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At least 307 records · Page 17

Oxygen availability is a major factor in determining the composition of microbial communities involved in methane oxidation

We have previously observed that methane supplied to lake sediment microbial communities as a substrate not only causes a response by bona fide methanotrophic bacteria, but also by non-methane-oxidizing bacteria, especially by members of the family Methylophilaceae. This result suggested that methane oxidation in this environment likely involves communities composed of different functional guilds, rather than a single type of microbe. To obtain further support for this concept and to obtain further insights into the factors that may define such partnerships, we carried out microcosm incubations with sediment samples from Lake Washington at five different oxygen tensions, while methane was supplied at the same concentration in each. Community composition was determined through 16S rRNA gene amplicon sequencing after 10 and 16 weeks of incubation. We demonstrate that, in support of our prior observations, the methane-consuming communities were represented by two major types: the methanotrophs of the family Methylococcaceae and by non-methanotrophic methylotrophs of the family Methylophilaceae. However, different species persisted under different oxygen tensions. At high initial oxygen tensions (150 to 225 µM) the major players were, respectively, species of the genera Methylosarcina and Methylophilus, while at low initial oxygen tensions (15 to 75 µM) the major players were Methylobacter and Methylotenera. These data suggest that oxygen availability is at least one major factor determining specific partnerships in methane oxidation. The data also suggest that speciation within Methylococcaceae and Methylophilaceae may be driven by niche adaptation tailored toward specific placements within the oxygen gradient.

54 ENVIRONMENTAL SCIENCES↗

Spatial Heterogeneity in Human Activities Favors the Persistence of Wolves in Agroecosystems

As human populations expand, there is increasing demand and pressure for land. Under this scenario, behavioural flexibility and adaptation become important processes leading to the persistence of large carnivores in human-dominated landscapes such as agroecosystems. A growing interest has recently emerged on the outcome of the coexistence between wolves and humans in these systems. It has been suggested that spatial heterogeneity in human activities would be a major environmental factor modulating vulnerability and persistence of this contentious species in agroecosystems. Here, we combined information from 35 den sites detected between 2011 and 2012 in agroecosystems of western Iran (Hamedan province), a set of environmental variables measured at landscape and fine spatial scales, and generalized linear models to identify patterns of den site selection by wolves in a highly-modified agroecosystem. On a landscape level, wolves selected a mixture of rangelands with scattered dry-farms on hillsides (showing a low human use) to locate their dens, avoiding areas with high densities of settlements and primary roads. On a fine spatial scale, wolves primarily excavated dens into the sides of elevated steep-slope hills with availability of water bodies in the vicinity of den sites, and wolves were relegated to dig in places with coarse-soil particles. Our results suggest that vulnerability of wolves in human-dominated landscapes could be compensated by the existence of spatial heterogeneity in human activities. Such heterogeneity would favor wolf persistence in agroecosystems favoring a land sharing model of coexistence between wolves and people.

59 BASIC BIOLOGICAL SCIENCES↗

Treatment and aging studies of GaAs(111)B substrates for van der Waals chalcogenide film growth

GaAs(111)B are commercially available substrates widely used for the growth of van der Waals chalcogenide films. Wafer-scale, high-quality crystalline films can be deposited on GaAs(111)B substrates using molecular beam epitaxy. However, two obstacles persist in the use of GaAs(111)B: first, the surface dangling bonds make it challenging for the growth of van der Waals materials; second, the As-terminated surface is prone to aging in air. This study investigated a thermal treatment method for deoxidizing GaAs(111)B substrates while simultaneously passivating the surface dangling bonds with Se. By optimizing the treatment parameters, we obtained a flat and completely deoxidized platform for subsequent film growth, with highly reproducible operations. Furthermore, through first-principle calculations, we find that the most energetically favorable surface of GaAs(111)B after Se passivation consists of 25% As atoms and 75% Se atoms. Finally, we discovered that the common storage method using food-grade vacuum packaging cannot completely prevent substrate aging, and even after thermal treatment, aging still affects subsequent growth. Therefore, we recommend using N2-purged containers for better preservation.

