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At least 163 records · Page 9

Meteoric 10Be Flux Calibration Data for the East River Watershed, Colorado, USA

This data package contains tabular and geospatial data used to quantify and model meteoric beryllium-10 fluxes in the East River watershed, Colorado, USA. The tabular component includes calibration-site data from five glacial moraine sites and includes environmental variables used to evaluate spatial controls on meteoric 10Be delivery, including elevation, mean annual precipitation (MAP), mean snow depth, and mean snow water equivalent (SWE). These site-level data were used to compare observed fluxes with environmental gradients across the watershed and to evaluate the effects of erosion correction on flux estimates. The package also includes supporting slope and curvature values used to assess topographic inputs to the erosion analysis. A second component of the data package contains updated manuscript tables and regression outputs used to summarize the relationships between meteoric 10Be flux and environmental predictors. These tables include meteoric 10Be sample information and AMS results, site-level environmental values, site-level meteoric 10Be inventory and flux values, watershed-averaged predicted fluxes, soil bulk density measurements, fine-fraction values, soil pH measurements, and regression statistics including slope, intercept, coefficient of determination, and p-value. The regression products include both standard linear regressions and regressions in which the intercept is constrained to pass through zero, and they support the analyses presented in the companion manuscript. Together, these tabular files provide the numerical basis for the manuscript tables and the regression-based interpretation of meteoric 10Be flux variability in a snow-dominated mountain watershed. The geospatial component of the package consists of GeoTIFF raster files used to generate the map products presented in Figures 2 and 6 of the companion manuscript. These rasters represent watershed-scale spatial layers for environmental variables and regression-based predictions of meteoric 10Be flux. This dataset contains comma-separated values files (.csv), Microsoft Excel files (.xlsx), GeoTIFF raster files (.tif), and upporting metadata files, including CSV data dictionaries and readme text files (.csv, .txt). The tabular files can be opened with standard spreadsheet software, and the raster files can be viewed and analyzed in GIS software such as ArcGIS Pro or QGIS. Together, these files document the numerical and spatial datasets used to calibrate and predict meteoric 10Be delivery in the East River watershed.

East River↗

Phyllosilicate Formation on Early Mars Via Open-System Acid Alteration of Basaltic Glass

Smectites are widespread on Mars, but neutral/alkaline conditions favorable for smectite formation have surprisingly not led to abundant carbonates. Smectite formation on Mars could also occur in acidic environments unfavorable for carbonate formation. Acidic smectite formation has been demonstrated in batch (closed hydrologic) systems, however, the mechanisms and octahedral composition of smectite forming in acidic flow-through (open hydrologic) systems are not fully understood. Stapafell basaltic glass was hydrothermally altered (190◦C) at two flow rates corresponding to low and high water to rock ratio (W/R) and initial pH (pH_0) values of 2, 3, 4 and 6, and a batch low W/R experiment was conducted at pH_0 2. Kaolinite, montmorillonite and chlorite formed at pH_0 2 at low W/R; no phyllosilicates formed at pH_0 2 at high W/R; and lizardite formed at pH_0 ≥3 at both W/R ratios. Lizardite, kaolinite, and montmorillonite in these experiments formed by precipitation from solution and chlorite likely formed through alteration of montmorillonite and/or basalt. Saponite formed at pH_0 2 in batch conditions by alteration of basaltic glass. Comparison of experimental data with martian phyllosilicate assemblages indicated that smectite formation on Mars likely occurred under water-limited conditions. Al-rich smectite could form in open-system low W/R subsurface environments under a narrow range of pH (pH <3) while saponite could form in closed low W/R systems under acidic to alkaline conditions. Combined open and closed hydrological regimes could be responsible for development of clay mineral stratigraphies observed on Mars. The acidic conditions required for formation of Al-rich smectite were unfavorable for carbonate precipitation, but carbonate precipitation could occur together with Fe/Mg-smectite in closed systems at pH >4. The lack of carbonates occurring together with Fe/Mg-smectite could be cause by low pCO2 in subsurface closed environments and/or by overall lack of carbonate precipitation despite significant oversaturation.

