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DOE OSTI2022

A combined experimental and modelling study of granite hydrothermal alteration

Geochemical reactions can induce significant changes of rock reservoir porosity and permeability via mineral dissolution and precipitation processes, affecting the long-term fluid behaviour within various geological systems. Here, the understanding and quantification of these reactions rely on field and experimental studies and on the predictions of reactive transport models. The present study was aimed at assessing the extent to which current geochemical models integrating available mineral dissolution/precipitation rate equations can reproduce the experimental data obtained from 4 to 17-day long hydrothermal alteration experiments of a muscovite-biotite granite and, thus, help provide an accurate description of the evolution of geothermal systems within granitic reservoirs. The experiments were conducted at a constant temperature of 180 °C and over an aqueous fluid pH range of 2 to 8.5, using both mixed-flow and static batch reactors. Modelled major element (K, Al, Si, Ca, and Mg) concentrations were generally in satisfactory agreement with the corresponding measured elemental fluxes – the differences between modelled and experimental values were generally within a factor of 5 – and the predicted identity and mass of formed secondary phases were consistent with the microscopic observations of the reacted solids. However, larger differences between measured and modelled element concentrations were observed when significant amounts of secondary phases formed, notably at pH 2 to 3, and for longer-term batch experiments. Much of this concentration difference stems from the underestimation of the amounts of Al-phases formed at acid to near-neutral pH. Although an idealized rock composition was considered, the observed mismatch between model calculations and experimental data can be attributed to inadequate mineral precipitation reaction rates and a poor description of reactive surface areas in existing geochemical modelling codes. More accurate quantification of precipitation kinetics, including nucleation and growth, and improved descriptions of the temporal change of mineral surface area would enhance the predictive capabilities of reactive transport models and benefit, particularly, the efforts aimed at increasing the sustainability of EGS reservoirs.

58 GEOSCIENCES↗

DOE OSTI2018

Long-term nitrogen fertilization decreases bacterial diversity and favors the growth of Actinobacteria and Proteobacteria in agro-ecosystems across the globe

Long-term Elevated nitrogen (N) input from anthropogenic sources may cause soil acidification and decrease crop yield, yet the response of the belowground microbial community to long-term N input and the input of N combined with phosphorus (P) and potassium (K) is still poorly understood. Here, we explored the effect of long-term N and NPK fertilization on soil bacterial diversity and community composition using meta-analysis of a global dataset. Nitrogen fertilization decreased soil pH, and increased soil organic carbon (C) and available N contents. Bacterial taxonomic diversity was decreased by N fertilization alone, but was increased by NPK fertilization. The effect of N fertilization on bacterial diversity depends on soil texture and water management, but independent of crop type or N application rate. Both soil pH and organic C content were positively related to changes in bacterial diversity under N fertilization, while soil organic C was the dominant factor determining changes in bacterial diversity under NPK fertilization. Microbial biomass C decreased with decreasing bacterial diversity under long-term N fertilization. Nitrogen fertilization increased the relative abundance of copiotrophic bacteria (i.e. Proteobacteria and Actinobacteria), but reduced the abundance of oligotrophic taxa (i.e. Acidobacteria), consistent with the general life history strategy theory for bacteria. The relative abundance of Proteobacteria was also increased by NPK fertilization. The positive correlation between N application rate and the relative abundance of Actinobacteria indicates that increased N availability favored the growth of Actinobacteria. This first global analysis of long-term N and NPK fertilization effect on bacterial diversity and community composition suggests that N input decreases bacterial diversity but favors the growth of copiotrophic bacteria, providing a reference for nutrient management strategies for maintaining belowground microbial diversity in agro-ecosystems worldwide.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Effect of Temperature and pH on Microbial Communities Fermenting a Dairy Coproduct Mixture