Engineering↗

An Open Benchmark of One Million High-Fidelity Cislunar Trajectories

Cislunar space spans from geosynchronous altitudes to beyond the Moon and will underpin future exploration, science, and security operations. We describe and release an open dataset of one million numerically propagated cislunar trajectories generated with the open-source Space Situational Awareness Python package (SSAPy). The model includes high-degree Earth/Moon gravity, solar gravity, and Earth/Sun radiation pressure; other planetary gravities are omitted by design for computational efficiency. Initial conditions uniformly sample commonly used osculating-element ranges, and each trajectory is propagated for up to six years under a single, fixed start epoch. The dataset is intended as a reusable benchmark for method development (e.g., space domain awareness, navigation, and machine-learning pipelines), a reference library for statistical studies of orbit families, and a starting point for community-driven extensions (e.g., alternative epochs). We report empirically observed stability trends (e.g., a band near ~5 GEO and persistence of some co-orbital classes including L4/L5 librators) as dataset descriptors rather than new dynamical results. The chief contribution is the scale, fidelity, organization (CSV/HDF5 with full state time series and metadata), and open availability, which together lower the barrier to comparative and data-driven studies in the cislunar regime.

79 ASTRONOMY AND ASTROPHYSICS↗

Improved Sensing Coils for SQUIDs

An improvement in the design and fabrication of sensing coils of superconducting quantum interference device (SQUID) magnetometers has been proposed to increase sensitivity. It has been estimated that, in some cases, it would be possible to increase sensitivity by about half or to reduce measurement time correspondingly. The pertinent aspects of the problems of design and fabrication can be summarized as follows: In general, to increase the sensitivity of a SQUID magnetometer, it is necessary to maximize the magnetic flux enclosed by the sensing coil while minimizing the self-inductance of this coil. It is often beneficial to fabricate the coil from a thicker wire to reduce its self-inductance. Moreover, to optimize the design of the coil with respect to sensitivity, it may be necessary to shape the wire to other than a commonly available circular or square cross-section. On the other hand, it is not practical to use thicker superconducting wire for the entire superconducting circuit, especially if the design of a specific device requires a persistent-current loop enclosing a remotely placed SQUID sensor. It may be possible to bond a thicker sensing-coil wire to thinner superconducting wires leading to a SQUID sensor, but it could be difficult to ensure reliable superconducting connections, especially if the bonded wires are made of different materials. The main idea is to mold the sensing coil in place, to more nearly optimum cross sectional shape, instead of making the coil by winding standard pre-fabricated wire. For this purpose, a thin superconducting wire loop that is an essential part of the SQUID magnetometer would be encapsulated in a form that would serve as a mold. A low-melting-temperature superconducting metal (e.g., indium, tin, or a lead/tin alloy) would be melted into the form, which would be sized and shaped to impart the required cross section to the coil thus formed.

Penanen, Konstantin↗

Multicopy Single-Stranded DNA Directs Intestinal Colonization of Enteric Pathogens

Multicopy single-stranded DNAs (msDNAs) are hybrid RNA-DNA molecules encoded on retroelements called retrons and produced by the action of retron reverse transcriptases. Retrons are widespread in bacteria but the natural function of msDNA has remained elusive despite 30 years of study. The major roadblock to elucidation of the function of these unique molecules has been the lack of any identifiable phenotypes for mutants unable to make msDNA. We report that msDNA of the zoonotic pathogen Salmonella Typhimurium is necessary for colonization of the intestine. Similarly, we observed a defect in intestinal persistence in an enteropathogenic E. coli mutant lacking its retron reverse transcriptase. Under anaerobic conditions in the absence of msDNA, proteins of central anaerobic metabolism needed for Salmonella colonization of the intestine are dysregulated. We show that the msDNA-deficient mutant can utilize nitrate but not other alternate electron acceptors in anaerobic conditions. Consistent with the availability of nitrate in the inflamed gut, a neutrophilic inflammatory response partially rescued the ability of a mutant lacking msDNA to colonize the intestine. These findings together indicate that the mechanistic basis of msDNA function during Salmonella colonization of the intestine is proper production of proteins needed for anaerobic metabolism. We further conclude that a natural function of msDNA is to regulate protein abundance, the first attributable function for any msDNA. Our data provide novel insight into the function of this mysterious molecule that likely represents a new class of regulatory molecules.