S J Ralston↗

Innovative use of CaO in combination with amino acid salt to convert CO 2 as CaCO 3 nanoparticles under mild pH and low temperature

The increasing demand for sustainable CO 2 management has driven the development of innovative methods that can convert point source CO 2 into value-added products. In this study, CaO in combination with amino acid salt was used to convert CO 2 into CaCO 3 nanoparticles. Different from the conventional method where CO 2 diffusion presents a major challenge in reacting with CaO to form CaCO 3 , amino acid salt solvent was applied to absorb CO 2 first and then rapidly reacted with CaO to form CaCO 3 nanoparticles (∼50 nm) at a low temperature (e.g., 60 °C). Our experiments showed that at a glycine (Gly)/NaOH ratio of 2:1 or 3:1, the solution pH values during the CO 2 absorption and conversion were about 8–9 at 60 °C, while at a ratio of 1:1, the solution pH values were about 9–11; without Gly, the solution pH values were about 12. Gly-optimized solvent substantially reduced corrosion risk to reactors. In addition, the use of amino acid (i.e., Gly) led to much smaller CaCO 3 particles, distinctly different chemical phases, and fundamentally different chemical reactions. Moreover, in the presence of Gly, the solution pH was completely reversed and the solution was regenerated for cyclic use when CaO was added. The solvent was recyclable and reusable, highlighting the cost-effectiveness and sustainability of this approach. The Gly-modulated CaCO 3 nanoparticles may have significant potential for industrial applications in the biomedicine, construction, plastics, and rubber industries.

36 MATERIALS SCIENCE↗

Permeability of membranes to amino acids and modified amino acids: mechanisms involved in translocation

The amino acid permeability of membranes is of interest because they are one of the key solutes involved in cell function. Membrane permeability coefficients (P) for amino acid classes, including neutral, polar, hydrophobic, and charged species, have been measured and compared using a variety of techniques. Decreasing lipid chain length increased permeability slightly (5-fold), while variations in pH had only minor effects on the permeability coefficients of the amino acids tested in liposomes. Increasing the membrane surface charge increased the permeability of amino acids of the opposite charge, while increasing the cholesterol content decreased membrane permeability. The permeability coefficients for most amino acids tested were surprisingly similar to those previously measured for monovalent cations such as sodium and potassium (approximately 10(-12)-10(-13) cm s-1). This observation suggests that the permeation rates for the neutral, polar and charged amino acids are controlled by bilayer fluctuations and transient defects, rather than partition coefficients and Born energy barriers. Hydrophobic amino acids were 10(2) more permeable than the hydrophilic forms, reflecting their increased partition coefficient values. External pH had dramatic effects on the permeation rates for the modified amino acid lysine methyl ester in response to transmembrane pH gradients. It was established that lysine methyl ester and other modified short peptides permeate rapidly (P = 10(-2) cm s-1) as neutral (deprotonated) molecules. It was also shown that charge distributions dramatically alter permeation rates for modified di-peptides. These results may relate to the movement of peptides through membranes during protein translocation and to the origin of cellular membrane transport on the early Earth.

Review↗

Covalent Triazine-Based Frameworks with Ru-tda Based Catalyst Anchored via Coordination Bond for Photoinduced Water Oxidation

Light-induced water splitting (hν-WS) for the production of hydrogen as a solar fuel is considered a promising sustainable strategy for the replacement of fossil fuels. An efficient system for hν-WS involves a photoactive material that, upon shining light, is capable of separating and transferring charges to catalysts for the hydrogen and oxygen evolution processes. Covalent triazine-based frameworks (CTFs) represent an interesting class of 2D organic light-absorbing materials that have recently emerged thanks to their tunable structural, optical and morphological properties. Typically, catalysts (Cat) are metallic nanoparticles generated in situ after photoelectroreduction of metal precursors or directly drop-casted on top of the CTF material to generate Cat-CTF assemblies. Here, in this work, the synthesis, characterization and photocatalytic performance of a novel hybrid material, Ru-CTF, is reported, based on a CTF structure featuring dangling pyridyl groups that allow the Ru-tda (tda is [2,2':6',2'“-terpyridine]-6,6'”-dicarboxylic acid) water oxidation catalyst (WOC) unit to coordinate via covalent bond. The Ru-CTF molecular hybrid material can carry out the light-induced water oxidation reaction efficiently at neutral pH, reaching values of maximum TOF of 17 h -1 and TONs in the range of 220 using sodium persulfate as a sacrificial electron acceptor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Development of a stoichiometric magnesium potassium phosphate cement (MKPC) for the immobilization of powdered minerals

