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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Cathodic NH 4 + leaching of nitrogen impurities in CoMo thin-film electrodes in aqueous acidic solutions

Electrocatalytic reduction of dinitrogen (N 2 ) to ammonium (NH 4 + ) in acidic aqueous solutions was investigated at ambient temperature and pressure using a cobalt–molybdenum (CoMo) thin-film electrode prepared by magnetron reactive sputtering. Increased concentrations of ammonium ions (NH 4 + ) were consistently detected in the electrolyte using ion chromatography (IC) after constant-potential electrolysis at various potentials (≤-0.29 V vs. RHE). Using a newly developed analytical method based on ammonia derivatization, performing the experiments with 15 N 2 -labelled gas led however to the detection of increased 14 NH 4 + concentrations instead of 15 NH 4 + . X-ray photoelectron spectroscopic (XPS) analysis of the electrode surface revealed the presence of Mo[triple bond, length as m-dash]N and Mo–NH x species. Several contamination sources were identified that led to substantial increases in the concentration of ammonium ions, including 15 NH 3 impurities in 15 N 2 gas. The observed ammonium concentrations can be consistently ascribed to leaching of nitrogen ( 14 N) impurities incorporated in the CoMo film during the sputtering process. Therefore, researchers in the field are urged to adopt extended protocols to identify and eliminate sources of ammonia contamination and to very carefully monitor the ammonium concentrations in each experimental step.

36 MATERIALS SCIENCE↗
NASA NTRS1991

Aqueous alteration of the Nakhla meteorite

Interior samples of three different Nakhla specimens contain an iron-rich silicate 'rust' (which includes a tentatively identified smectite), Ca-carbonate (probably calcite), Ca-sulfate (possibly gypsum or bassanite), Mg-sulfate (possibly epsomite or kieserite), and NaCl (halite); the total abundance of these phases is estimated as less than 0.01 weight percent of the bulk meteorite. Rust veins are truncated and decrepitated by fusion crust and are preserved as faulted segments in partially healed olivine crystals, indicating that the rust is preterrestrial in origin. Because Ca-carbonate and Ca-sulfate are intergrown with the rust, they are also indicated to be of preterrestrial origin. Similar textural evidence regarding origins of the NaCl and Mg-sulfate is lacking. Impure and poorly crystallized sulfates and halides on the fusion crust of the meteorite suggest leaching of interior (preterrestrial) salts from the interior after Makhla arrived on earth, but coincidental addition of these same salts by terrestrial contamination cannot be exluded. At least the clay-like silicate 'rust', Ca-carbonate, and Ca-sulfate were formed by precipitation from water-based solutions on the Nakhla parent planet, although temperature and pressure conditions of aqueous precipitation are unconstrained by currently available data. It is possible that aqueous alteration on the parent body was responsible for the previously observed disturbance of the Rb-Sr geochronometer in Nakhla at or near 1.3 Ga.

Gooding, James L.↗
NASA NTRS1974

Development of sputtered techniques for thrust chambers, task 1

Filler materials proposed for use in the sputter fabrication regeneratively cooled thrust chambers were evaluated. Low melting castable alloys, CERROBEND. CERROCAST, and CERROTRU, slurry applied SERMETEL 481 and flame-sprayed aluminum were investigated as filler materials. Sputter deposition from a cylindrical cathode inverted magnestron was used to apply an OFHC copper closeout layer to filled OFHC copper ribbed-wall cylindrical substrates. The sputtered closeout layer structure was evaluated with respect to filler material contamination, predeposition machining and finishing operations, and deposition parameters. The application of aluminum by flame-spraying resulted in excessiver filler porosity. Though the outgassing from this porosity was found to be detrimental to the closeout layer structure, bond strengths in excess of 10,500 psi were achieved. Removal of the aluminum from the grooves was readily accomplished by leaching in a 7.0 molar solution of sodium hydroxide at 353 K. Of the other filler materials evaluated, CERROTRU was found to be the most suitable material with respect to completely filling the ribbed-wall cylinders and vacuum system compatibility. However, bond contamination resulted in low closeout layer bond strength with the CERROTRU filler. CERROBEND, CERROCAST, and SERMETEL 481 were found to be unacceptable as filler materials.

