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DOE OSTI2015

Use of micro-reactors to obtain new insights into the factors influencing tricalcium silicate dissolution

A micro-reactor approach, developed previously, is used to study the early dissolution of tricalcium silicate. This approach uses micron-sized gaps mimicking particles in close contact to understand dissolution, nucleation, and growth processes. The main factors influencing the dissolution kinetics of tricalcium silicate are presented. We show that the presence of defects caused by polishing does not affect the extent of dissolution. A strong effect of aluminum in solution reducing the extent of dissolution is however identified. This effect is highly dependent on the pH, and is much lower above pH 13. We show also that superplasticizers reduce the extent of dissolution; however, the exact reason for this effect is not clear.

36 MATERIALS SCIENCE↗

DOE OSTI2013

Upscaling Calcite Growth Rates from the Mesoscale to the Macroscale

Quantitative prediction of mineral reaction rates in the subsurface remains a daunting task partly because a key parameter for macroscopic models, the reactive site density, is poorly constrained. Here we report atomic force microscopy (AFM) measurements on the calcite surface of monomolecular step densities, treated as equivalent to the reactive site density, as a function of aqueous calcium-to-carbonate ratio and saturation index. Data for the obtuse step orientation are combined with existing step velocity measurements to generate a model that predicts overall macroscopic calcite growth rates. The model is quantitatively consistent with several published macroscopic rates under a range of alkaline solution conditions, particularly for two of the most comprehensive data sets without the need for additional fit parameters. The model reproduces peak growth rates and its functional form is simple enough to be incorporated into reactive transport or other macroscopic models designed for predictions in porous media. However, it currently cannot model equilibrium, pH effects, and may overestimate rates at high aqueous calcium-to-carbonate ratios. The discrepancies in rates at high calcium-to-carbonate ratios may be due to differences in pre-treatment, such as exposing the seed material to SI 1.0 to generate/develop growth hillocks, or other factors.

Bracco, Jacquelyn N.↗

DOE OSTI2024

Degradation of Poly- and Perfluoroalkyl Substances (PFAS) in Water via High Power, Energy-Efficient Electron Beam Accelerator

