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At least 739 records · Page 41

NRAP-Open-IAM: Generic Aquifer Component Development and Testing

The Generic Aquifer Model calculates the concentrations of dissolved salt and dissolved CO 2 surrounding a leaking legacy well. The Generic Aquifer model can also estimate the size of an “impact plume” where concentration changes exceed user-specified thresholds. The model is a component of NRAP-Open-IAM, an open-source Integrated Assessment Model (IAM) developed by the National Risk Assessment Partnership (NRAP) to perform risk assessment for geologic CO 2 storage. The input parameters were selected to cover a wide range of groundwater aquifers and leakage rates. The generic aquifer model was developed using a generative adversarial deep learning network, trained using a large synthetic dataset of STOMP multiphase flow simulations. The deep learning model predictions of dissolved salt and dissolved CO 2 in the aquifer compare well to the original STOMP simulation results. The extent of aquifer impacted by leaking CO 2 or brine is calculated using a user-defined mass fraction threshold. The aquifer impact volumes calculated based on STOMP simulation results compare well to those calculated based on the deep learning model. In a provided python script, gridded observation results from the generic aquifer component of NRAP-Open-IAM are converted to HDF5 format files for monitoring design with the DREAM code.

54 ENVIRONMENTAL SCIENCES↗

Assessment of Carbonated Brine Injection as Low-risk Strategy for Geologic Carbon Storage

The main objective of this early-phase research was to evaluate the techno-economic feasibility and risk associated with combined brine and CO 2 storage in SWD wells using brine dissolution in the North Dakota portion of the Williston Basin. Three simulation studies were conducted to investigate: (1) CO 2 phases at different conditions, (2) wellbore compatibility, and (3) long-term storage fate in reservoir. (1) A simple reservoir model and injection simulations were created using data to represent the BEST (brine extraction and storage test) site, an operational SWD facility located near Watford City, North Dakota. The pressure evolution caused by CO 2 comingled in produced water injectate in a layer cake reservoir was then modeled while tracking aqueous CO 2 throughout the project. The salinity of the injection water, the salinity of the reservoir brine, and the amount of dissolved CO 2 comingled in the injection water were varied. (2) A wellbore corrosion model was performed using the CO 2 concentrations selected based on the reservoir modeling to examine the carbonated produced water impact on wellbore. (3) Reactive transport modeling was conducted with the optimal CO 2 concentration for this injection site to study the rock-fluid interactions and CO 2 fate in the reservoir. Results suggest that CO 2 dissolved in produced water can be injected without appreciably increasing subsurface pressure or leakage risks. Pressure buildup was found to vary with salinity but not with CO 2 mass fraction. Simulation results show that lower CO 2 percent mass fraction leads to a higher amount of CO 2 that can be dissolved at a higher injection salinity. Furthermore, the long-term goal of dissolution trapping in a traditional carbon storage project is accomplished from the start, mitigating risks associated with potential migration of buoyant CO 2 , so long as the reservoir pressure and temperature are used to determine the maximum mass fraction of the dissolved CO 2 .

54 ENVIRONMENTAL SCIENCES↗

Evaluation of the Potential for Precipitation of Solids during Storage of Non-Aluminum SNF Solutions

