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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1984

Use of Thematic Mapper for water quality assessment

The evaluation of simulated TM data obtained on an ER-2 aircraft at twenty-five predesignated sample sites for mapping water quality factors such as conductivity, pH, suspended solids, turbidity, temperature, and depth, is discussed. Using a multiple regression for the seven TM bands, an equation is developed for the suspended solids. TM bands 1, 2, 3, 4, and 6 are used with logarithm conductivity in a multiple regression. The assessment of regression equations for a high coefficient of determination (R-squared) and statistical significance is considered. Confidence intervals about the mean regression point are calculated in order to assess the robustness of the regressions used for mapping conductivity, turbidity, and suspended solids, and by regressing random subsamples of sites and comparing the resultant range of R-squared, cross validation is conducted.

Horn, E. M.↗
NASA NTRS1990

Studies of mechano-chemical interactions in the tribological behavior of materials

Mechano-chemical interaction studies can contribute to the understanding of wear and friction of materials. Specific examples of experimental results relative to the subject are discussed. There are two parts: one describes the synergistic effect of corrosion and wear of iron sliding on sapphire in sulfuric acid, and the other describes the effect of surface films on the wear and friction of plasma-deposited diamondlike carbon (amorphous hydrogenated carbon) films in sliding contact with silicon nitride. The concentration of acid (pH) is an important factor in controlling the iron loss caused by wear-corrosion processes in sulfuric acid. The mechanical action can cause chemical reactions to proceed much faster than they would otherwise. The diamondlike carbon (DLC) films are shown to behave tribologically much like bulk diamond. In a dry nitrogen environment, a mechano-chemical reaction produces a substance which greatly decreases the coefficient of friction. In a moist air environment, mechano-chemical interactions drastically reduce the wear life of DLC films and water vapor greatly increases friction.

Miyoshi, Kazuhisa↗
NASA NTRS1990

Studies of mechanochemical interactions in the tribological behavior of materials

Mechanochemical interaction studies can contribute to the understanding of wear and friction of materials. Specific examples of experimental results relative to the subject are discussed. There are two parts: one describes the synergistic effect of corrosion and wear of iron sliding on sapphire in sulfuric acid, and the other describes the effect of surface films on the wear and friction of plasma-deposited diamondlike carbon (amorphous hydrogenated carbon) films in sliding contact with silicon nitride. The concentration of acid (pH) is an important factor in controlling the iron loss caused by wear-corrosion processes in sulfuric acid. The mechanical action can cause chemical reactions to proceed much faster than they would otherwise. The diamondlike carbon (DLC) films are shown to behave tribologically much like bulk diamond. In a dry nitrogen environment, a mechanochemical reaction produces a substance which greatly decreases the coefficient of friction. In a moist air environment, mechanochemical interactions drastically reduce the wear life of DLC films and water vapor greatly increases friction.

Miyoshi, Kazuhisa↗
NASA NTRS1993

Thermally altered palagonitic tephra - A spectral and process analog to the soil and dust of Mars

Six palagonitic soil samples (PH-1 through PH-6) which were collected at 30-cm intervals from a lava slab on Mauna Kea, Hawaii, are studied. The samples present an alteration sequence caused by heating during emplacement of molten lava over a preexisting tephra cone. Techniques employed include visible and near-IUR spectroscopy, Moessbauer spectroscopy, and magnetic analysis. The four samples closest to the slab (PH-1 through PH-4) were strongly altered in response to heating during its emplacement; their iron oxide mineralogy is dominated by nanophase ferric oxide. The sample adjacent to the slab (PH-1) has a factor of 3 less H2O and contains crystalline hematite and magnetite in addition to nanophase ferric oxide. It is argued that localized thermal alteration events may provide a volumetrically important mechanism for the palagonitization of basaltic glass and the production of crystalline ferric oxides on Mars.

