Alkali Metal Research Articles

Exploring the effects of the alkaline earth metal cations on the electronic structure, photostability and radiation hardness of lead halide perovskites

The growing interest to the application of perovskite solar cells (PSC) in aerospace requires great attention to the design of new absorber materials with enhanced photostability and radiation hardness. We addressed this challenge through the B-site engineering by partial replacing of Pb2+ in the complex halides with Ca2+, Sr2+, and Ba2+. Change in the material electronic properties suggests the incorporation of the substituent cations in the perovskite lattice. However, when the loading of alkaline earth halides is high, they tend to segregate to the film surface and grain boundaries. The modification of MAPbI3 and Cs0.12FA0.88PbI3 by replacing a 1% of Pb2+ with alkaline earth metal cations resulted in improvements in the photostability and radiation hardness under exposure to gamma rays and electrons beam. Depending on the material formulation, it was possible to mitigate the photochemical and radiation-induced Pb0 formation and the univalent cation phase segregation. The best of the designed perovskite absorbers could successfully tolerate high doses of gamma rays (5.5 MGy) and electron fluences (3 × 1016 e/cm2), thus outperforming significantly the non-modified material. These findings feature the incorporation of alkaline earth metal cations as a promising approach for the development of PSC with enhanced radiation hardness for aerospace applications.

Ligand-Controlled Copper-Catalyzed Halo-Halodifluoromethylation of Alkenes and Alkynes Using Fluorinated Carboxylic Anhydrides.

Polyhalogenated molecules are often found as bioactive compounds in nature and are used as synthetic building blocks. Fluoroalkyl compounds hold promise for the development of novel pharmaceuticals and agrochemicals, as the introduction of fluoroalkyl groups is known to improve lipophilicity, membrane permeability, and metabolic stability. Three-component 1,2-halo-halodifluoromethylation reactions of alkenes are useful for their synthesis. However, general methods enabling the introduction of halodifluoromethyl (CF2X) and halogen (X') groups in the desired combination of X and X' are lacking. To address this gap, for the first time, we report a three-component halo-halodifluoromethylation of alkenes and alkynes using combinations of commercially available fluorinated carboxylic anhydrides ((CF2XCO)2O, X=Cl and Br) and alkali metal halides (X'=Cl and Br). In situ prepared fluorinated diacyl peroxides were identified as important intermediates, and the use of appropriate bipyridyl-based ligands and a copper catalyst was essential for achieving high product selectivity. The synthetic utility of the polyhalogenated products was demonstrated by exploiting differences in the reactivities of their C-X and C-X' bonds to achieve selective derivatization. Finally, the reaction mechanism and ligand effect were investigated using experimental and theoretical methods to provide important insights for the further development of catalytic reactions.

Theoretical prediction of two-dimensional metallic AM2B8 (AM = K, Rb, Cs) as anode materials for Na-ion batteries

The development of two-dimensional anode materials with superior performance is becoming a critical undertaking for the advancement of Na-ion battery technology. Using isoelectronic substitution strategies, we predicted three alkali metal borides AM2B8 (AM = K, Rb, Cs) based on the SrB8 monolayer. Ab initio molecular dynamics simulations and phonon dispersion relationship calculations demonstrated their stability. Using density functional theory, we predict the feasibility of these three new metal nanosheets as anodes for Na-ion batteries. The AM2B8 monolayer retains its metallicity after the insertion of Na ions, ensuring that the anode has good electrical conductivity. In addition, AM2B8 has a low diffusion barrier and open circuit voltage (K2B8 is 0.08 eV and 0.26 V) during charge/discharge. In the voltage range that inhibits dendrite growth, K2B8 can reach the maximum theoretical specific capacity (326 mAh/g). These results indicate that AM2B8, especially K2B8, is a promising anode material for Na-ion batteries.

Alkaline Earth Bismuth Fluorides as Fluoride-Ion Battery Electrolytes.

Fluoride-ion batteries have several potential advantages over lithium-ion batteries. Materials development is still needed, however, to realize electrolytes with sufficiently high anion conductivity and compatibility with anode and cathode layers. Fluoride compounds are difficult to synthesize directly as single crystals but can be realized from oxide film precursors via topotactic chemistry techniques. Here, we create crystalline alkaline earth bismuth fluoride films BaBiF5 and SrBiF5 through oxide molecular beam epitaxy and topotactic fluorination. We characterize their ionic conductivities and demonstrate their potential as electrolytes. Finally, we realize epitaxial synthesis of BaBiF5 on BaF2 substrates, providing a route to thin film fluoride-ion battery devices.

