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At least 253 records · Page 14

Biomass burning and marine aerosol processing over the southeast Atlantic Ocean: a TEM single-particle analysis

This study characterizes single-particle aerosol composition from filters collected during the ObseRvations of Aerosols above CLouds and their intEractionS (ORACLES) and CLoud–Aerosol–Radiation Interaction and Forcing: Year 2017 (CLARIFY-2017) campaigns. In particular the study describes aged biomass burning aerosol (BBA), its interaction with the marine boundary layer and the influence of biomass burning (BB) air on marine aerosol. The study finds evidence of BBA influenced by marine boundary layer processing as well as sea salt influenced by BB air. Secondary chloride aerosols were observed in clean marine air as well as in BB-influenced air in the free troposphere. Higher-volatility organic aerosol appears to be associated with increased age of biomass burning plumes, and photolysis or oxidation may be a mechanism for the apparent increased volatility. Aqueous processing and interaction with the marine boundary layer air may be a mechanism for the presence of sodium on many aged potassium salts. By number, biomass burning potassium salts and modified sea salts are the most observed particles on filter samples. The most commonly observed BC coatings are inorganic salts. These results suggest that atmospheric processes such as photolysis, oxidation and cloud processing are key drivers in the elemental composition and morphology of aged BBA. Fresh BBA inorganic salt content, as it has an important role in the particles' ability to uptake water, may be a key driver in how aqueous processing and atmospheric aging proceed.

54 ENVIRONMENTAL SCIENCES↗

A novel methodology for assessing the hygroscopicity of aerosol filter samples

Abstract. Due to US regulations, concentrations of hygroscopic inorganic sulfate and nitrate have declined in recent years, leading to an increased importance of the hygroscopic nature of organic matter (OM). The hygroscopicity of OM is poorly characterized because only a fraction of the multitude of organic compounds in the atmosphere is readily measured, and there is limited information on their hygroscopic behaviors. Hygroscopicity of aerosol is traditionally measured using a humidified tandem differential mobility analyzer (HTDMA) or electrodynamic balance (EDB). EDB measures water uptake by a single particle. For ambient and chamber studies, HTDMA measurements provide water uptake and particle size information but not chemical composition. To fill this information gap, we developed a novel methodology to assess the water uptake by particles collected on Teflon filters. This method uses the same filter sample for both hygroscopicity measurements and chemical characterization, thereby providing an opportunity to link the measured hygroscopicity with ambient particle composition. To test the method, hygroscopic measurements were conducted in the laboratory for ammonium sulfate, sodium chloride, glucose, and malonic acid, which were collected on 25 mm Teflon filters using an aerosol generator and sampler. Constant-humidity solutions (CHSs), including potassium chloride, barium chloride dihydrate, and potassium sulfate, were employed in a saturated form to maintain the relative humidity (RH) at approximately 84 %, 90 %, and 97 % in small chambers. Our preliminary experiments revealed that, without the pouch, water uptake measurements were not feasible due to rapid water loss during weighing. Additionally, we observed some absorption by the aluminum pouch itself. To account for this, concurrent measurements were conducted for both the loaded and the blank filters at each RH level. Thus, the dry loaded and blank Teflon filters were placed in aluminum pouches with one side open and in RH-controlled chambers for more than 24 h. The wet loaded samples and wet blanks were then weighed using an ultramicrobalance to determine the water uptake by the respective compound and the blank Teflon filter. The net amount of water absorbed by each compound was calculated by subtracting the water uptake of the blank filter from that of the wet loaded filter. Hygroscopic parameters, including the water-to-solute (W / S) ratio, molality, mass fraction solute (mfs), and growth factors (GFs), were calculated from the measurements. The results obtained are consistent with those reported by the Extended Aerosol Inorganics Model (E-AIM) and previous studies utilizing HTDMA and EDB for these compounds, highlighting the accuracy of this new methodology. This new approach enables the hygroscopicity and chemical composition of individual filter samples to be assessed so that in complex mixtures, such as chamber and ambient samples, the total water uptake can be parsed between the inorganic and organic components of the aerosol.