Bell, James F., III↗
DOE OSTI2020

Iodine Co-Precipitation with Calcium Carbonate in the Presence of Silica Ions - 20360

Historical releases of I-129 to the subsurface at the U.S. Department of Energy Hanford Site have resulted in large dilute plumes that cover an area of over 50 km{sup 2}. The most concentrated I-129 plume is associated with the 200 West Area in the 200-UP-1 operable unit of the Hanford Central Plateau, where peak concentrations have been measured up to 30 times the drinking water standard of 1 pCi/L. The mobility of iodine depends on many factors, including chemical speciation, pH, redox conditions, as well as the presence of organic matter, calcium carbonate minerals and microbial activities. Speciation measurements estimate that the majority of the iodine (∼76%) in Hanford groundwater exists as iodate. Information on processes that affect iodate mobility in the Hanford subsurface support evaluation of environmental management options for the I-129 plumes. Iodate can be incorporated into calcium carbonate, which is a potential mechanism of naturally attenuating radioiodine in groundwater. However, the silica content in porewater may impact the contaminant-calcium carbonate incorporation process. Silica is one of the most abundant elements in nature and can have an impact on chemical weathering of alkaline-earth carbonates in the environment. Hence, this research aims to advances knowledge of the iodine co-precipitation process with calcium carbonate in the presence of silica. This information supports the technical basis evaluation of natural attenuation for I-129. Samples for these studies were prepared using calcium carbonate-forming solutions that included certified grade sodium meta-silicate nonahydrate (Na{sub 2}SiO{sub 3}), calcium chloride dehydrate (CaCl{sub 2}.2H{sub 2}O), sodium carbonate (NaCO{sub 2}), and sodium hydroxide (NaOH) solutions for pH adjustments. Triplicate samples were prepared with silica concentrations in the solution of 0 mM, 0.5 mM and 20 mM, mixed with an iodate standard (1000 ppm of IO{sub 3}{sup -} in H{sub 2}O) and sampled over a one-week period. Preliminary data analyses suggest that less iodine remains in solution in the presence of silica (average remaining aqueous fraction 0.23±0.03 at 20 mM of Si) relative to samples without silica (0.52±0.06); an indication that more iodine has been sorbed or incorporated into precipitates. However, the mechanisms for this behavior are still under investigation and need to be interpreted relative to pore water compositions that are representative of Hanford site-specific conditions. Scanning electron microscope equipped with energy dispersive spectroscopy (SEM-EDS) analyses were performed to observe the solid phase morphology in these experiments and showed rhombohedral calcite crystals covered with amorphous Si floccules. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

A novel shogaol analog suppresses cancer cell invasion and inflammation, and displays cytoprotective effects through modulation of NF-κB and Nrf2-Keap1 signaling pathways

Natural compounds containing vanilloid and Michael acceptor moieties appear to possess anti-cancer and chemopreventive properties. The ginger constituent shogaol represents one such compound. In this study, the anti-cancer potential of a synthetic novel shogaol analog 3-phenyl-3-shogaol (3-Ph-3-SG) was assessed by evaluating its effects on signaling pathways. At non-toxic concentrations, 3-Ph-3-SG suppressed cancer cell invasion in MDA-MB-231 and MCF-7 breast carcinoma cells through inhibition of PMA-activated MMP-9 expression. At similar concentrations, 3-Ph-3-SG reduced expression of the inflammatory mediators nitric oxide (NO), inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2) and prostanglandin-E{sub 2} (PGE{sub 2}) in RAW 264.7 macrophage-like cells. Inhibition of cancer cell invasion and inflammation by 3-Ph-3-SG were mediated through suppression of the nuclear factor-kappaB (NF-κB) signaling pathway. The 3-Ph-3-SG also demonstrated cytoprotective effects by inducing the antioxidant response element (ARE)-driven genes NAD(P)H quinone oxidoreductase-1 (NQO1) and heme oxygenase-1 (HO-1). Cytoprotection by 3-Ph-3-SG was achieved at least partly through modification of cysteine residues in the E3 ubiquitin ligase substrate adaptor Kelch-like ECH-associated protein 1 (Keap1), which resulted in accumulation of transcription factor NF-E2 p45-related factor 2 (Nrf2). The activities of 3-Ph-3-SG were comparable to those of 6-shogaol, the most abundant naturally-occurring shogaol, and stronger than those of 4-hydroxyl-null deshydroxy-3-phenyl-3-shogaol, which attested the importance of the 4-hydroxy substituent in the vanilloid moiety for bioactivity. In summary, 3-Ph-3-SG is shown to possess activities that modulate stress-associated pathways relevant to multiple steps in carcinogenesis. Therefore, it warrants further investigation of this compound as a promising candidate for use in chemotherapeutic and chemopreventive strategies. - Highlights: • Novel shogaol 3-phenyl-3-shogaol suppressed cancer cell invasion and inflammation. • Anti-invasive and anti-inflammatory effects were NF-κB-dependent. • 3-Phenyl-3-shogaol induced ARE-driven genes to achieve cytoprotection. • Cytoprotective effects were brought about by modification of cysteines in Keap1. • Chemopreventive activities of 3-phenyl-3-shogaol and 6-shogaol were comparable.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2012