Non-aluminum clad spent nuclear fuels (NASNF) stored in the L-Area basin will be dissolved in H-Canyon using the 6.3D electrolytic dissolver. The solutions will be stored in either the hot or warm canyon until the preparation of a sludge batch for the Defense Waste Processing Facility. Spent nuclear fuel solutions could be stored for 1-2 years before transfer to the H-Area Tank Farm depending on the interval between sludge batches. The solution level in the storage tanks will be maintained; therefore, precipitation of solids due to evaporation is not an issue. However, the precipitation of solids from completely dissolved SNF due to solution instabilities has been observed during intermediate storage of solutions generating hydrated oxides.The presence of fissile material in these solids is generally associated with zirconium molybdate, which is known to act as a host lattice for Pu and can carry the actinides upon precipitation. The formation of zirconium molybdate solids which carry fissile material is a potential concern for the storage of NASNF solutions. To address this concern, the Savannah River National Laboratory performed a literature review to identify knowledge gaps which may require experimental work to determine if the formation of solids is a concern during storage of these solutions. Based on the literature review, the precipitation of zirconium molybdate solids from the Campaign 1 NASNF solutions during intermediatestorage is expected. This conclusion is supported by the identification of zirconium molybdate solids found on the H-Canyon 6.1D Dissolver MK-12 insert spacer. The formation of the zirconium molybdate solids is attributed to hydrolysis and radiolytic processes in the nitric acid solution. As the molybdate solids form, U and Pu can substitute for Zr in the crystal lattice resulting in co-precipitation. Generally, the Pu substitutes directly into the crystal lattice during precipitation while the U associated with the molybdate solids more likely absorbs from the solution. The U in the NASNF solutions is present as uranyl nitrate, a 2+ cation which will not substitute as easily into the molybdate crystal lattice for the Zr 4+ ion.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of Nitrate, Nitrite, Ammonia, and Tritium in D0220 Cores

This report describes characterization of nitrogen species (nitrate, nitrite, ammonia) in aqueous and solid phases in cores taken in borehole D0220 (well 299-E25-245) under crib 216-A-37-1 at the Hanford Site in 2022 to evaluate (a) the types of nitrogen species currently in the vadose zone and (b) the migration of nitrogen species in the vadose zone. Ammonia and tritium from PUREX decladding condensate were sporadically discharged to the crib from 1977 to 1989. During discharge operations, the estimated travel time through the vadose zone to groundwater was 2.5 to 9 months. By 2003, a characterization borehole (C4106) showed residual pore water with elevated tritium and nitrate in the first 100 ft of the vadose zone, which is likely from the crib. However, there was significantly more nitrate present at the shallowest depth (15 to 22 ft), which may indicate a different source for nitrate, such as adsorbed ammonia slowly being oxidized or nitrogen species precipitates slowly dissolving. In this study, more extensive nitrogen species characterization was done on D0220 cores (drilled in 2022) at 40- and 262-ft depths, which included (a) aqueous nitrate, nitrite, and tritium; (b) adsorbed ammonia; (c) nitrogen in carbonates (or other minerals dissolved in acidic acid); (d) nitrogen in iron oxides (or other minerals dissolved in oxalic acid); and (e) nitrogen in hard-to-extract minerals (minerals dissolved in nitric acid). High pore water nitrate (226 to 331 mg/L) at 40-ft depth measured in D0220 (2022) compared to 60 mg/L at 40-ft depth in C4106 (2003) may indicate nitrate is migrating deeper. Tritium concentrations (pore water 132,000 to 148,000 pCi/L) measured in D0220 at 40-ft depth in 2022 were considerably higher than in C4106 at 40-ft depth (160 pCi/L). Additional nitrogen species mass was present in adsorbed and precipitated phases in D0220 cores. Low adsorbed ammonia was measured at 40.1- and 261.7-ft depths. Low concentrations of carbonate associated nitrogen and iron oxide-associated nitrogen were present at 40.1 and 40.6 ft depths. Nitrogen species in solid phase extractions indicate nitrogen precipitates or aqueous nitrate or ammonia trapped in sediment microfractures that are coated by precipitates. Overall, the nitrogen species and tritium characterization at two depths in D0220 showed that additional nitrogen species were present in the vadose zone. In addition, elevated pore water nitrate in D0220 at 40 ft depth from 2022 may indicate vertical migration compared to C4106 nitrate profile from 2003. Analysis of additional depths in D0220 and spatial variability of the nitrate plume along the length of the crib (from surface electrical resistivity) would be extremely useful for this comparison.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Plutonium Solubility and Supernate Concentration for Neutralized Fast Critical Assembly Discards to Savannah River Site Tank Waste