Environmental Molecular Sciences Laboratory↗

Metabolic Reprogramming During Purine Stress in the Protozoan Pathogen Leishmania donovani

The ability of Leishmania to survive in their insect or mammalian host is dependent upon an ability to sense and adapt to changes in the microenvironment. However, little is known about the molecular mechanisms underlying the parasite response to environmental changes, such as nutrient availability. To elucidate nutrient stress response pathways in Leishmania donovani, we have used purine starvation as the paradigm. The salvage of purines from the host milieu is obligatory for parasite replication; nevertheless, purine-starved parasites can persist in culture without supplementary purine for over 3 months, indicating that the response to purine starvation is robust and engenders parasite survival under conditions of extreme scarcity. To understand metabolic reprogramming during purine starvation we have employed global approaches. Whole proteome comparisons between purine-starved and purine-replete parasites over a 6-48 h span have revealed a temporal and coordinated response to purine starvation. Purine transporters and enzymes involved in acquisition at the cell surface are upregulated within a few hours of purine removal from the media, while other key purine salvage components are upregulated later in the time-course and more modestly. After 48 h, the proteome of purine-starved parasites is extensively remodeled and adaptations to purine stress appear tailored to deal with both purine deprivation and general stress. To probe the molecular mechanisms affecting proteome remodeling in response to purine starvation, comparative RNA-seq analyses, qRT-PCR, and luciferase reporter assays were performed on purine-starved versus purine-replete parasites. While the regulation of a minority of proteins tracked with changes at the mRNA level, for many regulated proteins it appears that proteome remodeling during purine stress occurs primarily via translational and/or post-translational mechanisms.

Environmental Molecular Sciences Laboratory↗

Inferring Soil Moisture Memory from Streamflow Observations Using a Simple Water Balance Model

Soil moisture is known for its integrative behavior and resulting memory characteristics. Soil moisture anomalies can persist for weeks or even months into the future, making initial soil moisture a potentially important contributor to skill in weather forecasting. A major difficulty when investigating soil moisture and its memory using observations is the sparse availability of long-term measurements and their limited spatial representativeness. In contrast, there is an abundance of long-term streamflow measurements for catchments of various sizes across the world. We investigate in this study whether such streamflow measurements can be used to infer and characterize soil moisture memory in respective catchments. Our approach uses a simple water balance model in which evapotranspiration and runoff ratios are expressed as simple functions of soil moisture; optimized functions for the model are determined using streamflow observations, and the optimized model in turn provides information on soil moisture memory on the catchment scale. The validity of the approach is demonstrated with data from three heavily monitored catchments. The approach is then applied to streamflow data in several small catchments across Switzerland to obtain a spatially distributed description of soil moisture memory and to show how memory varies, for example, with altitude and topography.

