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At least 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2010

Hopewell Beneficial CO2 Capture for Production of Fuels, Fertilizer and Energy

For Phase 1 of this project, the Hopewell team developed a detailed design for the Small Scale Pilot-Scale Algal CO2 Sequestration System. This pilot consisted of six (6) x 135 gallon cultivation tanks including systems for CO2 delivery and control, algal cultivation, and algal harvesting. A feed tank supplied Hopewell wastewater to the tanks and a receiver tank collected the effluent from the algal cultivation system. The effect of environmental parameters and nutrient loading on CO2 uptake and sequestration into biomass were determined. Additionally the cost of capturing CO2 from an industrial stack emission at both pilot and full-scale was determined. The engineering estimate evaluated Amine Guard technology for capture of pure CO2 and direct stack gas capture and compression. The study concluded that Amine Guard technology has lower lifecycle cost at commercial scale, although the cost of direct stack gas capture is lower at the pilot scale. Experiments conducted under high concentrations of dissolved CO2 did not demonstrate enhanced algae growth rate. This result suggests that the dissolved CO2 concentration at neutral pH was already above the limiting value. Even though dissolved CO2 did not show a positive effect on biomass growth, controlling its value at a constant set-point during daylight hours can be beneficial in an algae cultivation stage with high algae biomass concentration to maximize the rate of CO2 uptake. The limited enhancement of algal growth by CO2 addition to Hopewell wastewater was due at least in part to the high endogenous CO2 evolution from bacterial degradation of dissolved organic carbon present at high levels in the wastewater. It was found that the high level of bacterial activity was somewhat inhibitory to algal growth in the Hopewell wastewater. The project demonstrated that the Honeywell automation and control system, in combination with the accuracy of the online pH, dissolved O2, dissolved CO2, turbidity, Chlorophyll A and conductivity sensors is suitable for process control of algae cultivation in an open pond systems. This project concluded that the Hopewell wastewater is very suitable for algal cultivation but the potential for significant CO2 sequestration from the plant stack gas emissions was minimal due to the high endogenous CO2 generation in the wastewater from the organic wastewater content. Algae cultivation was found to be promising, however, for nitrogen remediation in the Hopewell wastewater.

09 BIOMASS FUELS↗
DOE OSTI2018

Intraday Water Quality Patterns in East Fork Poplar Creek with an Emphasis on Mercury and Monomethylmercury

We conducted a diel sampling campaign at three locations along the Hg contaminated East Fork Poplar Creek (EFPC) in Oak Ridge, Tennessee to (i) quantify diel patterns of particulate and dissolved mercury (Hg) and monomethylmercury (MMHg) (Hg D , Hg P , MMHg D , and MMHg P , respectively) and associated water quality parameters along a longitudinal gradient of EFPC during the summer season, (ii) determine if diel patterns in Hg and/or MMHg are related to the daily photocycle or any other short term cycle, such as wastewater treatment plant discharge, (iii) determine if diel variability in turbidity and dissolved organic matter (DOM) composition correspond to particulate Hg P or MMHg P and dissolved organic carbon (DOC) or dissolved Hg D or MMHg D . Samples were collected every two hours for a 30 hour period. The farthest upstream site was located at the boundary of Y-12 and the City of Oak Ridge (EFK 23.4) while two additional sites were located 7.2 kilometers (Wiltshire Drive, EFK 16.2) and 18 kilometers (Horizon Center, EFK 5.4) downstream of EFK 23.4). Hg P and MMHg P concentrations increased overnight at EFK 16.2 and EFK 5.4 coincident with increases in turbidity and total suspended solids (TSS). These overnight increases were likely due to diel changes in the activity of macrobiota (re)suspending contaminated sediments in the creek. Both Hg D and MMHg D were higher during the day at EFK 23.4 and EFK 5.4. The underlying causes for the patterns in Hg D and MMHg D are less clear but correspond with similar patterns in DOC concentration and DOM composition. Photochemical reactions may also play a role in these Hg D , MMHg D , DOC, and DOM patterns. Total loads of both Hg and MMHg increased with downstream distance. The greatest increase in loading occurred in the reach from EFK 23.4 to EFK 16.2 which encompasses areas where the Historic Release Deposits (HRD) have been identified. These results demonstrate that diffuse legacy sources of Hg, outside of Y-12, contribute Hg load to EFPC. Both total and dissolved MMHg loads increased approximately linearly with downstream distance. Particluate MMHg loading increased in the upper reach but did not change over the lower reach. The HRD may contribute to MMHg P load in the upper reach but most of the total, dissolved, and particulate MMHg appears to originate from in-stream production. Due to intraday patterns in concentration and flow rate, loading estimates are best derived from diel sampling campaigns. Intraday patterns in Hg and MMHg concentration and speciation have implications with respect to biotic exposure. Greater biotic activity and feeding during times of higher concentration would correspond to greater exposure than estimated from daily or longer-term averages. Both Hg and MMHg responded rapidly to processes governing their concentration. This latter point is encouraging from the perspective of site remediation as it suggests that MMHg concentrations and flux in EFPC would respond rapidly to appropriate remedial actions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