The Savannah River Site (SRS) plans to dissolve non-irradiated stainless steel (SS)-clad bundles of Fast Critical Assembly (FCA) materials in eighteen batches.1 FCA dissolution is currently underway in the 6.3D dissolver by simultaneous chemical and electrolytic dissolution, which is required to generate the harsh conditions necessary for dissolution of metal-oxide (MOX) and non-aluminum spent nuclear fuels (NASNFs).2 Nitric acid and potassium fluoride are used to promote chemical dissolution.2 Gadolinium will be added during processing as a thermal neutron poison for criticality control. There are no plans for recovering plutonium from this waste stream. After FCA dissolution, the acidic (HNO3/KF) “discards” containing the dissolved metals will be neutralized by addition of 50 wt% sodium hydroxide to a final free hydroxide concentration of 1.2 M.1 Neutralization will precipitate a slurry of insoluble solids, predominantly metal oxides/hydroxides of plutonium, uranium, and SS components. Small fractions of the SS components, Pu, U, and Gd will remain dissolved in the supernate. The neutralized slurry will be composited to existing radioactive waste storage tanks within the SRS Concentration, Storage, and Transfer Facilities (CSTF) containing other similar sludge batch (SB) materials.1 The fate of soluble plutonium and freshly-precipitated, colloidal plutonium from this process are of concern since the total Pu can challenge the waste acceptance criteria (WAC) at the downstream SRS Liquid Waste (LW) facility. Supernate decants including the neutralized FCA discards (nFCAd) within the CSTF will be composited with salt batch (StB) materials and transferred to the SRS Salt Waste Processing Facility (SWPF), where total plutonium is also of concern.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of a bench-scale dissolution concept for the direct extraction of nuclear fuel

Current used nuclear fuel reprocessing efforts utilize a hydrometallurgical approach in which the UNF is dissolved in hot nitric acid followed by solvent extraction into an organic solvent to harvest target nuclides. Previous studies have shown that the dissolution and loading process could be combined into a single organic dissolution/extraction step, producing loaded organic in a single step process. This single step process also includes the advantage of selectively targeting key nuclides in the dissolution while leaving undesirable constituents as part of the undissolved solids. This process is referred to hereafter as direct extraction. Ongoing research from multiple national labs has proven the effectiveness of this technique at research scale. Therefore, potential methods to implement direct extraction at both bench and industrial scale have been developed. The key features of potential dissolver system designs were identified via the team at Pacific Northwest National Laboratory and several designs based on industrial counterparts were assessed for feasibility. This report summarizes the advantages and disadvantages of multiple methods, concluding with a path forward to create multiple unique dissolver designs. The first design will be a single stage recirculating eductor mixer. The second design recommendation is a stator rotor static mixing flow loop design. Each dissolver could be utilized separately, simultaneously, or in series to answer questions surrounding reaction kinetics including residence time, provide a proof of concept for targeted extractions of specific nuclides, and inform needs for industrial scale implementation

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

SPRUCE Outflow Chemistry Data for Experimental Plots Beginning in 2016

This data set includes the chemistry of outflow waters in the SPRUCE experiment plots located in the S1 bog of the USDA Forest Service Marcell Experimental Forest (MEF) in northern Minnesota, 40 km north of Grand Rapids. These data are post-treatment data from the warming and elevated carbon dioxide (CO2) treatments associated with the SPRUCE experiment. There are ten experimental plots in SPRUCE: five temperature treatments (+0, +2.25, +4.5, +6.75, +9°C) at ambient CO2, and the same five temperature treatments at elevated CO2 (+500 ppm). Sample collection and analyses started in March of 2016 and will continue for the duration of the experiment. Samples were analyzed for pH, specific conductivity, anion concentrations (chloride, sulfate), cation concentrations (calcium, potassium, magnesium, sodium, aluminum, iron, manganese, silicon, strontium), nutrient concentrations (ammonium, nitrate, soluble reactive phosphorus, total nitrogen, total phosphorus), and total organic carbon (TOC) concentrations. Subsets of the samples have been analyzed for natural-abundance stable isotopes of water (δ18O-H2O and δD-H2O), dissolved carbon dioxide (δ13C-CO2), and dissolved methane (δ13C-CH4), and concentrations of total mercury (Thg), methylmercury (MeHg), ferrous iron (Fe2+), ferric iron (Fe3+), dissolved inorganic carbon (DIC), and dissolved methane (CH4).