Soil Moisture↗

Fuel-Cladding Eutectic Study of Legacy Fast Flux Test Facility (FFTF) MFF HT9/U-10Zr Metallic Fuel

This report presents the first systematic investigation of fuel-cladding eutectic interaction (FCEI) in irradiated HT9/U-10Zr metallic fuel from the Fast Flux Test Facility (FFTF) Materials Fuels Form (MFF) program, using differential scanning calorimetry (DSC) coupled with scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Two irradiated fuel cross-sections, MNT07H (9.5 at% burnup, x/L = 0.78) and MNT08H (7.0 at% burnup, x/L = 0.93), were subjected to three successive isothermal annealing rounds (R1–R3) at 820°C for 20 minutes each, yielding a cumulative transient duration of one hour. This study directly addresses a recognized gap in the existing FCEI database, which previously lacked irradiated HT9/U-10Zr data at burnup levels above 8 at%. Two principal findings emerge from the study. First, for both samples, FCEI remained spatially confined within the pre-existing fuel-cladding chemical interaction (FCCI) zone boundaries after R3, with no measurable eutectic penetration into unaffected cladding beyond the original FCCI layer. This self-limiting behavior is consistent with historical Fuel Behavior Test Apparatus (FBTA) results and is attributed to the near-eutectic phase composition of the FCCI zone, which rapidly absorb the available eutectic-forming constituents and then stall penetration once the FCCI zone is consumed. A comparison with unirradiated surrogate data further supports this mechanism: whereas a U–34 at.% Fe sample would be expected to show ~176 µm of iron penetration under comparable conditions, the irradiated samples exhibited only ~20 µm, a discrepancy attributed to irradiation-induced interfacial porosity and pre-existing FCCI composition gradients. Second, for MNT08H, FCEI was observed exclusively on the half of the cladding circumference where pre-existing steady-state FCCI was present, with no detectable FCEI on the opposite half. Three hypotheses are proposed to explain this asymmetry: the inhibiting role of a zirconium-rich rind at the fuel-cladding interface; the chemical sequestration of iron by redistributed zirconium within the fuel matrix; and the persistence of fuel-cladding gaps on the FCEI-free half that preclude direct contact. All three hypotheses require further experimental investigation. The results extend the empirical FCEI database into higher-burnup territory and demonstrate the viability of DSC-based testing as a substitute for the no-longer-available FBTA apparatus. Future work will include additional cross-section testing, compilation of the full FCEI dataset, model evaluation, and DSC testing of ternary fuel compositions to broaden the experimental basis for safety assessment of sodium-cooled fast reactor systems.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Prioritization of in silico models and molecular descriptors for the assessment of ready biodegradability

Ready biodegradability is a key property for evaluating the long-term effects of chemicals on the environment and human health. As such, it is used as a screening test for the assessment of persistent, bioaccumulative and toxic substances. Regulators encourage the use of non-testing methods, such as in silico models, to save money and time. A dataset of 757 chemicals was collected to assess the performance of four freely available in silico models that predict ready biodegradability. They were applied to develop a new consensus method that prioritizes the use of each individual model according to its performance on chemical subsets driven by the presence or absence of different molecular descriptors. This consensus method was capable of almost eliminating unpredictable chemicals, while the performance of combined models was substantially improved with respect to that of the individual models. - Highlights: • Consensus method to predict ready biodegradability by prioritizing multiple QSARs. • Consensus reduced the amount of unpredictable chemicals to less than 2%. • Performance increased with the number of QSAR models considered. • The absence of 2D atom pairs contributed significantly to the consensus model.

54 ENVIRONMENTAL SCIENCES↗

Interactions between Kuroshio Extension and Central Tropical Pacific lead to preferred decadal-timescale oscillations in Pacific climate

Abstract The Kuroshio Extension (KE) exhibits prominent decadal fluctuations that enhance the low-frequency variability of North Pacific climate. Using available observations, we show evidence that a preferred decadal timescale in the KE emerges from the interaction between KE and the central tropical Pacific via Meridional Modes. Specifically, we show that changes in the KE states apply a persistent downstream atmospheric response (e.g. wind stress curl, 0–12 months timescales) that projects on the atmospheric forcing of the Pacific Meridional Modes (PMM) over 9 months timescales. Subsequently, the PMM energizes the central tropical Pacific El Niño Southern Oscillation (CP-ENSO) and its atmospheric teleconnections back to the Northern Hemisphere (1–3 months timescale), which in turn excites oceanic Rossby waves in the central/eastern North Pacific that propagate westward changing the KE (~3 years timescales). Consistent with this hypothesis, the cross-correlation function between the KE and the PMM/CP-ENSO indices exhibits a significant sinusoidal shape corresponding to a preferred spectral power at decadal timescales (~10 years). This dynamics pathway (KE→PMM/CP-ENSO→KE) may provide a new mechanistic basis to explain the preferred decadal-timescale of the North Pacific and enhance decadal predictability of Pacific climate.

