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Geophysical Characterization and Monitoring of the 200 Area Treated Effluent Disposal Facility to Support Permit Renewal; TEDF Geophysical Monitoring

The Treated Effluent Disposal Facility (TEDF), located in the 200 East Area of the Hanford Site, is a site where non-hazardous and non-radioactive liquid wastes are disposed into two state-permitted infiltration basins. In 2016, the Washington State Department of Ecology denied a permit renewal request for TEDF due to the inability to adequately assess the impact of TEDF discharge water on the underlying groundwater quality. TEDF overlies the relatively impermeable Ringold Lower Mud (RLM) unit, whose upper contact lies in the vadose zone approximately 30 m below ground surface and approximately 10 m above the water table boundary. The RLM is assumed to isolate TEDF discharge water from the natural groundwater aquifer, which is monitored using wellbores screened below the RLM. Therefore, samples collected from monitoring wells near TEDF are not considered representative of TEDF discharge water. Rather, TEDF discharge water is assumed to mound on top of the RLM to form a perched aquifer. To support permitting of the TEDF, a new monitoring well is required that can be used to sample water from the presumed perched water aquifer above the RLM. Ideally, the screened section of the well would be located at the peak of the perched water mound(s), which presumably occurs at the point of maximum vertical flux from TEDF to the RLM, or equivalently where the dominant infiltration flow paths reach the RLM. This report describes how time-lapse 3D electrical resistivity tomography (ERT) was used in conjunction with nominal TEDF discharge operations to image the dominant flow paths from each pond to the RLM. Results are summarized in Figure ES.1. Figure ES.1A shows a satellite image of the TEDF overlain by an array of surface ERT electrodes. The solid and dashed black circles denote the zones of maximum vertical flux at the RLM within the south and north ponds, respectively, and presumably the regions where perched water peaks during discharge. Figure ES.1B shows time-lapse difference imaging results approximately 15 days after switching discharge from the south pond to the north pond. Blue iso-surfaces beneath the north pond denote regions of increasing bulk electrical conductivity caused by increasing saturation due to infiltrating water. Red iso-surfaces beneath the south pond denote regions that were previously saturated during the south pond discharge and are now de-saturating, causing a decrease in bulk electrical conductivity. In both cases, the zones of maximum change mark the dominant flow paths to the RLM. Figure ES.1C shows time-lapse imaging results approximately 15 days after switching discharge from the north pond to the south pond. In this case, blue iso-surfaces mark the dominant flow paths to the RLM from the south pond. The red iso-surfaces mark the dominant flow paths that existed during discharge to the north pond. The regions of maximum change in bulk conductivity (due to saturation or desaturation) that mark the primary flow paths are equivalent in both cases and denoted by the dashed solid and black circles. If a perched water zone forms on the RLM, it is likely to mound within or near the dashed circle during discharge to the north pond, and in the solid circle during discharge to the south pond. In other words, if perched water mounding occurs, the circles mark the optimum locations suggested by the ERT imaging for monitoring boreholes to be placed, enabling samples to be collected that are representative of TEDF discharge impacts on groundwater quality.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Monthly Sewer Monitoring Report for LLNL Livermore Site, April 2020

Lawrence Livermore National Laboratory (LLNL) collects effluent samples from its sewer outfall at the B196 Sewer Monitoring Station (SMS). Effluent flow-proportional composite samples are collected at the SMS on a daily (midnight-to-midnight), weekly (Thursday through Wednesday), and “monthly” (composited from daily) basis; effluent grab samples are also collected each month at that same location. Certified contract laboratories analyzes these compliance samples, and results (Tables 1–3) are used to establish LLNL compliance with the 2019–2020 Wastewater Discharge Permit (Permit 1250) granted by the City of Livermore Water Resources Division (WRD). Supplemental analyses for biochemical oxygen demand (BOD) and total suspended solids (TSS) are performed onsite and reported (Table 4) for the calculation and assessment of sewer service charges. Quarterly, effluent is sampled for metals (24-hour composite) and cyanide (grab sample) concentrations (mg/L). The results are presented in Table 5. In addition to the sampling noted above, the SMS continuously monitors LLNL sewage effluent in real-time for flow rate, pH, metals, and radioactivity. Standard measurement methods are used to monitor flow and pH to determine permit compliance. Unique nonstandard analytical methods monitor for the presence of metals and radioactivity using x-ray fluorescence (XRF) and gamma spectroscopy, respectively. If an anomalous condition is detected by the monitoring system, an alarm activates LLNL’s Sewer Diversion Facility (SDF) and Livermore Water Reclamation Plant (LWRP) operators are notified that a potential release has occurred.

