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Using low volume eDNA methods to sample pelagic marine animal assemblages

Environmental DNA (eDNA) is an increasingly useful method for detecting pelagic animals in the ocean but typically requires large water volumes to sample diverse assemblages. Ship-based pelagic sampling programs that could implement eDNA methods generally have restrictive water budgets. Studies that quantify how eDNA methods perform on low water volumes in the ocean are limited, especially in deep-sea habitats with low animal biomass and poorly described species assemblages. Using 12S rRNA and COI gene primers, we quantified assemblages comprised of micronekton, coastal forage fishes, and zooplankton from low volume eDNA seawater samples (n = 436, 380–1800 mL) collected at depths of 0–2200 m in the southern California Current. We compared diversity in eDNA samples to concurrently collected pelagic trawl samples (n = 27), detecting a higher diversity of vertebrate and invertebrate groups in the eDNA samples. Differences in assemblage composition could be explained by variability in size-selectivity among methods and DNA primer suitability across taxonomic groups. The number of reads and amplicon sequences variants (ASVs) did not vary substantially among shallow (<200 m) and deep samples (>600 m), but the proportion of invertebrate ASVs that could be assigned a species-level identification decreased with sampling depth. Using hierarchical clustering, we resolved horizontal and vertical variability in marine animal assemblages from samples characterized by a relatively low diversity of ecologically important species. Low volume eDNA samples will quantify greater taxonomic diversity as reference libraries, especially for deep-dwelling invertebrate species, continue to expand.

59 BASIC BIOLOGICAL SCIENCES↗

Polar primary aerosols across the ocean-sea ice-snow-atmosphere interface: From sources to impacts

Primary aerosols play a critical role in polar climate systems, influencing cloud formation, precipitation, radiative balance, and surface energy budgets. This paper provides a comprehensive synthesis of primary aerosol sources, transformation and removal processes, and broader atmospheric impacts in polar regions, emphasizing their links to ocean and sea ice biogeochemistry. These aerosols (including sea salt, primary organic aerosol, and primary biological aerosol particles) originate from marine and cryospheric environments and are emitted through physical processes, such as wave breaking, bubble bursting, and blowing snow. Emission sources include seawater, sea ice, snow, and freshwater from river discharge and glacial runoff. Once airborne, these particles can serve as a chemical reservoir, influencing atmospheric composition and reactivity, and as seeds for cloud droplet and ice crystal formation, influencing cloud microphysics and polar climate. Despite their importance, many of the processes governing primary aerosol emissions and transformations remain poorly constrained. The most pressing knowledge gaps pertain to emission processes, limited spatiotemporal observational coverage, instrumentation constraints, parameterization development, and the integration of interdisciplinary expertise. To improve our understanding of primary aerosol drivers and their response to climate, future research efforts should prioritize strategically coordinated and cross-disciplinary process studies, advancements in measurement technologies and coverage, and close collaboration between modelers and observational scientists to inform and refine model parameterizations. As polar regions continue to undergo profound changes marked by increased precipitation, reduced sea and land ice, freshening oceans, and shifting ecosystem dynamics, characterizing present-day primary aerosol populations is vital. Improved understanding will be essential for anticipating future changes in aerosol-radiation and aerosol-cloud interactions and their implications for polar and global climate systems.

Aerosol-cloud↗

HERO WEC V1 Upgrade - 2023 Laboratory Testing (processed data)

The following submission includes processed laboratory data from NREL's Hydraulic and Electric Reverse Osmosis Wave Energy Converter (HERO WEC), in the form of MATLAB workspaces. This dataset was created using NREL's Large Amplitude Motion Platform (LAMP) and collected between August and September 2023. Included with this submission is a test log of all the processed data "HERO WEC LAMP test run log.xlsx" so that the user can easily find the data of interest. Additionally, more detailed descriptions of the type of data and how it was processed, or calculated, can be found in the document titled "Lamp Data Description.docx". The MATLAB workspaces can be visualized using the file "LAMP_Data_Viewer_Ver2.m/mlx". The user simply needs to upload the workspace of interest and run the file "LAMP_Data_Viewer_Ver2.m/mlx". Both the .m and .mlx file format has been provided depending on the user's preference. The MATLAB workspaces have been separated into zip files corresponding to either Drivetrain, Hydraulic, or Electric configuration runs representing the respective test cases that were run. The drivetrain runs were used to characterize the drivetrain only (no pump or generator). The Hydraulic runs represent the configuration when the seawater pump is installed, and the Electric runs represents the configuration when the generator is installed. The following sub-categories of data are included for each type: - DW - Deep water sine wave profile (not run in drivetrain configuration) - Heave - Heave only sine wave profile - Heave_NoRO (hydraulic configuration only) - Heave_ACC (hydraulic configuration only) - IR - Surge and heave irregular wave profile (not run in drivetrain configuration) - RW - Heave only profile created from real world encoder data (not run in drivetrain configuration) For those interested in the raw, unprocessed, data the authors have created a separate submission, linked below. This submission includes the raw TDMS files and associated files necessary to translate the data into either python or MATLAB formats. This data set has been developed by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Funding provided U.S. Department of Energy Office of Energy Efficiency and Renewable Energy Water Power Technologies Office.