Mullaly, J. R.↗
DOE OSTI2023

Review of Mercury Sequestration in Cementitious Waste Forms

Decontaminated salt solution from Tank 50 at the Savannah River Site (SRS) is known to contain dissolved mercury species which are present as hydroxides and oxides. These species are reported in analytical measurements as the organic cation [CH 3 Hg] + and the inorganic cation Hg 2+ . The salt solution is mixed with cementitious reagents, blast-furnace slag (BFS) and thermally beneficiated Class F fly ash in the Saltstone Processing Facility and pumped into engineered Saltstone Disposal Units, (SDUs), to produce a solidified waste form. The solidified waste form, saltstone, encapsulates and chemically stabilizes the mercury and other contaminants, sequestering them from release into the environment. With the discovery of methylmercury in the salt solution, testing was performed to determine the extent to which saltstone prepared with methylmercury (MeHg) retains mercury in the Toxicity Characteristic Leaching Procedure (TCLP). Results from this testing indicated that the amount of mercury extracted remained below the regulatory limit, and that the saltstone formulation with a greater proportion of BFS performed slightly better at retaining Hg in the solid.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

AN ACID BAKING APPROACH TO ENHANCE RARE EARTH ELEMENT RECOVERY FROM BITUMINOUS COAL SOURCES

Rare earth elements (REE) are a group of 17 elements typically classified as light and heavy rare earth elements, which play a crucial role in developing the latest technologies for energy, defense, and medical sectors. Even though REEs have been found in more than 200 minerals, only bastnaesite, monazite and xenotime are commercially exploited for REE extraction. However, the recent exponential increase in REE demand has spurred countries such as the United States into research for the extraction of REEs from secondary sources such as coal, acid mine drainage, and coal ash. Several coal sources (e.g., Fire Clay seam coal) across the United States have been identified to contain elevated concentrations of rare earth elements (>600 ppm), and various researchers have investigated the feasibility of both physical and hydrometallurgical extraction techniques for rare earth concentration and subsequent extraction. However, both physical and direct leaching were concluded to be inefficient for RE beneficiation and extraction due to low recoveries. Alternatively, thermal treatment provides promising means for RE recovery from bituminous coal sources. The positive impact of thermal treatment/calcination was established to be due to the decarbonization and dehydroxylation of the clays, which released entrapped rare earth elements within the dominant minerals and converted them into an acid-soluble form. Nonetheless, the improvement in recovery was limited to the light REEs (LREEs) with an insignificant increase in the heavy REEs (HREE). It was demonstrated that the light and heavy REEs in the material were associated with difficult-to-leach minerals such as monazite, xenotime, and zircon, which were not decomposed by simple calcination due to their high thermal stability. Hence, roasting in the presence of chemicals was necessary to ensure the decomposition of those REE-containing minerals. As such, this study was focused on the acid baking treatment of bituminous coals with an aim to enhance REE recovery, especially HREEs. Based on the presence of REE minerals like monazite and xenotime, three pre-leach treatment methods, i.e., 1) roasting, 2) direct acid baking, and 3) acid baking after roasting were investigated. Roasting tests at 600 ⁰C revealed that the recovery of light REEs (LREEs) was enhanced while the recovery of HREEs remained relatively unaffected. LREE and HREE recovery values of 38.3% and 21.3%, respectively, were achieved using a 50 g/L sulfuric acid solution at 5% solid concentration and a solution temperature of 75 ⁰C for 2 hours. Comparatively, direct acid baking at 250 °C provided substantial increased LREE and HREE recovery values to approximately 49.4% and 53.0%, respectively, using an equivalent acid dosage. Recoveries were maximized to 77.0% and 79.6% for LREE and HREE, respectively, by roasting followed by acid baking. Similar results were obtained from the treatment of a second bituminous coal source. Due to strong correlations between REE and Al recovery values, tests were performed on kaolinite and illite, which were prominent clay minerals within the source coals. These experiments revealed that the REE recovery improvements were likely a result of dehydroxylation of clays and subsequent release and decomposition