Chemical Changes Research Articles

Hyperexpansion of genetic diversity and metabolic capacity of extremophilic bacteria and archaea in ancient Andean lake sediments

BackgroundThe Andean Altiplano hosts a repertoire of high-altitude lakes with harsh conditions for life. These lakes are undergoing a process of desiccation caused by the current climate, leaving terraces exposed to extreme atmospheric conditions and serving as analogs to Martian paleolake basins. Microbiomes in Altiplano lake terraces have been poorly studied, enclosing uncultured lineages and a great opportunity to understand environmental adaptation and the limits of life on Earth. Here we examine the microbial diversity and function in ancient sediments (10.3–11 kyr BP (before present)) from a terrace profile of Laguna Lejía, a sulfur- and metal/metalloid-rich saline lake in the Chilean Altiplano. We also evaluate the physical and chemical changes of the lake over time by studying the mineralogy and geochemistry of the terrace profile.ResultsThe mineralogy and geochemistry of the terrace profile revealed large water level fluctuations in the lake, scarcity of organic carbon, and high concentration of SO42--S, Na, Cl and Mg. Lipid biomarker analysis indicated the presence of aquatic/terrestrial plant remnants preserved in the ancient sediments, and genome-resolved metagenomics unveiled a diverse prokaryotic community with still active microorganisms based on in silico growth predictions. We reconstructed 591 bacterial and archaeal metagenome-assembled genomes (MAGs), of which 98.8% belonged to previously unreported species. The most abundant and widespread metabolisms among MAGs were the reduction and oxidation of S, N, As, and halogenated compounds, as well as aerobic CO oxidation, possibly as a key metabolic trait in the organic carbon-depleted sediments. The broad redox and CO2 fixation pathways among phylogenetically distant bacteria and archaea extended the knowledge of metabolic capacities to previously unknown taxa. For instance, we identified genomic potential for dissimilatory sulfate reduction in Bacteroidota and α- and γ-Proteobacteria, predicted an enzyme for ammonia oxidation in a novel Actinobacteriota, and predicted enzymes of the Calvin–Benson–Bassham cycle in Planctomycetota, Gemmatimonadota, and Nanoarchaeota.ConclusionsThe high number of novel bacterial and archaeal MAGs in the Laguna Lejía indicates the wide prokaryotic diversity discovered. In addition, the detection of genes in unexpected taxonomic groups has significant implications for the expansion of microorganisms involved in the biogeochemical cycles of carbon, nitrogen, and sulfur.EPcqnK6xUD66cr6MUL2q3UVideo

Novel antimicrobial polyvinyl alcohol film by incorporating β-cyclodextrin/berberine inclusion complex preserving the storage quality of salmon fillets

Antimicrobial packaging film mediated by photodynamic inactivation (PDI) based on biodegradable polymers is promising. The photosensitizer berberine chloride (BBR) was encapsulated into the β-cyclodextrin (CD) to exert its aggregation-induced emission (AIE) property. On this basis, novel PDI-mediated polyvinyl alcohol (PVA) films were fabricated by incorporating the CD/BBR inclusion complex. The PVA/CD/BBR films had high light transmittance (∼70 %) in the visible light range, and possessed good biodegradability with the water absorption of 76 % and water solubility of 31 %. Besides, the films exhibited good mechanical properties with the tensile strength of 62.53 MPa at elongation break of 69.14 %, owing to the formation of hydrogen bonds between the PVA and CD/BBR. The PDI-mediated films were irradiated (14.4 J/cm2) to produce ROS to kill ∼4 log CFU/mL of Listeria monocytogenes and Vibrio parahaemolyticus. In addition, the films potently inactivated native bacteria (0.92 log CFU/g) on salmon fillets after 9 days of storage, and maintained their sensory quality, water holding capacity, and notably, inhibited the chemical changes of salmon fillets to extend the shelf-life for at least 3 days.