Density functional investigation of the heterogeneous nucleation of graphite on divalent metal oxides and sulfides

Controlling the nucleation of graphite during solidification of spheroidal and lamellar graphite irons is achieved through minor additions of certain active elements such as Mg, Ca, Sr, Ba and Mn. In the present work, interfaces of graphite with alkaline earth oxides, sulfides and MnS are investigated by density functional simulations of model structures where interfacial strain has been optimized by controlling the twisting angle between the two materials. The bulk stabilities, surface energies and interfacial energies between the nucleant phases, graphite and iron are calculated. A new graphite nucleation model for estimating undercooling based on interfacial energies is proposed. It is found that CaS is the most potent nucleant particle in spheroidal graphite iron and MnS in lamellar graphite iron. The main driver of nucleation potency is found to be of chemical nature rather than related to lattice misfit.

Elucidating the Role of Alkali Metal Carbonates in Impact on Oxygen Vacancies for Efficient and Stable Perovskite Solar Cells.

Effectively suppressing nonradiative recombination at the SnO2/perovskite interface is imperative for perovskite solar cells. Although the capabilities of alkali salts at the SnO2/perovskite interface have been acknowledged, the effects and optimal selection of alkali metal cations remain poorly understood. Herein, a novel approach for obtaining the optimal alkali metal cation (A-cation) at the interface is investigated by comparatively analyzing different alkali carbonates (A2CO3; Li2CO3, Na2CO3, K2CO3, Rb2CO3, and Cs2CO3). Theoretical calculations demonstrate that A2CO3 coordinates with undercoordinated Sn and O on the surface, effectively mitigating oxygen vacancy (VO) defects with increasing A-cation size, whereas Cs2CO3 exhibits diminished preferability owing to enhanced steric hindrance. The experimental results highlight the crucial role of Rb2CO3 in actively passivating VO defects, forming a robust bond with SnO2, and facilitating Rb+ diffusion into the perovskite layer, thereby enhancing charge extraction, alleviating deep-level trap states and structural distortion in the perovskite film, and significantly suppressing nonradiative recombination. X-ray absorption spectroscopy analyses further reveal the effect of Rb2CO3 on the local structure of the perovskite film. Consequently, a Rb2CO3-treated device with aperture area of 0.14 cm2 achieves a notable efficiency of 22.10%, showing improved stability compared to the 20.11% achieved for the control device.

Полевая электронная спектроскопия молекулярно-напыленного оксидного термокатода

The results of a study of the emission characteristics of a molecular-sprayed oxide thermocathode based on triple carbonate of alkaline earth metals with an emission layer thickness of ~1 µm in the operating temperature range of 590-730 °C. are presented. The results are in good agreement with those obtained earlier for a serial oxide thermocathode with an emission layer thickness of ~100 µm applied by pulverization, and correspond to the model of a "spotted cathode" - a superposition of emission spots at different stages of activation. An idea of the activation phenomenon occurring at a given temperature in a certain range of values of the electric field strength on the surface of emission spots is detailed both with an increase and a decrease in the anode voltage. The energy spectra of the emitted electrons of a separate emission spot with a half-height width of ~100 meV have been obtained. The values of the potential change of the emitting surface of the cathode within the probed region of 0.9 V and the potential drop on the emission layer under the probed region of 4.1 V were measured.

Deciphering the evolution of electronic and magnetic properties in alkali doped nickel oxide: An In-silico approach

In this study, we employed the DFT+U method to systematically explore the electronic, and magnetic properties of nickel oxide doped with alkali metal atoms (Li, Na, K). The Hubbard potential-U was judiciously applied to all doped compound resulting from alkali doping, and were found to exhibited half-metallic properties. A noteworthy observation was the half-metallic band gap in the spin-down channel, which exhibited a linear variation with the increasing value of the Hubbard potential. Furthermore, the total magnetic moment was discernible in the supercells, with all supercells demonstrating 100% spin polarization at the Fermi level. Consequently, the findings from this study hold significant potential for applications in spintronics, thereby paving the way for future research in this domain.