54 ENVIRONMENTAL SCIENCES↗

Monthly Sewer Monitoring Report for LLNL Livermore Site (Jun 2020)

Lawrence Livermore National Laboratory (LLNL) collects effluent samples from its sewer outfall at the B196 Sewer Monitoring Station (SMS). Effluent flow-proportional composite samples are collected at the SMS on a daily (midnight-to-midnight), weekly (Thursday through Wednesday), and “monthly” (composited from daily) basis; effluent grab samples are also collected each month at that same location. Certified contract laboratories analyze these compliance samples, and results are used to establish LLNL compliance with the 2019 - 2020 Wastewater Discharge Permit (Permit 1250) granted by the City of Livermore Water Resources Division (WRD). Supplemental analyses for biochemical oxygen demand (BOD) and total suspended solids (TSS) are performed onsite and reported for the calculation and assessment of sewer service charges. Quarterly, effluent is sampled for metals (24-hour composite) and cyanide (grab sample) concentrations (mg/L).

54 ENVIRONMENTAL SCIENCES↗

Biosignature Preservation Potential of Sulfate-Rich Rocks From Hogwallow Flats, Jezero Crater, Mars

The Mars 2020 Perseverance Rover discovered fine grained sedimentary rocks in the Hogwallow Flats member of the Shenandoah Formation at the ~3.6- to 3.8-billion-year-old Jezero crater, Mars. Mudstones and sandstones at the 3-meter-thick Hogwallow Flats (HWF) outcrop, and a laterally equivalent outcrop known as “Yori Pass”, show extensive evidence of diagenesis (alteration after deposition). Enhanced preservation of organic matter and other biosignatures can occur in early diagenetic environments associated with aqueous alteration in a lake, floodplain or pro-deltaic setting, as envisaged for HWF and Yori Pass [1]. Three drilled rock cores were collected from HWF-type bedrock as part of the Mars Sample Return Program. They are considered to be the samples with the highest potential to preserve organic compounds and biosignatures out of all samples collected so far by Perseverance (as of mission Sol 1000) [2]. This work outlines the implications of diagenesis for biosignature preservation in rock samples for possible return to Earth.

Mars 2020↗

Measurement of isotopic abundances in collected stratospheric ozone samples

Enrichment of heavy O3 isotopes has been measured in collected stratospheric samples. A balloon-borne cryogenic sampler was used to gather six O3 samples between 26 and 35 km in three flights. Subsequent laboratory mass spectrometer analysis of rare O3 isotopes at both mass 49 and 50 has resulted in more precise measurements than have previously been reported with in situ and ground-based techniques. In one flight, (O-50)3 was enriched by 12-16 percent and (O-49)3 by 9-11 percent, both increasing with altitude. In the remaining two flights, the isotope enrichment was nearly mass-independent at 8-9 percent. The enrichments in O3 at mass 50 are less than the large 40 percent value observed in some stratospheric measurements but similar to (O-49)3 and (O-50)3 fractionations produced in laboratory-generated ozone.