of REE-bearing minerals such as monazite, xenotime and zircon. Subsequently, a parametric study was conducted to identify the impact of acid baking parameters on rare earth element recovery. The factors investigated using a three-level statistical experimental program were acid baking time, acid solution concentration, baking temperature, and acid solution-to-solids ratio which were found to significantly impact REE and contaminant element (Al, Fe, and Ca) recovery. An increase in baking temperature up to around 250 ⁰C improved the light and heavy REE recovery values by more than 50 absolute percentage points relative to performances achieved when direct leaching. As aforementioned, acid baking was needed to both decompose the clay minerals and liberate the REE minerals, which allowed access for the acid to solubilize the REEs. Acid concentration of the solution used for acid baking was studied as a means of minimizing the amount of acid needed to achieve a target REE recovery. However, thermo-gravimetric and differential scanning calorimetry analysis (TGA-DSC) of sulfuric acid under oxidizing atmosphere revealed that the addition of water decreased the evaporation temperature, which explains the lower REE recovery values obtained when using acid concentrations less than 100%. Using pure sulfuric acid at an acid-to-solid ratio of 0.8:1 resulted in recovery values of around 70% for both LREEs and HREEs. The decomposition reaction time was relatively quick with 65% of the TREEs recovered within the first 10 minutes. Following the identification of optimum operating conditions through the parametric study, a systematic leaching study was carried out to examine the impact of leaching parameters, such as solid-to-liquid (S/L) ratio, temperature, and time, on REE recovery using acid baking conditions of 1:1 acid to solids ratio at 250 °C for 30 minutes. The solid-to-liquid ratio was varied from 1-20% by weight at 25 °C, 50 °C, and 75 °C solution temperatures. The results indicated that reaction time and solution temperature considerably impacted the recovery of heavy and light REEs. Interestingly, LREE recovery reduced from 68% at 5% S/L to 58% at 20%S/L, whereas HREE recovery of 78% remained unaffected. The decrease in the LREE recovery was determined to be due to La and Ce precipitation, likely through isomorphic substitution with calcium in gypsum. The kinetic data indicated that 67% LREE and 77% HREE recovery could be obtained within the first 15 minutes of the reaction, suggesting fast reaction kinetics. Furthermore, raising the solution temperature from 25 °C to 75 °C increased the LREE and HREE recovery from 60% and 32% to 67% and 79%, respectively. The kinetic modeling results demonstrated that the rate-limiting step in the LREE dissolution was diffusion and chemical reaction, whereas the HREE extraction was controlled by only chemical reaction. The leaching study concluded that using 20% S/L at 75 °C for 15 minutes maximized LREE and HREE recovery. The lab-scale precipitation study showed that Fe and Al in solution could be removed at pH 4.5 followed by REE precipitation at pH 6.0 using 6 mol/L NaOH. Finally, the bench-scale data was used to develop a process flowsheet for REE recovery from low-grade bituminous coal sources using acid baking. Finally, based on the proposed flowsheet, a concentrated RE-cake obtained through selective precipitation at pH 6.5 was re-leached using HCl at pH 1.5. The resultant leachate was used to identify the impact of various operating parameters on REE recovery and purity with an aim to maximize REE precipitation efficiency while minimizing the oxalic acid dosage. The operating parameters for this investigation were oxalic acid dosage, iron (III) contamination, solution pH and temperature. The resultant model suggested that oxalic acid dosage and reaction pH are the most significant factors for the REE precipitation efficiency, followed by the interaction of oxalic dosage and Fe concentration. Test results indicated that increasing the oxalic acid concentration from 0g/L to 80g/L improved the REE precipitation efficiency from approximately 4.2% to 95.0%. Furthermore, raising the solution pH from 0.5 to 2.5 considerably enhanced the precipitation efficiency from 0.0% to 98.9%. A solution temperature elevation decreased REE recovery, which indicated an exothermic reaction between REEs and oxalate anions. Finally, a high level of Fe contamination adversely impacted REE precipitation efficiency. The speciation analysis revealed that the dominant iron species in the solution system were Fe-(C₂O₄)₃³⁻, Fe-(C₂O₄)²⁻, and Fe-(C₂O₄)⁺, which consumed the majority of the oxalate anions