54 ENVIRONMENTAL SCIENCES↗

Hydrothermal Corrosion of Coatings on Silicon Carbide in Boiling Water Reactor Conditions

SiC/SiC ceramic matrix composites are an attractive material for use as accident tolerant fuel cladding. However, despite its resistance to corrosion in high-temperature steam, SiC is known to dissolve in high-temperature water, necessitating the use of corrosion-resistant coatings. Here, samples were exposed in 288°C water with 2 ppmw dissolved oxygen to simulate boiling water reactor (BWR) normal water chemistry (NWC) and 288°C water with 150 ppbw dissolved hydrogen to simulate BWR hydrogen water chemistry. Several candidate coatings were tested: Cr, CrN, TiN, and ZrN. All coatings were applied by physical vapor deposition onto chemical vapor deposition SiC (CVD-SiC) substrates. Two uncoated SiC/SiC variants were also exposed and degraded more rapidly compared to CVD-SiC, especially in NWC. Cr and CrN coated specimens were found to have low mass change, suggesting they are promising candidate coatings. Lastly, TiN coatings were found to oxidize rapidly, suggesting that coatings would fully oxidize during service in BWR environments. ZrN coatings dissolved completely during exposure.

36 MATERIALS SCIENCE↗

Cosmogenic nuclide and solute flux data from central Cuban rivers emphasize the importance of both physical and chemical mass loss from tropical landscapes

We use 25 new measurements of in situ produced cosmogenic 26 Al and 10 Be in river sand, paired with estimates of dissolved load flux in river water, to characterize the processes and pace of landscape change in central Cuba. Long-term erosion rates inferred from 10 Be concentrations in quartz extracted from central Cuban river sand range from 3.4–189 Mg km –2 yr –1 (mean 59, median 45). Dissolved loads (10–176 Mg km –2 yr –1 ; mean 92, median 97), calculated from stream solute concentrations and modeled runoff, exceed measured cosmogenic- 10 Be-derived erosion rates in 18 of 23 basins. This disparity mandates that in this environment landscape-scale mass loss is not fully represented by the cosmogenic nuclide measurements. The 26 Al / 10 Be ratios are lower than expected for steadystate exposure or erosion in 16 of 24 samples. Depressed 26 Al/ 10 Be ratios occur in many of the basins that have the greatest disparity between dissolved loads (high) and erosion rates inferred from cosmogenic nuclide concentrations (low). Depressed 26 Al/ 10 Be ratios are consistent with the presence of a deep, mixed, regolith layer providing extended storage times on slopes and/or burial and extended storage during fluvial transport. River water chemical analyses indicate that many basins with lower 26 Al/ 10 Be ratios and high 10 Be concentrations are underlain at least in part by evaporitic rocks that rapidly dissolve. Our data show that when assessing mass loss in humid tropical landscapes, accounting for the contribution of rock dissolution at depth is particularly important. In such warm, wet climates, mineral dissolution can occur many meters below the surface, beyond the penetration depth of most cosmic rays and thus the production of most cosmogenic nuclides. Our data suggest the importance of estimating solute fluxes and measuring paired cosmogenic nuclides to better understand the processes and rates of mass transfer at a basin scale.

54 ENVIRONMENTAL SCIENCES↗

Concentration-Discharge Relationships in the Six Largest Arctic Rivers, 2003-2019

This dataset provides the results of the analysis of the relationship of dissolved analyte concentrations and river discharges in the six largest Arctic rivers across the global panarctic region (see Figure 1 in documentation file *.pdf). Long-term measurements of dissolved analyte concentrations and river discharge have been collected for each of the Kolyma, Lena, Mackenzie, Ob, Yenisey, and Yukon rivers by the Arctic Great Rivers Observatory (ArcticGRO) project from ~2003-present (Shiklomanov, 2021). The relationship of dissolved analyte concentrations and discharges in each river was characterized by statistical analysis of the slope of the log(concentration) vs log(discharge) (b), the coefficient of variation ratio (CVc/CVq), the 2.5% and 97.5% confidence intervals of b, and assigning a chemostatic, flushing, diluting, or non-systematic behavior category according to Koger (2018). The summary of these analyses for all six rivers is provided in one .csv file. The concentrations of 20 dissolved analytes and discharge measurement data for the individual Kolyma, Lena, Mackenzie, Ob, Yenisey, and Yukon rivers are also provided with this dataset. There are seven *.csv files; one for each river plus the statistical summary. These public ArcticGRO data at "https://www.arcticgreatrivers.org" (Shiklomanov, 2021) were downloaded on Feb 13, 2020, but each river has different measurement dates over the sampling and analysis period. The ArcticGRO metadata document (*.pdf) downloaded on Feb 13, 2020 is also included in this dataset. The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort 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↗