Schueler, B.↗

Isolation and characterization of 13 microsatellite loci for the Neotropical otter, Lontra longicaudis, by next generation sequencing

The Neotropical otter, Lontra longicaudis, is an ecologically important species for freshwater ecosystems that is threatened due to habitat destruction and hunting. However, there is limited information regarding the population sizes, genetic diversity, genetic structure and gene flow of the species, which is crucial for the elaboration of conservation plans. The aim of this study was to isolate and characterize microsatellites for L. longicaudis, using Illumina paired-end-sequencing. Initial amplification tests were performed in 48 loci, out of which, 13 yielded high-quality PCR products and thus were further evaluated. Genetic diversity and discrimination power of the 13 microsatellite loci was assessed using 19 non-invasive samples collected in the Jamapa basin in Veracruz, Mexico and blood samples from six captive individuals. All loci were polymorphic, the number of alleles per locus ranged from 4 to 10, the observed heterozygosity from 0.21 to 0.69, and the expected heterozygosity from 0.55 to 0.82. The combined set of 13 microsatellites showed a high power for discriminating among individuals (probability of identity P ID = 1.551 × 10 -16 ) and among siblings (probability of identity of siblings P IDSIB = 3.349 × 10 -06 ). A combination of nine loci are sufficient to discriminate among siblings with high confidence (P IDSIB < 0.0001). The new set of microsatellites for the Neotropical otter reported here will provide a useful genetic tool to assess population genetic patterns and ecological parameters of the species.

59 BASIC BIOLOGICAL SCIENCES↗

A Five-Year Assessment of Corn Stover Harvest in Central Iowa, USA

Sustainable feedstock harvest strategies are needed to ensure bioenergy production does not irreversibly degrade soil resources. The objective for this study was to document corn (Zea mays L.) grain and stover fraction yields, plant nutrient removal and replacement costs, feedstock quality, soil-test changes, and soil quality indicator response to four stover harvest strategies for continuous corn and a corn-soybean [Glycine max. (L.) Merr.] rotation. The treatments included collecting (1) all standing plant material above a stubble height of 10 cm (whole plant), (2) the upper-half by height (ear shank upward), (3) the lower-half by height (from the 10 cm stubble height to just below the earshank), or (4) no removal. Collectable biomass from Treatment 2 averaged 3.9 ({+-}0.8) Mg ha{sup -1} for continuous corn (2005 through 2009), and 4.8 ({+-}0.4) Mg ha{sup -1} for the rotated corn (2005, 2007, and 2009). Compared to harvesting only the grain, collecting stover increased the average N-P-K removal by 29, 3 and 34 kg ha{sup -1} for continuous corn and 42, 3, and 34 kg ha{sup -1} for rotated corn, respectively. Harvesting the lower-half of the corn plant (Treatment 3) required two passes, resulted in frequent plugging of the combine, and provided a feedstock with low quality for conversion to biofuel. Therefore, Treatment 3 was replaced by a 'cobs-only' harvest starting in 2009. Structural sugars glucan and xylan accounted for up to 60% of the chemical composition, while galactan, arabinan, and mannose constituted less than 5% of the harvest fractions collected from 2005 through 2008. Soil-test data from samples collected after the first harvest (2005) revealed low to very low plant-available P and K levels which reduced soybean yield in 2006 after harvesting the whole-plant in 2005. Average continuous corn yields were 21% lower than rotated yields with no significant differences due to stover harvest. Rotated corn yields in 2009 showed some significant differences, presumably because soil-test P was again in the low range. A soil quality analysis using the Soil Management Assessment Framework (SMAF) with six indicators showed that soils at the continuous corn and rotated sites were functioning at an average of 93 and 83% of their inherent potential, respectively. With good crop management practices, including routine soil-testing, adequate fertilization, maintenance of soil organic matter, sustained soil structure, and prevention of wind, water or tillage erosion, a portion of the corn stover being produced in central Iowa, USA can be harvested in a sustainable manner.