54 ENVIRONMENTAL SCIENCES↗

Electrochemical cells for direct oxide reduction, and related methods

A method of direct oxide reduction includes forming a molten salt electrolyte in an electrochemical cell, disposing at least one metal oxide in the electrochemical cell, disposing a counter electrode comprising a material selected from the group consisting of osmium, ruthenium, rhodium, iridium, palladium, platinum, silver, gold, lithium iridate, lithium ruthenate, a lithium rhodate, a lithium tin oxygen compound, a lithium manganese compound, strontium ruthenium ternary compounds, calcium iridate, strontium iridate, calcium platinate, strontium platinate, magnesium ruthenate, magnesium iridate, sodium ruthenate, sodium iridate, potassium iridate, and potassium ruthenate in the electrochemical cell, and applying a current between the counter electrode and the at least one metal oxide to reduce the at least one metal oxide. Related methods of direct oxide reduction and related electrochemical cells are also disclosed.

Tripathy, Prabhat K.↗

Molten salt compositions with enhanced heat transfer and reduced corrosion properties

A heat transfer (exchange) composition comprising a halide salt matrix having dispersed therein nanoparticles comprising elemental carbon in the absence of water and surfactants, wherein said halide is fluoride or chloride, wherein the halide salt may be an alkali halide salt (e.g., lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, sodium chloride, potassium chloride, rubidium chloride, and eutectic mixtures thereof) or an alkaline earth halide salt (e.g., fluoride or chloride salt of beryllium, magnesium, calcium, strontium, or barium), and wherein the nanoparticles comprising elemental carbon may be solid or hollow, and wherein the composition may further include nanoparticles comprising a fissile material (e.g., U, Th, or Pu) dispersed within the composition. Molten salt reactors (MSRs) containing these heat transfer compositions in coolant loops in thermal exchange with a reactor core, as well operation of such MSRs, are also described.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Mixed metal sorbents for CO 2 /H 2O displacement desorption

The disclosure generally relates to CCS sorbents, particularly for CO 2 /H 2O displacement desorption process. The sorbents include an aluminum oxide support that includes two alkali metal salts impregnated on the support. The two alkali metals include a potassium metal salts and a second alkali metal salt which is not potassium. The second metal salt disrupts poisoning effects that degrade sorbent lifetime. The sorbents demonstrate improved CO 2 loadings and better H 2O /CO 2 ratios, as well as improved stability. Compositions and methods of making are disclosed.

Bai, Chuansheng↗

KVOPO 4 cathode for sodium ion batteries

An electrode comprising: NaVOPO 4 having orthorhombic crystalline symmetry and space group Pna2 1 , as an active intercalation host material, wherein the electrode is capable of electrochemical insertion and release of greater than one sodium ion per vanadium, wherein the NaVOPO 4 is formed by a solid phase synthesis process from a heated powdered mixture of ammonium metavanadate, ammonium phosphate monobasic, and potassium carbonate, to yield NaVOPO 4 having corner-sharing VO 6 octahedra and PO 4 tetrahedra, defining two types of tunnels comprising a first type of tunnel formed of rings of two PO 4 tetrahedra and a second type of tunnel formed of rings of three PO 4 tetrahedra and three VO 6 octahedra, followed by substitution of the potassium ions with sodium ions.

Whittingham, M. Stanley↗

Exploring the Neutron Substructure with Advanced Polarized Helium-3 Targets (Or: How I Learned to Stop Worrying and Love Spectroscopy)