The goal of the 2-year workplan was to see if electron beam (EB) could be used to break down a sub-set of the larger chemical family of per and polyfluoroalkylated substances (PFAS) in an energy efficient and economical manner when compared to conventional water treatment technologies. Year one (Y1) work focused on sample EB treatment work in the Fermi National Accelerator Laboratory’s (FNALs) Accelerator Applications Demonstration and Development (A2D2) EB accelerator. While there are reportedly thousands of types of PFAS, for the point of most of the work herein, a small subset was examined, typically perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA). PFOA and PFOS are two of the most well studied PFAS and are studied for baseline evaluations and are considered most useful. The work from Y1 provided information about the optimal operating parameters and additives to use when treating PFOS and PFOA via EB. The data were then used to see where in a water treatment system an EB accelerator would be best suited to treat PFAS. A conventional water treatment technology, GAC, was then compared to e-beam treatment technology with respect to energy and costs for treatment. In year two (Y2), several conventional e-beam accelerator designs, and FNAL’s developmental compact SRF accelerator design, were evaluated for their suitability in PFAS treatment, from an energy efficiency and cost standpoint. Several EB parameters were evaluated and optimized for the removal of PFOA and PFOS from water at normal pressure and temperature, measured as total PFAS removal. Under the optimized test conditions both PFOA showed complete destruction to inorganic fluoride, and PFOS to inorganic fluoride and sulfate, with mass balance. The effect on PFAS removal relative to solution pH, total EB dose, EB dose rate, dissolved oxygen concentration (DO), temperature, and initial PFAS concentration were evaluated. In general, PFOA was easier to destroy than PFOS. Degradation products, typically observed under less-than-optimal EB conditions, provided insight to degradation mechanisms. Products were identified to rule out possible deleterious biproduct formation. The water radiolysis radical reaction kinetics with PFOS and PFOA were not dependent on the initial concentration over 5-orders of magnitude from 2 μg/L to 20 mg/L. This is thought to be because there was an overabundance of the reactive water radiolysis radicals relative to PFAS molecules and largely attributed to aqueous electrons. The reaction rates appeared to be diffusion limited. Testing at higher concentrations (100-200 mg/L) showed a decrease in removal efficiency, suggesting alternative kinetics, possibly second order rates, at higher concentrations. In all, we successfully defined a set of optimal EB parameters to treat PFOA and PFOS at concentrations of 20 mg/L in water with destruction efficiencies near 100%. We further tested the optimized EB parameters with other types of PFAS, including shorter and longer fluorocarbon chain homologs of PFOA and PFOS, and PFAS with alternative functional groups such as sulfonamides. Based on our results EB can be optimized as an effective destructive technology for removing PFAS from water. The conditions optimized for PFOA and PFOS were less effective with ultra-short fluorocarbon compounds like TFMS, PFES, PFPS and PFBS, and likely require re-optimization of parameters to them. In all, it was determined that from a cost and energy efficiency standpoint, EB would be best applied to waste streams with relatively high concentrations of PFOS and PFOA and is not as cost effective as GAC treatment for removing low concentrations of PFAS from water. Higher concentrations of PFAS can be found in the wastewater of conventional treatment processes such as RO and IE and therefore EB may be used to supplement such treatment technologies. Some real-world IE regeneration wash water and RO reject water containing higher concentrations of PFAS and obtained from pilot scale industrial wastewater treatment system at a fluorochemical manufacturing facility, showed that EB could remove PFAS from such types of wastewaters. The IE regenerant wash water appeared to be the most efficient of the two types of wastewaters tested. However, some further optimization of the EB parameters for the specific PFAS types present in those wastewaters may be required. Also, the effects of co-present TOC and mineral salts should be considered during such optimization efforts. From the experimental Y1 results it was seen that the aqueous electron drives degradation of the PFAS. In a hypothetical water treatment skid using EB for PFAS destruction the parameters of the system should be optimized to promote aqueous electron production. Before EB treatment, the PFAS should be preconcentrated when possible, the pH should be raised to pH 10 or higher to enhance aqueous electron production, and the water should be nitrogen purged to remove dissolved oxygen to minimize aqueous electron scavenging. An excel spreadsheet was created that calculates optimal conditions based on inlet PFAS concentration and desired outlet concentration, by optimizing the accelerator power, dose rate, water treatment rate, pH and dissolved oxygen levels to reach the desired endpoint. Given this information on accelerator operating conditions five different EB accelerator systems were compared. One EB system was a continuous-wave, linear superconducting accelerator being designed at Fermilab. Three other EB systems (IMPELA at 5% and 25% duty factor and the ILU-14) were normal conducting pulsed linear accelerators. The fifth system was an IBA Rhodotron which is a normal conducting, circular, continuous-wave accelerator. The accelerator efficiency (% of the incoming power that is used in water treatment) was the dominating factor in accelerator choice. The radio frequency (RF) power supply and the accelerator design (superconducting versus warm technology) drive the accelerator efficiency. The IBA Rhodotron was seen to be the most energy efficient commercially available technology with a wall-plug (total) power efficiency of 43% at 400 kW. The Fermilab design, with a prototype for a different application currently being fabricated, was the most energy efficient at 55% when driven by a Klystron RF power supply and as high as 77% when powered by a magnetron. As the Fermilab design was the most energy efficient by approximately 10-30%, further design work was done on the accelerator and beam delivery system specific to the destruction of PFAS in water. The Fermilab design is unique from industrial accelerators in that is superconducting. Superconducting technology allows for the acceleration of electrons without losses. The accelerator must be cooled to below the point where it is superconducting and is operated around 4 degrees Kelvin. The bulk of the design work for the accelerator is on making the accelerator as energy efficient as possible so that it does not require liquid helium and can be cooled with conduction cooling via cryocoolers. Final design work resulted in an EB accelerator that would operate at minimally 200 kW and 10 MeV. Prototype construction would cost $\$ $7.8 million dollars when driven by a Klystron power supply. A second version of the same accelerator would cost $\$ $5.5 million dollars when driven by a magnetron that is still under development. The commercially available 300 kW IBA Rhodotron cost was estimated at approximately $\$ $9 million. While it is hard to directly compare, an operational GAC system used by 3M for groundwater treatment capital cost (2022 dollars) was estimated to cost $\$ $3.3 million. While the capital expense of the EB accelerator systems was higher than GAC, the accelerator EB treatment would result in destruction of the PFAS and not just sequestration of PFAS to form a new waste stream that requires further treatment or disposal. The operating cost to destroy the PFAS via 400 kw EB system was less than $\$ $1000/kg of PFAS destroyed when treating at a 20 mg/L PFAS concentration, compared to GAC with operating costs that calculated at $\$ $27,530 per kg of PFAS sequestered when treating 100 μg/L PFOA and PFOS combined concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2009

Biosensors for EVA: Muscle Oxygen and pH During Walking, Running and Simulated Reduced Gravity