Fermi level limitation in Na1/2Bi1/2TiO3–BaTiO3 piezoceramics by electrochemical reduction of Bi

The (electro)chemical stability of undoped and Zn-doped 0.94Na1/2Bi1/2TiO3–0.06BaTiO3 lead-free piezoceramics (NBT–6BT) was studied. For this purpose, the Fermi level at the interface between NBT–6BT and Sn-doped In2O3 (ITO) electrode is varied by gradually reducing the ITO film either by annealing in vacuum or by applying a voltage across a Pt/NBT–6BT/ITO. The chemical and electronic changes are monitored in situ by x-ray photoelectron spectroscopy. The experiments reveal the formation of metallic Bi when the Fermi level is reaching a value of 2.23 ± 0.10 eV above the valence band maximum, while no reduction of Ti is observed. The electrochemical reduction of Bi constitutes an upper limit of the Fermi level at ≈1 eV below the conduction band minimum. High electron concentrations in the conduction band and a contribution of free electrons to the electrical conductivity of NBT–6BT can, therefore, be excluded. The reduction occurs for an ITO work function of 4.2–4.3 eV. As typical electrode materials such as Ag, Cu, Ni, or Pt have higher work functions, an electrochemical instability of the electrode interfaces in ceramic capacitors is not expected. Under the given experimental conditions (350 °C, electric fields <40 V/mm), no degradation of resistance and no enrichment of Na at the interface are observed.

An innovative approach to control the Hf/Ti ratio in monolayers grown via atomic partial layer deposition

The Hf/Ti ratio was precisely controlled at monolayer thickness using atomic partial layer deposition (APLD). HfxTi1−xO2 films with varying Hf concentrations were deposited by adjusting the pulse time of Hf precursors within a single atomic layer. Characterization using x-ray reflectivity, x-ray photoelectron spectroscopy, and spectroscopic ellipsometry confirmed the presence of Hf, Ti, and O in the films. Increasing the Hf content caused the binding energies of the O 1s peak to shift to higher values, indicating a chemical environment change from TiO2-like to HfO2-like. A higher Hf content also increased the relative atomic percentages of Hf, Ti, and O, altering the film properties. The mass density and optical properties were notably sensitive to changes in the Hf/Ti ratio at monolayer thickness. The potential of APLD to reduce dimensionality through precise control of both thickness and composition renders it especially appropriate for applications requiring highly specific material properties.

Enhanced Piezocatalytic Water Splitting by Platinum‐Decorated Barium Titanate

AbstractPiezocatalysis has emerged as a promising field of research that uses mechanical energy to drive a chemical change. There is growing evidence that piezocatalysts can perform challenging chemical conversions from organic transformations to water splitting. A key challenge to piezocatlaysis is mitigating the inherent high relative permittivity of a ferroelectric material. This high permittivity restricts the transfer of carriers required for a chemical reaction to occur and reduces the reaction rate. Here the concept of producing a co‐catalyst system is taken to enhance carrier mobility increasing the observed reaction rate. The study highlights the importance of determining the sonochemical and piezocatalytic contributions to catalysis. The combination of a Pt metal co‐catalyst with BaTiO3 through a simple solid‐state method led to a four fold increase in the rate of H2 production compared to BaTiO3 and sonochemical reactions in the absence of a catalyst. BaTiO3/Pt is found to exhibit stable piezocatalytic performance over 12 h. Where there is a deviation from steady‐state water splitting, it is shown that this is due to mechanical removal of Pt rather than a phase change in the catalyst system. This work confirms the additive benefits of hybrid materials for improving piezocatalytic processes.

Isolation and utilization of lignin-containing nanocellulose as a bio-based coating for preserving perishable fruit

The use of nanocellulose in coatings for preserving perishable fruits and vegetables is increasing because it can maintain the shelf-life by delaying ripening and quality deterioration. In this research, lignin-containing nanocellulose (LCNC) was extracted from sugarcane bagasse through steam explosion followed by acid hydrolysis. The LCNC suspension with varying concentrations (0.3 %, 0.6 %, and 1.0 % w/v) in water was utilized as bio-based coating on mango to extend the shelf life. The physical and chemical changes of mangoes every 5 days were determined and compared with cellulose nanocrystal (CNC) coating (without lignin). The transmission electron microscopy (TEM) analysis revealed LCNC has smaller size with average length of 127.13 ± 26.21 nm and a diameter of 4.36 ± 0.96 nm compared to the CNC. The LCNC offered antioxidant activiity and UV-shielding properties. The mangoes treated with CNC showed changes in color after coating and the highest reduction of ripening during storage. At 1.0 % w/v, LCNC could delay the fruit ripening for at least 10 days compared to mangoes without coating. It also showed a higher preservation of peel color, titrate acidity, and firmness of the mangoes than the CNC coated. The findings suggested that LCNC could be a promising bio-based nanocoating for mangoes to delay their ripening and deterioration.