As we seek to understand the smallest, physical aspects of our universe, we cannot simply rely on our senses to probe the world around us as we did in the past. The smallest physical elements of our universe behave in strange, probabilistic ways and are completely invisible to the naked eye/ear/etc. So, we design clever experiments (such as scattering experiments) to probe these minute realms. Then, just as with the larger, observable world, we devise models and equations to describe what we think is happening. Due to the nature of the physical universe at the quantum scale and with the aid of symmetries such as Lorentz invariance, we can write down equations that describe the scattering, but the expressions contain functions, which we call ?form factors? and ?structure functions?, that we cannot compute from first principles. We can, however, formulate models that make predictions for these functions. By comparing our predictions with the observed data, we can gain insight into the validity of our models and thus a better physical understanding of what is happening at these minuscule scales. Studying the constituents inside of the nucleus of an atom adds another layer of difficulty if we can?t remove those components from the nucleus. This is the case with the neutron. When not bound in the nucleus with protons and other neutrons, the neutron will decay into a proton after about 15 minutes. So, we?re forced to study the neutron while it is still bound in the nucleus of an atom such as helium-3 (3He). For the last 1,000 years (rounding up), our group has developed high quality, polarized 3He targets made of an aluminosilicate glass. These targets are made in order to perform experiments at Jefferson Lab (JLab), experiments which let us determine the form factors and structure functions of the neutron by scattering polarized electrons from polarized neutrons (or rather polarized 3He). The specific experiments reported on in this thesis push the bounds of our understanding of the internal structure of the neutron. Good science is often about pushing experimental techniques to a new level. Toward that goal we study our polarized 3He targets both to advance the technology and to choose the best ones for our experiments. We do this using a process called nuclear magnetic resonance (NMR) to gauge the maximum polarization of a target and how fast the polarization decays with time. While these tests primarily provide us information that make analysis of our experimental scattering data possible, they also let us determine whether or not a target-cell is useful or even, dare I say, of spectacular quality. Our latest targets utilize a novel convection design allowing 3He to be polarized and quickly moved in front of the electron-beam, making it possible to use larger targets with higher electron-beam currents than ever before. This means more electrons scatter and we get more data. And by studying our targets in detail prior to using them in our experiments, we have found techniques to take effects which could have been detrimental to target quality and turn them to our advantage! It?s a real case of making lemonade out of lemons. We also use laser spectroscopy to study the absorption lines of alkali-metals in the target (potassium and rubidium, specifically). We add these alkali-metals to our target to facilitate polarizing the 3He. We can use the measurement of these pressure broadened absorption lines to determine the 3He density inside of the target with great precision. Historically, we understood the width of these lines would be dependent on the temperature of the target. Specifically, if I raise the temperature, the width should get bigger. I found that was not the case, which was very confusing at first, though very exciting now that I realize the data are self-consistent and suggestive of unexpected behavior. This thesis details the development of high quality, glass, polarized 3He targets for the 2020 An 1 /dn 2 and 2023 Gn E experiments, which utilized the first 3He convection targets and broke records in target quality. This thesis also covers the initial development of metal windows for the next-generation of 3He target-cells. Finally, this thesis documents the temperature dependence of the width of potassium (K) and rubidium (Rb) absorption lines as measured with laser spectroscopy.

Jantzi, Christopher↗

VOPO 4 cathode for sodium ion batteries

An electrode comprising a space group Pna2 1 VOPO 4 lattice, capable of electrochemical insertion and release of alkali metal ions, e.g., sodium ions. The VOPO 4 lattice may be formed by solid phase synthesis of KVOPO 4 , milled with carbon particles to increase conductivity. A method of forming an electrode is provided, comprising milling a mixture of ammonium metavanadate, ammonium phosphate monobasic, and potassium carbonate; heating the milled mixture to a reaction temperature, and holding the reaction temperature until a solid phase synthesis of KVOPO 4 occurs; milling the KVOPO 4 together with conductive particles to form a conductive mixture of fine particles; and adding binder material to form a conductive cathode. A sodium ion battery is provided having a conductive NaVOPO 4 cathode derived by replacement of potassium in KVOPO 4 , a sodium ion donor anode, and a sodium ion transport electrolyte. The VOPO 4 , preferably has a volume greater than 90 Å 3 per VOPO 4 .