Atomic structure of the sweet-tasting protein thaumatin I at pH 8.0 reveals the large disulfide-rich region in domain II to be sensitive to a pH change

Highlights: Black-Right-Pointing-Pointer Structure of a recombinant thaumatin at pH 8.0 determined at a resolution of 1.0 A. Black-Right-Pointing-Pointer Substantial fluctuations of a loop in domain II was found in the structure at pH 8.0. Black-Right-Pointing-Pointer B-factors for Lys137, Lys163, and Lys187 were significantly affected by pH change. Black-Right-Pointing-Pointer An increase in mobility might play an important role in the heat-induced aggregation. -- Abstract: Thaumatin, an intensely sweet-tasting plant protein, elicits a sweet taste at 50 nM. Although the sweetness remains when thaumatin is heated at 80 Degree-Sign C for 4 h under acid conditions, it rapidly declines when heating at a pH above 6.5. To clarify the structural difference at high pH, the atomic structure of a recombinant thaumatin I at pH 8.0 was determined at a resolution of 1.0 A. Comparison to the crystal structure of thaumatin at pH 7.3 and 7.0 revealed the root-mean square deviation value of a C{alpha} atom to be substantially greater in the large disulfide-rich region of domain II, especially residues 154-164, suggesting that a loop region in domain II to be affected by solvent conditions. Furthermore, B-factors of Lys137, Lys163, and Lys187 were significantly affected by pH change, suggesting that a striking increase in the mobility of these lysine residues, which could facilitate a reaction with a free sulfhydryl residue produced via the {beta}-elimination of disulfide bonds by heating at a pH above 7.0. The increase in mobility of lysine residues as well as a loop region in domain II might play an important role in the heat-induced aggregation of thaumatin above pH 7.0.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Soil pH influences the structure of virus communities at local and global scales

The influence of biotic and abiotic factors on viral communities across environmental gradients in soil is relatively unknown. While soil pH strongly influences microbial community structure, it is unclear whether there is a similar influence on soil viruses. In this study, prokaryotic and viral communities were characterized in soils from a long-term pH-manipulated soil gradient (pH 4.5 and 7.5), and viral populations also compared to those of other soils ranging in pH (4.0–7.5). Viral communities were significantly influenced by pH at the local scale with 99% of viral operational taxonomic units restricted to pH 4.5 or 7.5 soil only. Analysis of viromes from six other European and North American soil systems demonstrated that a selection of viral clusters from acidic and neutral pH soils were more associated with those from the local gradient pH 4.5 or 7.5 soils, respectively. While direct pH effects on virion integrity and indirect selection via host composition were not distinguished, the results reveal that soil pH is a factor in structuring viral communities at local and global scales.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

pH-SWITCHABLE DYNAMIC BINARY COMPLEXES AS VISCOSITY MODIFYING AGENTS

The study of supramolecular structures has been gaining a lot of momentum in recent years due to their potential application in several interesting areas such as medicine, catalysis, energy, oil and gas, etc. Hydraulic fracturing is one area where the ongoing demand for novel viscosity modifiers has prompted researchers to explore various facets of chemistry. In this study, a dynamic binary complex (DBC) solution is presented, with the potential to be useful in the hydraulic fracturing domain. It has a supramolecular structure that is formed by the self-assembly of oleic acid and diethylenetriamine into an elongated network under alkaline conditions. With less than 2 wt% of constituents in aqueous solution, a viscous gel that exhibits high viscosities even under shear was formed. It was sensitive to pH and salinity, and its zero-shear viscosity could be tuned by a factor of ~280 by changing the pH. Furthermore, its viscous properties were pronounced in the presence of salt. Sand settling tests revealed its potential to hold up sand particles for extended periods of time, longer than 24 hours. In conclusion, this DBC solution system has potential to be utilized as a smart pH-switchable hydraulic fracturing fluid that can be prepared using seawater.