During lunar excursions in the EVA suit, real-time measurement of metabolic rate is required to manage consumables and guide activities to ensure safe return to the base. Metabolic rate, or oxygen consumption (VO2), is normally measured from pulmonary parameters but cannot be determined with standard techniques in the oxygen-rich environment of a spacesuit. Our group developed novel near infrared spectroscopic (NIRS) methods to calculate muscle oxygen saturation (SmO2), hematocrit, and pH, and we recently demonstrated that we can use our NIRS sensor to measure VO2 on the leg during cycling. Our NSBRI-funded project is looking to extend this methodology to examine activities which more appropriately represent EVA activities, such as walking and running and to better understand factors that determine the metabolic cost of exercise in both normal and lunar gravity. Our 4 year project specifically addresses risk: ExMC 4.18: Lack of adequate biomedical monitoring capability for Constellation EVA Suits and EPSP risk: Risk of compromised EVA performance and crew health due to inadequate EVA suit systems.

Lee, S. M. C.↗

DOE OSTI2016

Corrosion of Aluminum in the Chemical Environment after a Loss of Coolant Accident (LOCA)

Probabilistic assessment of Generic Safety Issue (GSI)- 191 generated further studies to improve the characterization of post-Loss of Coolant Accident (LOCA) aluminum release from corrosion sources, since the current industry approach of assessing aluminum release is only valid for deterministic assessments of GSI-191. The nuclear industry has long accepted that solution pH, solution temperature, sump chemical constituents and the phenomena of silicate or phosphate 'inhibition' affects the quantity of aluminum released and the quality of results obtained from models used to predict aluminum release. While improvements in the characterization of aluminum release has been made, the impacts of solution velocity, concurrent corrosion of other metals [6], and trace amount of chemical constituents such as chloride and sulfate ions on aluminum release in post-LOCA conditions have not been assessed. Those factors are well known to influence aluminum corrosion, and will be investigated in this work. The effect of flow on aluminum corrosion rate is characterized using different hydrodynamic system, which has not been investigated in GSI-191 related studies. The corrosion rate depends on the mass-transfer rate which is a function of flow velocity and flow pattern. The inhibition effect of silicon on aluminum corrosion is characterized, and the representative silicon concentration in post-LOCA condition has the potential to significantly inhibit the aluminum corrosion rate. The experiments that investigated silicon effects on aluminum corrosion also showed that calcium leached from Cal-sil can slow corrosion and that the silicon inhibition effect on aluminum corrosion became less pronounced at higher temperature and lower pH. Trace chloride and fluoride ions slightly increased aluminum corrosion rate, and the presence of sulfite ions could mitigate this harmful effect. The corrosion of zinc significantly retarded the aluminum corrosion rate, while presence of copper and carbon steel has little effect on aluminum corrosion in both galvanic and non-galvanic corrosion cases. This work is not complete and is currently evaluating high temperature (>95 C) test with all parameters mentioned and evaluation of the effects on variable boron concentrations at set conditions; Therefore an improved aluminum release model for probabilistic aluminum release model is not proposed. However, this work shows the important impact on aluminum corrosion of parameters not characterized by other studies. To obtain representative aluminum release results for use in GSI-191 probabilistic analysis, the model should be built on data obtained from experiments that account for all parameters that may impact aluminum corrosion and release. (authors)

36 MATERIALS SCIENCE↗

DOE OSTI2016

The Effect of Bicarbonate on Autunite Dissolution in the Presence of Shewanella oneidensis under Oxygen Restricted Conditions - 16429