54 ENVIRONMENTAL SCIENCES↗

Research opportunities on immunocompetence in space

The most significant of the available data on the effects of space flight on immunocompetences and the potential operational and clinical significance of reported changes are as follows: (1) reduced postflight blastogenic response of peripheral lymphocytes from space crew members; (2) postflight neutrophilia persisting up to 7 days; (3) gingival inflammation of the Skylab astronauts; (4) postflight lymphocytopenia, eosinopenia, and monocytopenia; (5) modifications and shifts in the microflora of space crews and spacecraft; and (6) microbial contamination of cabin air and drinking water. These responses and data disclose numerous gaps in the knowledge that is essential for an adequate understanding of space-related changes in immunocompetence.

Beisel, W. R.↗

In-space Servicing, Assembly, and Manufacturing (ISAM) State of Play 2022 Edition

The future of spaceflight will yield increasingly more ambitious missions to support civil, national security, and commercial space sectors. Achieving these ambitious missions is not feasible using the traditional paradigm of launching an integrated, fully functioning system on a single launch vehicle. For example, science and human exploration missions will desire payloads that are larger than any foreseeable launch vehicle fairing, national security missions will require persistent assets that are mobile and resilient, and commercial space missions will require cost-effective ways to update to the latest technology on orbit. In-space Servicing, Assembly, and Manufacturing (ISAM) can vastly expand the performance, availability, and lifetime of space systems compared to the traditional paradigm of launching an asset with no intent to ever touch it again. ISAM capabilities foster an ecosystem that changes the space operations paradigm, creating the foundation for sustainable exploration and serving as a multiplier for other capabilities like space logistics, power generation, and reusability. Previous achievements in ISAM have enabled ambitious human and robotic space missions. NASA’s International Space Station (ISS) operations and maintenance, servicing missions of the Hubble Space Telescope (HST), and Northrop Grumman’s Mission Extension Vehicle (MEV) demonstrate the dramatic operational missions that can be achieved using ISAM capabilities. Many current and upcoming flight demonstrations are advancing areas that will enable the next generation of civil, national security, and commercial space missions. This document describes the current state of ISAM missions, capabilities, and developments. Compiling and organizing the available ISAM capabilities will help mission designers incorporate ISAM technologies into their concepts, create the starting point for technology development plans and roadmaps, and provide technologists a survey of the field they are developing. This document divides the ISAM capabilities into 11 capability areas that describe the functions or activities that would be performed in space using ISAM. This version of the ISAM State of Play is part of a continuing journey to encourage the use of ISAM capabilities in space. Compiling and organizing the current state of ISAM provides a simple resource for those working in the ISAM ecosystem to ensure that the advancements being made build upon the investments of the past. The state of play is ever changing as new capabilities are developed, and this document will be periodically updated to ensure that it is relevant to those who need it in the future.

ISAM↗

Meaningful and efficient? Enduring challenges to Aboriginal participation in environmental assessment