Stereoisomeric separation and chiral recognition mechanism study of star cyclodextrin polymer as the chiral stationary phase

BackgroundAs the derivatives of cyclodextrin (CD), cyclodextrin polymers (CDPs) effectively increase the concentration of CD units and construct supramolecular structures with unique stereoselectivity by the structure design. CDPs have shown significant potential in chiral separation, however, the process of stereoselective interactions on chiral stationary phases (CSPs) and the specific contribution of intermolecular forces are still a challenge issue. A comprehensive understanding of the chiral recognition mechanism of CDPs will help to optimize chiral separation conditions and design new CSPs. ResultsThe star CDP with a supermolecular structure was synthesized by grafting β-CD onto the external 6-position hydroxyl groups using β-CD as the parent nucleus. The enhanced host-guest recognition ability of CD supramolecular polymer structure provided better inclusion interaction and increased chiral recognition of the isomers. The Star-CD CSP with star CDP as a chiral ligand performed satisfactory stereoisomer separation ability with the separation factor (α) up to 2.0 for various quinoline alkaloid isomers and 1.89 for catechins. To elucidate its chiral separation mechanism, molecular docking was used to construct the three-dimensional visual models of the binding sites and the contribution of non-covalent interactions between Star-CD CSP and quinoline alkaloid isomers. In addition, the formation sites of non-covalent interactions on the CD monomers of the polymer side chains were confirmed from the actual geometric structure by analyzing the NMR chemical shift changes before and after the formation of complexes between Star-CD polymers and isomers. Combined with the mutual evidence of molecular simulation and chiral NMR, the specific recognition mechanism of selector-selectand complexes was comprehensively expounded. SignificanceThe multi-mode CSP based on cyclodextrin supramolecular structure provides new ideas for the stereoisomeric separation of complex chiral components with multiple chiral centers in natural products. Not limited to the macroscopic performance of the chromatographic separation, molecular docking explored the theoretical model of chiral recognition from the molecular level. The chiral NMR analysis confirmed the credibility of the model from the geometry structure, and then the recognition mechanism of multi-mode CSP was fully elaborated combining the above three aspects.

Surface Iodide Defects Control the Kinetics of the CsPbI3 Perovskite Phase Transformation.

Halide perovskites are technologically interesting across a wide range of optoelectronic devices, especially photovoltaics, but material stability has proven to be challenging. One degradation mode of note is the meta stability of the perovskite phase of some material compositions. This was studied by tracking the change of CsPbI3 from its optoelectronically relevant perovskite phase to its thermodynamically stable nonperovskite phase, δ-CsPbI3. We explore kinetics as a function of surface chemistry and observe a quantitatively similar, ∼5-fold, reduction in the phase transition rate between neat films and those treated with CsI and CdI2. Using XPS to explore surface chemistry changes across samples, we link the reduction in the phase transition rate to the surface iodide concentration. When informed by previous theoretical studies, these experiments point to surface iodide vacancies as the nucleation sites for δ-CsPbI3 growth and show that phase nucleation is the rate limiting step in δ-CsPbI3 formation for CsPbI3 perovskite thin films.

Natural light driven plastic leaching effects on carbon chemistry in the tropical coastal waters of eastern Arabian sea: An experimental study

This study examined the effects of solar light driven plastic degradation on carbon chemistry in the coastal waters of eastern Arabian Sea along the west coast of India. The research was conducted through experimental incubations exposed to natural sunlight at multiple locations between December 2023–February 2024. Photodegradation induced a significant pH decrease (up to 0.38 ± 0.02) between controls and plastic incubations ranging from 8.17 ± 0.01 to 7.54 ± 0.02 with the highest variation in the Mumbai coast ranging from 8.13 ± 0.01 to 7.75 ± 0.03. pH variations are primarily caused by the leaching of organic acids and CO2 release during solar irradiated incubation. Plastic leaching due to natural light irradiation and subsequent changes in the water chemistry is of prime significance with dissolved organic carbon (DOC) leaching of 0.002–0.03% of plastic weight into the coastal waters. Our estimations suggest 15–75 metric tonnes (MT) of DOC release per year by plastic pollution in the eastern Arabian Sea coastal waters. Further, the fluorescent dissolved organic matter (FDOM) fragmentation, a part of DOC, may act as an organic source of synthetic contaminants and would promote heterotrophic microbial action in the coastal waters. Photodegradation of plastic and the interaction of natural DOC and plastic-derived DOC resulted in longer wavelengths FDOM, which may affect the penetration of photosynthetically active radiation in the water column, thereby impacting primary production. Finally, future research work focussing on the role of plastic pollution in coastal ocean acidification and vice-versa is essential and will be increasingly intense in the upcoming decades.