16 TIDAL AND WAVE POWER↗

HERO WEC V1 Upgrade - 2023 Laboratory Testing (Raw Data)

This submission contains the original, unprocessed data from the 2023 Large Amplitude Motion Platform (LAMP) testing of NREL's Hydraulic and Electric Reverse Osmosis Wave Energy Converter (HERO WEC). This data serves as a companion to MHKDR #520. Data was collected using NREL's Modular Ocean Data AcQuisition (MODAQ) system in TDMS format. Specifications of TDMS files can be found on the NI website. The TDMS files have been separated into zip files corresponding to either Drivetrain, Hydraulic, or Electric configuration runs representing the respective test cases that were run. The drivetrain runs were used to characterize the drivetrain only (no pump or generator). The Hydraulic runs represent the configuration when the seawater pump is installed, and the Electric runs represents the configuration when the generator is installed. The following sub-categories of data are included for each type: - DW - Deep water (monochromatic sine wave) profile (not run in drivetrain configuration) - Heave - Heave only (monochromatic sine wave) profile - Heave_NoRO (hydraulic configuration only) - Heave_ACC (hydraulic configuration only) - IR - Surge and heave irregular wave profile (not run in drivetrain configuration) - RW - Heave only profile created from real world encoder data (not run in drivetrain configuration) Reference documents: - "HERO WEC Lamp Test Run Log.xlsx": contains specifications for each test run - "Lamp Data Description.docx": provides detailed information about data types and processing methods For those interested in the processed data the authors have created a separate submission, MHKDR #520, linked below. This data set has been developed by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Funding provided U.S. Department of Energy Office of Energy Efficiency and Renewable Energy Water Power Technologies Office.

16 TIDAL AND WAVE POWER↗

Stable water isotopes and tritium data from porewater at Elkhorn Slough

Salt marshes are dynamic hydrologic systems where terrestrial groundwater, terrestrial surface water, and seawater mix due to bi-directional flows and pressure gradients. Due to the counteracting terrestrial and marine forcings that control these environments, we do not comprehensively understand water fluxes in these complex coastal systems. To understand the water sources, flow directions, and velocities in salt marsh porewater, we collected geochemical tracers across a hillslope-to-salt marsh continuum in a salt marsh experiencing daily inundation of estuarine surface water (SW) from tides and mixing of fresh seasonal groundwater. The experimental transect is located at the Elkhorn Slough National Estuarine Research Reserve.Here we present a data table (.csv) with the results of electrical conductivity, stable water isotopes, and tritium in porewater across several elevations in the hillslope-to-salt marsh continuum (information in the data set). We analyzed the stable water isotope samples by cavity ring-down spectroscopy in a Picarro L2130-i at the University of California Santa Cruz (accuracy of 0.025‰ and 0.1‰ for δ18O and δ2H, respectively). We measured the electric conductivity of the samples with an Orion Star™ A329 multiparameter meter (0.5% accuracy, Thermo Fisher Scientific, Massachusetts, USA). We analyzed 3H samples at Lawrence Livermore National Laboratory by helium-3 accumulation (Clarke et al., 1976; Surano et al., 1992).