02 PETROLEUM↗
DOE OSTI2021

Supramolecular dynamic binary complexes with pH and salt-responsive properties for use in unconventional reservoirs

Hydraulic fracturing of unconventional reservoirs has seen a boom in the last century, as a means to fulfill the growing energy demand in the world. The fracturing fluid used in the process plays a substantial role in determining the results. Hence, several research and development efforts have been geared towards developing more sustainable, efficient, and improved fracturing fluids. Herein, we present a dynamic binary complex (DBC) solution, with potential to be useful in the hydraulic fracturing domain. It has a supramolecular structure formed by the self-assembly of low molecular weight viscosifiers (LMWVs) oleic acid and diethylenetriamine into an elongated entangled network under alkaline conditions. With less than 2 wt% constituents dispersed in aqueous solution, a viscous gel that exhibits high viscosities even under shear was formed. Key features include responsiveness to pH and salinity, and a zero-shear viscosity that could be tuned by a factor of ~280 by changing the pH. Furthermore, its viscous properties were more pronounced in the presence of salt. Sand settling tests revealed its potential to hold up sand particles for extended periods of time. In conclusion, this DBC solution system has potential to be utilized as a smart salt-responsive, pH-switchable hydraulic fracturing fluid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Engineering of synthetic, stress-responsive yeast promoters

Advances in synthetic biology and our understanding of the rules of promoter architecture have led to the development of diverse synthetic constitutive and inducible promoters in eukaryotes and prokaryotes. However, the design of promoters inducible by specific endogenous or environmental conditions is still rarely undertaken. In this study, we engineered and characterized a set of strong, synthetic promoters for budding yeast Saccharomyces cerevisiae that are inducible under acidic conditions (pH ≤ 3). Using available expression and transcription factor binding data, literature on transcriptional regulation, and known rules of promoter architecture we improved the low-pH performance of the YGP 1 promoter by modifying transcription factor binding sites in its upstream activation sequence. The engineering strategy outlined for the YGP 1 promoter was subsequently applied to create a response to low pH in the unrelated CCW 14 promoter. We applied our best promoter variants to low-pH fermentations, enabling ten-fold increased production of lactic acid compared to titres obtained with the commonly used, native TEF 1 promoter. Our findings outline and validate a general strategy to iteratively design and engineer synthetic yeast promoters inducible to environmental conditions or stresses of interest.

Biochemistry & Molecular Biology↗
DOE OSTI2022

Simulated Hydrological Dynamics and Coupled Iron Redox Cycling Impact Methane Production in an Arctic Soil

The fate of organic carbon (C) in permafrost soils is important to the climate system due to the large global stocks of permafrost C. Thawing permafrost can be subject to dynamic hydrology, making redox processes an important factor controlling soil organic matter (SOM) decomposition rates and greenhouse gas production. In iron (Fe)-rich permafrost soils, Fe(III) can serve as a terminal electron acceptor, promoting anaerobic respiration of SOM and increasing pH. Current large-scale models of Arctic C cycling do not include Fe cycling or pH interactions. Here, a geochemical reaction model was developed by coupling Fe redox reactions and C cycling to simulate SOM decomposition, Fe(III) reduction, pH dynamics, and greenhouse gas production in permafrost soils subject to dynamic hydrology. In this study we parameterized the model using measured CO 2 and CH 4 fluxes as well as changes in pH, Fe(II), and dissolved organic C concentrations from oxic and anoxic incubations of permafrost soils from polygonal permafrost sites in northern Alaska, United States. In simulations of repeated oxic-anoxic cycles, Fe(III) reduction during anoxic periods enhanced CO 2 production, while the net effect of Fe(III) reduction on cumulative CH 4 fluxes depended on substrate C availability. With lower substrate availability, Fe(III) reduction decreased total CH 4 production by further limiting available substrate. With higher substrate availability, Fe(III) reduction enhanced CH 4 production by increasing pH. Our results suggest that interactions among Fe-redox reactions, pH and methanogenesis are important factors in predicting CH 4 and CO 2 production as well as SOM decomposition rates in Fe-rich, frequently waterlogged Arctic soils.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Partitioning of Recombinant Pseudomonas putida POS-F84 Proline Dehydrogenase in Aqueous Two-Phase Systems: Optimization Using Response Surface Methodology