Ordinary Portland Cement (OPC)-based materials are not systematically adapted for immobilizing industrial hazardous waste, e.g. for aluminium powder or plutonium waste sludge. In such case, Magnesium Potassium Phosphate Cements (MKPC) represent an interesting alternative. }The originality of this research is to develop a formulation of a MKPC paste for hazardous waste immobilization, which incorporates a maximum amount of such waste, preferably in powdered form. To this purpose, a stoichiometric MKPC paste is selected, and its properties are improved by powdered waste addition. }Firstly, the physico-chemical mechanisms generating expansion in stoichiometric MKPC paste are analyzed. Swelling is attributed to a pH gradient in the paste, due to the progressive sedimentation of MgO particles in the fresh mix. }Secondly, over-stoichiometric MgO is replaced by varying amounts of minerals simulating the waste, of different mineralogy and granulometry, in order to achieve sufficient workability and no swelling. An optimal formulation is proposed, which incorporates powdered fly ash at a fine-to-cement mass ratio (F/C) of 1. Its mechanical performance and endogenous dimensional changes are comparable to typical over-stoichiometric pastes, and they stabilize between 7 and 28 days.

36 MATERIALS SCIENCE↗

Chemical mechanisms and kinetic modeling of calcium aluminate cements hydration in diluted systems: Role of aluminium hydroxide formation

Calcium aluminate cements are niche cements used in the refractory industry and in non-structural applications for building chemistry with short return-to-service delay. The later applications use theses cements in combination with calcium sulfates for long-term stability. By being niche cements, the knowledge of calcium aluminate cements hydration is not as extensive as that of Portland cement. In the present paper, the calcium aluminate cements are studied in diluted suspensions as a function of different parameters such as the suspension concentration or the quantity of added calcium sulfates. The objective is to identify their baseline chemical mechanisms. This work demonstrates the essential role of hydroxide ions fluxes, i.e. quantity going in and out of the liquid phase per unit of time. The main quantitative flux is the formation of aluminium hydroxide but the activation of this reaction is difficult. This difficulty allows calcium aluminate to be used as cement by creating a dormant period (workability) for the overall reactivity. The identification of the key role of aluminium hydroxide formation explains the influence of the temperature, some mechanisms of setting admixtures and the early age of calcium aluminate cements.

36 MATERIALS SCIENCE↗

Effective cation exchange capacity of calcium silicate hydrates (C-S-H)

The binding of alkalis and calcium to calcium silicate hydrate (C-S-H) can be measured by cation exchange using cobalt hexamine solution with adapted pH. The effective cation exchange capacity (CEC) decreased at higher Ca/Si in C-S-H. A maximum of charge{sub exch}/Si of 0.08–0.10 was measured at Ca/Si = 0.8 decreasing to 0.01–0.02 at Ca/Si = 1.6. At high Ca/Si, only a minor fraction of Ca was present at exchangeable sites, while most of the Ca{sup 2+} present in interlayer or surface was specifically bound and thus not exchangeable. In contrast, sodium was present only at exchangeable sites in the C-S-H, more at low than at high Ca/Si. An increase of pH in the presence of 100 mmol/L NaOH increased the effective CEC of C-S-H by 5–10% indicating a limited influence of pH on the deprotonation of the silanol groups.

36 MATERIALS SCIENCE↗

Sequestration and release of nitrite and nitrate in alkali-activated slag: A route toward smart corrosion control

Intercalating the corrosion inhibitive ions in hydrotalcite is a promising approach to improve the long-term efficiency of inhibitors in corrosion protection of steel in reinforced concrete. In this work, the potential of autogenously generating nitrite- and nitrate-intercalated hydrotalcite in alkali-activated slag (AAS) is investigated. The results show that the added nitrite and nitrate ions are preferably uptaken in the interlayer structure of hydrotalcite in AAS, and the sequestered nitrite and nitrate are released upon chloride exposure in seawater and NaCl solution. The incorporation of nitrite and nitrate has little detrimental effects on the chloride binding capacity of AAS but slightly enhances the chloride ingress due to the pore coarsening effect. Similar to ordinary Portland cement (OPC), AAS is more permeable to the chloride in seawater than NaCl solution. However, unlike the release of bound chloride contributed by ettringite formation in seawater-exposed OPC, the enhanced chloride ingress in seawater-exposed AAS is primarily attributed to the aggravated pH reduction at the exposure front due to brucite formation. This study contributes to the design of alkali-activated binders with a smart inhibitor releasing ability for mitigating corrosion of steel in concrete.