Organic-rich industrial residues can serve as renewable feedstocks for the generation of useful products by microbial fermentation. We investigated fermenting communities enriched in a mixture of ultra-filtered milk permeate (UFMP) and acid whey from cottage cheese (CAW), two dairy coproducts rich in lactose. To evaluate how operational pH and temperature affect microbial communities and fermentation products, we operated 12 bioreactors for 140 days, each fed a 1:1 mixture of UFMP and CAW at either 35 °C or 50 °C and at either a pH of 4.8 or 5.5. The bioreactors operated at a pH of 4.8 resulted in the incomplete conversion of lactose, while those operated at a pH of 5.5 consistently fermented lactose, primarily into lactic, acetic, and hexanoic acids. The metagenomic analyses revealed that microbial communities obtained at a pH of 5.5 were dominated by lactic acid-producing organisms. Additionally, an inverse relationship was found between the abundance of chain elongating organisms and lactic acid accumulation, with 50 °C reducing the abundance of these organisms and enhancing lactic acid yields. We conclude that the pH and temperature are important determinants of the fermentation of dairy coproducts with a pH of 5.5 and 50 °C yielding the most promising results for lactic acid production. Additional research is required to better understand the factors affecting functional consistency of the process.

Biotechnology & Applied Microbiology↗

DOE OSTI2021

Machine-learning-accelerated multimodal characterization and multiobjective design optimization of natural porous materials

Natural porous materials such as nanoporous clays are used as green and low-cost adsorbents and catalysts. The key factors determining their performance in these applications are the pore morphology and surface activity, which are typically represented by properties such as specific surface area, pore volume, micropore content and pH. The latter may be modified and tuned to specific applications through material processing and/or chemical treatment. Characterization of the material, raw or processed, is typically performed experimentally, which can become costly especially in the context of tuning of the properties towards specific application requirements and needing numerous experiments. In this work, we present an application of tree-based machine learning methods trained on experimental datasets to accelerate the characterization of natural porous materials. The resulting models allow reliable prediction of the outcomes of experimental characterization of processed materials (R2 from 0.78 to 0.99) as well as identification of key factors contributing to those properties through feature importance analysis. Furthermore, the high throughput of the models enables exploration of processing parameter–property correlations and multiobjective optimization of prototype materials towards specific applications. We have applied these methodologies to pinpoint and rationalize optimal processing conditions for clays exploitable in acid catalysis. One of such identified materials was synthesized and tested revealing appreciable acid character improvement with respect to the pristine material. Specifically, it achieved 79% removal of chlorophyll-a in acid catalyzed degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Dynamic Control of Photocatalytic Proton Reduction through the Mechanical Actuation of a Hydrogel Host Matrix

This paper describes a photocatalytic hydrogen evolution system that is dynamically and reversibly responsive to the pH of the surrounding solution through actuation of a micro-hydrogel (microgel) matrix that hosts the photocatalysts (CdSe/CdS nanorods). Here, the reversible actuation occurs within 0.7 s (swelling) and 1.7 s (contraction). A ΔpH of 0.01 relative to the pK a of the tertiary amine on the microgel polymer (7.27) results in a reversible change in the average diameter of the microgel hosts by a factor of 2.5 and a change in the photocatalytic turnover frequency (TOF) by a factor of five. Kinetic isotope effect and photoluminescence quenching experiments reveal that the scavenging of the photoexcited hole by sulfite ions is the rate-limiting step and leads to the observed response of the TOF to pH through actuation of the microgel. Molecular dynamics simulations quantify a greater local concentration of sulfite hole scavengers for pH < pK a .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2012