Empirical modeling the partition behavior and recovery of a recombinant Pseudomonas putida POS-F84 proline dehydrogenase (ProDH) in aqueous two-phase systems (ATPS) was carried out by response surface methodology (RSM). Polyethylene glycol 1000 (PEG-1000) concentration, sodium carbonate concentration, and pH, which were the most important factors, were chosen for modeling the partition feature of enzyme. The adequacy of the models was investigated by means of variance analysis. Also, to confirm the efficiency of the ATPS in partition and purification of recombinant ProDH, purity and enzymatic activity was studied. After numerical optimization, an optimal ATPS composed of 14.33% PEG-1000 and 11.79% sodium carbonate at pH 7.48 was achieved. Yield, purification factor, and recovery were 81.41%, 60.82, and 270.82%, respectively. Purified recombinant ProDH was found as a single protein band into the upper PEG-rich phase and the specific activity was calculated to be 46.23 ± 2.1 U/mg. Collectively, our data showed that the RSM could be an appropriate and powerful tool to define the best ATPS system for recovery and purification of P. putida ProDH.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Parametric study and speciation analysis of rare earth precipitation using oxalic acid in a chloride solution system

Oxalic acid precipitation is a common step in the purification of rare earth elements (REE) from a concentrated pregnant leach solution (PLS). However, the presence of contaminants such as Al, Fe, and Ca in given amounts decreases the REE precipitation efficiency and product purity while also increasing the amount of oxalic acid needed to maximize recovery. As such, a statistically designed test program was performed to identify the optimal conditions necessary for a relatively low REE content PLS containing elevated concentrations of contaminant ions. The performance objective was maximization of REE precipitation efficiency while minimizing the oxalic acid dosage. A central composite design was utilized to quantify performance impacts and identify the ultimate set of parameter values for oxalic acid dosage, Fe(III) contamination concentration, solution pH, and reaction 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 indicate that increasing the oxalic acid concentration from 0 g/L to 80 g/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. Here, to further the understanding of the REE-oxalate system, a fundamental solution chemistry study was performed using the equilibrium constants of the reactions. The study resulted in the development of oxalate speciation diagrams and provided an analysis of the REE precipitation characteristics at various oxalate anion concentrations and Fe(III) contamination levels using MINTEQ software. The dominant Fe(III) species in the solution system were found to be Fe-(C 2 O 4 ) 3 3- , Fe-(C 2 O 4 ) 2- , and Fe-(C 2 O 4 ) + , which consume the majority of the oxalate anions. The simulated model was found to be in agreement with the experimental findings and helped to explain the adverse impact of increased iron concentrations on REE precipitation efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2007

Microbial Extremophiles in Aspect of Limits of Life

During Earth's evolution accompanied by geophysical and climatic changes a number of ecosystems have been formed. These ecosystems differ by the broad variety of physicochemical and biological factors composing our environment. Traditionally, pH and salinity are considered as geochemical extremes, as opposed to the temperature, pressure and radiation that are referred to as physical extremes (Van den Burg, 2003). Life inhabits all possible places on Earth interacting with the environment and within itself (cross species relations). In nature it is very rare when an ecotope is inhabited by a single species. As a rule, most ecosystems contain the functionally related and evolutionarily adjusted communities (consortia and populations). In contrast to the multicellular structure of eukaryotes (tissues, organs, systems of organs, whole organism), the highest organized form of prokaryotic life in nature is the benthic colonization in biofilms and microbial mats. In these complex structures all microbial cells of different species are distributed in space and time according to their functions and to physicochemical gradients that allow more effective system support, self-protection, and energy distribution. In vitro, of course, the most primitive organized structure for bacterial and archaeal cultures is the colony, the size, shape, color, consistency, and other characteristics of which could carry varies specifics on species or subspecies levels. In table 1 all known types of microbial communities are shown (Pikuta et a]., 2005). In deep underground (lithospheric) and deep-sea ecosystems an additional factor - pressure, and irradiation - could also be included in the list of microbial communities. Currently the beststudied ecosystems are: human body (due to the medical importance), and fresh water and marine ecosystems (due to the reason of an environmental safety). For a long time, extremophiles were terra incognita, since the environments with aggressive parameters (compared to the human body temperature, pH, mineralization, and pressure) were considered a priori as a dead zone.

