIO sponsored space based sensor experiment with a full complement of optical sensors. Because of the possible deleterious effect of both molecular and particulate contamination on these sensors, a suite of environmental monitoring instruments are also being flown with the spacecraft. These instruments are the Total Pressure Sensor based on the cold-cathode gauge, a quadrupole mass spectrometer, a Bennett-type ion mass spectrometer, a cryogenic quartz crystal microbalance (QCM), four temperature-controlled QCM's, and a Xenon and Krypton Flash Lamp Experiment. These instruments have been fully space-qualified, are compact and low cost, and are possible candidate sensors for near-term planetary and atmospheric monitoring. The philosophy adopted during design and fabrication, calibration and ground testing, and modeling will be discussed .

Uy, O. M.↗

Metal–Organic Frameworks for Per- and Polyfluoroalkyl Substances Treatment in Contaminated Water

Per- and polyfluoroalkyl substances (PFAS) are synthetic pollutants known for their chemical stability, environmental persistence, and toxicological risks. Their widespread use has led to extensive contamination, particularly in aquatic systems. Conventional treatment methods often face challenges such as high energy consumption and the production of secondary pollutants. Metal− organic frameworks (MOFs), with their high surface areas and tunable structures, have emerged as promising materials for PFAS remediation. This review summarizes recent progress in MOF-based PFAS adsorption and degradation, highlighting key frameworks such as MIL, UiO, and ZIF. Mechanistic insights into adsorption behavior and regeneration capabilities are discussed, along with the catalytic performance of MOF composites and postmodified systems in degradation pathways. The review concludes with design strategies for next-generation MOF materials aimed at efficient, sustainable PFAS removal under realistic conditions.

Adsorption↗

Ecosystems and Networks Integrated with Genes and Molecular Assemblies (ENIGMA): Molecular and Computational Technologies for Environmental Microbiology (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 Reservation (ORR). 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 primary goal of this subcontract was to develop experimental and computational tools to advance our understanding of microbial adaptation and community assembly in contaminated environments, with specific efforts in high-throughput genomic methods, microbial ecology tools, and studies of heavy metal contamination impacts.

54 ENVIRONMENTAL SCIENCES↗

Evaluating the feasibility of LA-ICP-TOF-MS for the analysis of environmental particle collections

Laser ablation-inductively coupled plasma-time-of-flight-mass spectrometry (LA-ICP-TOF-MS) was employed to rapidly analyze environmental particle samples collected using aerosol contaminate extractors (ACE). The ACE particle collectors were placed at various distances (0.5, 1.3, and 4.5 km) from a source that released Ru-bearing particles. Samples for measurement were then generated (as sub-samples) from the ACE collection plates via particle “lift off” with gunshot residue (GSR) tabs. The LA-ICP-TOF-MS method was employed such that 10+ samples could be analyzed in a single unattended analytical session. A 3 × 1 mm area of individual GSR tab samples were analyzed in less than 30 minutes. This provided spatially resolved elemental and isotopic measurements of the particulate content and confirmed the presence of Ru-bearing particles within the complex background environmental particle loading. As anticipated, measurements showed collectors closest to the source had the highest concentration of the released Ru-bearing particles, while all collectors, regardless of distance, contained similar levels of background particles (e.g., Fe and Sr). Sequential scanning electron microscopy – automated particle analysis (SEM-APA) and LA-ICP-TOF-MS analysis was employed for method validation and a demonstration of the multi-modal approach. The same 2-dimensional region was analyzed by both methods and the particles identified via SEM-APA were also detected using LA-ICP-TOF-MS, with 100% accuracy. Overall, LA-ICP-TOF-MS demonstrated its utility for rapid elemental and isotopic particle analysis from environmental air samples.