Uranium is a key contaminant at many U.S. Department of Energy sites that served a leading role in the nation's defense for over 50 years. Uranium contamination of soil and groundwater is of great environmental concern due to the toxicological properties of the uranyl species. In an effort to decrease the concentration of soluble uranium, tripolyphosphate injections were identified as a feasible remediation strategy for sequestering uranium in situ in contaminated groundwater at the Hanford Site (WA). The introduction of sodium tripolyphosphate into uranium-bearing porous media results in the formation of uranyl phosphate minerals (autunite) of general formula (X{sub 1-2}[(UO{sub 2})(PO{sub 4})]{sub 2-1}.nH{sub 2}O), where X is a monovalent or divalent cation. The stability of the uranyl phosphate minerals in the subsurface is a critical factor since it determines the long-term effectiveness of the sodium tripolyphosphate injection as a remediation strategy. The behavior of uranium and its mobility in the subsurface are affected by various factors such as the chemistry of pore water, groundwater and soil minerals, the presence of complex-forming ligands, and micro-organisms that thrive under these conditions. Bicarbonate presence in the aqueous phase facilitates uranium desorption from soil and sediments and promotes the release of U(VI) into the aqueous phase, thus increasing uranium mobility in natural waters. In neutral or basic pH conditions, uranium can readily complex with a wide variety of ligands such as carbonate and form soluble uranyl-carbonato complexes such as UO{sub 2}(CO{sub 3}){sub 2}{sup 2-} and UO{sub 2}(CO{sub 3}){sub 3}{sup 4-}. Bicarbonate complexes have been identified in contaminated pore water at the Hanford Site. Furthermore, the presence of bacteria can significantly affect uranium mobility since bacteria may bio-enhance the release of U (VI) from uranyl-phosphate minerals, thus liberating uranium in the aqueous phase in an effort to obtain phosphorous, a vital nutrient for their metabolism. The Columbia River at the site exhibits large stage variations, causing fluctuations in the water table. These water table fluctuations and multiple rise-and-fall cycles in the river created an oxic-anoxic interface in this region. Previous assessments of Hanford sediment samples collected from this area noted a decline in cultivable aerobic bacteria and suggested the presence of facultative anaerobic bacteria. Shewanella oneidensis MR1 is a common bacterial group in soils and Shewanella species have been found in the Hanford soil. Shewanella oneidensis is a facultative anaerobic species which also belongs to a group known as dissimilatory metal-reducing bacteria (DMRB), due to their ability to reduce metals as a part of their metabolic pathway. Therefore, understanding the role of Shewanella is a critical factor affecting the outcome of environmental remediation. The objective of this research was to demonstrate the significance of bacteria-uranium interactions and investigate the effect of bicarbonate in the aqueous phase on Ca-autunite dissolution in the oxygen-restricted conditions. Sterile 100-mL glass mixed bioreactors with weighed amounts of ground Ca-autunite particles were used for initial experimentation. These autunite-containing bioreactors were injected with bacterial cells after the autunite equilibrated with the media solution amended with 0 mM, 3 mM 5 mM and 10 mM concentrations of bicarbonate. Additional abiotic samples were prepared without bacterial inoculation to provide a control for the biotic samples. The concentration of U(VI) determined in the aqueous phase was in direct correlation to the concentration of bicarbonate present in the solution. It was noted that an increase in bicarbonate concentration led to higher U(VI) concentration in the aqueous phase. A sharp decrease in U(VI) concentration was observed in the bicarbonate-free samples, probably due to a microbe mediated reduction of U(VI) to U(IV). In the case of samples amended with 3 mM bicarbonate, a slight, yet significant, decrease in U(VI) was also observed compared to the abiotic control. However, compared to the abiotic controls, there was no change in U(VI) levels in the aqueous phase as a result of bacterial inoculation for the samples amended with 5 and 10 mM bicarbonate for a period of time as long as 50 days. These results imply that the uranyl-carbonate complexes (UO{sub 2}(CO{sub 3}){sub 2}{sup 2-} and UO{sub 2}(CO{sub 3}){sub 3}{sup 4-}) that are present in carbonate-rich environments might be interfering with the microbial reduction in the oxygen- restricted conditions; however, this conclusion requires further investigation. Finally, the data indicate that release of U, P and Ca from autunite was non-stoichiometric. In conclusion, the high stability of uranyl-phosphate complexes makes them a strong candidate for the remediation efforts to sequester uranium in the subsurface. Nevertheless, in a bicarbonate-rich environment, Ca-autunite has a high probability of dissolution and the presence of metal-reducing bacteria does not seem to impede this process in the presence of higher bicarbonate concentrations under oxygen restricted conditions. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS2017

Evidence Report: Risk of Renal Stone Formation

The formation of renal stones poses an in-flight health risk of high severity, not only because of the impact of renal colic on human performance but also because of complications that could potentially lead to crew evacuation, such as hematuria, infection, hydronephrosis, and sepsis. Evidence for risk factors comes from urine analyses of crewmembers, documenting changes to the urinary environment that are conducive to increased saturation of stone-forming salts, which are the driving force for nucleation and growth of a stone nidus. Further, renal stones have been documented in astronauts after return to Earth and in one cosmonaut during flight. Biochemical analysis of urine specimens has provided indication of hypercalciuria and hyperuricemia, reduced urine volumes, and increased urine saturation of calcium oxalate and calcium phosphate. A major contributor to the risk for renal stone formation is bone atrophy with increased turnover of the bone minerals. Dietary and fluid intakes also play major roles in the risk because of the influence on urine pH (more acidic) and on volume (decreased). Historically, specific assessments on urine samples from some Skylab crewmembers indicated that calcium excretion increased early in flight, notable by day 10 of flight, and almost exceeded the upper threshold for normal excretion (300mg/day in males). Other crewmember data documented reduced intake of fluid and reduced intake of potassium, phosphorus, magnesium, and citrate (an inhibitor of calcium stone formation) in the diet. Hence, data from both short-duration and long-duration missions indicate that space travel induces risk factors for renal stone formation that continue to persist after flight; this risk has been documented by reported kidney stones in crewmembers.