Pikuta, Elena V.↗
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↗
DOE OSTI2021

Ecosystems and Networks Integrated with Genes and Molecular Assemblies (ENIGMA) (Final Scientific/Technical Report, Subcontract Award No. 6953691)

The overarching objective the Baliga lab is to develop a mechanistic understanding of the field relevant metabolic processes underlying community partitioning of respiration pathways and physiological state shifts. In order to dissect how environmental perturbations influence microbial regulatory networks, we have constructed data-driven models that capture the dynamic interplay between abiotic and biotic factors during laboratory simulations. Specifically, we have developed multiple computational models (i.e., cMonkey2, EGRIN 2.0, and multiple genome-scale metabolic models) connecting environmental influence to genome-encoded regulatory programs. In addition, we have generated new tools such as Live Anaerobic Cell Sorting (LAnCS) and Fluidized Bed Reactors (FBRs) to investigate the dynamics of community partitioning of metabolic processes supporting sulfate or nitrate respiration, which are two critical activities observed from the field site at Oak Ridge National Labs (ORNL). This framework of connecting field phenomena with laboratory simulations and computational modeling has created the Environmental Simulations and Modelling (EnvSim) campaign within ENIGMA. The campaign, which spans multiple laboratories across ENIGMA and is led by the Baliga group, has established synthetic communities (SynComs) to discover, characterize, and dissect key microbial processes relevant to field observations, such as emissions of the greenhouse gas nitrous oxide (N 2 O). For example, the EnvSim campaign so far has deduced four potential mechanisms that may account for the N 2 O emissions at the FRC and are currently being investigated by labs across ENIGMA. Denitrification may be driven by complete denitrifiers, however, their NosZ enzymes, which catalyze the final step in denitrification by converting N 2 O to N 2 , may be sensitive at a lower pH. Additionally, the denitrification process could be partitioned among organisms and some may have pH-sensitive NosZ genes. Another factor contributing to variable N 2 O emissions relates to the metal co-factors involved in the denitrification pathway. For instance, excess Cu, Al, Mn, U, Ni, Co, Cu, and/or Cd may have inhibitory effects on multiple enzymatic steps during denitrification, while the enzymatic production of nitrite, the precursor of N 2 O, can be limited by the essential metal Mo. Lastly, abiotic production of N 2 O may occur as a result of chemodenitrification, in which metals like Fe, Mn, and some organic compounds can drive redox reactions that convert nitrogen cycle intermediates to N 2 O under the right conditions. Current investigations and analyses have generated multiple transcriptomic profiles aiding the refinement of new metabolic and gene regulatory network model for our denitrifying SynCom. In sum, the previous funding cycle has generated 33 peer-reviewed publications spanning predictive network biology to co-operativity of mutualistic interspecies interactions of evolved communities. Our integration of multiple omics datasets and the development of new network modelling tools has revealed important insights that can explain field observed phenomenon and generated new hypotheses to be investigated in the field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Effects of pH on the nano/micro structure of calcium silicate hydrate (C-S-H) under sulfate attack

Calcium silicate hydrate (C-S-H), the most important Portland cement hydration product, determines the mechanical properties and durability of cementitious materials. In marine environment, C-S-H often suffers from sulfate attack – one of the most common and severe degradations for concrete. pH is considered as a critical factor in determining the deterioration behavior of C-S-H during sulfate attack, of which the significance may be overlooked. This study focused on the role of pH on the deterioration of C-S-H in terms of the composition and nano/micro structure under sulfate attack. The results show that lowering pH aggravates the decalcification of C-S-H, whereas a strong alkaline condition is beneficial to increase the resistance to deterioration. An increase in the mean chain length together with the proportion of large pores (>10 nm) is observed when C-S-H is subjected to low-pH sulfate attack (pH = 10–12), resulting in a relatively loose structure. The deep analysis on defective tobermorite model reveals that calcium at the interlayer of C-S-H nanostructure is readily removed under sulfate attack, thereby improving the potential of Si-O-Si groups formation and increases the mean chain length of C-S-H.

36 MATERIALS SCIENCE↗