The Role of Mafic Intrusions in Producing Alkaline Vent Fluids at the Lost City Hydrothermal Field: Evidence from Stable Potassium Isotopes

The alkaline, H2-rich vent fluids of the Lost City Hydrothermal Field (LCHF) have generally been attributed to serpentinization of tectonically uplifted mantle peridotite. However, elevated concentrations of highly incompatible and fluid mobile trace alkali metals, Rb and Cs, indicate reaction with relatively unaltered mafic components (Seyfried et al., 2015). Here, we present high-precision stable-K isotope analyses of LCHF vent fluids, which provide new constraints on source-rock lithology and support more quantitative estimates of fluid:rock ratio, providing a new constraint on heat and mass transfer processes. We find that δ41K values of LCHF vent fluids (0.03–0.07 ‰) are distinct from local seawater (0.13 ± 0.02 ‰). In combination with near-seawater concentrations of K (10.4 ± 0.1 mmol/kg), these data are incompatible with hydrothermal alteration of peridotite alone, which is highly depleted in K. Instead, K-isotope and concentration data are consistent with hydrothermal alteration of mafic rocks (e.g., gabbro or diabase) at a fluid:rock ratio of 6–26, a range that agrees well with Rb, Cs, and 87Sr/86Sr-based estimates of fluid:rock ratio, updated here to reflect derivation from mafic source rocks.Geochemical modeling of hydrothermal fluid-rock reactions indicates that LCHF vent fluids can be effectively reproduced by a two-stage reaction in which seawater initially reacts at 200–300 °C with mafic rocks at in a fluid:rock ratio of ∼ 10 —as constrained by the above isotopic and trace-element systematics— and subsequently reacts with peridotite at a fluid:rock ratio of ∼ 30 at roughly the same temperature, pressure conditions. We also note that LCHF vent fluids are ∼ 2 % depleted in Cl compared to seawater, which may reflect admixture of a vapor component derived from ongoing phase separation at higher (> 450 °C) temperatures. We thus propose that the LCHF represents waning-stage hydrothermal activity initiated by a discrete off-axis mafic intrusion that has subsequently cooled to intermediate temperatures conducive to olivine hydrolysis and production of alkaline vent fluids. In this interpretation, alkaline H2-rich vent fields occupy a narrow thermal window in the expected evolution of hydrothermal activity associated with episodic off-axis mafic intrusions into tectonically exposed ultramafic host rocks and are thus likely to be rare on the modern seafloor.

Progress on Biomass Coal Co-firing for Indonesia Power Plant

Abstract PT. PLN Indonesia Power (PLN IP) collaborated with other research institutions has conducted several studies to investigate the possibility of using biomass for co-firing with biomass in coal power plant. This review paper integrates results of the previous study results carried out by the authors. Biomass has some disguise disadvantageous such as low energy density, high alkaline metals, high volatile mater, handling difficulties, which may cause derating in power plant and some problem in the combustion facilities such as slagging, corrosion, abrasion, and agglomeration. The investigation carried out reveals that the use of multi-type biomass could eliminate the derating. The pre-treatment of the biomass such as drying and pelletizing could improve not only the energy density but also diminishing the slagging potential.

Realization of controlled Remote implementation of operation

Controlled remote implementation of operation (CRIO) enables to implement operations on a remote state with strong security. We transmit implementations by entangling qubits in photon-cavity-atom system. The photons transferred in fiber and the atoms embedded in optical cavity construct CZ gates. The gates transfer implementations between participants with the permission of controller. We also construct nonadiabatic holonomic controlled gate between alkali metal atoms. Decoherence and dissipation decrease the fidelity of the implementation operators. We apply anti-blockade effect and dynamical scheme to improve the robustness of the gate.