In-Situ Chemical Precipitation of Radioactive Liquid Waste - 12492

This paper presented in-situ chemical precipitation for radioactive liquid waste by using chemical agents. Results are reported on large-scale implementation on the removal of {sup 137}Cs, {sup 134}Cs and {sup 60}Co from liquid radioactive waste generating from Nuclear Research and Training Centre. Total amount of liquid radioactive waste was 35 m{sup 3} and main radionuclides were Cs-137, Cs- 134 and Co-60. Initial radioactivity concentration of the liquid waste was 2264, 17 and 9 Bq/liter for Cs-137, Cs-134 and Co-60 respectively. Potassium ferro cyanide was selected as chemical agent at high pH levels 8-10 according to laboratory tests. After the process, radioactive sludge precipitated at the bottom of the tank and decontaminated clean liquid was evaluated depending on discharge limits. By this precipitation method decontamination factors were determined as 60, 9 and 17 for Cs-137, Cs-134 and Co-60 respectively. At the bottom of the tank radioactive sludge amount was 0.98 m{sup 3}. It was transferred by sludge pumps to cementation unit for solidification. By in situ chemical processing 97% of volume reduction was achieved. Using the optimal concentration of 0.75 M potassium ferro cyanide about 98% of the {sup 137}Cs can be removed at pH 8. The Potassium ferro cyanide precipitation method could be used successfully in large scale applications with nickel and ferrum agents for removal of Cs-137, Cs-134 and Co- 60. Although DF values of laboratory test were much higher than in-situ implementation, liquid radioactive waste was decontaminated successfully by using potassium ferro cyanide. Majority of liquid waste were discharged as clean liquid. %97.2 volumetric amount of liquid waste was cleaned and discharged at the original site. Reduced amount of sludge transportation in drums is more economical and safer method than liquid transportation. Although DF values could be different for each of applications related to main specifications of original liquid waste, this study shows that in-situ treatment of liquid waste by using potassium ferro cyanide is not only a cost effective method but also reduce radiological risks as well. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2016

Destabilization of mitochondrial functions as a target against breast cancer progression: Role of TPP{sup +}-linked-polyhydroxybenzoates

Mitochondrion is an accepted molecular target in cancer treatment since it exhibits a higher transmembrane potential in cancer cells, making it susceptible to be targeted by lipophilic-delocalized cations of triphenylphosphonium (TPP{sup +}). Thus, we evaluated five TPP{sup +}-linked decyl polyhydroxybenzoates as potential cytotoxic agents in several human breast cancer cell lines that differ in estrogen receptor and HER2/neu expression, and in metabolic profile. Results showed that all cell lines tested were sensitive to the cytotoxic action of these compounds. The mechanism underlying the cytotoxicity would be triggered by their weak uncoupling effect on the oxidative phosphorylation system, while having a wider and safer therapeutic range than other uncouplers and a significant lowering in transmembrane potential. Noteworthy, while the TPP{sup +}-derivatives alone led to almost negligible losses of ATP, when these were added in the presence of an AMP-activated protein kinase inhibitor, the levels of ATP fell greatly. Overall, data presented suggest that decyl polyhydroxybenzoates-TPP{sup +} and its derivatives warrant future investigation as potential anti-tumor agents. - Highlights: • TPP{sup +}-polyhydroxybenzoates are cytotoxic to various subtypes of breast cancer cells. • Cytotoxicity is not-dependent on the expression of estrogen/growth factor receptors. • Cytotoxicity appears to be triggered by a weak mitochondrial uncoupling effect. • Effects include loss of transmembrane potential and apoptosis was detected. • TPP{sup +}-polyhydroxybenzoates inhibit migration of highly metastatic cells.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2022

Intermediate polaronic charge transport in organic crystals from a many-body first-principles approach

Abstract Charge transport in organic molecular crystals (OMCs) is conventionally categorized into two limiting regimes − band transport, characterized by weak electron-phonon (e-ph) interactions, and charge hopping due to localized polarons formed by strong e-ph interactions. However, between these two limiting cases there is a less well understood intermediate regime where polarons are present but transport does not occur via hopping. Here we show a many-body first-principles approach that can accurately predict the carrier mobility in this intermediate regime and shed light on its microscopic origin. Our approach combines a finite-temperature cumulant method to describe strong e-ph interactions with Green-Kubo transport calculations. We apply this parameter-free framework to naphthalene crystal, demonstrating electron mobility predictions within a factor of 1.5−2 of experiment between 100 and 300 K. Our analysis reveals the formation of a broad polaron satellite peak in the electron spectral function and the failure of the Boltzmann equation in the intermediate regime.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Regional and global elevational patterns of microbial species richness and evenness