Influence of grain sizes and secondary phases on the mechanical behavior and corrosion resistance in a non-equiatomic NiCrCoFeMoAlTi high-entropy alloy

Single-phase face-center cubic (FCC) structured Ni27.7Cr24Co23.5Fe15.7Mo1.6Al3Ti4.5 high-entropy alloy (HEA) samples with different grain sizes were first achieved, suggesting smaller grain size improved corrosion resistance and strength. Subsequently, aging was performed on the sample with the smallest grain size (∼9.5 μm), leading to the formation of lots of nano-sized spherical coherent L12 precipitates at FCC grain interior, along with some σ phase and non-spherical L12 precipitates at grain boundaries. Therefore, a superior combination of mechanical and corrosion properties was achieved. Secondary phases caused chemical and structural changes in the passive film due to galvanized corrosion, leading to slightly lower corrosion resistance.

Wettability Behaviour of Metal Surfaces after Sequential Nanosecond and Picosecond Laser Texturing.

This study examines the wettability behaviour of 304 stainless steel (304SS) and Ti-6Al-4V (Ti64) surfaces after sequential nanosecond (ns) and picosecond (ps) laser texturing; in particular, how the multi-scale surface structures created influence the lifecycle of surface hydrophobicity. The effect of different post-process treatments is also examined. Surfaces were analysed using Scanning Electron Microscopy (SEM), a white light interferometer optical profiler, and Energy Dispersive X-ray (EDX) spectroscopy. Wettability was assessed through sessile drop contact angle (CA) measurements, conducted at regular intervals over periods of up to 12 months, while EDX scans monitored elemental chemical changes. The results show that sequential (ns + ps) laser processing produced multi-scale surface texture with laser-induced periodic surface structures (LIPSS). Compared to the ns laser case, the (ns + ps) laser processed surfaces transitioned more rapidly to a hydrophobic state and maintained this property for much longer, especially when the single post-process treatment was ultrasonic cleaning. Some interesting features in CA development over these extended timescales are revealed. For 304SS, hydrophobicity was reached in 1-2 days, with the CA then remaining in the range of 120 to 140° for up to 180 days; whereas the ns laser-processed surfaces took longer to reach hydrophobicity and only maintained the condition for up to 30 days. Similar results were found for the case of Ti64. The findings show that such multi-scale structured metal surfaces can offer relatively stable hydrophobic properties, the lifetime of which can be extended significantly through the appropriate selection of laser process parameters and post-process treatment. The addition of LIPSS appears to help extend the longevity of the hydrophobic property. In seeking to identify other factors influencing wettability, from our EDX results, we observed a significant and steady rate of increase in the carbon content at the surface over the study period.

Unveiling the Mn3+/ Mn4+ and Ni2+ potential as a high-capacity material for next-generation energy storage devices

In this study, we synthesized MnOx nanowires via hydrothermal methods and explored the impact of nickel (Ni) doping on their morphology and electrochemical properties. We investigated the structural and chemical changes induced by Ni incorporation by utilizing TEM and XPS analyses. Our results revealed that Ni doping influenced the distribution of manganese oxidation states, with 1.6 wt% Ni-doped nanowires exhibiting the optimized condition. Also, we observed a balance between the Mn3+/Mn4+ ratio with the Ni doping. Electrochemical characterization demonstrated enhanced capacity in Ni-MnOx nanowires at the 1.6 wt% Ni doping level. Galvanostatic charge-discharge measurements confirmed the superior performance of this level of Ni doping; moreover, the fabrication of asymmetric supercapacitor cells using these nanowires showed improved energy storage capabilities. The main results showed exceptionally high capacity (955.55 and 383.33 mAh g−1 at 1 and 20 A g−1, respectively) and an excellent rate capability. Cycling stability tests over 8500 cycles demonstrated excellent retention of capacity, underscoring the durability of the optimized Ni-MnOx nanowires, with a retention of 85 % of its initial capacity. Thus, this study emphasizes the significance of Ni doping in MnOx nanowires for enhancing electrochemical performance when the synthetic process is controlled, offering valuable insights for high-performance energy storage device development.