Chemical Signatures Associated with the Freshening of Northern Atlantic Waters Between 1972 and 1981

Further insight into the possible causes of the freshening of deep water in the northern Atlantic between the GEOSECS survey (1972) and the TTO survey (1981) is provided by measurements of dissolved silica and dissolved oxygen. As all the northern end member waters are low in dissolved silica content and high in dissolved oxygen content, the message carried by these chemical properties of silica has to do with the extent to which the waters in the northern Atlantic have mixed with the high silica content waters of Antarctic origin. A change in the degree and pattern of this intrusion is noted between the GEOSECS and TTO surveys.

Broecker, W. S.↗

Sulfur transformations in the sediments of a New Hampshire salt marsh

Summer sulfate reduction and sulfide and iron chemistry were monitored in marsh soils along a gradient from a creekside Spartina alterniflora region to an inland area dominated by S. patens. Sulfate reduction rates measured using S-35 increased from 0.4 in June to as much as 4.5 micro-mole/ml(sup -1)d(sup -1) in July in S. alterniflora soils with most rapid rates occurring in the upper few cm. Rates in S. patens soils were approximately equal to 5-8 fold slower with the most rapid rates occurring generally in soils deeper than 10 cm. The recovery percentage of reduced S-35 sulfur varied with depths at both locations; dissolved and acid-volatile sulfides dominating S. alterniflora regions while chromium-reducible solid phases were abundant in S. patens soils. Dissolved sulfide in S. alterniflora soils increased throughout the summer to approximately equal to 2.8 mM while sulfide in S. patens soils was abundant only in soils deeper than 15 cm. Dissolved sulfide covaried inversely with iron. Diel studies demonstrated that sulfide and iron varied approximately equal to two-fold in response to a semi-diurnal tide. Dissolved sulfide turnover was most rapid during periods of active plant growth.

Hines, Mark E.↗

C-O volatiles in Apollo 15 and Apollo 17 picritic glasses

A15 and A17 primitive picritic glasses have been examined by FTIR for the presence of dissolved C-O species to determine the role of C-O gasses on driving lunar fire-fountains. A15 green and yellow glasses were extensively studied and found to be free of dissolved C species down to FTIR detection limits (10-100 ppm; species and sample specific). Preliminary data on A17 orange glasses are similarly devoid of FTIR detectable C-O species. Re-analyses of the C-O driving mechanism theory for mare volcanism demonstrates the need to determine the fO2 of the lunar interior; the factor that most critically determined the role of C gasses in the fire-fountaining events. Oxygen fugacities equivalent to IW-0.5 and above imply dissolved CO3(=) in the primitive glasses at levels above FTIR detection. The f02's below IW-0.5 imply concentrations of CO3(=) below FTIR detection. Recent data suggesting lunar mantle fO2's of IW-2 or less, strongly mitigate against finding FTIR measurable dissolved CO3(=) consistent with the findings of this study.