Although elevational gradients in microbial biodiversity have attracted increasing attention recently, the generality in the patterns and underlying mechanisms are still poorly resolved. Further, previous studies focused mostly on species richness, while left understudied evenness, another important aspect of biodiversity. Here, we studied the elevational patterns in species richness and evenness of stream biofilm bacteria and diatoms in six mountains in Asia and Europe. We also reviewed published results for elevational richness patterns for soil and stream microbes in a literature analysis. Our results revealed that even within the same ecosystem type (that is, stream) or geographical region, bacteria and diatoms showed contrasting patterns in diversity. Stream microbes, including present stream data, tend to show significantly increasing or decreasing elevational patterns in richness, contrasting the findings for soil microbes that typically showed nonsignificant or significantly decreasing patterns. In all six mountains for bacteria and in four mountains for diatoms, species richness and evenness were positively correlated. The variation in bacteria and diatom richness and evenness were substantially explained by anthropogenic driven factors, such as total phosphorus (TP). However, diatom richness and evenness were also related to different main drivers as richness was mostly related to pH, while evenness was most explained by TP. Our results highlight the lack of consistent elevational biodiversity patterns of microbes and further indicate that the two facets of biodiversity may respond differently to environmental gradients.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2017

The timescales of mineral redox reactions

Redox-reactive minerals can serve as electron donors or acceptors for abiotic reactants or microbial metabolic processes, and hence can play important roles in terrestrial and aquatic environments, particularly if their reaction rates are comparable to those of other biogeochemical processes. Under such circumstances, their reactions can control metal and contaminant bioavailability and change the permeability of soils and sediments. While the thermodynamic driving force for a mineral redox reaction is frequently a good predictor of relative rates of reaction, there are many examples in which kinetic factors limit reaction rate. Understanding the thermodynamic and kinetic aspects of mineral reaction rates, and their sensitivity to environmental conditions such as temperature or pH, is important for anticipating the biogeochemical evolution of natural environments subjected to change. Achieving this goal requires knowledge of the reaction pathway, the timescales of intermediate steps, and the lifetimes of metastable reaction states. Mineral redox reactions proceed through a combination of steps that can include electron and proton transfer, the breaking or formation of bonds, and mineral dissolution or phase transformation. The combination of conventional kinetics approaches, newly-developed ultrafast time-resolved methods and molecular simulation can provide elucidation of such complex reaction pathways. This chapter summarizes key concepts in mineral and interfacial redox reactions with illustrations from the rich geochemistry of iron and ironbearing minerals.

58 GEOSCIENCES↗

DOE OSTI2021

Future changes in isoprene-epoxydiol-derived secondary organic aerosol (IEPOX SOA) under the Shared Socioeconomic Pathways: the importance of physicochemical dependency

Abstract. Secondary organic aerosol (SOA) is a dominant contributor of fine particulate matter in the atmosphere, but the complexity of SOA formation chemistry hinders the accurate representation of SOA in models. Volatility-based SOA parameterizations have been adopted in many recent chemistry modeling studies and have shown a reasonable performance compared to observations. However, assumptions made in these empirical parameterizations can lead to substantial errors when applied to future climatic conditions as they do not include the mechanistic understanding of processes but are rather fitted to laboratory studies of SOA formation. This is particularly the case for SOA derived from isoprene epoxydiols (IEPOX SOA), for which we have a higher level of understanding of the fundamental processes than is currently parameterized in most models. We predict future SOA concentrations using an explicit mechanism and compare the predictions with the empirical parameterization based on the volatility basis set (VBS) approach. We then use the Community Earth System Model 2 (CESM2.1.0) with detailed isoprene chemistry and reactive uptake processes for the middle and end of the 21st century under four Shared Socioeconomic Pathways (SSPs): SSP1–2.6, SSP2–4.5, SSP3–7.0, and SSP5–8.5. With the explicit chemical mechanism, we find that IEPOX SOA is predicted to increase on average under all future SSP scenarios but with some variability in the results depending on regions and the scenario chosen. Isoprene emissions are the main driver of IEPOX SOA changes in the future climate, but the IEPOX SOA yield from isoprene emissions also changes by up to 50 % depending on the SSP scenario, in particular due to different sulfur emissions. We conduct sensitivity simulations with and without CO2 inhibition of isoprene emissions that is highly uncertain, which results in factor of 2 differences in the predicted IEPOX SOA global burden, especially for the high-CO2 scenarios (SSP3–7.0 and SSP5–8.5). Aerosol pH also plays a critical role in the IEPOX SOA formation rate, requiring accurate calculation of aerosol pH in chemistry models. On the other hand, isoprene SOA calculated with the VBS scheme predicts a nearly constant SOA yield from isoprene emissions across all SSP scenarios; as a result, it mostly follows isoprene emissions regardless of region and scenario. This is because the VBS scheme does not consider heterogeneous chemistry; in other words, there is no dependency on aerosol properties. The discrepancy between the explicit mechanism and VBS parameterization in this study is likely to occur for other SOA components as well, which may also have dependencies that cannot be captured by VBS parameterizations. This study highlights the need for more explicit chemistry or for parameterizations that capture the dependence on key physicochemical drivers when predicting SOA concentrations for climate studies.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1966

