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At least 37 records · Page 2

A method for precision anodize stripping

Felt templates saturated with etch solution remove anodized finish from aluminum without damage to the surface. The solution is a combination of nitric acid, chromic acid, and hydrofluoric acid.

Peters, R. L.↗

Elimination of color rings on film negatives

Abrasive grinding of glass surface, using grinding-grit size of 22.5 micron, prevents formation of interference ring during photoprocessing. To polish irregularities for improved light transmission, contact surface is bathed in aqueous solution of sulfuric acid and hydrofluoric acid.

Fleetwood, C. M., Jr.↗

Sulfur, Chlorine, and Flourine Degassing and Atmospheric Loading by the 1783 - 1784 AD Laki (Skaftar Fires) Eruption in Iceland

The 1783-1784 Laki tholeiitic basalt fissure eruption in Iceland was one of the greatest atmospheric pollution events of the past 250 years, with widespread effects in the northern hemisphere. The degassing history and volatile budget of this event are determined by measurements of pre-eruption and residual contents of sulfur, chlorine, and fluorine in the products of all phases of the eruption. In fissure eruptions such as Laki, degassing occurs in two stages: by explosive activity or lava fountaining at the vents, and from the lava as it flows away from the vents. Using the measured sulfur concentrations in glass inclusions in phenocrysts and in groundmass glasses of quenched eruption products, we calculate that the total accumulative atmospheric mass loading of sulfur dioxide was 122 Mt over a period of 8 months. This volatile release is sufficient to have generated approximately 250 Mt of H2SO4 aerosols, an amount which agrees with an independent estimate of the Laki aerosol yield based on atmospheric turbidity measurements. Most of this volatile mass (approximately 60 wt.%) was released during the first 1.5 months of activity. The measured chlorine and fluorine concentrations in the samples indicate that the atmospheric loading of hydrochloric acid and hydrofluoric acid was approximately 7.0 and 15.0 Mt, respectively. Furthermore, approximately 75% of the volatile mass dissolved by the Laki magma was released at the vents and carried by eruption columns to altitudes between 6 and 13 km. The high degree of degassing at the vents is attributed to development of a separated two-phase flow in the upper magma conduit, and implies that high-discharge basaltic eruptions such as Laki are able to loft huge quantities of gas to altitudes where the resulting aerosols can reside for months, or even 1-2 years. The atmospheric volatile contribution due to subsequent degassing of the Laki lava flow is only 18 wt.% of the total dissolved in the magma, and these emissions were confined to the lowest regions of the troposhere and therefore important only over Iceland. This study indicates that determination of the amount of sulfur degassed from the Laki magma batch by measurements of sulfur in the volcanic products (the petrologic method) yields a result which is sufficient to account for the mass of aerosols estimated by other methods.

Thordarson, T.↗

Determination of the gram-positive bacterial content of soils and sediments by analysis of teichoic acid components

Many gram-positive bacteria form substituted polymers of glycerol and ribitol phosphate esters known as teichoic acids. Utilizing the relative specificity of cold concentrated hydrofluoric acid in the hydrolysis of polyphosphate esters it proved possible to quantitatively assay the teichoic acid-derived glycerol and ribitol from gram-positive bacteria added to various soils and sediments. The lipids are first removed from the soils or sediments with a one phase chloroform-methanol extraction and the lipid extracted residue is hydrolyzed with cold concentrated hydrofluoric acid. To achieve maximum recovery of the teichoic acid ribitol, a second acid hydrolysis of the aqueous extract is required. The glycerol and ribitol are then acetylated after neutralization and analyzed by capillary gas-liquid chromatography. This technique together with measures of the total phospholipid, the phospholipid fatty acid, the muramic acid and the hydroxy fatty acids of the lipopolysaccharide lipid A of the gram-negative bacteria makes it possible to describe the community structure environmental samples. The proportion of gram-positive bacteria measured as the teichoic acid glycerol and ribitol is higher in soils than in sediments and increases with depth in both.