Fluorinated Hollow Porous Carbon Spheres as High-Performance Cathode Material for Primary Battery

Fluorinated carbon cathode materials have extremely high theoretical specific energy among known cathode materials of lithium primary batteries. Nevertheless, current fluorinated carbon cannot meet the performance demands of future applications due to the rate performance. This work innovatively applies hollow carbon spheres with a porous structure as carbon sources to prepare fluorinated hollow porous carbon spheres (FHPCS) with high energy density and power density. The porous structure provides more reaction sites for the fluorination process and also shortens the diffusion path of lithium ions during the discharge. Additionally, the hollow porous structure offers more interfacial contact areas and reduces volumetric expansion during discharge reactions. The Li/CFx primary battery has a maximum specific energy of 2007 Wh kg−1 and a maximum power density of 30,400 W kg−1 and can have a capacity retention rate of 80.8% at a current density of 16 A g−1. In addition, FHPCS also has the highest specific energy of 1999 Wh kg−1 and 1711 Wh kg−1 in Na/CFx and K/CFx primary batteries, respectively. The diffusion efficiency of an alkali metal ion is analyzed by the different discharge depths with electrochemical impedance spectroscopy and galvanostatic intermittent titration technique. This effort introduces a new high-performance fluorinated carbon featuring a hollow porous structure and puts forward an innovative approach to designing fluorinated carbon materials.

Structural and Luminescent Characteristics of Divalent Europium Activated Barium Aluminate with the Tridymite Structure Synthesized by the Sol-Gel Technique

Abstract: In this study, alkaline earth aluminates were investigated as potential hosts for new blue luminescent materials with nanoparticles. Ba1-xEuxAl2O4 with the stuffed tridymite hexagonal structure was successfully synthesized at 900 °C under controlled sol-gel conditions. Divalent europium was effectively used to activate this host material, producing a brilliant blue-emitting phosphor. Its spectral photoluminescence at 408 nm appears to be in a region close to the laser blue region, with chromaticity coordinate values suitable for the standard blue of the PAL TV system. Keywords: Blue phosphors, BaAl2O4, Divalent Europium (Eu2+), Sol-Gel synthesis, Critical energy transfer.

Enhancing the potential application of food-waste biochar as a sustainable bio-solid fuel: Analysis of post-treatment and combustion behavior

Food-waste biochar holds significant potential as a bio-solid fuel for achieving carbon neutrality; however, its high content of sodium (Na), potassium (K), calcium (Ca), chlorine (Cl), and nitrogen, inhibits its potential use. This study explored the effects of post-treatment with ascorbic, acetic, citric, and iminodiacetic acids on the properties of food-waste biochar and volatile ionic substances to establish a foundation for assessing both the environmental impact and practical use of food waste. Post-treatment with organic acids achieved 92% Cl-removal efficiency and induced deformation of the functional groups of food-waste biochar surfaces, leading to the re-adsorption of alkali and alkaline earth metals. This re-adsorption of alkali metal ions showed a distinct correlation with NOx mitigation. The amount of re-adsorbed Na and K varied based on the types of organic acids, resulting in different NOx emission reduction effects. Iminodiacetic acid was particularly effective in alleviating Ca and PO4 volatilization, whereas citric acid exhibited the highest Ca elution performance, and the Ca-contained leachate is a potential source of CO2 storage through indirect mineral carbonation. Acetic acid is the most feasible alternative, considering both economic and environmental aspects. The findings suggest that the post-treatment of food-waste biochar effectively mitigates air pollutants during combustion and is beneficial for sustainable biosolid fuel production and bio-waste management.

Experimental investigation on the thermal performance of high temperature two-phase loop thermosyphon

High-temperature two-phase loop thermosyphons (TPLTs) have the potential to be applied in high-temperature thermochemical conversions, concentrated solar energy, and nuclear energy. However, there has been limited investigation on the thermal performance of TPLTs so far. This work experimentally examines the thermal performance of TPLTs using alkali metals (NaK alloy and pure Na) as working fluids, aiming for internal energy recovery of a double-riser reactor. The effects of filling ratios (FRs), heating temperature, and altitude difference between the evaporator and condenser are investigated regarding start-up characteristics and steady-state performance. The experimental results show that the TPLT with NaK as the working fluid can successfully complete the start-up when the heating temperature is set to above 650 °C under the test conditions. However, the TPLT using pure Na as the working fluid can't successfully complete the start-up from a frozen state without a preheating operation. According to the variations in thermal resistance, an FR of 38% in the TPLT allows for the best heat-transfer performance under steady state when compared to the conditions that FRs are equal to 25% and 50%. Additionally, placing the condenser slightly higher than the evaporator is beneficial for improving the steady-state performance. However, if the condenser is lower than the evaporator, its steady-state performance is remarkably degraded.