Compression springs at elevated temperatures

The behavior of compression springs is affected by increased temperatures. The most significant factors affecting springs are a loss of load and length (relaxation), and a change in the modulus of rigidity. Relaxation will reduce preset loads or change the location of supported components whereas a change in the modulus of rigidity will alter the spring rate. Both factors must be taken into account when designing compression springs. Curves and equations are presented (for music wire, 18-8 stainless steel, 17-7 PH, and Inconel-X) which can aid in the design of compression springs for use at elevated temperatures.

Spring↗

NASA NTRS1994

Ammonia on the prebiotic Earth: Iron(II) reduction of nitrite

Theories for the origin of life require the availability of reduced nitrogen. In the non-reducing atmosphere suggested by geochemical evidence, production in the atmosphere and survival of NH3 against photochemical destruction are problematic. Electric discharges and impact shocks would produce NO rather than HCN or NH3. Conversion of NO to nitrous and nitric acid (by way of HNO) and precipitation in acid rain would provide a source of fixed nitrogen to the early ocean. One solution to the NH3 problem may have been the reduction of nitrite/nitrate in the ocean with aqueous ferrous iron, Fe(2+): 6Fe(+2) + 7 H2O + NO2(-) yields 3Fe2O3 + 11 H(+) + NH3. We have measured the kinetics of this reaction as a function of temperature, pH, and concentrations of salts, Fe(+2), and NO2(-). Cations (Na(+), Mg(2+), K(+)) and anions (Cl(-), Br(-), SO4(2-)) increase the rate by factors of 4 to 8. Although a competing pathway yields N2, the efficiency of the conversion of nitrite to ammonia ranges from 25% to 85%. Nitrate reduction was not consistently reproducible; however, when it was observed, its rate was slower by at least 8X than that of nitrite reduction. If the prebiotic atmosphere contained 0.2 to 10 atmospheres CO2 as suggested by Walker (1985), the Fe(+2) concentration and the rate would have been limited by siderite (FeCO3) solubility.

Summers, David P.↗

NASA NTRS1992

Oxygen transport and cardiovascular function at extreme altitude: lessons from Operation Everest II

Operation Everest II was designed to examine the physiological responses to gradual decompression simulating an ascent of Mt Everest (8,848 m) to an inspired PO2 of 43 mmHg. The principal studies conducted were cardiovascular, respiratory, muscular-skeletal and metabolic responses to exercise. Eight healthy males aged 21-31 years began the "ascent" and six successfully reached the "summit", where their resting arterial blood gases were PO2 = 30 mmHg and PCO2 = 11 mmHg, pH = 7.56. Their maximal oxygen uptake decreased from 3.98 +/- 0.2 L/min at sea level to 1.17 +/- 0.08 L/min at PIO2 43 mmHg. The principal factors responsible for oxygen transport from the atmosphere to tissues were (1) Alveolar ventilation--a four fold increase. (2) Diffusion from the alveolus to end capillary blood--unchanged. (3) Cardiac function (assessed by hemodynamics, echocardiography and electrocardiography)--normal--although maximum cardiac output and heart rate were reduced. (4) Oxygen extraction--maximal with PvO2 14.8 +/- 1 mmHg. With increasing altitude maximal blood and muscle lactate progressively declined although at any submaximal intensity blood and muscle lactate was higher at higher altitudes.