Mudstone diagenesis with depth and thermal maturity in the Cenomanian–Turonian Eagle Ford group. PART II: Diagenetic processes and paragenetic sequence

The Cenomanian–Turonian (C–T) Eagle Ford Group (EFG) is composed of massive, laminated, and/or burrowed limestones, marls, and lime mudstones deposited on the drowned south Texas shelf below storm-wave base. A burial diagenesis investigation using seven cored wells from shallow to deep burial (depth ranges from 7684 to 13,670 ft [2342 to 4166.6 m]; BHT from 183 to 285 °F [83.9–140.6 °C]) and from east (San Marcos Arch) to west (Maverick Basin) delineated a complex diagenetic history as a result of changes in water chemistry, redox condition, and burial history. The second part of this comprehensive study shows the variety of diagenesis and paragenesis. This study focuses especially in the organic-rich Lower Eagle Ford (LEF) member deposited largely under anoxic/euxinic conditions. Processes such as near seafloor sulfate-reduction, Fe-reduction, and methanogenesis drive various chemical reactions during lithification. Feldspar diagenesis included albitization and transformation of K-feldspar to kaolinite and albite, and from kaolinite to Mg-chlorite with depth. Clay mineral diagenesis is complex with authigenic kaolinite, mixed kaolinite/Mg-chlorite, and Mg-chlorite form in biota tests and matrix. Additionally, calcite dissolution, burial dolomitization, late Fe-chlorite replacement, and oxidation of pyrite to marcasite are also observed. Detritus-derived smectite starts to transform to mixed layered clay, illite-smectite (I/S) in the oil window; however, illitization trends were not observed in depth. This is because most smectite forms from alteration of volcanic ashes and the volcanic origin of the disorientated smectite did not follow regular illitization kinetics. The increase in Mg content from illitization transforms not only the kaolinite to chlorite, but precipitates authigenic dolomites. The clay minerals precipitated in the original interparticle pores, further reducing porosity, and impacted permeability, fluid saturation, wettability, and capillary pressure. With thermal maturation, bitumen and oil conversion increases oil-wetness of the rock and the resistivity measurement from wireline logs.

Effects of antioxidants on chemical and rheological properties of asphalt binders from different crude oil sources

Antioxidants can effectively mitigate or delay the oxidative aging degradation of asphalt binder, thereby improving pavement durability. While research has largely concentrated on the application of antioxidants to asphalt binders from a single source, limited studies have explored their effects on binders derived from different crude oil sources. Moreover, the relationship between the chemical and rheological properties of antioxidant-modified asphalt binders remains insufficiently understood. In this study, three antioxidants - zinc diethyldithiocarbamate (ZDC), Irganox 1010 and kraft lignin - were utilized and blended with base binders sourced from three distinct regions globally. Fourier transform infrared spectroscopy (FTIR) was utilized to analyze the impact of these antioxidants on the chemical composition of aged binders. Additionally, dynamic shear rheometer (DSR) and bending beam rheometer (BBR) tests were conducted to assess the high- and low-temperature performance of the antioxidant-modified binders, identifying the most effective antioxidant. The linear amplitude sweep (LAS) test further evaluated the performance of ZDC across binders from different crude oil sources. The results revealed three key findings: first, chemical functional group changes due to antioxidants are not always reflected in rheological performance; second, ZDC demonstrated superior performance across different base binders, as evidenced by improved aging indices, high-temperature rutting resistance, and enhanced fatigue and low-temperature cracking resistance; and third, asphalt binders from different crude oil sources exhibit varying sensitivities to antioxidant type and dosage. This study underscores the necessity of determining optimal antioxidant dosages for different asphalt binders, as the relationship between antioxidant dosage and effectiveness is not straightforward.