Sibonga, Jean D.↗

DOE OSTI2025

Developing aqueous solubilizing agents as an alternative to solvent extraction

Here, advancing separations science is important for the entire field of chemistry. One partitioning technique that would benefit from improvement is solvent extraction. Despite its effective and widespread use, the method suffers from some problems: generation of flammable organic waste, lengthy process times, and safety concerns associated with contacting organic solvents with acidic aqueous solutions. We developed an alternative separation method inspired by solvent extraction that side-steps those issues. Toward this end, we identified that the functionality of an extractant (an agent used in solvent extraction to pull analytes from the aqueous phase into the organic phase) would change if it was modified for water solubility. In this alternative scenario, the extractant transforms into an “aqueous solubilizing agent.” We discovered that adding this aqueous solubilizing agent alongside a precipitating agent caused the contaminants to precipitate, but not the analyte. This separation concept was demonstrated within the bounds of one of the most difficult partitioning problems, separating minor actinides (Am 3+ ) from lanthanides (Ln 3+ ). We discovered that the (HSO 3 Ph) 4 BTP (aq) aqueous solubilizing agent prevented Am 3+ (aq) from precipitating with Ln 3+ (aq) when f-element precipitating agents (NaF (aq) or HF (aq) ) were added. This separation boasts impressive Am 3+ (aq) recovery yield (90 ± 2 %), near quantitative Ln 3+ (aq) removal, and high separation factors [>3000, Am 3+ (aq) vs. Nd 3+ (aq) ]. It seems likely – given the large number of candidate extractants that could be modified for aqueous solubility and the numerous combinations of existing solubilizing and precipitating agents – that this alternative approach could be used broadly in place of solvent extraction and solve other important separation problems.

(HSO3Ph)4BTP(aq)↗

DOE OSTI2011

Electron-Impact Water-Jet Microfocus Source for Water-Window Microscopy

We demonstrate high-brightness operation of an electron-impact water-jet-anode soft x-ray source with an increased power loading of 15 times compared to our previously published results, with a corresponding increase in {approx}525-eV x-ray intensity of 6.4 times. This has been accomplished by improving the vacuum pumping system and the electron focusing optics, and increasing the liquid-jet velocity. The source now operates up to 120-W e-beam power and at a 525-eV brightness of 3.5x10{sup 9} ph/(sx{mu}m{sup 2}xsrxline). The source concept has potential to increase the x-ray brightness by another order of magnitude by optimizing the e-beam focusing and upgrading the power supply. Currently, spot enlargement with increased power is determined to be the most important limiting factor.

07 ISOTOPE AND RADIATION SOURCES↗

DOE OSTI2019

Iron-mediated oxidation of methoxyhydroquinone at Rifle, Colorado

In this study, the oxidation of 2-methoxyhydroquinone (MH2Q) by ferric iron (Fe(III)) under dark conditions in the absence and presence of oxygen was investigated within a pH range of 4 – 6. While Fe(III) was capable of stoichiometrically oxidizing MH2Q under anaerobic conditions, catalytic oxidation of MH2Q was observed in the presence of O2 due to further cycling between oxygen, semiquinone radicals, and iron species. A detailed kinetic model was developed to describe the predominant mechanisms, which indicated that both the undissociated and mono-dissociated anions of MH2Q were kinetically active species towards Fe(III) reduction, with the mono-dissociated anion being the key species accounting for the pH dependence of the oxidation. The generated radical intermediates, namely semiquinone and superoxide, are of great importance in reaction chain propagation. The kinetic model may provide critical insight into the underlying mechanisms of the thermodynamic and kinetic characteristics of metal-organic interactions and assist in understanding and predicting the factors controlling iron and organic matter transformation and bioavailability in aquatic systems.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