36 MATERIALS SCIENCE↗

Continuous optical in-situ pH monitoring during early hydration of cementitious materials

A luminescent sensor technique for pH analyses has been tested in cementitious media. The optical sensors monitor in-situ pH every 5 s during early hydration reactions over a period of 100 h from initial fluid up to consolidated stage. The pH development was analysed in calcium aluminate, calcium sulfoaluminate and OPC/slag cements up to a pH level of 13.3 and directly correlated with the heat of hydration. Thus tracing the dissolution and formation processes of solid phases via pH sensor monitoring is possible. This measurement technique enables the recording of continuous and highly reproducible pH data sets from slurries, pastes, and hardening materials leading to new vistas for individual (trans)formation pathways of solids, hydration and consolidation reactions in high alkaline cementitious systems.

36 MATERIALS SCIENCE↗

Evaluation of phenolic antioxidant capacity in beverages based on laccase immobilized on screen-printed carbon electrode modified with graphene nanoplatelets and gold nanoparticles

A simple and highly sensitive electrochemical biosensor based on laccase immobilized onto a gold nanoparticles/graphene nanoplatelets-modified screen-printed carbon electrode (LACC/AuNP/GNPl/SPCE) was developed for the determination of hydroquinone (HQ) and other phenolic compounds. The biosensor shows excellent electro-catalytic activity towards oxidation of hydroquinone at a potential of -0.05 V (vs Ag/AgCl, 3 M KCl) in phosphate buffer as supporting electrolyte (0.1 M, pH 7.0) using hydrodynamic amperometry. Analytical characteristics uncover that the LACC/AuNP/GNPl/SPCE comprises a wide linear range for the dependence of the signal on HQ concentrations from 4 to 130 µM with a detection limit (3σ) of 1.5 µM. The repeatability (5 measurements, 100 µM hydroquinone) is ±2% and the reproducibility (5 biosensors, 100 µM hydroquinone) is ±3%. Interference studies of most common compounds with the determination of hydroquinone demonstrated negligible effects. Finally, the biosensor and the analytical method were applied to the determination of phenolic antioxidant capacity (AOC) in wine and blueberry syrup based on Trolox (6‑hydroxy‑2,5,7,8-tetramethylchromane-2-carboxylic acid) and hydroquinone equivalents. The results were evaluated by using their calibration curves which were satisfactory and agreed well with the results obtained by the reference method Trolox Equivalent Antioxidant Capacity assay (TEAC-Assay).

60 APPLIED LIFE SCIENCES↗

PLEKHA7 signaling is necessary for the growth of mutant KRAS driven colorectal cancer

Plekha7 (Pleckstrin homology [PH] domain containing, family A member 7) regulates the assembly of proteins of the cytoplasmic apical zonula adherens junction (AJ), thus ensuring cell-cell adhesion and tight-junction barrier integrity. Little is known of Plekha7 function in cancer. In colorectal cancer (CRC) Plekha7 expression is elevated compared to adjacent normal tissue levels, increasing with clinical stage. Plekha7 was present at plasma membrane AJ with wild-type KRas (wt-KRas) but was dispersed in cells expressing mutant KRas (mut-KRas). Fluorescence lifetime imaging microscopy (FLIM) indicated a direct Plekha7 interaction with wt-KRas but scantily with mut-KRas. Inhibiting Plekha7 specifically decreased mut-KRas cell signaling, proliferation, attachment, migration, and retarded mut-KRAS CRC tumor growth. Binding of diC8-phosphoinositides (PI) to the PH domain of Plekha7 was relatively low affinity. This may be because a D175 amino acid residue plays a “sentry” role preventing PI(3,4)P{sub 2} and PI(3,4,5)P{sub 3} binding. Molecular or pharmacological inhibition of the Plekha7 PH domain prevented the growth of mut-KRas but not wt-KRas cells. Taken together the studies suggest that Plekha7, in addition to maintaining AJ structure plays a role in mut-KRas signaling and phenotype through interaction of its PH domain with membrane mut-KRas, but not wt-KRas, to increase the efficiency of mut-KRas downstream signaling.