The interaction between sludge and microplastics during thermal hydrolysis of sludge

In municipal wastewater treatment plants (WWTPs), large number of microplastics (MPs) accumulated in wastewater migrated into sludge. Thermal hydrolysis of sludge (THS) was one of the most promising processes for promoting changes in molecular structure of MPs. The physicochemical properties and degradative pathways of polyethylene (PE) and polyethylene terephthalate (PET) in THS under different temperatures were studied in this paper. It was found that there was a mutual promotion relationship between sludge degradation and MPs aging. The presence of PE and PET MPs not only increased organics and nitrogen concentrations of sludge filtrate, but also enhanced the transformation of organics like proteins. Sludge accelerated the aging of PE and PET MPs. The friability of PE and PET MPs was increased with more surface fragmentation and breakage under the temperature of 120 ℃−180 ℃. Moreover, PE and PET MPs occurred thermal oxidation and reduction reactions with significant chemical structure changes at 160 °C and 140 °C, respectively. Pristine PE and PET had multiple carbon and oxygen active sites. During THS reaction, not only PE and PET reacted hydrolysis/decomposition to produce short-chain hydroxyl-terminated compounds, but also hydrothermal shear broke the polymer molecules and formed carboxyl-terminated and olefin-terminated low-carbon chains. This study provided some promising sign for in situ microplastic removal during sludge treatments.

Dissolution of EAF slag minerals in aqueous media: Effects of sonication on brownmillerite and gehlenite

The accumulation of electric arc furnace slag (EAFS) in landfills has been causing severe environmental problems. This study examines the dissolution properties of EAFS minerals, including brownmillerite and gehlenite, essential for their possible use in resource recovery. An investigation was conducted to compare the effects of sonication and stirring on mineral dissolution while also assessing the usage of citrate as a complexing agent for gehlenite. Synthetic brownmillerite and gehlenite minerals were dissolved in aqueous solutions at room temperature using a 1:100 g/ml ratio. The dissolved elements were measured using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES), while zeta potential and X-ray Photoelectron Spectroscopy (XPS) were used to assess changes in surface chemistry. Brownmillerite had significant dissolution extents, with Al and Ca dissolving up to 16 % and 8 %, respectively, in contrast to gehlenite, which dissolved less than 2 % under similar conditions. Sonication significantly increased the dissolution of brownmillerite by up to 100 %, although its impact on gehlenite dissolution varied depending on the duration of time. Besides, adding citrate enhanced the leaching of Al and Ca from gehlenite by facilitating complexation. XPS data demonstrated differences in elemental ratios on brownmillerite and gehlenite surfaces affected by the method used and the presence of citrate. Lastly, the dissolution extents of Al and Ca from EAFS were up to 12 %, depending on time and mixing method, with a preference for sonication over stirring. In conclusion, this study showed that minerals in EAFS have distinct dissolution characteristics, and sonication and citrate can considerably enhance dissolution.

A preliminary evaluation of the effects of aquatic environments on the recovery of fingermarks on porous substrates

Latent fingermark detection can become increasingly difficult in the weeks following deposition, due to chemical and physical changes influenced by environment. There has been increased research interest into ageing mechanisms of fingermark residue, however these studies have typically been conducted in dry, indoors conditions. Less information is available regarding degradation processes that may occur in scenarios involving water and the potential longevity of porous substrates under such conditions. A pilot study was conducted to investigate the performances of Oil Red O (ORO) and physical developer (PD) on samples submerged in different aquatic environments in a laboratory setting. Charged fingermarks from three donors were deposited on copy paper and immersed in either salt water or freshwater; still or with water flow. Samples were treated at multiple intervals (1, 12, 20 and 40 days) after submersion. Results showed that high quality of development could be achieved up to 40 days after immersion. The overall performances of ORO and PD were generally unaffected in the early stages of the study. Physical and chemical degradation of both latent residue and substrate were observed, which were increased by salt and water movement. While PD appeared to be less affected by potential chemical changes, it was less effective than ORO due to substrate degradation in moving salt water. These results present the first steps towards better understanding the practical effects of degradation processes specific to fingermarks on porous substrates underwater.

Does the diversity of vegetation and diatoms correlate with soil and water factors in a tropical cloud forest's complex land use/land cover scenario?