Non-NASA Center↗

DOE OSTI2021

Evaluation of overtime phenotypic variation of yeasts in chronic vulvovaginal candidosis cases

Abstract Chronic vulvovaginal candidosis results either from reinfection or from the ability of Candida spp. to persist in the vulva and/or vagina. Persistence is usually associated with increased antifungal (mainly azoles) resistance rates, which can explain treatment failure, and/or increased expression of virulence factors by Candida spp. The aim of this study was to assess the mechanisms leading to Candida spp persistence, by studying sequential isolates from women with chronic vulvovaginal candidosis, focusing on strains genotypes, azole resistance, and ability to form biofilms along the period of clinical evaluation. The strains were identified at species level by automated analysis of biochemical profiles and molecular typing evaluated by polymorphic DNA analysis. The capacity to form biofilm was assessed with a microtiter plate assay. Fluconazole susceptibility was determined by the microdilution broth assay at both pH 7 (following the recommended guideline) and pH 4.5 (as representative of vaginal pH). We studied samples from 17 clinically recurrent cases. In 53% of the chronic cases there were two or more isolates that had a phylogenetic relationship while the remaining (47%) were caused by different species. In those cases where related strains were involved in recurrence, we verified an increase in MIC at pH 7 and also an increased capacity to form biofilms over time. Significant correlation between these two parameters was observed only in cases caused by C. glabrata, evidencing the importance of these two factors to enhance persistence in the vaginal mucosa for this particular species.

Faria-Gonçalves, Paula↗

DOE OSTI2018

Erratum to: “The Fluorescence and Electronic Structure of Phenyl-Substituted Tetraazachlorin Molecules” [Optics and Spectroscopy 117, 722 (2014)]

should read “porphyrazine” instead of “porphyrazin”;should read “intersystem crossing” instead of “intercombinational conversion”;should read “mirror-symmetrical” instead of “reflection-symmetric”;should read “fluorescence enhancement” instead of “fluorescence buildup.”Page 722, Abstract, lines 9–10 from the top, the sentence should read:This characteristic increases upon tetrapyrrole phenylation.Page 727, left column, lines 17–18 from the top, the sentence should read:The vibronic transition parts of the emission spectrum are diffuse, (…)Page 727, left column, lines 29–30 from the top, the sentence should read:Note that the Stokes shift in these cases is relatively large.Page 729, left column, lines 8–10 from the bottom, the sentence should read:For H{sub 2}Ph{sub 8}TAC{sup mp} and H{sub 2}Ph{sub 6}TAC{sup tm}, the enhancement of fluorescence is weaker than in the former case: on cooling, τ{sub F} is increased by a factor of 4–5 in MTHF and by a factor of only 2.6–3 in toluene.Page 729, right column, lines 9–10 from the footnote, the sentence should read:It is seen from Table 1 that our results agree reasonably well with previously reported data.Page 730, left column, lines 16–19 from the top, the sentence should read:The lifetime for the outgassed H{sub 2}TAP solution intoluene (τ{sub T}{sup 0}) was measured by A.S. Stasheuski as phosphorescence decay at λ{sub reg} = 1070 nm using the setup described in [29].Page 730, left column, lines 20–23 from the top, the sentence should read:The τ{sub T} value derived from the kinetics of the rise of singlet oxygen luminescence [26] for the nonoutgassed solution at λ{sub reg} = 1272 nm is 162 ns;Page 730, right column, lines 25–27 from the top, the sentence should read:Therefore, for H{sub 2}TAP (λ{sub F}{sup 00}≈ 620 nm), the internal conversion probability should not be high.Page 731, left column, the heading of Table 2 should read:Bond lengths in the porphine macrocycle (Å).Page 731, left column, lines 3–6 from the top, the sentence should read:For elucidating the mechanism of the deactivation of the S{sub 1} state, it was of essential interest to see whether the enhancement of H{sub 2}TAP fluorescence would be observed at 77 K.Page 733, left column, lines 2–3 from the top, the sentence should read:The corresponding difference for the H{sub 2}P–H{sub 2}C pair is 0.013 Å.Page 733, left column, lines 14–16 from the top, the sentence should read:The macrocycle undergoes additional contraction, and the symmetry of its conjugated system is very close to D{sub 2h}.Page 733, right column, line 21 from the top should read:Replacement of the methine bridges (…)Page 734, left column, lines 8–11 from the figure caption, the sentence should read:This is the main reason of the large bathochromic shift of the Soret band of H{sub 2}Ph{sub 8}TAP and MgPh{sub 8}TAP [16] relative to H{sub 2}TAP and MgTAP, respectively.Page 734, left column, lines 1–4 from the bottom, the sentence should read:The complete INDO/Sm calculation yields the corresponding quantitative characteristics, which are in good agreement with experimental data (see below).Page 740, left column, reference no. 25 should read:25. V. A. Galievsky, A. S. Stasheuski, V. V. Kiselyov, A. I. Shabusov, M. V. Belkov, and B. M. Dzhagarov, Instrum. Exp. Tech. 53, 568 (2010).25. V. A. Galievsky, A. S. Stasheuski, V. V. Kiselyov, A. I. Shabusov, M. V. Belkov, and B. M. Dzhagarov, Instrum. Exp. Tech. 53, 568 (2010).30. V. L. Ermolaev and E. B. Sveshnikova, Acta Phys. Pol. 34, 771 (1968).