54 ENVIRONMENTAL SCIENCES↗

Modeled sub-hourly nitrate concentrations in subsurface water across a salt marsh system in Elkhorn Slough, California

Salt marshes are dynamic hydrologic systems where terrestrial groundwater, terrestrial surface water, and seawater mix due to bi-directional flows and pressure gradients. Salt marshes are known to remove excess nitrate from water thereby improving water quality in coastal systems. However, our knowledge of the short-term processes (e.g., intra-tidal) in salt marshes is limited. Further, we lack knowledge about how these short-term dynamics may change as a function of seasonality. To address this knowledge gap, we develope a sampling methodology that allowed us to continuously measure nitrate in subsurface water at three different depths across three marsh elevations at sub-hourly time steps. Here we present a data table with the results of nitrate in porewater across the three salt marsh elevations (information in the data set). We analyzed nitrate with a s::can spectrophotometer. We used the UV-Vis absorbance of the samples to calculate nitrate concentrations using a local calibration library. More information about the methodology can be found in Grande et al (2023). Seasonal and Tidal Variations in Hydrologic Inputs Drive Salt Marsh Porewater Nitrate Dynamics, Hydrological Processes.

54 ENVIRONMENTAL SCIENCES↗

Oxygen Isotope Microanalysis By Secondary Ion Mass Spectrometry Suggests Continuous 300-million-year History of Calcite Cementation and Dolomitization in the Devonian Bakken Formation

Calcite cementation and dolomitization are key diagenetic processes in many sedimentary systems. Unravelling detailed histories and timescales of cementation and replacement is, however, often compromised by the limited spatial resolution of many analytical techniques; in some cases multiple grains are co-analyzed so that diagenetic histories are blurred and reaction periods are difficult to establish. In this study we have used 10-micrometer-resolution, in situ secondary ion mass spectrometry to determine the oxygen isotope composition of 197 individual, 10–50-micrometer-size crystals of dolomite and calcite from six samples in a single core of Upper Devonian middle Bakken Member siltstones and sandstones, the major tight oil formation of the Williston basin, USA. This amount of data places important constraints on the range of temperatures and times that carbonate cementation and replacement occurred. Petrographic data show that microcrystalline calcite cement is an early phase, and combined with mineralogical data suggest that much of the dolomite replaces calcite. Over spatial scales of less than a centimeter, analyses of individual calcite crystals have a range of 5‰ for δ 18 O in the group of crystals, and for the group of individual dolomite crystals, 10‰. These sub-centimeter ranges are as great as those observed in previous studies of carbonate cements sampled over many meters and remind us that previous low-resolution studies may have inadvertently analyzed mixed phases. There is no relationship between dolomite texture and isotopic composition at this spatial scale; microscale backscattered electron imagery and scanning electron microscopy cathodoluminescence zoning is seen, but cannot be resolved with a 10-micrometer spot size. Assuming, since it is an early cement, that calcite precipitated from seawater (δ 18 O = –1.5‰), it formed at ca. 15–40°C, mainly at the lower temperatures. Present-day formation waters in Devonian rocks in this region have oxygen isotope compositions of 7–8‰ VSMOW. Using these values as a likely dolomitizing fluid, we suggest that dolomitization occurred continuously between 40 and 140°C over 150–200 million years, most likely in a fluid with a high Mg/Ca ratio resulting from gypsum formation in local evaporites. Finally, we suggest that this exceptionally low rate of dolomitization was controlled by the low rate of supply of Mg in a very sluggish flow regime; dolomitization is incomplete because of a limited supply of Mg.

58 GEOSCIENCES↗

Assessing Potential Acidification of Marine Archaeological Wood Based on Concentration of Sulfur Species

The presence of sulfur in marine archaeological wood presents a challenge to conservation. Upon exposure to oxygen, sulfur compounds in waterlogged wooden artifacts are being oxidized, producing sulfuric acid. This speeds the degradation of the wood, potentially damaging specimens beyond repair. Sulfur K-edge x-ray absorption spectroscopy was used to identify the species of sulfur present in samples from the timbers of the Mary Rose, a preserved 16th century warship known to undergo degradation through acidification. The results presented here show that sulfur content varied significantly on a local scale. Only certain species of sulfur have the potential to produce sulfuric acid by contact with oxygen and seawater in situ, such as iron sulfides and elemental sulfur. Organic sulfurs, such as the amino acids cysteine and methionine, may produce acid but are integral parts of the wood's structure and may not be released from the organic matrix. The sulfur species contained in the sample reflect the exposure to oxygen while submerged, and this exposure can differ greatly over time and position. A better understanding of the species pathway to acidifications required, along with its location, in order to suggest a more customized and effective preservation strategy. Waterlogged archaeological wood, frequently in the form of shipwrecks, is being excavated for historical purposes in many countries around the world. Even after extensive efforts towards preservation, scientists are discovering that accumulation of sulfate salts results in acidic conditions on the surfaces of the artifacts. Sulfuric acid degrades structural fibers in the wood by acid hydrolysis of cellulose, accelerating the decomposition of the ship timbers. Determining the sulfur content of waterlogged wood is now of great importance in maritime archaeology. Artifact preservation is often more time consuming and expensive than the original excavation; but it is key to the availability of objects for future study as well as maintaining the integrity of historical data and preserving the value of museum pieces. Sulfur occurs in a wide number of oxidation states from -2 to +6, and appears in numerous organic and inorganic compounds in nature. However, it is a very minor component of wood. Sulfur K-edge x-ray absorption spectroscopy (XAS) is a valuable technique because it has the ability to detect very low concentrations of sulfur in the specimen. XAS is also sensitive to differences in oxidation states, as well as long and short range order in molecules.