This paper explores the underlying practice-based challenges to meaningful and efficient Aboriginal participation in environmental assessment (EA) - participation that provides meaningful opportunities for Aboriginal communities to shape EA, yet assures a degree of efficiency for project proponents who need to obtain EA approvals in a timely and financially viable manner. We do so based on an analysis of the EA policy community's experience with uranium exploration and mining in Saskatchewan, Canada. Many of the challenges to meaningful and efficient Aboriginal participation that emerged are multi-dimensional, often concerning participation processes, decision-making, and relationships. Although scholars have explored many of these issues and have proposed numerous solutions, challenges persist in practice. Several other issues also emerged from our study that have received limited attention, including the non-commitment to early and ongoing participation by smaller project proponents, and the EA exemption of exploration projects; the limited availability of information to project developers on local right holders and Aboriginal interests; expectations about the integration of traditional knowledge and land use in EA not aligning with the information that is available to proponents; confusion about who is responsible for initiating early participation and consultation processes; the lack of early relationship building with potentially affected communities, particularly by governments; and the lack of other viable avenues, outside EA, for Aboriginal communities to raise more strategic issues of concern that affect traditional lands and treaty rights.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Foundational insights into the mechanical and molecular evolution of porcine skin gelatin during gelation

Gelatin is a widely used material in biomedical fields, particularly in regenerative medicine and tissue engineering, due to its biocompatibility and versatile properties. While prior research has explored methods to enhance gelatin's mechanical strength and stability, fundamental studies on gelatin, specifically its curing process, mechanical stiffness, and chemical evolution during gelation, remain limited. This study uses ultrasonic testing and Fourier Transform Infrared Spectroscopy (FTIR) to examine gelatin's stiffness and molecular changes during gelation. Samples of 175 and 300 Porcine Skin Bloom Strength Gelatin at concentrations of 2% and 6% (w/v) were analyzed. Through transmission ultrasonic testing helped identify key transition points in gelation, with higher concentrations exhibiting delayed transitions. FTIR revealed that C-N bond formation peaks early while N-H bond deformation persists. A correlation emerged between sound speed and peak absorbance, suggesting that changes in molecular mobility may contribute to the observed sound speed behavior during periods of active bond formation. However, as gelation continues, fewer bonding components may be available, potentially decreasing molecular movement and contributing to the observed increase in sound speed. These findings provide insights into gelatin's mechanical and chemical evolution, offering a framework for improved control over its gelation kinetics. Swept-Frequency Acoustic Interferometry (SFAI) was performed at the end of the curing process to measure the sound speed, enabling the calculation of the bulk moduli of the gelatin samples. The combined use of ultrasonic and FTIR testing provides a non-destructive method for characterizing gelatin and other biomaterials. This approach advances understanding of gelatin curing behavior and supports the development of safer biomaterials with tailored mechanical properties for various applications such as tissue engineering and regenerative medicine.

Biomaterials↗

Radiation hydrodynamics modeling of the highest compression inertial confinement fusion ignition experiment from the National Ignition Campaign

The recently completed National Ignition Campaign (NIC) on the National Ignition Facility (NIF) showed significant discrepancies between post-shot simulations of implosion performance and experimentally measured performance, particularly in thermonuclear yield. This discrepancy between simulation and observation persisted despite concerted efforts to include all of the known sources of performance degradation within a reasonable two-dimensional (2-D), and even three-dimensional (3-D), simulation model, e.g., using measured surface imperfections and radiation drives adjusted to reproduce observed implosion trajectories [Clark et al., Phys. Plasmas 20, 056318 (2013)]. Since the completion of the NIC, several effects have been identified that could explain these discrepancies and that were omitted in previous simulations. In particular, there is now clear evidence for larger than anticipated long-wavelength radiation drive asymmetries and a larger than expected perturbation seeded by the capsule support tent. This paper describes an updated suite of one-dimensional (1-D), 2-D, and 3-D simulations that include the current best understanding of these effects identified since the NIC, as applied to a specific NIC shot. The relative importance of each effect on the experimental observables is compared. In combination, these effects reduce the simulated-to-measured yield ratio from 125:1 in 1-D to 1.5:1 in 3-D, as compared to 15:1 in the best 2-D simulations published previously. While the agreement with the experimental data remains imperfect, the comparison to the data is significantly improved and suggests that the largest sources for the previous discrepancies between simulation and experiment are now being included.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Cadmus v1.0

This software package is for distributed computation of persistent (co)homology. It is primarily intended for Topological Data Analysis (TDA) audience and scientists who use TDA methods and apply them to datasets that are too big to handle on a single machine. There are very few codes available for this; Cadmus outperforms DIPHA, if the user is interested in cohomology. The accompanying paper explaining the algorithm was accepted to ALENEX 26.