Ribitol/analogs & derivatives↗

Internal structure of the nanogratings generated inside bulk fused silica by ultrafast laser direct writing

The aim of the present work was to characterize the internal structure of nanogratings generated inside bulk fused silica by ultrafast laser processing and to study the influence of diluted hydrofluoric acid etching on their structure. The nanogratings were inscribed at a depth of 100 μm within fused silica wafers by a direct writing method, using 1030 nm radiation wavelength and the following processing parameters: E = 5 μJ, τ = 560 fs, f = 10 kHz, and v = 100 μm/s. The results achieved show that the laser-affected regions are elongated ellipsoids with a typical major diameter of about 30 μm and a minor diameter of about 6 μm. The nanogratings within these regions are composed of alternating nanoplanes of damaged and undamaged material, with an average periodicity of 351 ± 21 nm. The damaged nanoplanes contain nanopores randomly dispersed in a material containing a large density of defects. These nanopores present a roughly bimodal size distribution with average dimensions for each class of pores 65 ± 20 × 16 ± 8 × 69 ± 16 nm{sup 3} and 367 ± 239 × 16 ± 8 × 360 ± 194 nm{sup 3}, respectively. The number and size of the nanopores increases drastically when an hydrofluoric acid treatment is performed, leading to the coalescence of these voids into large planar discontinuities parallel to the nanoplanes. The preferential etching of the damaged material by the hydrofluoric acid solution, which is responsible for the pores growth and coalescence, confirms its high defect density.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Task-Specific Ionic Compounds for In-Field Sample Preparation Poster

In the event of a nuclear detonation, actinide and fission product-containing debris can be analyzed to provide information about the nature of the device. In-field sample dissolution prior to transport to a laboratory is critical for reducing the time between an event and delivery of information to decision makers. However, the best dissolution methods utilize liquid strong acid solutions, which are incompatible with field collection Standard Operating Procedure. What is required are solid materials that, when mixed with water in the field, can provide the strong digestion and dissolution properties of nitric and hydrofluoric acids. Fluorohydrogenate ionic liquids have shown a remarkable ability to dissolve a wide range of materials, from refractory actinide oxides to cementitious material such as calcium silicates. These strong dissolution properties are due to the neutral hydrofluoric acid that is bound to the anion component of the ionic liquid. Because these materials are liquids, they are also incompatible with Standard Operating Procedure. However, the physiochemical properties of ionic liquids, such as the melting point, can be readily tuned through minor modification of the molecular structure of the cations and anions. Thus, we hypothesize that by synthesizing modified cations, novel ionic compounds with melting points above ambient but with the same anion and bound hydrofluoric acid – and thus similar digestion and dissolution properties – as current fluorohydrogenate ionic liquids can be produced. These solid materials would be compatible with current Standard Operating Procedure, and would allow for rapid, in-field dissolution of samples, shortening the time to actionable information after an event.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The influence of H{sub 2}O{sub 2} concentration to the structure of silicon nanowire growth by metal-assisted chemical etching

A simple and low cost method to produce well aligned silicon nanowires at large areas using Ag-assisted chemical etching at room temperature were presented. The structure of silicon nanowires growth by metal-assisted chemical etching was observed. Prior to the etching, the silicon nanowires were prepared by electroless metal deposited (EMD) in solution containing hydrofluoric acid and hydrogen peroxide in Teflon vessel. The silver particle was deposited on substrate by immersion in hydrofluoric acid and silver nitrate solution for sixty second. The silicon nanowires were growth in different hydrogen peroxide concentration which are 0.3M, 0.4M, 0.5M and 0.6M and 0.7M.The influence of hydrogen peroxide concentration to the formation of silicon nanowires was studied. The morphological properties of silicon nanowires were investigated using field emission scanning electron microscopy (FESEM) and Energy Dispersive X-Ray Spectroscopy (EDS).