Rutherford, Malcolm J.↗

Interpretation of the coastal zone color scanner signature of the Orinoco River plume

The Caribbean Sea is an area that traditionally has been considered oligotrophic, even though the Orinoco River contributes large quantities of fresh water, nutrients, and other dissolved material to this region during the wet boreal (fall) season. Little is known about the impact of this seasonal river plume, which extends from Venezuela to Puetro Rico shortly after maximum discharge. Here, we present results from a study of the bio-optical characteristics of the Orinoco River plume during the rainy season. The objective was to determine whether the coastal zone color scanner (CZCS) and the follow-on sea-viewing wide-field-of-view sensor (SeaWiFS) satellite instrument can be used to assess the concentrations of substances in large river plumes. Recent in situ shipboard measurements were compared to values from representative historical CZCS images using established bio-optical models. Our goal was to deconvolve the signatures of colored dissolved organic carbon and phytoplankton pigments within satellite images of the Orinoco River plume. We conclude that the models may be used for case 2 waters and that as much as 50 percent of the remotely sensored chlorophyll biomass within the plume is an artifact due to the presence of dissolved organic carbon. Dissolved organic carbon originates from a number of sources, including decay of dead organisms, humic materials from the soil, and gelbstoff.

Hochman, Herschel T.↗

Module for Oxygenating Water without Generating Bubbles

A module that dissolves oxygen in water at concentrations approaching saturation, without generating bubbles of oxygen gas, has been developed as a prototype of improved oxygenators for water-disinfection and water-purification systems that utilize photocatalyzed redox reactions. Depending on the specific nature of a water-treatment system, it is desirable to prevent the formation of bubbles for one or more reasons: (1) Bubbles can remove some organic contaminants from the liquid phase to the gas phase, thereby introducing a gas-treatment problem that complicates the overall water-treatment problem; and/or (2) in some systems (e.g., those that must function in microgravity or in any orientation in normal Earth gravity), bubbles can interfere with the flow of the liquid phase. The present oxygenation module (see Figure 1) is a modified version of a commercial module that contains >100 hollow polypropylene fibers with a nominal pore size of 0.05 m and a total surface area of 0.5 m2. The module was originally designed for oxygenation in a bioreactor, with no water flowing around or inside the tubes. The modification, made to enable the use of the module to oxygenate flowing water, consisted mainly in the encapsulation of the fibers in a tube of Tygon polyvinyl chloride (PVC) with an inside diameter of 1 in. (approx.=25 mm). In operation, water is pumped along the insides of the hollow fibers and oxygen gas is supplied to the space outside the hollow tubes inside the PVC tube. In tests, the pressure drops of water and oxygen in the module were found to be close to zero at water-flow rates ranging up to 320 mL/min and oxygen-flow rates up to 27 mL/min. Under all test conditions, no bubbles were observed at the water outlet. In some tests, flow rates were chosen to obtain dissolved-oxygen concentrations between 25 and 31 parts per million (ppm) . approaching the saturation level of approx.=35 ppm at a temperature of 20 C and pressure of 1 atm (approx.=0.1 MPa). As one would expect, it was observed that the time needed to bring a flow of water from an initial low dissolved-oxygen concentration (e.g., 5 ppm) to a steady high dissolved-oxygen concentration at or near the saturation level depends on the rates of flow of both oxygen and water, among other things. Figure 2 shows the results of an experiment in which a greater flow of oxygen was used during the first few tens of minutes to bring the concentration up to approx.=25 ppm, then a lesser flow was used to maintain the concentration.

Gonzalez-Martin, Anuncia↗

Weathering in the Forelands of Two Rapidly Retreating Alpine Glaciers of Volcanic Bedrock in the Three Sisters, Oregon, USA

The glaciers of the Three Sisters volcanoes in Cascadia have retreated dramatically over the past century. In order to understand ongoing chemical weathering and solute transport in the proglacial valleys, waters were sampled from glacier outwash streams, local snowmelt, and proglacial springs and lakes at Collier and Diller Glaciers. To understand weathering and transport processes in the proglacial plains, infrared orbital remote sensing data was used to map compositional variability and highlight weathering products, which were then ground-truthed with laboratory mineralogical and chemical analyses of sediments. The hydrochemistry is significantly affected by a sub- and proglacial mafic weathering system lacking carbonate minerals. Here we report major ion concentrations in meltwaters for the summer 2016 and 2017 melt seasons. Total cation concentrations range from 3 to 250 μeq/l and dissolved bicarbonate concentrations range from 2 to 200 μeq/l. Other dissolved anions are negligible compared to bicarbonate. Dissolved silica concentrations range from 2 to 260 μmol/l, comparable to total dissolved cation concentrations. The highest cation and silica concentrations were measured in moraine-sourced springs. Compositional remote sensing analysis identified alteration zones in the proglacial plains at both Collier and Diller indicating potential hydrated silica. This analysis is consistent with laboratory analysis of sediment samples, which indicate the presence of poorly crystalline phases weathering products, including hydrated silica. Weathered materials are preferentially deposited on moraines due to aeolian and glacial transport, as well as intra-moraine alteration, and at abandoned stream terraces due to fluvial transport. Geochemical measurements indicate that the predominant form of chemical weathering in these periglacial mafic systems is the carbonation of feldspar as well as reactive volcanic glass. The presence of poorly crystalline silicates, as indicated by remote sensing datasets and laboratory analysis, is consistent with rapid weathering of feldspars and glass and formation of Fe-Al-Si-bearing mineraloids in these proglacial valleys. This weathering regime has wide-ranging implications for atmospheric CO2 drawdown due to cold-climate volcanic rock weathering.