A High Separation Factor for 165Er from Ho for Targeted Radionuclide Therapy

Background: Radionuclides emitting Auger electrons (AEs) with low (0.02–50 keV) energy, short (0.0007–40 µm) range, and high (1–10 keV/µm) linear energy transfer may have an important role in the targeted radionuclide therapy of metastatic and disseminated disease. Erbium-165 is a pure AE-emitting radionuclide that is chemically matched to clinical therapeutic radionuclide 177Lu, making it a useful tool for fundamental studies on the biological effects of AEs. This work develops new biomedical cyclotron irradiation and radiochemical isolation methods to produce 165Er suitable for targeted radionuclide therapeutic studies and characterizes a new such agent targeting prostate-specific membrane antigen. Methods: Biomedical cyclotrons proton-irradiated spot-welded Ho(m) targets to produce 165Er, which was isolated via cation exchange chromatography (AG 50W-X8, 200–400 mesh, 20 mL) using alpha-hydroxyisobutyrate (70 mM, pH 4.7) followed by LN2 (20–50 µm, 1.3 mL) and bDGA (50–100 µm, 0.2 mL) extraction chromatography. The purified 165Er was radiolabeled with standard radiometal chelators and used to produce and characterize a new AE-emitting radiopharmaceutical, [165Er]PSMA-617. Results: Irradiation of 80–180 mg natHo targets with 40 µA of 11–12.5 MeV protons produced 165Er at 20–30 MBq·µA−1·h−1. The 4.9 ± 0.7 h radiochemical isolation yielded 165Er in 0.01 M HCl (400 µL) with decay-corrected (DC) yield of 64 ± 2% and a Ho/165Er separation factor of (2.8 ± 1.1) · 105. Radiolabeling experiments synthesized [165Er]PSMA-617 at DC molar activities of 37–130 GBq·µmol−1. Conclusions: A 2 h biomedical cyclotron irradiation and 5 h radiochemical separation produced GBq-scale 165Er suitable for producing radiopharmaceuticals at molar activities satisfactory for investigations of targeted radionuclide therapeutics. This will enable fundamental radiation biology experiments of pure AE-emitting therapeutic radiopharmaceuticals such as [165Er]PSMA-617, which will be used to understand the impact of AEs in PSMA-targeted radionuclide therapy of prostate cancer.

165Er↗

DOE OSTI2018

Probing Translocation in Mutants of the Anthrax Channel: Atomically Detailed Simulations with Milestoning

Anthrax toxin consists of a cation channel and two protein factors. Translocation of the anthrax protein factors from endosomal to the cytosolic compartment is a complex process which utilizes the cation channel. An atomically detailed understanding of the function of the anthrax translocation machinery is incomplete. We introduce atomically detailed simulations of the lethal factor and channel mutants. Kinetic and thermodynamic properties of early events in the translocation process are computed within the Milestoning theory and algorithm. Several mutants of the channel illustrate that long-range electrostatic interactions provide the dominant driving force for translocation. No external energy input is needed because the lower pH in the endosome relative to the cytosol drives the initial translocation process forward. Channel mutants with variable sizes cause smaller effects on translocation events relative to charge manipulations. Comparison with available experimental data is provided.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

The chemistry of TALSPEAK: A review of the science

Here, the TALSPEAK Process (Trivalent Actinide Lanthanide Separation with Phosphorus-reagent Extraction from Aqueous Komplexes) was originally developed at Oak Ridge National Laboratory by B. Weaver and F.A. Kappelmann in the 1960s. It was envisioned initially as an alternative to the TRAMEX process (selective extraction of trivalent actinides by tertiary or quaternary amines over fission product lanthanides from concentrated LiCl solutions). TALSPEAK proposed the selective extraction of trivalent lanthanides away from the actinides, which are retained in the aqueous phase as aminopolycarboxylate complexes. After several decades of research and development, the conventional TALSPEAK process (based on di-(2-ethylhexyl) phosphoric acid (extractant) in 1,4-di-isopropylbenzene (diluent) and a concentrated lactate buffer containing diethylenetriamine-N,N,N',N",N"-pentaacetic acid (actinide-selective holdback reagent)) has become a widely recognized benchmark for advanced aqueous partitioning of the trivalent 4f/5f elements. TALSPEAK chemistry has also been utilized as an actinide-selective stripping agent (Reverse TALSPEAK) with some notable success. Under ideal conditions, conventional TALSPEAK separates Am 3+ from Nd 3+ (the usual limiting pair) with a single-stage separation factor of about 100; both lighter and heavier lanthanides are more completely separated from Am 3+ . Despite this apparent efficiency, TALSPEAK has not seen enthusiastic adoption for advanced partitioning of nuclear fuels at process scale for two principle reasons: 1) all adaptations of TALSPEAK chemistry to process scale applications require rigid pH control within a narrow range of pH, and 2) phase transfer kinetics are often slower than ideal. To compensate for these effects, high concentrations of the buffer (0.5-2 M H/Na lactate) are required. Acknowledgement of these complications in TALSPEAK process development has inspired significant research activities dedicated to improving understanding of the basic chemistry that controls TALSPEAK (and related processes based on the application of actinide-selective holdback reagents). In the following report, advances in understanding of the fundamental chemistry of TALSPEAK that have occurred during the past decade will be reviewed and discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Search for [C II] emission in z = 6.5-11 star-forming galaxies