09 BIOMASS FUELS↗

Two modes of sea-ice gravity drainage

Processes that change the vertical salinity profile of sea ice have a significant impact on sea-ice properties and biogeochemistry. One of the most important processes affecting sea-ice salinity is gravity drainage where cold dense brine within newly formed sea ice drains out and is replaced by seawater resulting in a significant desalination of the sea ice. Using time-resolved bulk salinity and temperature observations of forming sea ice we show that gravity drainage occurs as two distinct modes: rapid drainage at the base of the ice and slow drainage occurring more deeply in the ice. We have developed a parameterization for gravity drainage, that includes these two modes, which is suitable for inclusion in a global climate model. The parameterization is included in an all new thermodynamic component, based on mushy layer theory, for the Los Alamos Sea Ice Model (CICE).

58 GEOSCIENCES↗

Modeling the Physical and Biochemical Influence of Ocean Thermal Energy Conversion Plant Discharges into their Adjacent Waters

This paper describes the modeling work by Makai Ocean Engineering, Inc. to simulate the biochemical effects of of the nutrient-enhanced seawater plumes that are discharged by one or several 100 megawatt OTEC plants. The modeling is needed to properly design OTEC plants that can operate sustainably with acceptably low biological impact.

16 TIDAL AND WAVE POWER↗

Membrane Technology for Produced Water in Lea County

Southeastern New Mexico (SENM) is rich in mineral resources, including oil and gas. Produced water is a byproduct from oil and gas recovery operations. SENM generates approximately 400 million barrels per year of produced water with total dissolved solids (TDS) as high as ~ 200,000 ppm. Typically, produced water is disposed of by transporting it to injection wells or disposal ponds, costing around $\$$1.2 billion per year with an estimated use of 0.3 million barrels of transportation fuel. New Mexico ranks first among U.S. states in potash production. Nationally, more than 85% of all potash produced comes from the Carlsbad potash district in SENM. Potash manufacturing processes use large quantities of water, including fresh water, for solution mining. If the produced water from oilfield operations can be treated and used economically in the potash industry, it will provide a beneficial use for the produced water as well as preserve valuable water resources in an area where fresh water is scarce. The goal of this current research was to develop a prototype desalination system that economically treats produced water from oil and/or natural gas operations for the beneficial use of industries located in southeastern New Mexico. Up until now, most water cleaning technologies have been developed for treating water with much lower quantities of TDS. Seawater with TDS of around 30,000 ppm is the highest concentration that has been seriously studied by researchers. Reverse osmosis (RO) technology is widely used; however the cost remains high due to high-energy consumption. Higher water fluxes and recoveries are possible with a properly designed Forward Osmosis (FO) process as large driving forces can be induced with properly chosen membranes and draw solution. Membrane fouling and breakdown is a frequent and costly problem that drives the cost of desalination very high. The technology developed by New Mexico Tech (NMT) researchers not only protects the membrane, but has also proven to generate higher water flux, based on the series of experiments conducted. Laboratory tests at NMT demonstrated that an unprecedented water flux of 1300 l/m2/hr (where typical flux is on the order of 0-3 l/m 2 /hr) can be achieved from a properly designed membrane module. The patent pending NMT system, which was designed and developed at NMT was successful in reducing the possibility for concentration polarization and thereby increasing the permeate water flux, while still maintaining a high salt rejection rate of 96% or greater. For feed solutions having a dissolved contaminant concentration greater than 10,000 ppm, preliminary economic analysis demonstrates that a well-designed FO process will outperform an RO process. Most produced water generated in SENM has TDS higher than 10,000 ppm. Therefore, it is logical to use FO to desalinate the water. Since the issues associated with concentration polarization has only recently been solved by our mechanically enhanced membrane module, the level of system maturity is not at the same level as that for RO. Our efforts going forward will be directed at taking the technology to a higher level of system maturity. With the superior cost effectiveness for FO, it is imperative that this technology reach a point that is competitive with RO in order to meet the expanding need for water for industries in SENM. NMT seeks to demonstrate the greater cost effectiveness by proving the process through a scaled up model. To ensure success, NMT feels it is important to demonstrate this technology in a larger system, (~ 100,000 GPD), before venturing to the commercial scale. This will build confidence in the process with the commercial sector. In addition, it will be possible to develop some of the operational processes around renewable energy sources for the scaled up model. This will further lower the operating costs and enhance the environmentally clean aspect of the process.