09 BIOMASS FUELS↗

Nanoparticles in road dust from impervious urban surfaces: distribution, identification, and environmental implications

Nanoparticles (NPs) resulting from urban road dust resuspension are an understudied class of pollutants in urban environments with strong potential for health hazards. The objective of this study was to investigate the heavy metal and nanoparticle content of PM2.5 generated in the laboratory using novel aerosolization of 66 road dust samples collected throughout the mega-city of Shanghai (China). The samples were characterized using an array of techniques including inductively-coupled plasma mass spectrometry, aerosol size distribution measurements, and scanning and transmission electron microscopy coupled with elemental characterization and electron diffraction. Principal metal concentrations were plotted geospatially. Results show that metals were generally enriched in aerosolized samples relative to the bulk dust. Elevated concentrations of metals were found mostly in downtown areas with intense traffic. Fe-, Pb-, Zn-, and Ba-containing NPs were identified using electron microscopy, spectroscopy, and diffraction, and we tentatively identify most of them as either engineered, incidental, or naturally occurring NPs. For example, dangerous Pb sulfide and sulfate NPs likely have an incidental origin and are also sometimes associated with Sn; we believe that these materials originated from an e-waste plant. Size distributions of most aerosolized samples presented a peak in the ultrafine range (<100 nm). We estimate that 3.2 ± 0.7 μg mg -1 of Shanghai road dust may become resuspended in the form of PM2.5. Aerosolization, as done in this study, seems to be a very useful approach to study NPs in dust.

54 ENVIRONMENTAL SCIENCES↗

Detection of a Space Capsule Entering Earth’s Atmosphere with Distributed Acoustic Sensing (DAS)

On 24 September 2023, the Origins, Spectral Interpretation, Resource Identification, and Security-Regolith Explorer sample return capsule (SRC) entered Earth’s atmosphere after successfully collecting samples from an asteroid. The known trajectory and timing of this return provided a rare opportunity to strategically instrument sites to record geophysical signals produced by the capsule because it travelled at hypersonic speeds through the atmosphere. For this work, we deployed two distributed acoustic sensing (DAS) interrogators to sample over 12 km of surface-draped fiber-optic cables, as well as six collocated seismometer-infrasound sensor pairs, spread across two sites near Eureka, Nevada. This campaign-style rapid deployment is the first reported recording of an SRC re-entry with any distributed fiber-optic sensing technology. The DAS interrogators recorded an impulsive arrival with an extended coda which had features that were similar to recordings from both the seismometers and infrasound sensors. While the signal-to-noise ratio of the DAS data was lower than the seismic-infrasound data, the extremely dense spacing of fiber-optic sensors allowed for more phases to be clearly distinguished and the visualization of the continuous transformation of the wavefront as it impacted the ground. Unexpectedly, the DAS recordings contain less low-frequency content than is present in both the seismic and infrasound data. The deployment conditions strongly affected the recorded DAS data; in particular, we observed that fiber selection and placement exert strong controls on data quality.

58 GEOSCIENCES↗

Summary of Expedited Results from Samples Supporting Tank Closure Cesium Removal (TCCR) Batch 3

Savannah River Remediation (SRR) is currently operating the Tank Closure Cesium Removal (TCCR) process to remove 137 Cs from tank waste supernate using an ion exchange process. As part of that process, Savannah River National Laboratory (SRNL) receives and analyzes samples in support of the qualification of each batch to be processed. SRNL recently received supernate samples retrieved from Tank 10H as well as in-tank batch contact samples for characterization in support of qualifying Batch 3 for processing through the TCCR unit. SRNL received and characterized a set of dip samples collected from Tank 10H (one surface and one variable depth sample). No solids were observed in either sample and therefore the samples were combined, and a suite of analyses were performed on the composite sample. The density of the combined sample was 1.174 g/mL (0.18 %RSD), which was consistent with the measured sodium concentration of 3.54 M (0.08 %RSD). The 137Cs activity in the sample was 4.75E+07 dpm/mL (4.28 %RSD) and the total Cs concentration was calculated to be 1.54 mg/L (1.16E-05 M). The in-tank batch contact samples consist of 0.1 g of crystalline silicotitanate (CST) contained within a teabag device. Duplicate samples were submerged in Tank 10H supernate for a period of about 13 days, after which time they were retrieved and transferred to SRNL for analysis. At SRNL the CST was rinsed to remove excess salt solution and the CST was then air dried before being digested for analysis. Results of the analysis indicated a 137 Cs loading of 3.66E+10 ± 1.40E+09 dpm/g or 16.5 ± 0.63 Ci/kg CST . This value represents a bounding upper limit as it includes the addition of two sigma uncertainty from replicate analysis of the individual teabag samples as well as the addition of the small amount of 137 Cs activity measured in the rinse solutions. The above values are based on the air-dried mass of CST. Correcting to the true dry mass using a F-factor of 0.8191 results in a maximum loading of 20.2 ± 0.77 Ci/kg CST .