CoDCon Project (Final Report)

The co-decontamination (CoDCon) project was established in FY 2016 with the objectives of (a) evaluating the uncertainty in the uranium (U)/plutonium (Pu) ratio in a mixed U/Pu product from a tributyl phosphate (TBP)–based solvent extraction flowsheet, and (b) developing and demonstrating on-line optical spectroscopy for real-time monitoring of key components (e.g., Pu, U, and HNO 3 concentrations) in the process solutions. We were interested in assessing the accuracy and precision to which a specific uranium-to-plutonium (U/Pu) ratio can be achieved, which for the purposes of this project was set at a U/Pu mass ratio of 7/3. The uncertainty associated with achieving this specific target U/Pu ratio was investigated during five flowsheet tests using laboratory-scale solvent extraction equipment. In addition, optical spectroscopic techniques were incorporated into the CoDCon solvent extraction testing system, allowing real time monitoring of all input and output process streams. Two CoDCon flowsheet tests were performed in FY 2018 using a simple dissolved fuel simulant containing only U (~1 M) and Pu (~15 mM) in nitric acid (HNO 3 ; ~3 M). In FY 2019, two additional flowsheet tests were performed. For the first of these (CoDCon Run 3), the dissolved fuel simulant was similar to that used in the first two tests, with the inclusion of 1 mM neptunium (Np). The second test conducted in FY 2019 (CoDCon Run 4) used a more representative dissolved fuel simulant, including addition of non-radioactive fission product elements. A fifth CoDCon flowsheet test (CoDCon Run 5) was conducted in FY 2020, with the following additional objectives: (1) routing of the technetium (Tc) in the simulated dissolved fuel solution to the solvent extraction raffinate, and (2) routing of the Np in the simulated dissolved fuel solution to the U/Pu product. All tests used a bank of sixteen 2 cm centrifugal contactors. The tests involved first loading the solvent (30 vol% TBP dissolved in n-dodecane) with U and Pu (and Np, for Run 5), then the Pu (and Np) was stripped from the loaded solvent with a U(IV) solution (~50 mM) and the flowsheet conditions were adjusted such that some U partitioned into the Pu-containing product stream. The amount of U accompanying the Pu was monitored in real time using optical spectroscopic techniques coupled with chemometric modeling. Based on the real-time spectroscopic measurement of the U/Pu ratio, adjustments were made to the flowrate of the fresh TBP solvent phase used to scrub U from the aqueous Pu-containing product. This proved to be a very effective way to control the U/Pu mass ratio in the product. This report presents the results of the CoDCon Run 5 test. The flowsheet tested in Run 5 was substantially different than that run in the prior tests, especially the solvent loading section of the flowsheet. Two key changes were made. First, based on the objective to extract all the Np and route it with the U/Pu product, pentavalent vanadium [V(V)] was added to the feed and scrub solutions. The purpose of the V(V) was to convert all the Np to the +6 oxidation state, which is extractable by TBP. Second, a high acid (8 M HNO 3 ) scrub was added to the flowsheet to scrub the Tc from the solvent. This was followed by a low acid scrub (0.05 M HNO 3 ) to reduce the residual HNO 3 concentration in the solvent prior to the Pu stripping step. The output from the low acid scrub was collected separately, rather than routing towards the raffinate. The modifications to the solvent loading part of the flowsheet were only partially successful. The treatment with V(V) was effective at converting the Np to Np(VI). Only 1.3% of the Np remained in the raffinate solution. However, ~40% of the Np stripped out of the solvent in the low acid scrub step; nearly 20% of the Pu also was stripped from the solvent during the low acid scrub. For further development, either modifications to the flowsheet, or concentration and recycle of the low acid stream into the

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Non-Fouling, Low Cost Electrolytic Coagulation & Disinfection for Treating Flowback and Produced Water for Reuse