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Dissolution of bulk specimens of silicon nitride

An accurate chemical characterization of silicon nitride has become important in connection with current efforts to incorporate components of this material into advanced heat engines. However, there are problems concerning a chemical analysis of bulk silicon nitride. Current analytical methods require the pulverization of bulk specimens. A pulverization procedure making use of grinding media, on the other hand, will introduce contaminants. A description is given of a dissolution procedure which overcomes these difficulties. It has been found that up to at least 0.6 g solid pieces of various samples of hot pressed and reaction bonded silicon nitride can be decomposed in a mixture of 3 mL hydrofluoric acid and 1 mL nitric acid overnight at 150 C in a Parr bomb. High-purity silicon nitride is completely soluble in nitric acid after treatment in the bomb. Following decomposition, silicon and hydrofluoric acid are volatilized and insoluble fluorides are converted to a soluble form.

Davis, W. F.↗

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗

Synthesis and characterization of F-doped Cs{sub 0.33}WO{sub 3−x}F{sub x} particles with improved near infrared shielding ability

F-doped Cs{sub 0.33}WO{sub 3−x}F{sub x} particles were successfully synthesized by the hydrothermal method with hydrofluoric acid as fluorine source, and a new kind of heat insulating films were prepared from dispersion of Cs{sub 0.33}WO{sub 3−x}F{sub x} nanoparticles in polyvinyl alcohol (PVA) aqueous solution. The effects of F doping on the crystal structure and morphology of Cs{sub 0.33}WO{sub 3−x}F{sub x} particles as well as the near-infrared (NIR) shielding ability and heat insulation properties of Cs{sub 0.33}WO{sub 3−x}F{sub x} films were investigated. The results indicated that HF acid addition could promote the formation of rod-like Cs{sub 0.33}WO{sub 3−x}F{sub x} particles during hydrothermal synthesis and increase the yield of Cs{sub 0.33}WO{sub 3−x}F{sub x} powders. Moreover, the as-prepared films from dispersion solution of Cs{sub 0.33}WO{sub 3−x}F{sub x} particles exhibited higher near-infrared (NIR) shielding ability and heat insulating properties than that of the undoped Cs{sub 0.33}WO{sub 3} film. Particularly, the as-prepared Cs{sub 0.33}WO{sub 3−x}F{sub x} sample with F/W (molar ratio)=0.45 showed best NIR shielding ability and transparent heat insulating performance. The formation mechanism of nanorod-like particles and the effects of F doping on the properties of Cs{sub 0.33}WO{sub 3−x}F{sub x} products were discussed. - Graphical abstract: F-doped Cs{sub 0.33}WO{sub 3−x}F{sub x} particles were successfully synthesized by the hydrothermal method with hydrofluoric acid as fluorine source. HF acid addition in the precursor solution could increase the yield of Cs{sub 0.33}WO{sub 3−x}F{sub x} powders and promote the formation of rod-like Cs{sub 0.33}WO{sub 3−x}F{sub x} particles. Moreover, the as-prepared Cs{sub 0.33}WO{sub 3−x}F{sub x} films from dispersion solution of Cs{sub 0.33}WO{sub 3−x}F{sub x} particles exhibited higher near-infrared (NIR) shielding ability and heat insulating properties than that of the undoped Cs{sub x}WO{sub 3} film. Particularly, the as-prepared Cs{sub 0.33}WO{sub 3−x}F{sub x} sample with F/W (molar ratio)=0.45 showed best NIR shielding ability and transparent heat insulating performance. - Highlights: • F-doped Cs{sub 0.33}WO{sub 3−x}F{sub x} powders were successfully synthesized by the hydrothermal method. • HF acid addition could promote the formation of rod-like Cs{sub 0.33}WO{sub 3−x}F{sub x} particles. • The near infrared shielding ability of Cs{sub 0.33}WO{sub 3} was further improved by F doping. • The Cs{sub 0.33}WO{sub 3−x}F{sub x} films exhibited higher transparent heat insulation than Cs{sub 0.33}WO{sub 3}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spinner For Etching Of Semiconductor Wafers

Simple, inexpensive apparatus coats semiconductor wafers uniformly with hydrofluoric acid for etching. Apparatus made in part from small commercial electric-fan motor. Features bowl that collects acid. Silicon wafer placed on platform and centered on axis; motor switched on. As wafer spins, drops of hydrofluoric acid applied from syringe. Centrifugal force spreads acid across wafer in fairly uniform sheet.