Whittingham, M. Stanley↗

Synthesis, characterization, and thermodynamic study of selected K-based zeolites

Potassium-rich zeolites often occur in cementitious systems, as K{sup +} is widespread in various cementitious materials, such as Portland, blended and alkali-activated cements. The knowledge of their stability and of thermodynamic models for solid solutions with Na{sup +} and Ca{sup 2+} are critical to understand long-term development and durability in such cements. Completing previous studies on Na- and Ca-based zeolites, the current work aims to determine the thermodynamic data of 14 types of K-based zeolites, which could possibly form in cementitious systems. The zeolites were synthesized hydrothermally, exchanged with K{sup +}, and characterized thoroughly with respect to framework structures, elemental compositions, water contents, and bond variations. Their thermodynamic properties were derived from the experimental solubility data, which allowed establishing predominance diagrams in the K{sub 2}O-SiO{sub 2}-Al{sub 2}O{sub 3}-H{sub 2}O system. The K-based zeolites typically showed the lowest solubility between 0 and 100 °C, with the notable exception of Ca-gismondine and two Na-based zeolites: natrolite and Na-mordenite.

36 MATERIALS SCIENCE↗

Direct air capture with amino acid solvent: Operational optimization using a crossflow air‐liquid contactor

Direct air capture (DAC) is a negative emission technology for removing CO2 from the atmosphere to maintain the CO 2 level within a reasonable range so as to address greenhouse effects. In this study, the operational optimization of lab-scale DAC has been investigated using a crossflow air-liquid contactor loaded with a three dimensionally printed Gyroid packing structure and a potassium sarcosinate solvent. The effects of various parameters, including feed air flow rate, liquid solvent flow rate, contactor geometry, and ambient temperature, are examined. The results demonstrate that the Gyroid packing design achieves comparable CO 2 capture performance to conventional packed beds but with a significantly lower pressure drop of up to 77.8%, suggesting its potential as an efficient and cost-effective solution for gas–liquid contactors in DAC. Additionally, the study explores the climate impact on CO 2 capture performance and finds that as the air temperature increases from 35 to 95°F at a fixed relative humidity of 80%, the CO 2 capture rate increased from 23.2% to 46.8% with better stability. The research highlights the importance of optimizing contactor design and operational conditions to improve the CO 2 capture rate and feasibility of DAC systems as a negative emission technology for addressing greenhouse effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High foliar K and P resorption efficiencies in old-growth tropical forests growing on nutrient-poor soils

Resorption is the active withdrawal of nutrients before leaf abscission. This mechanism represents an important strategy to maintain efficient nutrient cycling; however, resorption is poorly characterized in old-growth tropical forests growing in nutrientpoor soils. We investigated nutrient resorption from leaves in 39 tree species in two tropical forests on the Guiana Shield, French Guiana, to investigate whether resorption efficiencies varied with soil nutrient, seasonality, and species traits. The stocks of P in leaves, litter, and soil were low at both sites, indicating potential P limitation of the forests. Accordingly, mean resorption efficiencies were higher for P (35.9%) and potassium (K; 44.6%) than for nitrogen (N; 10.3%). K resorption was higher in the wet (70.2%) than in the dry (41.7%) season. P resorption increased slightly with decreasing total soil P; and N and P resorptions were positively related to their foliar concentrations. We conclude that nutrient resorption is a key plant nutrition strategy in these old-growth tropical forests, that trees with high foliar nutrient concentration reabsorb more nutrient, and that nutrients resorption in leaves, except P, are quite decoupled from nutrients in the soil. Seasonality and biochemical limitation played a role in the resorption of nutrients in leaves, but species-specific requirements obscured general tendencies at stand and ecosystem level.