Executive Summary This Final Report is composed of two major sections. The first section presents experimental results obtained in the laboratory during Budget Period 1. The second section presents results from the field test conducted during Budget Period 2. Laboratory Results This research investigated a novel electrochemical process for producing a ferric iron coagulant for use in treating flowback and produced water from hydraulic fracturing and oil production operations. The treatment system improves the effectiveness and lowers the cost of coagulation processes using Fe3+ as the coagulant. The electrolytic coagulant generation (ECG) system uses an electrochemical cell to produce acid and base from oilfield brine solutions. The acid is used to dissolve scrap iron to provide a Fe3+ coagulating agent. The base is used to neutralize the treated water. Compared to conventional electrocoagulation (EC), the main advantage of the ECG system is an order of magnitude lower cost for the source of iron. The second advantage over conventional EC is that it can deliver Fe3+ doses greater than 1 mM, since it is not limited by the amount of dissolved oxygen in the water required to oxidize ferrous to ferric iron. The capital costs for conventional EC and the ECG system are similar, but the operational costs for the ECG system are an order of magnitude lower than conventional EC. The combined costs for iron and electrical energy for treating 1 m3 of FPW with 1 mM Fe3+ is estimated to be $0.87 for conventional EC, and $0.087 for the ECG system. The estimated all-in cost for treating FPW with a 2 mM Fe3+ dose is $0.73/m3 ($0.12/bbl). Field Test Results The field test was conducted at the Paul Foster Central Tank Battery (CTB) in Lea County, New Mexico from November 10, 2022 through December 15, 2022. The feed water to the system was produced water from the Tatanka 1H formation. After approximately two weeks of testing, the initial batch of produced water had been treated and no untreated produced water was available. Thus, after this time, the feed water to the system consisted of previously treated water (i.e., recycled water). The recycled water had nearly all colloidal particles removed, and had a much lower alkalinity due to precipitation of carbonate minerals during the first pass through the system. Although the recycled water was not an ideal test solution due to its low particulate concentrations, its lower alkalinity did allow us to identify the main problem with the treatment system. The main problem with the treatment system was caused by the high alkalinity of the initial feed water (5.4 meq/L) that consumed a significant fraction of the electrochemically generated acid. This resulted in pH values exiting the iron contact tank that were too high to dissolve enough iron to effectively treat the produced water. Tests performed with recycled water with lower alkalinity did not have this issue, and dissolved iron concentrations greater than 20 mM could be achieved. One consistent observation was that effluent water from the iron contact tank was always free of particulates, even when fed with circumneutral solutions. This suggests that there is no need to dissolve high concentrations of iron if all the water to be treated is passed through the scrap iron canister. In this case, dissolved O2 and hypochlorous acid can promote sufficient iron corrosion to provide an effective coagulating agent – even in neutral pH water. This solves the problem resulting from highly alkaline produced water. Modifications to the design of the treatment system were made based on the field test results. These modifications will add minimal additional cost, and were tested in bench-scale laboratory experiments. In short-term testing, the modified treatment process was able to remove colloidal FeS particulates to levels below detection. Long-term, steady state testing will be required to determine whether the modified process is suitable for commercial treatment systems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Slow Strain Rate Testing of A537 Tank Wall Material

At Savannah River Site (SRS), High-Level Waste is stored in below-grade carbon steel tanks. This waste in part consists of sludge, salt cake, and/or supernate. Preparation of this waste for future processing involves dissolution of the salt cake layer. The salt dissolution process can create conditions that leave the carbon steel tanks susceptible to localized corrosion. The salt to be dissolved contains high concentrations of nitrate, that once released, create an environment that may be conducive to pitting corrosion and/or stress corrosion cracking (SCC) of carbon steel. The salt dissolution process also liberates interstitial liquid trapped between the salt crystals. This liquid is initially high in nitrite and hydroxide concentration. High pH and greater ratios of nitrite to nitrate act as inhibitors to minimize corrosion of carbon steel in high nitrate environments. However, as dissolution proceeds, the concentration of nitrate will increase, while the hydroxide and nitrite concentration of the interstitial liquid will deplete and become insufficient to prevent the onset of corrosion attack. Tank blending and the addition of inhibitors are used to ensure adequate concentrations of hydroxide and nitrite. However, this is not desirable during salt dissolution as it can reduce process efficiency and increase the amount of waste that needs processing. This testing program was designed to examine the risk of SCC associated with utilizing the pitting factor (PF) and nitrite/nitrate (NO 2 - /NO 3 - ) ratio limits for handling dissolved salt solutions at an elevated temperature in the carbon steel waste tanks. The previously identified limits are a PF of 1.2 and an NO 2 - /NO 3 - ratio of 0.15. The results indicate that as long as the NO 2 - /NO 3 - ratio exceeds 0.1 and the PF is above approximately 0.8, there is a discernible safety margin between the open circuit potential (OCP) and the critical cracking potential (CCP) observed during applied potential testing. However, this margin, defined by the difference between the OCP and CCP, is relatively narrow, ranging from 0.1 to 0.25 volts. This small margin raises concerns about potential shifts in OCP during waste retrieval operations, which could inadvertently increase the risk of SCC if the OCP approaches or exceeds the CCP. These results confirm that dissolved salt solutions provide a potent chemistry that, under certain conditions, makes carbon steel susceptible to SCC. The next question to consider is the influence these results have on decisions for storage and retrieval of waste from the tanks. For Type III/IIIA waste tanks, the risk of SCC remains very low. First, and most importantly, the post-weld stress relief of the tanks has reduced the residual stress near the welds. Thus, without the stress component, SCC risk is minimized. The material of construction (A537 Carbon steel) for the Type III/IIIA tanks is superior to the steel in its resistance to SCC than the steel that was utilized for the Type I, II, and IV tanks (A285 carbon steel). From a chemistry control standpoint for a Type III/IIIA tank directly involved with handling dissolved salt solutions, the PF and NO 2 - /NO 3 - ratio limits may be utilized wherein chemistry control provides an extra layer of defense against SCC. Chemistry control for a Type III/IIIA tank minimizes the risk for a tank that may receive the dissolved salt solution, particularly if that tank is a Type I, II, or IV waste tank. On the other hand, if the dissolved salt solution is handled by a Type I, II, or IV waste tank the risk of SCC is real. The potent chemistry, absence of stress relief, and inferior material result in a condition that is conducive to cracking. Efforts should be made to either avoid transferring waste that may not meet the PF and NO 2 - /NO 3 - ratio criteria to one of these tanks or if it is unavoidable, take measures to minimize the consequences of a leak. As shown by these tests, even if the PF and NO 2 - /NO 3 - ratio criteria are met, there is a risk that the tank potential may be disturbed in the positive direction and the risk of SCC increase.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1992