rare earth elements, acid baking, high-temperature↗
NASA NTRS2006

Determination of Silicon in Hydrazine

Inductively coupled plasma-mass spectrometry (ICP-MS) is a highly sensitive technique sometimes used for the trace determination of silicon at a mass-to-charge (m/z) ratio of 28, the most abundant natural isotope of silicon. Unfortunately, ICP-MS is unable to differentiate between other sources of m/z 28 and false positive results for silicon will result when other sources of m/z 28 are present. Nitrogen was a major source of m/z 28 and contributes to the m/z 28 signal when hydrazine sample or nitric acid preservative is introduced into the plasma. Accordingly, this work was performed to develop a sample preparation step coupled with an ICP-MS analysis that minimized non-silicon sources of m/z 28. In the preparatory step of this method, the hydrazine sample was first decomposed predominately to nitrogen gas and water with copper-catalyzed hydrogen peroxide. In the analysis step, ICP-MS was used without nitric acid preservative in samples or standards. Glass, a potential source of silicon contamination, was also avoided where possible. The method was sensitive, accurate, and reliable for the determination of silicon in monopropellant grade hydrazine (MPH) in AF-E-332 elastomer leaching tests. Results for silicon in MPH were comparable to those reported in the literature for other studies.

McClure, Mark B.↗
DOE OSTI2020

Evaluation of the Change in Uranium Mobility in Sediments from the Hanford 300-FF-5 Stage B Polyphosphate Field Injection

The purpose of this study was to evaluate the change in uranium mobility in the periodically re-wetted zone (PRZ) and upper unconfined aquifer of the Hanford Site’s 300-FF-5 operable unit as a result of Stage B polyphosphate (PO 4 ) injections. These 300 Area sediments are beneath or near the former North Process Pond, which has previously been shown to contain metatorbernite [Cu(UO 2 ) 2 (PO 4 ) 2 •8H 2 O] and uranophane [Ca(UO 2 ) 2 (SiO 3 OH) 2 •5H 2 O], along with aqueous and adsorbed uranium (U), and small amounts of U in calcite as a result of acidic disposal with a significant number of co-contaminants. Previous laboratory-scale studies have identified multiple mechanisms that decrease uranium mobility with polyphosphate injection: (a) precipitation of a low-solubility uranium-phosphate mineral (autunite); (b) precipitation of a Ca-phosphate solid that incorporates U; (c) precipitation of Ca-phosphate mineral (apatite group minerals) that coats existing uranium phases (i.e., U in calcite, U in Fe-oxides), reducing uranium leaching; and (d) aqueous Ca-U-carbonate species adsorption onto apatite. Given the significant amount of apatite precipitation, other U phases such as carbonates could also coprecipitate with apatite. To quantify differences in solubility, leachability, and phases of uranium between pre- and post-PO 4 -treated sediments, different types of analyses were conducted, including analysis of uranium in (a) a carbonate solution extraction from sediment over 1000 h (41.67 days), (b) six sequential liquid extractions from sediment over approximately 1 week, (c) leaching of uranium from sediments in one dimensional (1-D) column experiments over 2 months, and (d) solid phase characterization of select sediments. An additional extraction and solid phase measurements were conducted to evaluate phosphate precipitate formation. Metals were also analyzed in sequential liquid extractions as indicators of (a) amendment injection delivery, (b) co-contaminant movement, and (c) changes in solid phases. Aqueous and solid phase carbonate measurements were also conducted to evaluate changes in carbonates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Parametric study of an acid baking process for rare earth element recovery from a bituminous-coal source

Acid baking treatment is widely used to extract rare earth elements (REEs) from refractory rare earth bearing minerals such as monazite and xenotime. Since these REE minerals have been identified in coal-based sources, a parametric study was conducted to evaluate the impact and optimize the parametric values associated with the acid-baking process when treating a bituminous coal source. The parameters studied using a three-level statistical experimental program were acid baking time, acid solution concentration, baking temperature, and acid solution-to-solids ratio and each were found to significantly impact REE and contaminant element recovery. An increase in baking temperature up to around 250°C improved the light and heavy REE recovery values by more than 50 absolute percentage points relative to performances achieved when direct leaching. Acid baking was needed to dehydroxylate the clays and liberate the REE minerals, which allowed access for the acid to solubilize the REEs. Acid concentration of the solution used for acid baking was studied as a means of minimizing the amount of acid needed to achieve a target REE recovery. However, thermo-gravimetric and differential scanning calorimetry analysis (TGA-DSC) of sulfuric acid under oxidizing atmosphere revealed that the addition of water decreased the evaporation temperature, which explains the lower REE recovery values obtained when using lower acid concentrations. Using pure sulfuric acid at an acid-to-solid ratio of 0.8:1 resulted in recovery values of around 70% for both LREEs and HREEs. The decomposition reaction time was relatively quick with 65% of the TREEs recovered within the first 10 minutes. Water leaching experiments performed on the acid-baked products under a temperature of 25°C instead of 75°C revealed an increase in REE recovery by 10 absolute percentage points, which was likely due to the high solubility of REE-sulfates at room temperatures.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS2013

Application of CO2 Snow Jet Cleaning in Conjunction with Laboratory Based Total Reflection X-Ray Fluorescence