02 PETROLEUM↗

The Effects of Iron Complexing Ligands on the Long Term Ecosystem Response to Iron Enrichment of HNLC waters (Final Activity Report)

Substantial increases in the concentrations of the stronger of two Fe(III) complexing organic ligand classes measured during the mesoscale Fe enrichment studies IronEx II and SOIREE appeared to sharply curtailed Fe availability to diatoms and thus limited the efficiency of carbon sequestration to the deep. Detailed observations during IronEx II (equatorial Pacific Ocean) and SOIREE (Southern Ocean –Pacific sector) indicate that the diatoms began re-experiencing Fe stress even though dissolved Fe concentrations remained elevated in the patch. This surprising outcome likely is related to the observed increased concentrations of strong Fe(III)-complexing ligands in seawater. Preliminary findings from other studies indicate that diatoms may not readily obtain Fe from these chemical species whereas Fe bound by strong ligands appears to support growth of cyanobacteria and nanoflagellates. The difficulty in assessing the likelihood of these changes with in-situ mesoscale experiments is the extended monitoring period needed to capture the long-term trajectory of the carbon cycle. A more detailed understanding of Fe complexing ligand effects on long-term ecosystem structure and carbon cycling is essential to ascertain not only the effect of Fe enrichment on short-term carbon sequestration in the oceans, but also the potential effect of Fe enrichment in modifying ecosystem structure and trajectory.

54 ENVIRONMENTAL SCIENCES↗

The Potential Impacts of OTEC Intakes on Aquatic Organisms at an OTEC Site under Development on Kauai, HI

Ocean thermal energy conversion (OTEC) is a marine renewable energy technology with the potential to contribute significantly to the baseload power needs of tropical island communities and remote U.S. military installations. As with other renewable energy technologies, however, there are potential challenges to its commercialization: technological, financial, social, and environmental. Given the large volumes of seawater required to drive the electricity-producing cycle, there is potential for the intakes to negatively impact the marine resources of the source waterbody through the impingement and entrainment of marine organisms.

13 HYDRO ENERGY↗

Amchitka Island, Alaska, Biological Monitoring Report 2011 Sampling Results

The Long-Term Surveillance and Maintenance (LTS&M) Plan for the U.S. Department of Energy (DOE) Office of Legacy Management (LM) Amchitka Island sites describes how LM plans to conduct its mission to protect human health and the environment at the three nuclear test sites located on Amchitka Island, Alaska. Amchitka Island, near the western end of the Aleutian Islands, is approximately 1,340 miles west-southwest of Anchorage, Alaska. Amchitka is part of the Aleutian Island Unit of the Alaska Maritime National Wildlife Refuge, which is administered by the U.S. Fish and Wildlife Service (USFWS). Since World War II, Amchitka has been used by multiple U.S. government agencies for various military and research activities. From 1943 to 1950, it was used as a forward air base for the U.S. Armed Forces. During the middle 1960s and early 1970s, the U.S. Department of Defense (DOD) and the U.S. Atomic Energy Commission (AEC) used a portion of the island as a site for underground nuclear tests. During the late 1980s and early 1990s, the U.S. Navy constructed and operated a radar station on the island. Three underground nuclear tests were conducted on Amchitka Island. DOD, in conjunction with AEC, conducted the first nuclear test (named Long Shot) in 1965 to provide data that would improve the United States' capability of detecting underground nuclear explosions. The second nuclear test (Milrow) was a weapons-related test conducted by AEC in 1969 as a means to study the feasibility of detonating a much larger device. Cannikin, the third nuclear test on Amchitka, was a weapons-related test detonated on November 6, 1971. With the exception of small concentrations of tritium detected in surface water shortly after the Long Shot test, radioactive fission products from the tests remain in the subsurface at each test location As a continuation of the environmental monitoring that has taken place on Amchitka Island since before 1965, LM in the summer of 2011 collected biological and seawater samples from the marine and terrestrial environment of Amchitka Island adjacent to the three detonation sites and at a background or reference site, Adak Island, 180 miles to the east. Consistent with the goals of the Amchitka LTS&M Plan, four data quality objectives (DQOs) were developed for the 2011 sampling event.