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Sample Type Adaptable RNA depletion performance data [Slides]

Sequencing data was aligned to rRNA data sets QIIME_16S_MiDAS_4.8.1 and SILVA_138.1_LSURef_NR99 using BWA. RNA used was a composite (pool) of wastewater RNA samples collected at LANL between April 2022 and December 2022. RNA sample was split into four aliquots (STAR depletion and STAR depletion no-probe-control as well as RiboZero and RiboZero no-probe-control). All sequencing libraries were prepared from the depleted RNA samples using the same library prep method and sequenced on Illumina platforms.

59 BASIC BIOLOGICAL SCIENCES↗

Assessing kelp nutrient bioextraction capacity in aquaculture farms in the US with implications for conservation and management

This proposal aimed to assess the carbon and nitrogen bioextraction capabilities of sugar kelp farms across a broad geographic range encompassing both the East and West Coasts of the United States. To meet this objective, the project team first developed a cost-effective sampling toolkit using readily available materials and an illustrated protocol to guide kelp farmers in standardized sample collection. Farmers were trained to use the toolkit and prepare samples for shipment to the University of Alaska Fairbanks, where laboratory analyses were conducted to quantify carbon and nitrogen removal. Results were then shared with collaborating farmers, farm managers, regulatory agencies, and the general public to disseminate findings and gauge interest in the bioextraction services offered by kelp aquaculture. The project also investigated temporal and species-specific differences in carbon and nitrogen removal as a complementary objective.

54 ENVIRONMENTAL SCIENCES↗

SPRUCE Pretreatment Plant Tissue Analyses, 2009 through 2013

This data set reports the results of elemental analyses of foliar and stem/woody twig plant tissues collected at the SPRUCE site in 2009, 2012, and 2013. Samples were obtained at various locations around the S1 Bog and from within the developing experimental treatment plots. These are pretreatment vegetation samples, collected prior to initiation of the SPRUCE experiment heating and elevated CO2 treatments. The experimental work was conducted in a Picea mariana [black spruce] – Sphagnum spp. bog forest in northern Minnesota, 40 km north of Grand Rapids, in the USDA Forest Service Marcell Experimental Forest (MEF).

54 ENVIRONMENTAL SCIENCES↗

Production rate calibration for cosmogenic 10 Be in pyroxene by applying a rapid fusion method to 10 Be-saturated samples from the Transantarctic Mountains, Antarctica

Measurements of multiple cosmogenic nuclides in a single sample are valuable for various applications of cosmogenic nuclide exposure dating and allow for correcting exposure ages for surface weathering and erosion and establishing exposure–burial history. Here we provide advances in the measurement of cosmogenic 10 Be in pyroxene and constraints on the production rate that provide new opportunities for measurements of multi-nuclide systems, such as 10 Be/ 3 He, in pyroxene-bearing samples. We extracted and measured cosmogenic 10 Be in pyroxene from two sets of Ferrar Dolerite samples collected from the Transantarctic Mountains in Antarctica. One set of samples has 10 Be concentrations close to saturation, which allows for the production rate calibration of 10 Be in pyroxene by assuming production–decay equilibrium. The other set of samples, which has a more recent exposure history, is used to determine if a rapid fusion method can be successfully applied to samples with Holocene to Last Glacial Maximum exposure ages. From measured 10 Be concentrations in the near-saturation sample set we find the production rate of 10 Be in pyroxene to be 3.74 ± 0.10 atoms g -1 yr -1 , which is consistent with 10 Be/ 3 He paired nuclide ratios from samples assumed to have simple exposure. Given the high 10 Be concentration measured in this sample set, a sample mass of ~ 0.5 g of pyroxene is sufficient for the extraction of cosmogenic 10 Be from pyroxene using a rapid fusion method. However, for the set of samples that have low 10 Be concentrations, measured concentrations were higher than expected. We attribute spuriously high 10 Be concentrations to failure in removing all meteoric 10 Be and/or a highly variable and poorly quantified procedural blank background correction.