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2016

Anisomycin-induced GATA-6 degradation accompanying a decrease of proliferation of colorectal cancer cell

Transcription factor GATA-6 plays a key role in normal cell differentiation of the mesoderm and endoderm. On the other hand, GATA-6 is abnormally overexpressed in many clinical gastrointestinal cancer tissue samples, and accelerates cell proliferation or an anti-apoptotic response in cancerous tissues. We previously showed that activation of the JNK signaling cascade causes proteolysis of GATA-6. In this study, we demonstrated that anisomycin, a JNK activator, stimulates nuclear export of GATA-6 in a colorectal cancer cell line, DLD-1. Concomitantly, anisomycin remarkably inhibits the proliferation of DLD-1 cells via G2/M arrest in a plate culture. However, it did not induce apoptosis under growth arrest conditions. Furthermore, the growth of DLD-1 cells in a spheroid culture was suppressed by anisomycin. Although 5-FU showed only a slight inhibitory effect on 3D spheroid cultures, the same concentration of 5-FU together with a low concentration of anisomycin exhibited strong growth inhibition. These results suggest that the induction of GATA-6 dysfunction may be more effective for chemotherapy for colorectal cancer, although the mechanism underlying the synergistic effect of 5-FU and anisomycin remains unknown. - Highlights: • Anisomycin induces proteolysis of GATA-6 in DLD-1 cells. • Anisomycin remarkably inhibits the proliferation of DLD-1 cells via G2/M arrest. • Anisomycin suppresses the growth of spheroids of DLD-1, and enhances the effect of 5-FU.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2021

Microbe-Encapsulated Silica Gel Biosorbents for Selective Extraction of Scandium from Coal Byproducts

Establishing an inexpensive and environmentally friendly scandium (Sc) supply is critical for the development of clean energy technologies. However, refining Sc from Sc-bearing sources using current technologies poses economic and environmental challenges due to its low concentration relative to base metals and chemically similar lanthanides. In this work, we developed a biosorption-based flow-through process for extraction of Sc from low-grade feedstocks. A novel biosorbent material was synthesized by encapsulating Arthrobacter nicotianae, a bacterium that selectively adsorbs Sc, within a porous silica matrix. Through the use of several complementary microscopy techniques, we demonstrated a highly porous biosorbent structure with a high cell-loading density and a homogenous cell distribution. Batch adsorption assays revealed selective Sc adsorption over lanthanides and common based metals, with the exception of Fe(III), as evidenced by separation factors greater than 50. The MESG particles were packed into fixed-bed columns to enable adsorption under flow-through conditions, which demonstrated effective Sc extraction at flow rates up to 0.08 cm/s and high stability for reuse; greater than 95% of the adsorption capacity was maintained after 10 consecutive adsorption/desorption cycles. When applied to a lignite coal leachate, whose Fe content was depleted through pH-mediated precipitation, the MESG particles yielded Sc breakthrough at 30 bed volumes, whereas all other metals broke through after only a few bed volumes. Following desorption, an eluate with a 124-fold increase in Sc purity was achieved relative to the lignite leachate with Sc constituting 96.4% of the total REEs. This study established a rapid, facile, and scalable cell immobilization approach that enables the use of microbial biomass for Sc recovery from low-grade sources.

Dong, Ziye↗