The role of certain infauna and vascular plants in the mediation of redox reactions in marine sediments

The mechanisms by which certain animals and plants affect redox processes in sediments was examined by studying three environments: (1) subtidal sediments dominated by the deposit-feeding polychaete Heteromastus filiformis; (2) a saltmarsh inhabited by the tall form of Spartina alterniflora; and (3) tropical carbonate sediments inhabited by three species of seagrasses. S-35-sulfide production rates were compared to pool sizes of dissolved sulfide and dissolved iron. In all of the sediments studied, rates of sulfide reduction were enhanced by macroorganisms while the rate of turnover of dissolved sulfide increased. The polychaete enhanced microbial activity and redox cycling primarily by subducting particles of organic matter and oxidized iron during sediment reworking. The Spartina species enhanced anaerobic activity by transporting primarily dissolved organic matter and oxidants. Although the final result of both animal and plant activities was the enhancement of sub-surface cycling of sulfur and iron, decreased dissolved sulfide and increased dissolved iron concentrations, the mechanisms which produced these results differed dramatically.

Hines, Mark E.↗
DOE OSTI2020

SRS Strategy for Tank 3 Salt Dissolution - Performance and Lessons Learned - 20441

The Savannah River Site (SRS) Tank Farms have 51 underground waste tanks used to store and process liquid nuclear waste materials. There are 4 different tank types, ranging in capacity from 2,840,000 to 4,920,000 L (750,000 to 1,300,000 Gal). Twenty-four of the tanks are older style and do not meet full secondary containment standards. The older style tanks are the initial focus of waste removal efforts for tank closure at SRS. Eight of these twenty-four tanks have completed waste removal and are filled with grout. Prior to salt dissolution, Tank 3 was a dry salt tank that contained 5.06 m (199.3 in) of salt and sludge waste. Additional salt waste was present on cooling coils above the salt layer up to approximately 5.59 m (220 in). Three mixing eductors were installed in Tank 3 to aid in dissolving salt waste in three tank riser access ports. A transfer pump was installed, and the transfer pump suction was located 25.4 cm (10 in) from the tank bottom. Well water was added to the tank through a downcomer until the dry bulk salt was covered with liquid. During the initial fill of Tank 3, approximately 242,000 L (64,000 Gal) of rain water were added from periodic F-Tank Farm (FTF) Catch Tank additions and approximately 17,000 L (4,500 Gal) of well water were added. Following liquid additions to cover the dry bulk salt, well water was added through the three mixing eductors in batches during each stage. Additionally, during the salt dissolution campaigns, the FTF Catch Tank was utilized to add rain water through a downcomer in the center tank riser access port as needed for volume relief in the FTF Catch Tank. Following liquid additions, the water was recirculated (internal to the tank) using the transfer pump, and a sample was pulled to confirm the target specific gravity (SpG) of the dissolved salt solution was achieved. The dissolved salt solution was then transferred to the receipt tank (Tank 7), and the mixing eductors were lowered as close to the new bulk salt layer as possible, to support subsequent dissolution campaigns. While the mixing jets were able to dissolve salt successfully in Tank 3, they did not do so in a completely uniform manner. Throughout dissolution, mounds were discovered under Riser 1, Riser 2, and the Center Riser. The mixing jets dissolved the salt around the edges of the tank well but were not as effective toward the center of the tank. FTF Catch Tank additions through the center tank riser access port downcomer were required to impact the mound under the center tank riser. FTF Catch Tank additions were sporadic as they were dependent on rainfall in the area. Additionally, all mixing jets were rarely able to be lowered to the same elevation, indicating some mounding in the bulk salt layer. Indexing of the mixing jets was also utilized to impact the salt mounds. Overall, Tank 3 salt dissolution was successful as approximately 1,476,000 L (390,000 Gal) of dissolved salt solution was transferred to Tank 7 over six stages. Slightly less than 852,000 L (225,000 Gal) of water were added to Tank 3. The original material balance prediction estimated that the bulk salt level in Tank 3 would be 3.88 m (152.8 in) after six salt dissolution stages. After six stages the actual bulk salt level was 3.38 m (133 in). This paper will discuss the salt removal strategy, each salt dissolution stage, and lessons learned for future salt dissolution. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Zirconium Sludge Criticality Calculations in Large Process Tanks

The Savannah River Site’s (SRS) H-Canyon recently re-activated its 6.3D electrolytic dissolver to dissolve stainless steel clad research reactor fuels from Japan. A potential new mission was identified to dissolve other long-cooled fuel stored at SRS that is not aluminum clad. In the basic process of dissolution, the spent fuel dissolves into nitric acid (bulk solution). The eight ft. high and four ft. radius 6.3D dissolver is unique in that it has a platinum-coated niobium insert to resist corrosion, and the niobium basket forms an anode and cathode arrangement within the charge chute (Fig 1,2). DC current flows from anode to cathode, at up to 10,000 amps at 45 volts, through the potential gradient in the nitric acid solution, which allows the stainless steel (or other non-aluminum cladding) of the fuel to dissolve.