Rutledge, Alicia M.↗

Abundant phosphorus expected for possible life in Enceladus’s ocean

Saturn’s moon Enceladus has a potentially habitable subsurface water ocean that contains canonical building blocks of life (organic and inorganic carbon, ammonia, possibly hydro-gen sulfide) and chemical energy (disequilibria for methanogenesis). However, its habit-ability could be strongly affected by the unknown availability of phosphorus (P). Here, we perform thermodynamic and kinetic modeling that simulates P geochemistry based on recent insights into the geochemistry of the ocean–seafloor system on Enceladus. We find that aqueous P should predominantly exist as orthophosphate (e.g., HPO422), and total dissolved inorganic P could reach 1027to 1022mol/kg H2O, generally increasing with lower pH and higher dissolved CO2, but also depending upon dissolved ammonia and silica. Levels are much higher than<10210mol/kg H2Ofrompreviousestimatesand close to or higher than∼1026mol/kg H2O in modern Earth seawater. The high P concentration is primarily ascribed to a high (bi)carbonate concentration, which decreases the concentrations of multivalent cations via carbonate mineral formation, allowing phosphate to accumulate. Kinetic modeling of phosphate mineral dissolution suggests that geologically rapid release of P from seafloor weathering of a chondritic rocky core could supply millimoles of total dissolved P per kilogram of H2Owithin105y, much less than the likely age of Enceladus’s ocean (108to 109y). These results provide further evidence of habitable ocean conditions and show that any oceanic life would not be inhibited by low P availability.

Enceladus ocean↗

Virus Infection of Phytoplankton Increases Average Molar Mass and Reduces Hygroscopicity of Aerosolized Organic Matter

Viral infection of phytoplankton is a pervasive mechanism of cell death and bloom termination, which leads to the production of dissolved and colloidal organic matter that can be aerosolized into the atmosphere. Earth-observing satellites can track the growth and death of phytoplankton blooms on weekly time scales but the impact of viral infection on the cloud forming potential of associated aerosols is largely unknown. Here, we determine the influence of viral-derived organic matter, purified viruses, and marine hydrogels on the cloud condensation nuclei activity of their aerosolized solutions, compared to organic exudates from healthy phytoplankton. Dissolved organic material derived from exponentially growing and infected cells of well-characterized eukaryotic phytoplankton host-virus systems, including viruses from diatoms, coccolithophores and chlorophytes, was concentrated, desalted, and nebulized to form aerosol particles composed of primarily of organic matter. Aerosols from infected phytoplankton cultures resulted in an increase in critical activation diameter and average molar mass in three out of five combinations evaluated, along with a decrease in organic kappa (hygroscopicity) compared to healthy cultures and seawater controls. The infected samples also displayed evidence of increased surface tension depression at realistic cloud water vapor supersaturations. Amending the samples with xanthan gum to simulate marine hydrogels increased variability in organic kappa and surface tension in aerosols with high organic to salt ratios. Our findings suggest that the pulses of increased dissolved organic matter associated with viral infection in surface waters may increase the molar mass of dissolved organic compounds relative to surface waters occupied by healthy phytoplankton or low phytoplankton biomass.

Atmospheric science↗