Three-dimensional alkaline earth metal-organic framework poly[[μ-aqua-aqua-bis-(μ3-carba-moyl-cyano-nitro-somethanido)barium] monohydrate] and its thermal decomposition.

In the structure of the title salt, {[Ba(μ3-C3H2N3O2)2(μ-H2O)(H2O)]·H2O} n , the barium ion and all three oxygen atoms of the water mol-ecules reside on a mirror plane. The hydrogen atoms of the bridging water and the solvate water mol-ecules are arranged across a mirror plane whereas all atoms of the monodentate aqua ligand are situated on this mirror plane. The distorted ninefold coord-ination of the Ba ions is completed with four nitroso-, two carbonyl- and three aqua-O atoms at the distances of 2.763 (3)-2.961 (4) Å and it is best described as tricapped trigonal prism. The three-dimensional framework structure is formed by face-sharing of the trigonal prisms, via μ-nitroso- and μ-aqua-O atoms, and also by the bridging coordination of the anions via carbonyl-O atoms occupying two out of the three cap positions. The solvate water mol-ecules populate the crystal channels and facilitate a set of four directional hydrogen bonds. The principal Ba-carbamoyl-cyano-nitro-somethanido linkage reveals a rare example of the inherently polar binodal six- and three-coordinated bipartite topology (three-letter notation sit). It suggests that small resonance-stabilized cyano-nitroso anions can be utilized as bridging ligands for the supra-molecular synthesis of MOF solids. Such an outcome may be anti-cipated for a broader range of hard Lewis acidic alkaline earth metal ions, which perfectly match the coordination preferences of highly nucleophilic nitroso-O atoms. Thermal analysis reveals two-stage dehydration of the title compound (383 and 473 K) followed by decomposition with release of CO2, HCN and H2O at 558 K.

Superlight Ambient Temperature Reversible Hydrogen Storage Media Based on Alkali and Alkali Earth Metal-Functionalized 2D Square-Octagon BCN Monolayer.

Energy has always been the engine of human beings; however, because of the environmental pollution caused by traditional fossil fuels, the development of more sustainable energy resources is urgently needed. The hydrogen storage medium is essential for its realization. Here, we introduce a hydrogen storage material, a two-dimensional (2D) square-octagon BCN (SO-BCN) monolayer, composed of lightweight elements (B, C, and N) and strategically functionalized with alkali and alkali earth metal atoms (Li, Na, Mg, and K). Notably, Li@SO-BCN and Mg@SO-BCN exhibit exceptional reversible hydrogen storage capabilities, surpassing the DOE standard of 5.5 wt %, with gravimetric capacities of 7.129 wt % and an impressive value of 11.656 wt %, alongside low adsorption energies of -0.21 eV/H2 and -0.268 eV/H2 at room temperature, respectively. Our investigation, which combines analysis of the atomic structure, electronic structure, and hydrogen process, reveals distinct mechanisms at play: Li activates the substrate, creating additional adsorption sites on the SO-BCN monolayer. Compared with Li, the functionalization of Mg atoms not only activates SO-BCN via charge transfer but also allows Mg2+ to act as a potent attractor for H2 molecule adsorption. This work provides both promising candidates for future hydrogen storage media based on 2D monolayers and a design paradigm for next-generation hydrogen storage materials, emphasizing the synergy of electron-donating species, substrate activation, and hierarchical porous structures.

Evaluation of Na2CO3-doped MCM-48-Li4SiO4 adsorbent for CO2 capture: Performance and DFT mechanism

Efficient CO2 adsorbents are crucial for addressing the global climate crisis. In this study the novel adsorbents were synthesized using an impregnation precipitation method with MCM-48 as the silica source and Li2CO3 as the lithium source. By doping alkali metal carbonate (Na2CO3), the ML-Na2CO3 adsorbent was created for high-temperature CO2 capture. The results showed that the maximum adsorption capacity of 35.63 wt% was achieved at 600℃ in the mixture (15 vol% CO2, the balance being N2)when the adsorbent contained 15 wt% Na2CO3, representing a 4.49 wt% increase compared to the undoped ML adsorbent. The adsorption kinetics analysis confirmed a good fit with the biexponential model. Density Functional Theory (DFT) simulations revealed that the adsorption energy increased by an average of 0.1035 eV and Oslab exhibited high activity in chemisorbing CO2, forming CO32−. Na2CO3 doping modified the electronic structure of Oslab and Lislab, resulting in increased high-energy electrons, reflective activity, and improved CO2 adsorption energy. Overall, incorporating Na2CO3 enhanced carbon dioxide adsorption performance by 114.42 %, indicating a promising potential for real flue gas CO2 adsorption applications.