The Genesis mission was the first mission returning solar material to Earth since the Apollo program [1,2]. Unfortunately the return of the space craft on September 8, 2004 resulted in a crash landing, which shattered the samples into small fragments and exposed them to desert soil and other debris. Thus only small fragments of the original collectors are available, each having different degrees of surface contamination. Thorough surface cleaning is required to allow for subsequent analysis of solar wind material embedded within. An initial cleaning procedure was developed in coordination with Johnson Space Center which focused on removing larger sized particulates and a thin film organic contamination acquired during collection in space [3]. However, many of the samples have additional residues and more rigorous and/or innovative cleaning steps might be necessary. These cleaning steps must affect only the surface to avoid leaching and re-distribution of solar wind material from the bulk of the collectors. To aid in development and identification of the most appropriate cleaning procedures each sample has to be thoroughly inspected before and after each cleaning step. Laboratory based total reflection X-ray fluorescence (TXRF) spectrometry lends itself to this task as it is a non-destructive and surface sensitive analytical method permitting analysis of elements from aluminum onward present at and near the surface of a flat substrate [4]. The suitability of TXRF has been demonstrated for several Genesis solar wind samples before and after various cleaning methods including acid treatment, gas cluster ion beam, and CO2 snow jet [5 - 7]. The latter one is non-invasive and did show some promise on one sample [5]. To investigate the feasibility of CO2 snow jet cleaning further, several flown Genesis samples were selected to be characterized before and after CO2 snow application with sample 61052 being discussed below.

Schmeling, M.↗
DOE OSTI2023

Influence of residual chlorine on Ru/TiO 2 active sites during CO 2 methanation

Titania-supported ruthenium (Ru/TiO 2 ) is an established catalyst for the hydrogenation of carbon dioxide to methane (Sabatier reaction). Chlorine contamination, owed to the RuCl 3 precursor, is demonstrated to have a detrimental impact on methanation activity. After calcination and reduction the catalyst contains residual chlorine, shown by XPS. An aqueous ammonia wash removes Cl without leaching Ru. The washed catalysts exhibit improvements in CH 4 site-time yields. Low Ru loading catalysts encounter the greatest activity enhancements after washing (~4.5-fold). DFT calculations indicate that chlorine and CO 2 directly compete for adsorption on Ru step sites, with Cl impeding the adsorption of CO 2 at under-coordinated sites and at higher Cl coverages. H 2 -chemisorption/TPR show that Cl removal lowers the onset of low temperature H 2 dissociation on Ru. Finally, DRIFTS provide evidence that the removal of Cl facilitates low temperature dissociative binding of CO 2 , indicated by the formation of surface bound linear CO species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2023

Fire Station #2, Former Sewage Treatment Plant #17, and Towway Area-SWMU 114 PFAS Site Assessment Progress Report Kennedy Space Center, Florida