Nigmetov, Arnur [Lawrence Berkeley National Labora↗

Demonstration and Validation of a Portable Raman Sensor for In-Situ Detection and Monitoring of Perchlorate (ClO 4 - )

Costs for environmental analysis and monitoring are increasing at a rapid rate and represent a significant percentage of the total and future remedial expenses at many U.S. Department of Defense (DoD) contaminated sites. It has been reported that about 30 to 40% of the remediation budget is usually spent on long-term monitoring (LTM), of which a large percentage represents laboratory analytical costs. Energetics such as perchlorate (ClO 4 - ) are among the most frequently detected contaminants in groundwater and surface water at or near military installations due to their persistence and mobility. Currently, the standard protocol entails collecting samples in the field, packaging them, and shipping them overnight to a designated laboratory for analysis. This process requires significant sample preparation and handling, and analytical results may not be available for several days to weeks. In this project, we developed and demonstrated a portable Raman sensor based on surface enhanced Raman scattering (SERS) technology to detect ClO 4 - in contaminated water. We summarize major accomplishments as follows: • A SERS sensor based on elevated gold (Au) nano-ellipse dimer architectures was designed and developed for ClO 4 - with a detection limit of ~10 -6 M (or 100 μg/L); The performance of these sensors was evaluated and optimized through variation of their geometric characteristics (i.e., dimer aspect ratio, dimer separation, etc.). • Large-scale commercial production of SERS substrate sensors via nanoimprinting by Nanova Inc. and Nanoimprint lithography (NIL) technology was successfully demonstrated. This is a substantial step forward toward the commercialization of the SERS sensors and may potentially lead to significantly reduced fabrication costs of SERS substrates. • Commercially produced SERS sensors were demonstrated to detect ClO 4 - at levels above 10 -6 M using a portable Raman analyzer. The performance of the commercial SERS sensors for ClO 4 - detection in the presence and absence of interferences was determined for a series of standard solutions. Sulfate (SO 4 2- ) was found to exhibit the greatest interference for the anions tested, which included Cl-, NO 3 - , and SO 4 2- . • Field demonstration of the portable Raman sensor with commercially produced SERS substrates was completed at two Department of Defense (DoD) sites; twice at the Indian Head Naval Surface Warfare Center, Indian Head, MD, and once at Redstone Arsenal, Huntsville, AL. Multiple wells were sampled at both DoD sites, where a standard addition method was employed using the sensor to determine the ClO 4 - 4 - and possibly other energetics that are both important for environmental monitoring and of interest for national security. However, we point out that SERS technology is also prone to interferences due to its sensitivity and responses to other ionic species, such as NO 3 - , SO 4 2- , and dissolved organics or co-contaminants present in the groundwater, which could potentially mask the SERS signal of the target analyte (i.e., ClO 4 - ). As such, SERS analysis was subject to significant variations (e.g., ±20% or more), and its detection limit for ClO 4 - -8 M) and was substantially higher than what we anticipated from laboratory studies. However, despite these complications, the portable Raman sensor developed in this project could be used as a rapid screening tool for ClO 4 - at concentrations above 10 -6 M. Future studies are warranted to further develop the technology and to optimize its performance, and eventually to bring the technology to the market. With additional development and demonstration, the sensor has the potential to reduce analytical costs by eliminating shipping and typical costs associated with laboratory analysis. A cost savings of 30–45% may be realized during a typical sampling event and, more importantly, the technology could allow rapid turn-around of information to decision makers for site characterization and remediation.

47 OTHER INSTRUMENTATION↗