59 BASIC BIOLOGICAL SCIENCES↗

Fine Root and Soil Organic Carbon Depth Distributions are Inversely Related Across Fertility and Rainfall Gradients in Lowland Tropical Forests

Humid tropical forests contain some of the largest soil organic carbon (SOC) stocks on Earth. Much of this SOC is in subsoil, yet variation in the distribution of SOC through the soil profile remains poorly characterized across tropical forests. We used a correlative approach to quantify relationships among depth distributions of SOC, fine root biomass, nutrients and texture to 1 m depths across 43 lowland tropical forests in Panama. The sites span rainfall and soil fertility gradients, and these are largely uncorrelated for these sites. We used fitted b parameters to characterize depth distributions, where b is a numerical index based on an asymptotic relationship, such that larger b values indicate greater concentrations of root biomass or SOC at depth in the profile. Root b values ranged from 0.82 to 0.95 and were best predicted by soil pH and extractable potassium (K) stocks. For example, the three most acidic (pH < 4) and Kpoor (< 20 g K m -2 ) soils contained 76 ± 5% of fine root biomass from 0 to 10 cm depth, while the three least acidic (pH > 6.0) and most K-rich (> 50 g K m -2 ) soils contained only 41 ± 9% of fine root biomass at this depth. Root b and SOC b values were inversely related, such that a large fine root biomass in surface soils corresponded to large SOC stocks in subsoils (50–100 cm). SOC b values were best predicted by soil pH and base cation stocks, with the three most base-poor soils containing 34 ± 8% of SOC from 50 to 100 cm depth, and the three most base-rich soils containing just 9 ± 2% of SOC at this depth. Nutrient depth distributions were not related to Root b or SOC b values. Here, these data show that large surface root biomass stocks are associated with large subsoil C stocks in strongly weathered tropical soils. Further studies are required to evaluate why this occurs, and whether changes in surface root biomass, as may occur with global change, could in turn influence SOC storage in tropical forest subsoils.

54 ENVIRONMENTAL SCIENCES↗

Identification of background limitations to ultra-sensitive $\mathrm{LSC}$ counting through $\mathrm{ICP}$-$\mathrm{MS}$ assay of $\mathrm{LSC}$ cocktails

We report the performance of LSC cocktails in ultra-sensitive applications was evaluated. Backgrounds from radioactive contaminations in commercially available and in-house developed liquid scintillation cocktails were measured and compared to the predicted background levels of the ultra-low background liquid scintillation counter. Through the ICP-MS assay of the cocktails and their constituents, potassium impurities in the surfactant component were identified as a significant source of background, potentially limiting the use of LSC counting in ultra-sensitive applications. This work lays the groundwork for future research towards ultrapure LSC cocktails for ultrasensitive LSC counting

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Study of Cu-Ni-Fe Alloys as Inert Anodes for Al Production in Low-Temperature KF-AlF{sub 3} Electrolyte

Cu-Ni-Fe-based alloys are considered as promising O{sub 2}-evolving anode materials for CO{sub 2}-free Al production. In the present study, biphased (as-cast) and monophased (postcasting homogenized) Cu{sub 65}Ni{sub 20}Fe{sub 15}, alloys, and monophased Ni{sub 65}Fe{sub 25}Cu{sub 10} alloy (in wt pct) are evaluated as O{sub 2}-evolving anodes for Al production in potassium cryolite at 700 °C. The produced Al purity is 99.6 wt pct, and the erosion rate is estimated at 0.4 cm year{sup −1} for both Cu{sub 65}Ni{sub 20}Fe{sub 15} anodes compared to 95.2 wt pct and 3.2 cm year{sup −1} for the Ni{sub 65}Fe{sub 25}Cu{sub 10} anode. The compositions, and morphologies of the surface oxide layer and the metal fluoride layer present at the oxide/alloy interface are compared for the three anodes. The deleterious impact of electrolyte infiltration on the surface oxide building is highlighted.

36 MATERIALS SCIENCE↗

Effects of carbonation on the retention of heavy metals in chemically activated BOF slag pastes

Basic Oxygen Furnace slag contains heavy metals, including vanadium, chromium and molybdenum. The leachability of these elements determines the industrial applicability of slag-based building products. This study investigates the post‑carbonation leaching of heavy metals from activated BOF slag pastes with the focus on the activator dosage and type (sodium and potassium citrate). Results reveal that the high degree of brownmillerite hydration boosts the leachability of heavy metals as its hydration product- hydrogarnet is less stable upon carbonation. With two leaching procedures, it is demonstrated that the carbonation resistance of pastes becomes the main attribute in preventing the leaching of heavy metals. It can be enhanced by optimising the activator dosage to facilitate the hydration of C{sub 2}S and consequent structural densification.