Wade, Brindley↗
DOE OSTI2012

Simulation of annual biogeochemical cycles of nutrient balance, phytoplankton bloom(s), and DO in Puget Sound using an unstructured grid model

Nutrient pollution from rivers, nonpoint source runoff, and nearly 100 wastewater discharges is a potential threat to the ecological health of Puget Sound with evidence of hypoxia in some basins. However, the relative contributions of loads entering Puget Sound from natural and anthropogenic sources, and the effects of exchange flow from the Pacific Ocean are not well understood. Development of a quantitative model of Puget Sound is thus presented to help improve our understanding of the annual biogeochemical cycles in this system using the unstructured grid Finite-Volume Coastal Ocean Model framework and the Integrated Compartment Model (CE-QUAL-ICM) water quality kinetics. Results based on 2006 data show that phytoplankton growth and die-off, succession between two species of algae, nutrient dynamics, and dissolved oxygen in Puget Sound are strongly tied to seasonal variation of temperature, solar radiation, and the annual exchange and flushing induced by upwelled Pacific Ocean waters. Concentrations in the mixed outflow surface layer occupying approximately 5–20 m of the upper water column show strong effects of eutrophication from natural and anthropogenic sources, spring and summer algae blooms, accompanied by depleted nutrients but high dissolved oxygen levels. The bottom layer reflects dissolved oxygen and nutrient concentrations of upwelled Pacific Ocean water modulated by mixing with biologically active surface outflow in the Strait of Juan de Fuca prior to entering Puget Sound over the Admiralty Inlet. The effect of reflux mixing at the Admiralty Inlet sill resulting in lower nutrient and higher dissolved oxygen levels in bottom waters of Puget Sound than the incoming upwelled Pacific Ocean water is reproduced. Finally, by late winter, with the reduction in algal activity, water column constituents of interest, were renewed and the system appeared to reset with cooler temperature, higher nutrient, and higher dissolved oxygen waters from the Pacific Ocean.

biogeochemical model, 3-D hydrodynamic model, nutr↗
DOE OSTI2018

Redox Fluctuations Control the Coupled Cycling of Iron and Carbon in Tropical Forest Soils

In this paper, oscillating redox conditions are a common feature of humid tropical forest soils, driven by an ample supply and dynamics of reductants, high moisture, microbial oxygen consumption, and finely textured clays that limit diffusion. However, the net result of variable soil redox regimes on iron (Fe) mineral dynamics and associated carbon (C) forms and fluxes is poorly understood in tropical soils. Using a 44-day redox incubation experiment with humid tropical forest soils from Puerto Rico, we examined patterns in Fe and C transformations under four redox regimes: static anoxic, "flux 4-day" (4d oxic, 4d anoxic), "flux 8-day" (8d oxic, 4d anoxic) and static oxic. Prolonged anoxia promoted reductive dissolution of Fe-oxides, and led to an increase in soluble Fe(II) and amorphous Fe oxide pools. Preferential dissolution of the less-crystalline Fe pool was evident immediately following a shift in bulk redox status (oxic to anoxic), and coincided with increased dissolved organic C, presumably due to acidification or direct release of organic matter (OM) from dissolving Fe(III) mineral phases. The average nominal oxidation state of water-soluble C was lowest under persistent anoxic conditions, suggesting that more reduced organic compounds were metabolically unavailable for microbial consumption under reducing conditions. Anoxic soil compounds had high H/C values (and were similar to lignin-like compounds) whereas oxic soil compounds had higher O/C values, akin to tannin- and cellulose-like components. Cumulative respiration derived from native soil organic C was highest in static oxic soils. These results show how Fe minerals and Fe-OM interactions in tropical soils are highly sensitive to variable redox effects. Shifting soil oxygen availability rapidly impacted exchanges between mineral-sorbed and aqueous C pools, increased the dissolved organic C pool under anoxic conditions implying that the periodicity of low-redox events may control the fate of C in wet tropical soils.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

2016 Floodplain Geochemistry from the East River Watershed, Colorado

This dataset includes groundwater geochemistry data from floodplain piezometers collected as a part of the Watershed Function Scientific Focus Area (SFA) located in the Upper Colorado River Basin. The data were collected in order to investigate the role of hyporheic exchange and other river corridor processes on riverine export of solutes. Floodplain piezometers installed in several meanders (Meander C, Meander D, and Meander O) in the vicinity of the Pumphouse were sampled at several dates in 2016. Data includes in-field measurements (pH, electrical conductivity, oxidation reduction potential, dissolved oxygen, dissolved Fe(II), dissolved sulfide, and groundwater level) along with laboratory measurements (dissolved inorganic carbon, dissolved organic carbon, metals and major cations). Five files are included in this dataset, including: sample locations and depths in a csv file (metadata.csv), aqueous geochemistry data in a csv file, analytical detection limits in a csv file, a file-level metadata (flmd.csv) file, and a data dictionary (dd.csv) file. Data that was below the detection limit is reported as one half of the detection limit and missing data is listed as "-9999".