Soil and water characteristics in micro basins with different land uses/land cover (LULC) can influence riparian vegetation diversity, stream water quality, and benthic diatom diversity. We analyzed 18 streams in the upper part of the La Antigua River basin, México, surrounded by cloud forests, livestock pastures, and coffee plantations. Concentrations of P, C, and N were elevated in the humus of forested streams compared to other land uses. In contrast, cations, ammonium, and total suspended solids (TSS) of water streams were higher in pastures and coffee plantations. These results indicate that LULC affects stream chemistry differently across land uses. Vegetation richness was highest (86-133 spp.) in forest streams and lowest in pastures (46-102), whereas pasture streams had the greatest richness of diatoms (9-24), likely due to higher light and temperatures. Some soil and water characteristics correlated with both true diversity and taxonomic diversity; soil carbon exchange capacity (CEC) correlated with vegetation diversity (r = 0.60), while water temperature correlated negatively (r = - 0.68). Diatom diversity was related to soil aluminum (r = - 0.59), magnesium (r = 0.57), water phosphorus (r = 0.88), and chlorophyll (r = 0.75). These findings suggest that land use affects riparian vegetation, while physical and chemical changes influence diatom diversity in stream water and soil. The lack of correlation between vegetation and diatom diversity indicates that one cannot predict the other. This research is an essential first step in understanding how land use changes impact vegetation and diatom diversity in mountain landscapes, providing valuable insights for environmental monitoring and conservation efforts in tropical cloud forests.

A second-order kinetic model for global analysis of vibrational polariton dynamics.

The interaction between cavity photons and molecular vibrations leads to the formation of vibrational polaritons, which have demonstrated the ability to influence chemical reactivity and change material characteristics. Although ultrafast spectroscopy has been extensively applied to study vibrational polaritons, the nonlinear relationship between signal and quantum state population complicates the analysis of their kinetics. Here, we employ a second-order kinetic model and transform matrix method (TMM) to develop an effective model to capture the nonlinear relationship between the two-dimensional IR (or pump-probe) signal and excited state populations. We test this method on two types of kinetics: a sequential relaxation from the second to the first excited states of dark modes, and a Raman state relaxing into the first excited state. By globally fitting the simulated data, we demonstrate accurate extraction of relaxation rates and the ability to identify intermediate species by comparing the species spectra with theoretical ground truth, validating our method. This study demonstrates the efficacy of a second-order TMM approximation in capturing essential spectral features with up to 10% excited state population, simplifying global analysis and enabling straightforward extraction of kinetic parameters, thus empowering our methodology in understanding excited-state dynamics in polariton systems.

Development of cement slurries with additives of nanoclay particles for the construction of oil wells at elevated temperatures

Relevance. Strength decrease is a phenomenon that becomes more pronounced as the temperature rises above 110°C. It is characterized by significant chemical and microstructural changes that Portland cement undergoes at high temperatures. Adding silica particles (SiO2) to cement can significantly increase cement resistance to strength reduction when the temperature exceeds 110°C. Nanoclays are currently used in the cement industry to increase the strength of the cement matrix due to their ability to fill capillary micropores and due to their relatively small particle size. Aim. To investigate the effect of adding nanoparticles (nanoclay) to Saudi grade G cement on compressive and tensile strength, and cement stone permeability under high temperature conditions (300°С). Objects. Six samples of cement mortars with different concentrations of nanoclay, cement stones from, tested after 7 and 28 days of hardening at 25 and 300°C. Methods. Cement chemical composition was evaluated by the X-ray fluorescence method with the WORKSTN-V Olympus Vanta X-ray fluorescence analyzer. Cement physical composition was evaluated by the method of ray diffraction on the Mastersizer 2000 laser particle size analyzer. The test of the grouting stone samples was carried out in accordance with ISO 10426-2:2003 on a hydraulic press 65-L1132. The tensile strength of the samples by the Brazilian method was tested in accordance with ASTM D 3967-08 standard on a hydraulic press 65-L1132. The permeability of the samples was determined by single-phase stationary filtration at a facility for studying the filtration and capacitance properties of the PIK-OFP-UCH core in accordance with ISO 10426-2:2003. Results. The data obtained showed that cement destruction at extremely high temperatures can be avoided by using nanoclay (up to 3% by weight of cement). The microstructure of the cement matrix was significantly affected due to the aggregation of nanoparticles when more than 3% of nanoclay was added. All rheological characteristics of the cement slurry were improved by the addition of nanoclay particles.