This PFAS Site Assessment Progress Report (SAPR) presents the findings of the 2022 PFAS investigation conducted from November 2021 through August 2022 at Solid Waste Management Unit (SWMU) 114 located within Kennedy Space Center (KSC), Florida. SWMU 114 includes area around Fire Station #2, Former Sewage Treatment Plant #17, the southern portion of the Shuttle Landing Facility Runway, Remote Launch Vehicle Hangar, and the Towway area. Fire Station #2 was constructed in 2008 and is currently active, housing fire station personnel and equipment, including aqueous film forming foam (AFFF). Releases of AFFF has occurred at SWMU 114. Previous environmental assessments have been performed at SWMU 114, including soil, groundwater, and surface water sampling for volatile organic compounds, polycyclic aromatic hydrocarbons, total petroleum hydrocarbons, and metals. No active remediation has been performed at the SWMU 114. PFAS site assessment field activities were conducted at SWMU 114 from November 2021 through August 2022. During the 2021-2022 Site Assessment, 124 direct-push samples were collected from 27 locations, 17 surface water samples were collected from 15 locations, 41 groundwater samples were collected from 37 newly installed monitoring wells, five concrete samples were collected from four locations, and one asphalt sample was collected. Additionally, two soil borings were advanced to 60 feet for lithologic descriptions, ten staff gauges were installed, and one round of water level measurements were collected from monitoring wells and staff gauges for groundwater flow determination. All groundwater and surface water samples were analyzed for 25 PFAS analytes by USEPA Method 537M. Concrete, and asphalt samples were analyzed by synthetic precipitation leaching procedure (SPLP) PFAS analysis by USEPA Modified Method 537M. Groundwater results were compared to the most recent Regional Screening Levels (RSLs) published by USEPA for residential tap water (USEPA, 2022a) to determine the extent of PFAS contamination at SWMU 114 for six PFAS analytes (PFOA, PFNA, PFBS, PFHxS, PFOS, and GenX). Surface water results were compared to the FDEP surface water screening levels (SW SLs) (FDEP, 2020) for PFOA and PFOS. The PFAS investigation concluded that groundwater exceeding RSLs extends east and south to Banana Creek and west to approximately the center of the SLF runway. The extent of PFAS is approximated to the north, to an area between Sharkey Road and Astronaut Road, where samples below the RSLs do not fully bound SWMU 114. At least two distinct PFAS source areas are located near Fire Station #2 and along Towway, at S114-MW0007S, within SWMU 114. Groundwater head measurements indicate that flow at SWMU 114 is generally similar across the shallow and intermediate water tables. A northeast to southwest trending groundwater divide is located near the middle of Towway where groundwater southeast of the divide flows to the south and groundwater northwest of the divide flows to the west. The groundwater divide generally separates the two areas of higher PFAS concentrations. Surface water samples indicated concentrations of PFOS above the SW SLs in surface water bodies across the site. Further assessment and sampling are required to better understand the interaction between groundwater and surface water at SWMU 114. Concrete and asphalt samples collected confirm that a significant release of AFFF occurred near the stormwater pond northwest of Fire Station #2. Additional concrete samples surrounding Fire Station #2 and at the northwest and southeast edges of the SLF tarmac indicate elevated PFOS concentrations. These results indicate that discharges of AFFF in these locations have infiltrated into asphalt and concrete and may act as a continuing source of PFAS to groundwater and surface water after rain events. Additional direct-push samples are required to delineate PFAS at SWMU 114. Samples may need to extend beyond the Former SLF Rescue Building and Morpheous Test Site to delineate PFAS in groundwater. Monitoring wells should be sampled and gauged quarterly to determine if seasonal impacts are observable, especially in shallow wells near surface water features. Furthermore, surface water samples should be collected from additional ditches to further define the extent of surface water impacts at SWMU 114 and extending along the SLF runway. Staff gauges should be gauged quarterly with groundwater gauging to determine surface water flow and interaction with groundwater. The PFAS sampling results and path forward for SWMU 114 were presented to the KSC Remediation Team in October 2022. Once the PFAS SAPR is approved, it will be submitted to the Florida Department of Environmental Protection.

Howard Franklin Fowler↗
DOE OSTI2024

Sorption kinetics and stability of conventional adsorbents for mercury remediation

In-situ remediation of mercury at numerous contaminated sites worldwide is a challenging and costly endeavor due to the persistency of this contaminant. In this study, we evaluated eight commercially available sorbent media ranging from carbon-, clays- and silica-based materials (PBC– Biochar, eSorb – Sorbster, nsPAC – Powdered Activated Carbon, fsPAC – Powdered Activated Carbon with Mackinawite, F300 – Filtrasorb 300, Si-SH – Silica Thiol, eBind – RemBind, Q-Clay – Organoclay PM-199), for their effectiveness in sorbing mercury (Hg 2+ ) and mercury complexed with dissolved organic matter (Hg-DOM). Under the chosen experimental conditions of this study, results showed that in the absence of DOM, the kinetic rates of Hg 2+ sorption onto the evaluated sorbents were in the order of 0.31 min-1 (Si-SH) to 2.98 min -1 (nsPAC), whereas in the presence of DOM, the rates varied from 0.16 min-1 (F300) to 0.95 min -1 (nsPAC). The measured sorption capacity for Hg 2+ in the absence of DOM varied from 3.02 mg/g (Q-Clay) to 35.15 mg/g (Si-SH), whereas in the presence of DOM, calculated partition coefficient (KD) ranged from 69.7 mL/g (Q-Clay) to 41,510 mL/g (Si-SH). Furthermore, kinetic data suggest liquid film diffusion was the rate-limiting steps governing mercury sorption onto the studied media. Overall, the obtained study parameters (kinetics/isotherm) are particularly important in informing robust engineering designs for deployment of the vast majority of evaluated sorbents. Thus, sorbent-based strategies offer viable solutions for cost-effective cleanup of mercury at industrially contaminated sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Flue-Gas Desulfurization Effluent Management using an Innovative Low-Energy Biosorpotion Treatment System to Remove Key Contaminants