36 MATERIALS SCIENCE↗

Corrosion sensitivity of nickel-based Alloy Inconel 600 in pressurized water reactor water chemistry: Can KOH replace LiOH?

Lithium hydroxide (LiOH) has been used to balance water acidity against boric acid moderators in the primary water of Western pressurized water reactor (PWR) designs for decades. However, the demand and the cost of lithium-7 has grown significantly since 2015. Potassium hydroxide (KOH) has been identified as a suitable and cost-effective substitute for LiOH and has been used successfully in Russian PWR designs for more than 40 years. However, it is important to know if alloys and water conditions used in Western PWR’s (Alloy 600) are similarly compatible with KOH additions. This work is focused on the aqueous corrosion behaviors of Alloy 600 with LiOH versus KOH additions at normal operating concentrations and crevice water chemistry at simulated PWR primary water conditions. TEM was used to characterize the formed oxide through diffraction analysis; SIMS was used to probe the cation ingress into the material; Atom probe tomography was used to determine the 3D elemental distribution within the oxide/metal structures; finally electrochemical impedance spectroscopy was used to discuss the structure and corrosion resistance of the oxide films. These advanced characterization techniques complement the weight measurments which showed lower mass gain in KOH than LiOH crevice water due to less oxide formation. Overall, the use of KOH as a potential alternative to LiOH in PWR is discussed.

Alloy 600↗

Opportunities and challenges in cathode development for non-lithium-ion batteries

Lithium (Li)-ion batteries have stimulated the societal transformation to clean energy systems. This carry-on electricity is revolutionizing how society communicates, functions, and evolves efficiently by enabling mobile electronics, zero-emission electric vehicles, and stationary energy storage. In preparation for the sustainable energy future, however, there are growing concerns about depleting critical elements used in the Li technology (e.g., lithium, cobalt, and nickel), especially for large-scale applications that will accelerate the rate of elemental consumption. Various non-Li-based rechargeable batteries composed of earth-abundant elements, such as sodium, potassium, magnesium, and calcium, have been proposed and explored as alternative systems to promote sustainable development of energy storage. In this perspective, we discuss challenges in Li-ion batteries in the sustainability aspect and provide our opinions on the potential applications of non-Li-based batteries. We also highlight the current status, important progress, and remaining challenges of the Li-alternative technologies.

25 ENERGY STORAGE↗

Solvothermal synthesis and solid-state characterization of metal-metal bonded tetracarboxylatoditechnetium(II,III) polymers

Investigations of solvothermal reactions with pertechnetate, [TcO 4 ] - , have produced four new low-valent Tc extended metal atom chain (EMAC) complexes with multiple metal-metal bonds. The thermal reaction of potassium pertechnetate with glacial acetic acid, under in-situ hydrogen production from the decomposition of sodium borohydride, yields purple elongated crystals determined to be tetraacetato ditechnetium (II,III) acetate (1), [Tc 2 (O 2 CCH 3 ) 4 (μ-O 2 CCH 3 ] n . Compound 1 was characterized by single crystal X-ray diffraction and its magnetic properties recorded between 10 and 300 K. Single crystal X-ray diffraction analysis of 1 indicates the Tc 2 +5 tetraacetato unit is linked by the carboxylate oxygens of the bridging acetate, similar to known chloride and bromide linkage polymers of composition [Tc 2 (μ-O 2 CCH 3 ) 4 Cl] n , and [Tc 2 (μ-O 2 CCH 3 ) 4 Br] n . Here, using the same synthetic method three similar compounds have been synthesized from propionic, benzoic and pivalic acid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