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2011

DISSOLUTION OF 3013-DE SAMPLE 10-16

The HB-Line Facility has a long-term mission to dissolve and disposition legacy fissile materials. HB-Line dissolves plutonium dioxide (PuO{sub 2}) from K-Area parting support of the 3013 Destructive Examination (DE) program. The PuO{sub 2}-bearing solids originate from a variety of unit operations and processing facilities, but all of the material is assumed to be high-fired (i.e., calcined in air for a minimum of two hours at {ge} 750 C). The Savannah River National Laboratory (SRNL) conducted dissolution flowsheet studies on 3013 DE Sample 10-16 (can R610826), which contains weapons-grade plutonium (Pu) as the fissile material. The dissolution flowsheet study was performed for 4 hours at 108 C on unwashed material using 12 M nitric acid (HNO{sub 3}) containing 0.20 M potassium fluoride (KF). After 4 hours at 108 C, the {sup 239}Pu Equivalent concentration was 32.5 g/L (gamma, 5.0% uncertainty). The insoluble residue comprised 9.88 wt % of the initial bulk weight, and contained 5.31-5.95 wt % of the initial Pu. The residue contained Pu in the highest concentration, followed by tungsten (W). Analyses detected 2,770 mg/L chloride (Cl{sup -}) in the final dissolver solution (3.28 wt %), which is significantly lower than the amount of Cl{sup -} detected by prompt gamma (9.86 wt %) and the 3013 DE Surveillance program (14.7 wt %). A low bias in chloride measurement is anticipated due to volatilization during the experiment. Gas generation studies found approximately 60 mL of gas per gram of sample produced during the first 30 minutes of dissolution. Little to no gas was produced after the first 30 minutes. Hydrogen gas (H{sub 2}) was not detected in the sample. Based on detection limits and accounting for dilution, the generated gas contained < 0.12 vol % H{sub 2}, which is well below the 4.0 vol % flammability limit for H{sub 2} in air. Filtration of the dissolver solution occurred readily. When aluminum nitrate nonahydrate (ANN) was added to the filtered dissolver solution at a 3:1 Al:F molar ratio, and stored at room temperature for 24 hours, the solution filtered approximately 6 times slower than when filtered 30 minutes after ANN addition, requiring 6 minutes to complete compared to 55 seconds for the first filtration. It is likely that the ambient-temperature solubility for ANN was exceeded. A 4-hour dissolution time at a temperature of 108 C in 12 M HNO{sub 3}/0.2 M KF is recommended for dissolution of this material.

08 HYDROGEN↗
DOE OSTI2020

NASNF Processing and Packaging Technical Study

The ABD program will require development of a strategy for the dispositioning the Non-Aluminum Spent Nuclear Fuel (NASNF), some of which will be very challenging to handle and dissolve as described in this report. Not all the NASNF is suitable for processing through the electrolytic dissolver. The strategy may involve dissolution of the majority of the NASNF inventory in the electrolytic dissolver combined with some other disposition alternative(s) for the fraction that is not suitable for electrolytic dissolution. This report highlights the risks and challenges associated with the baseline approach of using the electrolytic dissolver to process all of the NASNF. In addition, the characteristics of the NASNF and how those characteristics relate to the risks associated with electrolytically dissolving the specific fuel types.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Soil properties and root characteristics across four lowland Panamanian forests from 0 - 1 m soil depths

Objectives:Fine roots significantly influence ecosystem-scale cycling of nutrients, carbon (C), and water, yet there is limited understanding of how fine root traits vary across and within tropical forests, some of Earth's most C-rich ecosystems. The biomass of fine roots can impact soil carbon storage, as root mortality is a primary source of new carbon to soils. A positive relationship has been observed between fine root biomass and soil carbon stocks in Panama (Cusack et al 2018). Beyond biomass, root characteristics like specific root length (SRL) could also influence soil carbon, as roots with higher SRL are less dense and thinner, potentially decomposing more easily or promoting soil aggregation. Understanding the effects of root morphology and tissue quality on soil carbon storage and with soil properties in general can improve predictions of landscape-scale carbon patterns. We aggregated new data of root biomass, morphology and nutrient content at 0-10 cm, 10-20 cm, 20-50 cm and 50-100 cm depth increments across four distinct lowland Panamanian forests and paired with already published datasets (Cusack et al 2018; Cusack and Turner 2020) of soil chemistry from the same sites and soil depths to explore relationship between soil carbon stocks and root characteristics.Datasets included:The datasets provided include .csv and .xlsx files for fine root characteristics and soil chemistry from four different forests across 0-10 cm, 10-20 cm, 20-50 cm, and 50-100 cm depth increments. Root characteristics include live fine root biomass, dead fine root biomass, coarse root biomass, specific root length, root diameter, root tissue density, specific root area, root %N, root %C, and root C/N ratio. Soil chemistry data includes total carbon (TC), dissolved organic carbon (DOC), bulk density, total phosphorus (TP), available phosphorus (AEM Pi), and various Mehlich-extractable elements such as aluminum, calcium, iron, potassium, manganese, phosphorus, and zinc. Nitrogen content measures include ammonium, nitrate, total dissolved nitrogen (TDN), dissolved inorganic nitrogen (DIN), and dissolved organic nitrogen (DON). The dataset also includes total exchangeable bases (TEB) and effective cation exchange capacity (ECEC) in both centimoles of charge per kilogram and micromoles of charge per gram. The soil chemistry data was obtained from Cusack et al (2018) and Cusack and Turner (2020) and paired with root characteristics data for the same depth increments and sites. Additionally, a .kml file is provided with coordinates for all 32 plots included in the study across four forests (n = 8 plots per site). Root data was averaged across these 8 plots per site and soil data was collected in one pit in each site. This dataset serves as baseline data before a throughfall exclusion experiment, Panama Rainforest Changes with Experimental Drying (PARCHED), was implemented. No special software is needed to open these files.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Organic matter concentration and composition of experimentally burned open air and muffle furnace vegetation chars across differing burn severity and feedstock types from Pacific Northwest, USA (v4).