Among the most critical water contaminants of concern affecting wide geographical regions and a number of industries and natural systems is selenium. Selenium found in surface, ground and wastewater in originates from natural sources, as well as industrial sources such as petroleum refineries, electronics manufacturing, pesticides, and coal power plants and mining also contribute to selenium contamination in water in the US. At high concentrations, selenium is toxic to human and wildlife. There are a number of technologies that have been used to treat selenium and other similar contaminants in water. Biological treatment of selenium has been used in the past to reduce soluble SeVI and/or SeIV to insoluble Se0, which is then filtered in the same vessel. The insoluble selenium (Se0) is then backwashed from the system and solids are separated for subsequent disposal, if they meet the leaching and water content criteria. In order to promote biological reduction to insoluble Se0, heating of bioreactor is needed in some applications, and excess food source (electron donor) is added so that all selenium can be filtered. An additional disadvantage of these systems is the significant amount of water lost due to extensive and frequent backwash and rinse cycles. When comparing the advantages and energy requirements of the various treatment technologies, RO membrane filtration immediately stands out due to the excessive energy expenditure needed to pump water across the membrane although RO is an effective way to remove selenium. In addition, RO requires extensive pretreatment, such as MF membrane, and frequent maintenance, rendering it an expensive option that may be out of reach for certain applications. In fact, although the performance was good during the pilot testing by the NSMP Working Group for treatment naturally occurring selenium in the surface water, the high electricity requirements and significant reject water stream made it an infeasible alternative. While conventional ion exchange maybe an effective treatment option, it requires frequent regeneration of the resin when applied to highly contaminated water, which leads to several tons of contaminant-laden, high-salinity brine that needs to be disposed off-site each day. One of the water systems in the west coast currently uses ion exchange for selenium treatment and has been trucking selenium laden hazardous brine waste weekly in the last several years. Pneumatic pumping and rinse water pumping required for ion exchange also increase the energy usage. In comparison, adsorption process is a passive treatment system where contaminated water comes in contact with an adsorption media in a vessel. Typically, there is no mixing, backwash, or recycle pumping required, thus significantly reducing the energy usage. A passive single-use adsorption system does not require backwash, thereby generating small amount of process waste, and producing the highest water yield among the alternatives. The energy and water efficiencies, and applicability for SeVI and SeIV are summarized in Table 1. Despite these benefits though, adsorption typically does not work for the most oxidized form of selenium (SeVI). The innovative biosorption process integrates both process to increase the treatment efficiency while minimizing energy, chemical, and time required to treat both SeVI and SeIV. Additional advantages include simple partial biological reduction with reduced on-site waste generation, which lead to water and electricity savings, and less operational need compared to biological treatment alone. This makes biosorption especially suitable for remote areas, where liquid backwash and brine disposal may be cost prohibitive or infeasible.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2020

Environmental Impacts of Reclaimed Asphalt Pavement on Leaching of Metals into Groundwater

To investigate the environmental impacts of reclaimed asphalt pavement (RAP) while it was freshly processed (i.e. hot mixed asphalt or HMA) and after being subjected to weathering, three RAP materials, namely north-RAP, central-RAP, south-RAP, from three plants and one fresh HMA loose mix sample (Fresh-HMA) throughout New Jersey, USA underwent four different weathering processes including: Ultraviolet (UV) and precipitation weathering on unbounded RAP, UV and precipitation weathering on compacted RAP, weathering by heat and moisture cycles, and groundwater flow-through leaching. Batch experiments were conducted to mimic releasing of trace elements in weak acidic leachate from landfills. North-RAP and central-RAP released levels of Pb greater than the United States Environmental Protection Agency (USEPA) primary drinking water maximum contaminant level (MCL) of 15 µg/L. Novel two-column experiments (a RAP column followed by a soil column) were conducted to investigate the release of trace elements from RAP and the attenuation effect of soil on potential pollutants. The results of these experiments showed that pollutants released from RAPs such as Mn and Ni were largely attenuated in the soil. The results suggest that RAP can be used as an unbound material in environments except those acidic (i.e., pH < 5 as in mines with sulfur-containing minerals and landfills with acidic environment).

batch extraction↗
NASA NTRS1985

High-Purity Silicon Seeds for Silane Pyrolysis

Seed particles for fluidized-bed production of silicon made by new contamination-free, economical method. In new method, large particles of semiconductor-grade silicon fired at each other by high-speed streams of gas and thereby break up into particles of suitable size for fluidized bed. No foreign materials introduced, and leaching unnecessary. Method used to feed fluidized-bed reactor for continuous production of high-purity silicon.