We present the search for the [C II] emission line in three z > 6.5 Lyα emitters (LAEs) and one J-dropout galaxy using the Combined Array for Research in Millimeter-wave Astronomy and the Plateau de Bure Interferometer. We observed three bright z ∼ 6.5-7 LAEs discovered in the Subaru Deep Field (SDF) and the multiple imaged lensed z ∼ 11 galaxy candidate found behind the galaxy cluster MACSJ0647.7+7015. For the LAEs IOK-1 (z = 6.965), SDF J132415.7+273058 (z = 6.541), and SDF J132408.3+271543 (z = 6.554) we find upper limits for the [C II] line luminosity of <2.05, <4.52, and <10.56 × 10{sup 8} L {sub ☉}, respectively. We find upper limits to the far-IR (FIR) luminosity of the galaxies using a spectral energy distribution template of the local galaxy NGC 6946 and taking into account the effects of the cosmic microwave background on the millimeter observations. For IOK-1, SDF J132415.7+273058, and SDF J132408.3+271543 we find upper limits for the FIR luminosity of <2.33, 3.79, and 7.72 × 10{sup 11} L {sub ☉}, respectively. For the lensed galaxy MACS0647-JD, one of the highest-redshift galaxy candidates to date with z{sub ph}=10.7{sub −0.4}{sup +0.6}, we put an upper limit in the [C II] emission of <1.36 × 10{sup 8} × (μ/15){sup –1} L {sub ☉} and an upper limit in the FIR luminosity of <6.1 × 10{sup 10} × (μ/15){sup –1} L {sub ☉} (where μ is the magnification factor). We explore the different conditions relevant for the search for [C II] emission in high-redshift galaxies as well as the difficulties for future observations with the Atacama Large Millimeter/submillimeter Array (ALMA) and the Cerro Chajnantor Atacama Telescope (CCAT).

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2018

Conservation management and ecosystem services in midwestern United States agricultural systems

The recognition that agricultural systems provide services beyond food production has motivated federal legislation and associated programs that promote sustainable management and conservation of productive working lands. This study evaluates the ability of the USDA Natural Resources Conservation Service's (NRCS) Conservation Measurement Tool (CMT), which has been used to determine eligibility for enrollment in the Conservation Stewardship Program, to reflect changes in ecosystem services resulting from the use of conservation management practices on croplands. This work evaluates four macroconcerns or outcomes (soil erosion, soil quality, water quality, and air quality) that are quantified within the tool by comparing CMT scores tabulated according to practices reported by farmers involved in grain producing operations in the US Midwest with soil health measures (dynamic soil properties [DSPs]) determined on 72 Illinois farm fields. Three management practice categories-Conventional, Conservation, and Organic-were evaluated. The CMT identified significant differences among management categories, and scores ranked consistently higher for Organic than Conventional or Conservation systems. Direct analysis of DSPs suggested that there were relatively small differences among soil health indicators measured on farms under varied management; this implies that the CMT might be overemphasizing the influence of selected management practices. The evaluation of multivariate relationships between the practices scored in the CMT and DSPs revealed that soil properties like soil pH and particulate organic matter-carbon (POM-C) can be used to improve the accuracy of the tool. They also show how relationships between questions (practices) and outcomes suggested by DSPs vary among farming categories and suggest this type of practice-based tool should be adapted by embedding factors to scale farming systems or, preferably, by adding questions that better describe important factors (e.g., plant productivity and fertilizer timing, rate, and form of application) and their interactions with other factors known to influence specific outcomes. This work shows how field data describing practices, properties, and outcomes can be used to statistically evaluate and refine conservation scoring tools.

conservation measurement tool↗

DOE OSTI2016

Performance of an i -SANEX System Based on a Water-Soluble BTP under Continuous Irradiation in a γ-Radiolysis Test Loop