This dataset represents results from an experimental study designed to compare how the chemical composition of organic matter changes across different burn conditions and feedstock materials. The dataset provides both solid and dissolved phase bulk concentration and organic matter characterization data from experimentally generated chars. Chars were created in a closed muffle furnace or on an open burn table from four different feedstock species representing vegetation commonly impacted by fire regimes across the Pacific Northwest, USA. This data can be used to compare how different burn conditions may influence resultant organic matter chemistry and help further our understanding of potential biogeochemical impacts on river corridors post-fire. This dataset is comprised of one data package readme, one data dictionary (dd), one file level metadata (flmd), fourteen burn table videos, burn table video metadata and three folders containing (A) data; (B) metadata and protocols; and (C) photos. The folder names and the file name of the data package readme include a version number which will be updated with future iterations of this data package. The data folder includes (1) solid carbon and solid nitrogen; (2) dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) and total dissolved nitrogen (TN); (3) pH; (4) thermocouple time series temperature; (5) methods codes; (6) installation methods; (7) excitation emissions matrix (EEM) methods information; (8) a folder of excitation emissions matrix (EEM) fluorescence and absorbance spectra in dissolved organic matter and EEMs processing instructions; (9) solid state carbon-13 and solution state phosphorus nuclear magnetic resonance (13-C NMR and 31-P NMR) data and methods; (10) benzene polycarboxylic acid (BPCA) concentration and stable isotope data; (11) FTICR-MS methods; (12) Inductively coupled plasma (ICP) data for total calcium, magnesium, iron, aluminum, potassium, phosphorus, sodium, and sulfur along with sodium hydroxide-ethylenediaminetetraacetic acid (sodium hydroxide-EDTA) extractable calcium, magnesium, iron, aluminum, potassium, phosphorus, and sulfur; (13) a folder of phosphorus, carbon, and nitrogen X-ray absorption near edge structure (P-XANES, N-XANES, C-XANES) data for samples and standards; (14) P-XANES, N-XANES, C-XANES methods; (15) molybdate reactive phosphorus; and (16) folder of high resolution characterization of organic matter via 21 Tesla Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) generated through the Environmental Molecular Sciences Laboratory (EMSL; https://www.pnnl.gov/environmental-molecular-sciences-laboratory). The FTICR folder contains .txt data files and a subfolder containing instruments for using Formularity (https://omics.pnl.gov/software/formularity) and an R script to process the data based on the user's specific needs. The metadata and protocols folder includes (1) international geo-sample number (IGSN) mapping file (2) burn and laboratory metadata; (3) burn protocol; (4) laboratory protocol; (5) vegetation collection metadata; and (6) vegetation collection protocol. The folder contains photos of the solid chars. All files are .csv, .txt, .pdf, .jpg, .jpeg, .R, .ref, or .mp4. The data package was originally published October 2022 (v1). It was updated April 2023 (v2; new data files), September 2023 (v3; new and corrected data files), and September 2024 (v4; new and added/updated files). Metadata files were also updated to reflect these changes. See the change history section in the readme for more details.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Extraction of Pure Plastic Resins From PCR Plastic Waste by Solvent-Targeted Recovery and Precipitation (STRAP)

For this work, we have been developing a solvent‐based plastic recycling technology called STRAP. The technology is based on dissolving a targeted plastic resin in a specific solvent that does not dissolve other resins. We have demonstrated STRAP in thousands of bench scale experiments for a large variety of wastes. Recently we have demonstrated the technology for PCR, using mixed plastic wastes (MPWs), from a wet Material Recovery Facility (MRF). The process includes (1) infrared (IR) characterization to determine the plastic composition for accurate selection of the solvent to be used for the extraction of the pure resins. (2) Shredding to the right size and aspect ratio required for flowable and fast dissolvable process. (3) Mixing the MPW in the first solvent to dissolve the first resin. (4) Filtration of the solution plastic blend, to separate the nondissolved plastic from the solution. (5) Further filtration of the solution to remove micron‐sized particle of pigments and fibers. (6) Cooling for precipitation. (7) Filtration of pure resins. (8) Drying of a pure resin. (9) Extrusion of the resin to pellets. (10) Generating films or other products from the pure resin. Steps 1–10 can be considered as one‐cycle that extracted the first resin. (11) A second resin can be extracted with a respective solvent from the plastic that did not dissolve in the first cycle and following steps 1–10 described above. The process also includes characterization of interim and final products. The effort includes building a pilot system at 25 kg/h throughput. We will present specific results for various PCR.