54 ENVIRONMENTAL SCIENCES↗

Ground Model Options in the NEC-4.2 Antenna Code

The antenna modeling code NEC–4 includes a capability for modeling antennas above or in a homoeneous ground using interpolation in tables of Sommerfeld integrals and asymptotic approximations for large distances. This model has been validated in a number of ways and yields accurate results for common antennas such as monopoles on ground stakes and ground screens and horizontal wires very close to the earth. The original NEC–4 Sommerfeld interpolation was set up for typical ground parameters and has difficulties covering the range of conductivity up to seawater at lower HF. Errors are sometimes seen in plots as discontinuities or spikes, especially in the H field which is obtained from a numerical evaluation of the curl of E. A new ground option has now been added in the version NEC–4.2 with a more accurate interpolation method and asymptotic approximations and direct evaluation of H. Filling the interpolation tables takes somewhat longer than in the original method, but time to fill the matrix is about the same. Since desktop computers are now more than an order of magnitude faster than the large computers used when NEC–4 was first released in 1992, it is reasonable to trade some speed for accuracy. The original Sommerfeld/interpolation method, which is still available, uses the input option GN2 while the new method is obtained with GN3. Some initial results of the new method are compared with the old solution here.

58 GEOSCIENCES↗

Report on Initial Direct Soil Leaching Experiments Using Post-Detonation Debris

A key challenge of nuclear forensics is reducing the time and manpower effort required to measure nuclear debris compositions. The overall motivation for this work is to explore development of a robust, automated system that can be used to concurrently analyze several elements/isotopes associated with the forensic signature of nuclear materials. The primary focus of this research has been to methodically investigate if rapid partial leaching of post-detonation debris can yield usable elemental and isotopic information for interpretation. The unique requirements of post-detonation nuclear forensics have not been fully adapted to or fully incorporated contemporary chemical separation techniques. Challenges include addressing the range of material matrices or mixed fission product and actinide compositions and concentrations that might be encountered. These include, but are not limited to, puddle melt glass, urban debris, seawater, air filters, iron-rich urban debris, asphalt, and silica sand. Separation of these elements and their subsequent measurement is a key element of related laboratory analysis activity. Existing practices at LLNL rely on proven but time-consuming and labor intensive processes. Significant time and labor savings are possible in chemical separations, however, if rapid processing methods can be adapted to post-detonation debris. Development of a simple and reliable leaching technique could shorten analytical times and would be useful as a field deployable method for the preliminary characterization of actinide isotopic ratios in soils. Measurement of isotopic ratios in the field using modern mass spectrometry capabilities such as Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is desirable, taking advantage of the extended range of isotopic systems measureable using such instruments. Sample introduction to these types of mass spectrometry instruments requires partial leaching or full dissolution of a sample to remove isobaric (same mass) interferences, and, in some cases, to concentrate the elements(s) of interest. To develop a field-deployable mass spectrometry capability, therefore, automated and robust leaching of likely debris samples (ranging from silicates and oxides to metals and urban materials such as concrete and asphalt), followed by separation/purification through cation exchange column chemistry is necessary. In a post-detonation environment, analysis of melt glasses via rapid leaching and ICP-MS could be a viable route to the same goal. This report presents initial leaching experiments on ‘uncontaminated’ soils, as well as data from melt glass from a single nuclear weapons test. Samples were characterized by gamma spectrometry, then aliquoted for rapid leaching experiments. Experiments were conducted using two different rapid acid treatments to leach the soils. Following leaching, the leachate solutions were analyzed by ICP-MS to determine if U isotopic composition. We present these data to address the question as to whether or not rapid (~1 hr) leaching techniques have the potential to yield meaningful U isotopic compositions, without the need for a complete (time consuming) sample dissolution and separation.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Analysis of dust samples collected from spent nuclear fuel interim storage containers at Hope Creek, Delaware, and Diablo Canyon, California