60 APPLIED LIFE SCIENCES↗

Probing time-resolved plasma-driven solution electrochemistry in a falling liquid film plasma reactor: Identification of HO$^−_2$ as a plasma-derived reducing agent

Many applications involving plasma–liquid interactions depend on the reactive processes occurring at the plasma–liquid interface. In this article, we report on a falling liquid film plasma reactor allowing for in situ optical absorption measurements of the time-dependence of the ferricyanide/ferrocyanide redox reactivity, complemented with ex situ measurement of the decomposition of formate. We found excellent agreement between the measured decomposition percentages and the diffusion-limited decomposition of formate by interfacial plasma-enabled reactions, except at high pH in thin liquid films, indicating the involvement of previously unexplored plasma-induced liquid phase chemistry enabled by long-lived reactive species. We also determined that high pH facilitates a reduction-favoring environment in ferricyanide/ferrocyanide redox solutions. In situ conversion measurements of a 1:1 ferricyanide/ferrocyanide redox mixture exceed the measured ex situ conversion and show that conversion of a 1:1 ferricyanide/ferrocyanide mixture is strongly dependent on film thickness. We identified three dominant processes: reduction faster than ms time scales for film thicknesses >100 µm, •OH-driven oxidation on time scales of <10 ms, and reduction on 15 ms time scales for film thickness <100 µm. We attribute the slow reduction and larger formate decomposition at high pH to HO$^−_2$ formed from plasma-produced H 2 O 2 enabled by the high pH at the plasma–liquid interface as confirmed experimentally and by computed reaction rates of HO$^−_2$ with ferricyanide. Overall, this work demonstrates the utility of liquid film reactors in enabling the discovery of new plasma-interfacial chemistry and the utility of atmospheric plasmas for electrodeless electrochemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Infrared spectral signatures of interfacial water at TiO 2 –electrolyte interfaces from deep potential molecular dynamics

Vibrational spectroscopy is a powerful tool for probing water at oxide–electrolyte interfaces, but its molecular interpretation can be challenging. Here, we employ deep potential long-range molecular dynamics simulations with layer-resolved spectral analysis to investigate the microscopic origins of the infrared (IR) response of water at the interface with anatase TiO 2 (101), a prototypical oxide surface. The calculated interfacial spectra exhibit characteristic modifications compared to bulk water IR spectra, including enhanced intensities, a red shifted and broadened stretching band, and a higher-frequency shoulder, in qualitative agreement with experiments. Spectral decomposition shows that these signatures originate mainly from the first interfacial water layer, dominated by surface-bound H 2 O at Ti 5C sites, with secondary contributions from the second layer. A moderate salt concentration (0.4 M NaCl) leaves both the interfacial structure and the spectra essentially unchanged, while tuning the pH strongly modulates the spectral intensity. We establish a scaling relation linking the spectral intensity to the surface water dissociation fraction and the dipole moment, both governed by interfacial electric fields. These findings provide a microscopic framework for interpreting IR spectra of oxide–electrolyte interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of hydrothermal synthesis conditions on up-conversion luminescence intensity of β-NaYF{sub 4} : Er{sup 3+}, Yb{sup 3+} submicron particles

The differences in the luminescence intensities of up-conversion β-NaYF{sub 4} : Er{sup 3+}, Yb{sup 3+} particles synthesised by the hydrothermal method under various synthesis conditions are studied. The results of the study lead to the conclusion that in order to achieve the maximum luminescence intensity in such particles, it is necessary to use ammonium fluoride and a medium with pH = 3. In this case, the length of the particles increases, up to the formation of rod-shaped particles. Based on the data on the size of the coherent scattering region and on microstresses, we can assume that the particles are polycrystals. At the same time, limiting the size of the coherent scattering region is possible due to the defective structure. When the nanoparticles are synthesised in a medium with pH = 3, hydrolysed regions containing OH groups are formed on the crystallite surface. The presence of these groups does not affect the intensity of up-conversion luminescence of submicron-size particles. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Exceedance Response Action (ERA) Level 1 Report and ERA Level 2 Action Plan

This report consolidates the requirements for an Exceedance Response Action (ERA) Level 1 and ERA Level 2 Action Plan for pH. A discharger’s baseline status for any given parameter changes to Level 1 status if sampling results indicate a Numeric Action Level (NAL) exceedance for that same parameter. NAL exceedance can be either of the following: (1) Instantaneous maximum NAL exceedance: Occurs when two or more analytical results for any single parameter within a reporting year exceed the instantaneous maximum NAL (for example for pH a value less than 6 or a value greater than 9); and (2) Annual NAL exceedance: Occurs when the average of all the analytical results for a parameter within a reporting year exceeds the annual NAL. A Discharger’s Level 1 status for any given parameter changes to Level 2 status if sampling results indicate a Numeric Action Level (NAL) exceedance for the same parameter while a Discharger is in Level 1.

54 ENVIRONMENTAL SCIENCES↗