Hsu, G. C.↗
DOE OSTI2021

Influence of Agricultural Managed Aquifer Recharge (AgMAR) and Stratigraphic Heterogeneities on Nitrate Reduction in the Deep Subsurface

Agricultural managed aquifer recharge (AgMAR) is a strategy whereby surface water is used to intentionally flood croplands to recharge underlying aquifers. However, nitrate (NO 3 - ) contamination in agriculturally intensive regions poses a threat to groundwater resources under AgMAR. We use a reactive transport model to understand the effects of AgMAR management strategies (i.e., by varying the frequency, duration between flooding events, and amount of water) on NO 3 - leaching to groundwater under different stratigraphic configurations and antecedent moisture conditions. We examine the potential of denitrification and nitrogen retention in deep vadose zone sediments (~15 m) using variable AgMAR application rates on two-dimensional representations of differently textured soils, soils with discontinuous bands/channels, and with preferential flow paths characteristic of agricultural fields. Simulations indicate finer textured sediments, alone or embedded within/adjacent to high flow regions, are important reducing zones providing conditions needed for denitrification. Simulation results suggest that applying water all-at-once rather than in increments transports higher concentrations of NO 3 - deeper into the profile, which may exacerbate groundwater quality. This transport into deeper depths can be aggravated by wetter antecedent soil moisture conditions. However, applying water all-at-once also increases denitrification within the vadose zone by promoting anoxic conditions. We conclude that AgMAR can be designed to enhance denitrification in the subsurface and reduce NO 3 - leaching to groundwater, while specifically accounting for lithologic heterogeneity, antecedent soil moisture conditions, and depth to the water table. Our findings are potentially relevant to other systems that experience flooding inundation such as floodplains and dedicated recharge basins.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Heterogeneous photo-Fenton-like degradation of emerging pharmaceutical contaminants in wastewater using Cu-doped MgO nanoparticles

In this study, a facile thermal decomposition method was utilized to synthesize Cu-doped MgO nanoparticles possessing mesoporosity. These mesoporous Cu doped MgO nanoparticles were shown to be efficient photo-Fenton-like catalysts for the degradation of emerging pharmaceutical contaminants in wastewater and were able to completely oxidize salicylic acid within 1 hour under optimized conditions. Tetracycline was shown to be converted to other intermediates with a large portion of it undergoing full mineralization. Batch experiments were conducted to demonstrate the effects of Cu loading on MgO, overall catalyst loading, and H 2 O 2 concentration on the salicylic acid and tetracycline conversion and rate constants. Quenching experiments revealed that both •OH radicals or HO 2 •/•O 2 - radicals were involved in the reaction, with the latter showing a higher contribution. The surface dissolution of MgO was shown to facilitate a high pH environment which completely prevented Cu from leaching out of the catalyst while retaining high activity. The catalyst reusability was shown to be satisfactory with high activity and conversion being preserved over five cycles.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2020

In situ reductive dissolution to remove Iodine-129 from aquifer sediments

The use of an aqueous reductant (Na-dithionite) with pH buffer (K-carbonate, pH 12) was evaluated in this laboratory study as a potential remedial approach for removing Fe oxide associated iodine and enhancing pump-and-treat extraction from iodine-contaminated sediments in the unconfined aquifer in the 200 West Area of the Hanford site. X-ray fluorescence data of untreated sediment indicated that iodine was largely associated with Fe (i.e., incorporated into Fe oxides), however, XANES data was inconclusive as to valence state. During groundwater leaching, aqueous and adsorbed iodine was quickly released, then additional iodine was slowly released potentially from dissolution of one or more surface phases. The Na-dithionite treatment removed greater iodine mass (2.9x) at a faster rate (1 to 4 orders of magnitude) compared to leaching with groundwater alone. Iron extractions for untreated and treated sediments showed a decrease in Fe(III)-oxides, which likely released iodine to aqueous solution. Solid phase inorganic carbon and aqueous Ca and Mg analysis further confirmed that significant calcite dissolution did not occur in these experiments meaning these phases did not release significant iodine. Although it was expected that, after treatment, 127 I concentrations would eventually be lower than untreated sediments, leaching experiments showed continued, elevated iodine concentrations for treated samples over 750 hours. Stop flow events during 1-D column leaching suggested that some iodide precipitated within the first few pore volumes. In the survey of metals during leaching, some silver was detected which could have been solubilized by the elevated pH of initial Na-dithionite injection. Then, silver (or other metals) could have subsequently precipitated with iodide during the initial stop flow event forming a slowly dissolving source. Although significantly greater iodine is removed with treatment, the long-term leaching needs to be investigated further as it may limit dithionite treatment at the field scale.

54 ENVIRONMENTAL SCIENCES↗