Here, the i -SANEX solvent formulation consisting of nominally 0.2 M TODGA/5% 1-octanol/dodecane was γ-irradiated under realistic conditions in the Idaho National Laboratory radiolysis test loop, in contact with both extraction and stripping aqueous phases. The extraction aqueous phase was 4.5 M HNO 3 , and the stripping aqueous phase was 0.018 M SO 3 –Ph–BTP/0.35 M HNO 3 . When irradiated in contact with only the 4.5 M HNO 3 phase, the TODGA solvent maintained excellent extraction performance for americium, cerium, europium, and neodymium to a maximum absorbed dose of nearly 0.9 MGy. The results for preliminary static, batch irradiations were consistent with test loop findings. When the aqueous phase was changed to that containing the aqueous soluble BTP, the irradiated aqueous phase showed a dramatic color change, but this does not appear to have had adverse effect on solvent extraction performance. The distribution ratios for both the lanthanides and actinides were invariant with absorbed dose, and the separation factors were essentially unchanged to a maximum absorbed dose of 174 kGy. The results of inductively coupled plasma mass spectrometry analysis of the aqueous and organic phases showed that ruthenium and strontium were not extracted in the presence of the irradiated BTP-aqueous phase. Molybdenum was extracted under both conditions. Further, the buildup of corrosion products of stainless steel in the presence of the BTP was not dramatically greater than in the nitric acid-only system. Phase separation times were not adversely affected by irradiation for either system. The results presented here indicate that the performance of the TODGA/SO 3 –Ph–BTP, i -SANEX process under test loop radiolysis is much better than expected based on a literature report using single-phase batch irradiation experiments, and better than might be predicted based on diglycolamide radiolysis studies alone.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2012

Insights into the Molecular Activation Mechanism of the RhoA-specific Guanine Nucleotide Exchange Factor, PDZRhoGEF

PDZRhoGEF (PRG) belongs to a small family of RhoA-specific nucleotide exchange factors that mediates signaling through select G-protein-coupled receptors via G{alpha}{sub 12/13} and activates RhoA by catalyzing the exchange of GDP to GTP. PRG is a multidomain protein composed of PDZ, regulators of G-protein signaling-like (RGSL), Dbl-homology (DH), and pleckstrin-homology (PH) domains. It is autoinhibited in cytosol and is believed to undergo a conformational rearrangement and translocation to the membrane for full activation, although the molecular details of the regulation mechanism are not clear. It has been shown recently that the main autoregulatory elements of PDZRhoGEF, the autoinhibitory 'activation box' and the 'GEF switch,' which is required for full activation, are located directly upstream of the catalytic DH domain and its RhoA binding surface, emphasizing the functional role of the RGSL-DH linker. Here, using a combination of biophysical and biochemical methods, we show that the mechanism of PRG regulation is yet more complex and may involve an additional autoinhibitory element in the form of a molten globule region within the linker between RGSL and DH domains. We propose a novel, two-tier model of autoinhibition where the activation box and the molten globule region act synergistically to impair the ability of RhoA to bind to the catalytic DH-PH tandem. The molten globule region and the activation box become less ordered in the PRG-RhoA complex and dissociate from the RhoA-binding site, which may constitute a critical step leading to PRG activation.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2014

Using cross correlations to calibrate lensing source redshift distributions: Improving cosmological constraints from upcoming weak lensing surveys

Cross correlations between the galaxy number density in a lensing source sample and that in an overlapping spectroscopic sample can in principle be used to calibrate the lensing source redshift distribution. In this paper, we study in detail to what extent this cross-correlation method can mitigate the loss of cosmological information in upcoming weak lensing surveys (combined with a cosmic microwave background prior) due to lack of knowledge of the source distribution. We consider a scenario where photometric redshifts are available and find that, unless the photometric redshift distribution p(z {sub ph}|z) is calibrated very accurately a priori (bias and scatter known to ∼0.002 for, e.g., EUCLID), the additional constraint on p(z {sub ph}|z) from the cross-correlation technique to a large extent restores the cosmological information originally lost due to the uncertainty in dn/dz(z). Considering only the gain in photo-z accuracy and not the additional cosmological information, enhancements of the dark energy figure of merit of up to a factor of four (40) can be achieved for a SuMIRe-like (EUCLID-like) combination of lensing and redshift surveys, where SuMIRe stands for Subaru Measurement of Images and Redshifts). However, the success of the method is strongly sensitive to our knowledge of the galaxy bias evolution in the source sample and we find that a percent level bias prior is needed to optimize the gains from the cross-correlation method (i.e., to approach the cosmology constraints attainable if the bias was known exactly).

79 ASTRONOMY AND ASTROPHYSICS↗