Manard, Benjamin T. [Oak Ridge National Laboratory↗

Status of the ISS Trace Contaminant Control System

A habitable atmosphere is a fundamental requirement for human spaceflight. To meet such a requirement, the cabin atmosphere must be constantly scrubbed to maintain human life and system functionality. The primary system for atmospheric scrubbing of the US on-orbit segment (USOS) of the International Space Station (ISS) is the Trace Contaminant Control System (TCCS). As part of the Environmental Control and Life Support Systems (ECLSS) atmosphere revitalization rack in the US Lab, the TCCS operates continuously, scrubbing trace contaminants generated primarily by two sources: the metabolic offgassing of crew members and the offgassing of equipment in the ISS. It has been online for approximately 95% since activated in February 2001. The TCCS is comprised of a charcoal bed, a catalytic oxidizer, and a lithium hydroxide post-sorbent bed, all of which are designed to be replaced onorbit when necessary. In 2006, all three beds were replaced following an observed increase in the system resistance that occurred over a period several months. The beds were returned to ground and subjected to a test, teardown and evaluation to investigate the root cause(s) of the decrease in flow rate through the system. In addition, various chemical and physical analyses of the bed materials were performed to determine contaminant loading and any changes in performance. This paper will mainly focus on the results of these analyses and how this correlates with what has been observed from archival sampling and onorbit events. This may provide insight into the future performance of the TCCS and rate of change for orbital replacement units in the TCCS.

Macatangay, Ariel V.↗

Overview of the International Space Station System Level Trace Contaminant Injection Test

Trace contaminant control onboard the International Space Station will be accomplished not only by the Trace Contaminant Control Subassembly but also by other Environmental Control and Life Support System subassemblies. These additional removal routes include absorption by humidity condensate in the Temperature and Humidity Control Condensing Heat Exchanger and adsorption by the Carbon Dioxide Removal Assembly. The Trace Contaminant Injection Test, which was performed at NASA's Marshall Space Flight Center, investigated the system-level removal of trace contaminants by the International Space Station Atmosphere Revitalization, and Temperature/Humidity Control Subsystems, (November-December 1997). It is a follow-on to the Integrated Atmosphere Revitalization Test conducted in 1996. An estimate for the magnitude of the assisting role provided by the Carbon Dioxide Removal Assembly and the Temperature and Humidity Control unit was obtained. In addition, data on the purity of Carbon Dioxide Removal Assembly carbon dioxide product were obtained to support Environmental Control and Life Support System Air Revitalization Subsystem loop closure.

Tatara, James D.↗

The Shuttle Environment Workshop, executive summary and workshop procedures

One of the main experimental monitors used to determine the environment in the payload bay was the Induced Environment Contamination Monitor. This package of instruments has made environmental measurements during STS flights with a high degree of success. This has shown that the shuttle environment is relatively free of contaminants, except for special instances of increased abundance of methane, water vapor and particulates. Results of these measurements are rapidly becoming more available. In establishing the Shuttle Environment Workshop, the findings were shared with scientific experimenters, users and other individuals who need to know what the Shuttle is like and what experimenters may expect in the payload bay. The Workshop was centered around results obtained from the environmental measurements made on the Shuttle. The program agenda for the workshop is given. The procedures and flow of communications for the workshop are indicated.

Lehmann, J.↗

Assessing Cyanobacterial Frequency and Abundance at Surface Waters Near Drinking Water Intakes Across the United States