58 GEOSCIENCES↗

Active Layer Hydrology in an Arctic Tundra Ecosystem: Quantifying Water Sources and Cycling Using Water Stable Isotopes: Supporting Data

Data include results from water isotope analyses (one *.csv file) for samples collected in Utqiagvik (Barrow), Alaska during August and September 2012. Samples were from surface and soil pore waters from 17 drainages that could be interlake (basins with polygonal terrain), different-aged drain thaw lake basins (young, medium, old, or ancient), or a combination of different aged basins. Samples taken in different drainage flow types at three different depths at each location in and around the Barrow Environmental Observatory. Precipitation stable isotope data are also included (added in October 2019 with no changes to previously released data). This dataset used in Throckmorton, et.al. 2016.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a 10-year research effort (2012-2022) to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Evaluation of digitally corrected ERTS images

The discussion is limited to processes by which a set of data samples collected on a geometrically distorted grid can be converted to samples on a different precisely specified grid. It is assumed that a mathematical expression for the desired transformation already exists. Concern will be the effects on image quality (specifically loss of resolution, photometric accuracy, and miscellaneous aberations) that result from various techniques used in accomplishing the resampling. The resampling techniques evaluated have included nearest neighbor, bilinear, cubic convolution, and various truncated versions of sinc (x). The conclusion is that cubic convolution yields substantially higher quality output data for scenes typically encountered and can, in some instances, substantially enhance one's ability to abstract information.

Taber, J. E.↗

The measurement of carbon monoxide and methane in the National Capital Air Quality Control Region. I - Measurement systems

The Carbon Monoxide Pollution Experiment (COPE) and the National Capital Air Quality Control Region (NCAQCR) undertook a series of measurements of atmospheric CO and CH4 to determine the accuracy of the airborne COPE Correlation Interfer4meter. The device, a modified Michelson interferometer, measures the atmospheric column density of CO and CH4 at 2.3 microns with tropospheric measurement sensitivities of 70 and 10 PPB, respectively. Data for evaluating the remote measurements included atmospheric column density measurements at a ground truth site using a van-mounted infrared Fourier spectrometer; continuous ground level gas chromatographic measurements; and chromatographic data from atmospheric grab samples collected by aircraft and at ground locations. The instruments and sampling techniques used in the experiment are described in detail.

Lebel, P. J.↗

The effect of sample holder material on ion mobility spectrometry reproducibility

When a positive detection of a narcotic occurs during the search of a vessel, a decision has to be made whether further intensive search is warranted. This decision is based in part on the results of a second sample collected from the same area. Therefore, the reproducibility of both sampling and instrumental analysis is critical in terms of justifying an in depth search. As reported at the 2nd Annual IMS Conference in Quebec City, the U.S. Coast Guard has determined that when paper is utilized as the sample desorption medium for the Barringer IONSCAN, the analytical results using standard reference samples are reproducible. A study was conducted utilizing papers of varying pore sizes and comparing their performance as a desorption material relative to the standard Barringer 50 micron Teflon. Nominal pore sizes ranged from 30 microns down to 2 microns. Results indicate that there is some peak instability in the first two to three windows during the analysis. The severity of the instability was observed to increase as the pore size of the paper is decreased. However, the observed peak instability does not create a situation that results in a decreased reliability or reproducibility in the analytical result.

Jadamec, J. Richard↗