Potentially corrosive environments may form on the surface of spent nuclear fuel dry storage canisters by deliquescence of deposited dusts. To assess this, samples of dust were collected from in-service dry storage canisters at two near-marine sites, the Hope Creek and Diablo Canyon storage installations, and have been characterized with respect to mineralogy, chemistry, and texture. At both sites, terrestrially-derived silicate minerals, including quartz, feldspars, micas, and clays, comprise the largest fraction of the dust. Also significant at both sites were particles of iron and iron-chromium metal and oxides generated by the manufacturing process. Soluble salt phases were minor component of the Hope Creek dusts, and were compositionally similar to inland salt aerosols, rich in calcium, sulfate, and nitrate. At Diablo Canyon, however, sea-salt aerosols, occurring as aggregates of NaCl and Mg-sulfate, were a major component of the dust samples. The seasalt aerosols commonly occurred as hollow spheres, which may have formed by evaporation of suspended aerosol seawater droplets, possibly while rising through the heated annulus between the canister and the overpack. The differences in salt composition and abundance for the two sites are attributed to differences in proximity to the open ocean and wave action. The Diablo Canyon facility is on the shores of the Pacific Ocean, while the Hope Creek facility is on the shores of the Delaware River, several miles from the open ocean.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE SBIR 2014 Topic 2.C – Phase I Final Report

Freshwater is a vital resource for human survival as well as a key component of a wide range of industrial and agricultural needs. However, only 0.65% of the world’s water resources are available as freshwater, and the demand on the world’s water reserves continues to increase, with the demand beginning to outpace the supply in many areas. A water-energy nexus is being reached that requires low –cost and –energy solutions for various degrees of treated water. In a 2012 survey, 88% of Americans were concerned about potential water shortages and approximately two-thirds of the world’s population will be suffering a water shortage over the next few years. Seawater and other saline water materials make up around 98% of the available water, representing an almost unlimited supply of water. The energy, cost and maintenance to remove salts and other unwanted compounds is a barrier to widespread implementation of salt-to-freshwater facilities. These facilities most commonly use reverse osmosis (RO) systems. Due to the high required pressures and moving parts these facilities consume much grid energy and require constant maintenance leading to high capital and operational costs. RO also generates highly concentrated brine that is costly to safely return to the ocean. Capacitive desalination (or capacitive deionization [CDI]) has no moving parts (aside from a low pressure pump and valves), operates at low pressure and does not generate brine that is hazardous to marine life. Not only can the capacitive charge/discharge be cycled almost indefinitely but the system uses low energy and capacitive discharge electrical current can be co-generated back to the system. However, CDI has not seen widespread use for large- or small- scale desalination because electrode efficiency limits the extraction rate below what is useful for most applications. Mainstream Engineering Corporation (MEC) has demonstrated an innovative new electrode structure for the high efficiency desalination of brackish water by capacitive deionization. Electrode manufacturing (nanomanufacturing) is a highly scalable and low-cost electrochemical self-assembly method using a templated process that Mainstream has pioneered and leveraged for several energy technologies over the last decade. The primary accomplishment for Phase I is the fabrication and demonstration of CDI electrode structures are: • Demonstrating the linear scalability of templated approach to the fabrication scaling the electrode structure. • Demonstrated the ability to tune the fabrication of the electrode structures to produce electrodes with a highly controllable aligned nanopore diameter and nanopore depth. • Demonstrated the efficient removal of a sodium chloride salt from brackish water with a 60 times improvement in mg-salt removed/g-carbon compared to a commercial system under the same conditions. • Demonstrated good reproducibility and stability of the electrode structure under realistic CDI operating conditions. • Demonstrated charge efficiency as high as 93% with an expected system level energy requirement of 0.7 to 1.5 kWh/m3 of water; significantly lower than the 2.9 to 3.7 kWh/m3 observed for RO systems Based on the performance characteristics of the electrodes, Mainstream was able to propose a modular and scalable capacitive deionization design that can be adapted to a wide range of conditions providing energy efficient desalination of brackish water.

36 MATERIALS SCIENCE↗