This study presents the first large-scale assessment of cyanobacterial frequency and abundance of surface water near drinking water intakes across the United States. Public water systems serve drinking water to nearly 90% of the United States population. Cyanobacteria and their toxins may degrade the quality of finished drinking water and can lead to negative health consequences. Satellite imagery can serve as a cost-effective and consistent monitoring technique for surface cyanobacterial blooms in source waters and can provide drinking water treatment operators information for managing their systems. This study uses satellite imagery from the European Space Agency’s Ocean and Land Colour Instrument (OLCI) spanning June 2016 through April 2020. At 300-m spatial resolution, OLCI imagery can be used to monitor cyanobacteria in 685 drinking water sources across 285 lakes in 44 states, referred to here as resolvable drinking water sources. First, a subset of satellite data was compared to a subset of responses (n = 84) submitted as part of the U.S. Environmental Protection Agency’s fourth Unregulated Contaminant Monitoring Rule (UCMR 4). These UCMR 4 qualitative responses included visual observations of algal bloom presence and absence near drinking water intakes from March 2018 through November 2019. Overall agreement between satellite imagery and UCMR 4 qualitative responses was 94% with a Kappa coefficient of 0.70. Next, temporal frequency of cyanobacterial blooms at all resolvable drinking water sources was assessed. In 2019, bloom frequency averaged 2% and peaked at 100%, where 100% indicated a bloom was always present at the source waters when satellite imagery was available. Monthly cyanobacterial abundances were used to assess short-term trends across all resolvable drinking water sources and effect size was computed to provide insight on the number of years of data that must be obtained to increase confidence in an observed change. Generally, 2016-2020 was an insufficient time period for confidently observing changes at these source waters; on average, a decade of satellite imagery would be required for observed environmental trends to outweigh variability in the data. However, five source waters did demonstrate a sustained short-term trend, with one increasing in cyanobacterial abundance from June 2016 to April 2020 and four decreasing.

remote sensing↗

Anion-exchanged and quaternary ammonium functionalized MIL-101-Cr metal-organic framework (MOF) for ReO 4 – /TcO 4 – sequestration from groundwater

There are few effective technologies for the sequestration of highly water-soluble pertechnetate (TcO 4 – ) from contaminated water despite the urgency of environmental and public health concerns. Here, anion exchanged and cetyltrimethylammonium bromide (CTAB) functionalized MIL-101-Cr-NO 3 were investigated for perrhenate (ReO 4 – ), a surrogate of TcO 4 – , sequestration from artificial groundwater. Cl – , I – , and CF 3 SO 3 – exchanged MIL-101-Cr proved more effective at ReO 4 – removal than the parent MIL-101-Cr-F. Compared to the parent framework, CTAB functionalized MIL-101-Cr-NO 3 increased ReO 4 – removal capacity from 39 to 139 mg/g, improved the reaction kinetics from ~30 to <10 min to reach full adsorption capacity and the selectivity for ReO 4 – over competing NO 3 – , CO 3 2– , SO 4 2– , and Cl – . Spectroscopic data indicated that the chemical speciation of Re in the exchanged MIL-101-Cr remained ReO 4 – , indicating synergistic sequestration through both anion exchange and non-ion exchange binding with the positively charged ligand of CTAB. These studies foreshadow potential applications of MOFs for the remediation of 99 TcO 4 – from contaminated environments.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Influence of Uranium Concentration and pH on U-Phosphate Biomineralization by Caulobacter OR37

Uranium contamination of soils and groundwater in the United States represents a significant health risk and will require multiple remediation approaches. Microbial phosphatase activity coupled to the addition of an organic P source has recently been studied as a remediation strategy that provides an extended release of inorganic P (Pi) into U-contaminated sites, resulting in the precipitation of meta-autunite minerals. Previous laboratory- and field-based biomineralization studies have investigated environments with relatively high U concentrations (>20 μM). However, most contaminated sites have much lower U concentrations (<2 μM). The Environmental Protection Agency (EPA) limit for U in drinking water is 0.126 μM. Reaching this regulatory limit becomes challenging as U concentrations approach autunite solubility. Furthermore, we studied the precipitation of U(VI)-phosphate minerals by an environmental isolate of Caulobacter sp. (strain OR37) from an Oak Ridge, Tennessee, U-contaminated site. Abiotic U(VI) solubility experiments reveal that U(VI)-phosphate minerals do not form in the presence of excess Pi (500 μM) when U(VI) concentrations are <1 μM and pH is <5. When OR37 cells are reacted under the same conditions with Pi or glycerol-2-phosphate, U(VI)-phosphate mineral formation was observed, along with the formation of intracellular polyphosphate granules. These results show that bacteria provide supersaturated microenvironments needed for U(VI)-phosphate mineralization while hydrolyzing organic P sources. This provides a pathway to lower U concentrations to below EPA limits for drinking water.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

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↗