Hydro-chemical characterization and irrigation suitability assessment of a tropical decaying river in India

Water pollution is a major concern for a decaying river. Polluted water reduces ecosystem services and human use of rivers. Therefore, the present study aims to assess the irrigation suitability of the Jalangi River water. A total of 34 pre-selected water samples were gathered from the source to the sink of the Jalangi River with an interval of 10 km and one secondary station’s data from February 2012 to January 2022 were used for this purpose. The Piper diagram exhibits that the Jalangi River water is Na+–HCO3− types, and the alkaline earth (Ca2+ + Mg2+) outperforms alkalises (Na+ + K+) and weak acids (HCO3− + CO32−) outperform strong acids (Cl− + SO42−). SAR values ranging from 0.35 to 0.64 show that water is suitable for irrigation and poses no sodicity risks. The %Na results show that 91.18% of water samples are good and acceptable for irrigation. RSC levels indicate a significant alkalinity hazard, with 94.12% of samples considered inappropriate for irrigation. PI findings show that 91.18% of water samples are suitable for irrigation. Apart from the spatial water samples, seasonal water samples exhibit a wide variations as per the nature of irrigation hazards. Gibbs plot demonstrates that the weathering of rocks determined the hydro-chemical evolution of Jalangi River water. This study identifies very little evaporation dominance for pre- and post-monsoon water. The analysis of variance (ANOVA) test illustrates that there are no spatial variations in water quality while seasonal variations are widely noted (p < 0.05). The results also revealed that river water for irrigation during monsoon is suitable compared to the pre-monsoon season. Anthropogenic interventions including riverbed agriculture, and the discharge of untreated sewage from urban areas are playing a crucial role in deteriorating the water quality of the river, which needs substantial attention from the various stakeholders in a participatory, and sustainable manner.

Experimental study and chemical equilibrium calculation on the mineral transformation of high-alkali coal under oxy-fuel condition

The study aimed to study the mineral transformation of high-alkali coal to address the ash-related issues in oxy-fuel combustion. However, the traditional ashing method alone is inappropriate to study the mineral transformation at the initial stage of coal combustion due to the high ashing temperature. Hence, both the plasma ashing method (<200 °C) and traditional ashing method (600–1200 °C) were employed in this research to prepare the ash samples for characterization. The plasma ashing method is an efficient way to determine the original minerals in coal because it can consume the organic matter at low temperature. The recirculation of flue gas in oxy-fuel combustion can lead to high SO2 and H2O concentrations, while their influences on mineral transformation need to be clarified. In this work, SO2 and H2O were injected into CO2 to simulate the recycled flue gas (RFG). Furthermore, the chemical equilibrium calculation was conducted besides multiple experimental tests to acquire more comprehensive information of mineral transformation. The results show that high sodium and calcium contents are determined in these high-alkali coals, and two of them are rich in iron. In O2/CO2 atmosphere, some sodium (e.g. NaCl) volatilizes into the gas phase and the others converts into aluminosilicates (e.g. NaAlSi3O8) during the heating process. The calcium salts (mainly CaCO3 and CaSO4) decompose and produce silicates, aluminosilicates, and magnesium silicates. The major iron-containing minerals are identified as FeS, FeS2, and Fe2O3. Both FeS and FeS2 are oxidized into Fe2O3 below 600 °C. Moreover, the kaolinite (Al2Si2O5(OH)4) in raw coals decomposes at low temperature (<600 °C). In O2/RFG atmosphere, the additions of SO2 and H2O enhance the sulfation of AAEMs (alkali and alkaline earth metals) and delay the decomposition of sulfates. The productions of some silicates, aluminosilicates, and magnesium silicates of AAEMs are inhibited to varying degrees, and there could be complicated salts containing sulfur (e.g. hauyne). The transformations of iron-containing minerals are little related to the presences of SO2 and H2O. This work obtained the transformations of main minerals in high-alkali coal under O2/CO2 and O2/RFG conditions, which helps to address the ash-related issues.