Lombardi, Frank↗

Direct Evidence of a Chemical Conversion Mechanism of Atomic-Layer-Deposited TiO 2 Anodes During Lithiation Using LiPF 6 Salt

Titanium dioxide has been identified as a prospective anode material for use in lithium ion batteries. The higher lithiation potential of TiO 2 versus other common anodes is more electrochemically compatible with most organic electrolytes, thus leading to reduced solid electrolyte interphase formation and overall more stable battery systems. However, in this study TiO 2 has exhibited poor cycling stability with common electrolytes containing lithium hexafluorophosphate (LiPF 6 ) salt. Combined electrochemical and spectroscopic analyses have revealed this to be due to the onset of reversible fluorination of the anode and chemical conversion of TiO 2 to TiOF 2 during lithiation. Comparison of electrochemical cycling of atomic-layer-deposited TiO2 anodes using LiPF6 with and without a hydrofluoric acid scavenger, tributylamine, to cycling using a nonfluorinated lithium perchlorate (LiClO 4 ) salt indicates that the in situ formation of hydrofluoric acid in the electrolyte from decomposition of the PF$_{6^–}$ anion alters the lithiation electrochemistry. X-ray photoelectron spectroscopy (XPS) analysis and time-of-flight secondary-ion mass spectrometry (ToF SIMS) depth profiling measurements confirmed the presence of TiF 2 and TiOF surface and bulk phases, respectively, in the electrode upon lithiation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimization of a Nafion Membrane-Based System for Removal of Chloride and Fluoride from Lunar Regolith-Derived Water

A long-term human presence in space will require self-sustaining systems capable of producing oxygen and potable water from extraterrestrial sources. Oxygen can be extracted from lunar regolith, and water contaminated with hydrochloric and hydrofluoric acids is produced as an intermediate in this process. We investigated the ability of Nafion proton exchange membranes to remove hydrochloric and hydrofluoric acids from water. The effect of membrane thickness, product stream flow rate, and acid solution temperature and concentration on water flux, acid rejection, and water and acid activity were studied. The conditions that maximized water transport and acid rejection while minimizing resource usage were determined by calculating a figure of merit. Water permeation is highest at high solution temperature and product stream flow rate across thin membranes, while chloride and fluoride permeation are lowest at low acid solution temperature and concentration across thin membranes. The figure of merit varies depending on the starting acid concentration; at low concentration, the figure of merit is highest across a thin membrane, while at high concentration, the figure of merit is highest at low solution temperature. In all cases, the figure of merit increases with increasing product stream flow rate.

Anthony, Stephen M.↗

High-field Q-slope mitigation due to impurity profile in superconducting radio-frequency cavities

In this study, we present new insights on the origin of the high-field Q-slope in superconducting radio-frequency cavities. Consequent hydrofluoric acid rinses are used to probe the radio-frequency performance as a function of the material removal of two superconducting bulk niobium cavities prepared with low temperature nitrogen infusion. The study reveals that nitrogen infusion affects only the first few tens of nanometers below the native oxide layer. The typical high-field Q-slope behavior of electropolished cavities is indeed completely recovered after a dozen hydrofluoric acid rinses. The reappearance of the high-field Q-slope as a function of material removal was modeled by means of London's local description of screening currents in the superconductor, returning good fitting of the experimental data and suggesting that interstitial impurities layers with diffusion length of the order to tens of nanometers can mitigate high-field Q-slope.