IR characterization↗
DOE OSTI2015

Geochemical drivers of organic matter decomposition in Arctic tundra soils

Climate change is warming tundra ecosystems in the Arctic, resulting in the decomposition of previously-frozen soil organic matter (SOM) and release of carbon (C) to the atmosphere; however, the processes that control SOM decomposition and C emissions remain highly uncertain. In this study, we evaluate geochemical factors that influence anaerobic production of carbon dioxide (CO 2 ) and methane (CH 4 ) in the active layers of four ice-wedge polygons. Surface and soil pore waters were collected during the annual thaw season over a two-year period in an area containing waterlogged, low-centered polygons and well-drained, high-centered polygons. We report spatial and seasonal patterns of dissolved gases in relation to the geochemical properties of Fe and organic C as determined using spectroscopic and chromatographic techniques. Iron was present as Fe(II) in soil solution near the permafrost boundary but enriched as Fe(III) in the middle of the active layer, similar to dissolved aromatic-C and organic acids. Dissolved CH 4 increased relative to dissolved CO 2 with depth and varied with soil moisture in the middle of the active layer in patterns that were positively correlated with the proportion of dissolved Fe(III) in transitional and low-centered polygon soils but negatively correlated in the drier flat- and high-centered polygons. These results suggest that microbial-mediated Fe oxidation and reduction influence respiration/fermentation of SOM and production of substrates (e.g., low-molecular-weight organic acids) for methanogenesis. As a result, we infer that geochemical differences induced by water saturation dictate microbial products of SOM decomposition, and Fe geochemistry is an important factor regulating methanogenesis in anoxic tundra soils.

58 GEOSCIENCES↗
DOE OSTI2016

Modern water/rock reactions in Oman hyperalkaline peridotite aquifers and implications for microbial habitability

The Samail ophiolite in Oman is undergoing modern hydration and carbonation of peridotite and may host a deep subsurface biosphere. Previous investigations of hyperalkaline fluids in Oman have focused on fluids released at surface seeps, which quickly lose their reducing character and precipitate carbonates upon contact with the O 2 /CO 2 -rich atmosphere. In this study, geochemical analysis of rocks and fluids from the subsurface provides new insights into the operative reactions in serpentinizing aquifers. Serpentinite rock and hyperalkaline fluids (pH > 10), which exhibit millimolar concentrations of Ca 2+ , H 2 and CH 4 , as well as variable sulfate and nitrate, were accessed from wells situated in mantle peridotite near Ibra and studied to investigate their aqueous geochemistry, gas concentrations, isotopic signatures, mineralogy, Fe speciation and microbial community composition.The bulk mineralogy of drill cuttings is dominated by olivine, pyroxene, brucite, serpentine and magnetite. At depth, Fe-bearing brucite is commonly intermixed with serpentine, whereas near the surface, olivine and brucite are lost and increased magnetite and serpentine is detected. Micro-Raman spectroscopy reveals at least two distinct generations of serpentine present in drill cuttings recovered from several depths from two wells. Fe K-edge X-ray absorption near-edge spectroscopy (XANES) analysis of the lizardite shows a strong tetrahedral Fe coordination, suggesting a mixture of both Fe(II) and Fe(III) in the serpentine. Magnetite veins are also closely associated with this second generation serpentine, and 2-10 μm magnetite grains overprint all minerals in the drill cuttings. Thus we propose that the dissolved H 2 that accumulates in the subsurface hyperalkaline fluids was evolved through low temperature oxidation and hydration of relict olivine, as well as destabilization of pre-existing brucite present in the partially serpentinized dunites and harzburgites. In particular, we hypothesize that Fe-bearing brucite is currently reacting with dissolved silica in the aquifer fluids to generate late-stage magnetite, additional serpentine and dissolved H 2 . Dissolved CH 4 in the fluids exhibits the most isotopically heavy carbon in CH 4 reported in the literature thus far. The CH 4 may have formed through abiotic reduction of dissolved CO 2 or through biogenic pathways under extreme carbon limitation. The methane isotopic composition may have also been modified by significant methane oxidation. 16S rRNA sequencing of DNA recovered from filtered hyperalkaline well fluids reveals an abundance of Meiothermus, Thermodesulfovibrionaceae (sulfate-reducers) and Clostridia (fermenters). The fluids also contain candidate phyla OP1 and OD1, as well as Methanobacterium (methanogen) and Methylococcus sp. (methanotroph). Finally, the composition of these microbial communities suggests that low-temperature hydrogen and methane generation, coupled with the presence of electron acceptors such as nitrate and sulfate, sustains subsurface microbial life within the Oman ophiolite.

58 GEOSCIENCES↗