43 PARTICLE ACCELERATORS↗

Application of DRIFTS, 13 C NMR, and py-MBMS to Characterize the Effects of Soil Science Oxidation Assays on Soil Organic Matter Composition in a Mollic Xerofluvent

Chemical oxidations are routinely employed in soil science to study soil organic matter (SOM), and their interpretation could be improved by characterizing oxidation effects on SOM composition with spectroscopy. We investigated the effects of routinely employed oxidants on SOM composition in a Mollic Xerofluvent representative of intensively managed agricultural soils in the California Central Valley. Soil samples were subjected to oxidation by potassium permanganate (KMnO4), sodium hypochlorite (NaOCl), and hydrogen peroxide (H2O2). Additionally, non-oxidized and oxidized soils were treated with hydrofluoric acid (HF) to evaluate reduction of the mineral component to improve spectroscopy of oxidation effects. Oxidized non-HF and HF-treated soils were characterized by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), 13C cross polarization magic angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectroscopy, and pyrolysis molecular beam mass spectrometry (py-MBMS), and for particle size distribution (PSD) using laser diffractometry (LD). Across the range of soil organic carbon (OC) removed by oxidations (14-72%), aliphatic C-H stretch at 3000-2800 cm-1 (DRIFTS) decreased with OC removal, and this trend was enhanced by HF treatment due to significant demineralization in this soil (70%). Analysis by NMR spectroscopy was feasible only after HF treatment, and did not reveal trends between OC removal and C functional groups. Pyrolysis-MBMS did not detect differences among oxidations, even after HF treatment of soils. Hydrofluoric acid entailed OC loss (13-39%), and for H2O2 oxidized soils increased C:N and substantially decreased mean particle size. This study demonstrates the feasibility of using HF to improve characterizations of SOM composition following oxidations as practiced in soil science, in particular for DRIFTS. Since OC removal by oxidants, mineral removal by HF, and the interaction of oxidants and HF observed for this soil may differ for soils with different mineralogies, future work should examine additional soil and land use types to optimize characterizations of oxidation effects on SOM composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid fusion method for the determination of refractory thorium and uranium isotopes in soil samples

Recently, approximately 80% of participating laboratories failed to accurately determine uranium isotopes in soil samples in the U.S Department of Energy Mixed Analyte Performance Evaluation Program (MAPEP) Session 30, due to incomplete dissolution of refractory particles in the samples. Failing laboratories employed acid dissolution methods, including hydrofluoric acid, to recover uranium from the soil matrix. The failures illustrate the importance of rugged soil dissolution methods for the accurate measurement of analytes in the sample matrix. A new rapid fusion method has been developed by the Savannah River National Laboratory (SRNL) to prepare 1-2 g soil sample aliquots very quickly, with total dissolution of refractory particles. Soil samples are fused with sodium hydroxide at 600 ºC in zirconium crucibles to enable complete dissolution of the sample. Uranium and thorium are separated on stacked TEVA and TRU extraction chromatographic resin cartridges, prior to isotopic measurements by alpha spectrometry on cerium fluoride microprecipitation sources. Plutonium can also be separated and measured using this method. Batches of 12 samples can be prepared for measurement in <5 hours.

54 ENVIRONMENTAL SCIENCES↗

Measurement of distribution coefficients on TODGA resin and development of a group separation for mixed activation and fission product samples

Batch equilibrium experiments were performed to determine the distribution coefficients for Sc, Ir, and Ta on N,N,N’,N’tetraoctyl-1,5-diglycolamide (TODGA) resin in various acid matrices. Distribution coefficients were determined in hydrochloric acid (Sc, Ir), nitric acid (Sc, Ta), and a mixture of nitric acid and 0.2M hydrofluoric acid (Sc, Ir, Ta). The distribution coefficients determined through these experiments were then utilized to create a group separation method for activation products, fission products, and environmental constituents.

Louie, Christina A.↗