Fractionation Factors Research Articles

Position-specific kinetic isotope effects for nitrous oxide: a new expansion of the Rayleigh model

Abstract. Nitrous oxide (N2O) is a potent greenhouse gas and the most significant anthropogenic ozone-depleting substance currently being emitted. A major source of anthropogenic N2O emissions is the microbial conversion of fixed nitrogen species from fertilizers in agricultural soils. Thus, understanding the enzymatic mechanisms by which microbes produce N2O has environmental significance. Measurement of the 15N / 14N isotope ratios of N2O produced by purified enzymes or axenic microbial cultures is a promising technique for studying N2O biosynthesis. Typically, N2O-producing enzymes combine nitrogen atoms from two identical substrate molecules (NO or NH2OH). Position-specific isotope analysis of the central (Nα) and outer (Nβ) nitrogen atoms in N2O enables the determination of the individual kinetic isotope effects (KIEs) for Nα and Nβ, providing mechanistic insight into the incorporation of each nitrogen atom. Previously, position-specific KIEs (and fractionation factors) were quantified using the Rayleigh distillation equation, i.e., via linear regression of δ15Nα or δ15Nβ against [-fln⁡f/(1-f)], where f is the fraction of substrate remaining in a closed system. This approach, however, is inaccurate for Nα and Nβ because it does not account for fractionation at Nα affecting the isotopic composition of substrate available for incorporation into the β position (and vice versa). Therefore, we developed a new expansion of the Rayleigh model that includes specific terms for fractionation at the individual N2O nitrogen atoms. By applying this Expanded Rayleigh model to a variety of simulated N2O synthesis reactions with different combinations of normal, inverse, and/or no KIEs at Nα and Nβ, we demonstrate that our new model is both accurate and robust. We also applied this new model to two previously published datasets describing N2O production from NH2OH oxidation in a methanotroph culture (Methylosinus trichosporium) and N2O production from NO by a purified Histoplasma capsulatum (fungal) P450 NOR, demonstrating that the Expanded Rayleigh model is a useful tool in calculating position-specific fractionation for N2O synthesis.

The soil-air interfacial migration process of volatile PFAS at the contaminated sites: Evidence from stable carbon isotopes with CSIA

Volatile per- and polyfluoroalkyl substances (PFAS) are prone to transport among various environmental media, with the soil-air interfacial migration process being an important pathway that significantly influences their environmental fate. To assess the migration and transformations of target volatile PFAS at contaminated site using compound-specific stable isotope analysis (CSIA), it is necessary to understand the isotopic fractionation that occurs during their transfer from soil to air. We have established methods for pre-treatment and GC/CSIA analysis methods of target volatile PFAS in soil and air samples and ensured the accuracy of carbon isotope analysis. GC/IRMS δ13C measurements showed optimal precision at instrumental response above 1.35–2.75 Vs, with recommended minimum on-column C levels of 1.67–5.00 nmol for target volatile PFAS. Stable carbon isotope fractionation factors related to the soil-air interfacial migration process for target volatile PFAS were determined by performing laboratory simulations. The observed εsoil-air values are all negative, suggesting that the soil-air interfacial migration process for target volatile PFAS is kinetic fractionation, the removal of molecules containing lighter isotopes. By comparing the simulated and experimentally observed δ13C (‰) values of target volatile PFAS, we found consistent trends in the soil and inverse trends in the air. These δ13C (‰) values and the related isotope fractionation model provide valuable insights into the isotopic behavior of target volatile PFAS during soil-air interfacial migration process, aiding in the assessment of their environmental fate.

Time delayed fractional diabetes mellitus model and consistent numerical algorithm

The diabetes mellitus model (DMM) is explored in this study. Many health issues are caused by this disease. For this reason, the integer order DMM is converted into the time delayed fractional order model by fitting the fractional order Caputo differential operator and delay factor in the model. It is proved that the generalized model has the advantage of a unique solution for every time t. Moreover, every solution of the system is positive and bounded. Two equilibrium states of the fractional model are worked out i.e. disease free equilibrium state and the endemic equilibrium state. The risk factor indicator, R0 is computed for the system. The stability analysis is carried out for the underlying system at both the equilibrium states. The key role of R0 is investigated for the disease dynamics and stability of the system. The hybridized finite difference numerical method is formulated for obtaining the numerical solutions of the delayed fractional DMM. The physical features of the numerical method are examined. Simulated graphs are presented to assess the biological behavior of the numerical method. Lastly, the outcomes of the study are furnished in the conclusion section.

A magnetohydrodynamic flow of a water-based hybrid nanofluid past a convectively heated rotating disk surface: A passive control of nanoparticles

Abstract One of the basic fluid mechanics problems of fluid flows over a revolving disk has both theoretical and real-world applications. The flow over a rotating disk has been the subject of numerous theoretical studies because it has many real-world applications in areas like rotating machinery, medical equipment, electronic devices, and computer storage. It is also crucial for engineering processes. Therefore, this article deals with a time-independent water-based hybrid nanofluid flow containing copper oxide and silver nanoparticles past a spinning disk. The Newtonian flow is taken into consideration in this analysis. The influence of magnetic field, thermophoresis, nonlinear thermal radiation, Brownian motion, and activation energy has been considered. The present analysis is modeled in a partial differential equation form and is then converted to ordinary differential equations using appropriate variables. A numerical solution using the bvp4c technique is accomplished using MATLAB software. The current results are matched with the previous literature and established a close relationship with previous studies. The purpose of this investigation is to numerically investigate the time-independent hybrid nanofluid flow comprising copper oxide and silver nanoparticles over a rotating disk surface. The results show that the increased magnetic parameters increase the friction force at the surface, which decreases the radial and azimuthal velocity distribution. At the sheet surface, the radial velocity of the hybrid nanofluid shows dominant performance compared to the nanofluid. On the other hand, the magnetic factor has dominant behavior on the azimuthal velocity component of the nanofluid flow compared to the hybrid nanofluid flow. The higher volume fraction and magnetic factor enhance the skin friction at the disk surface. Furthermore, greater surface drag is found for the hybrid nanofluid flow. The higher solid volume fraction, temperature ratio, and Biot number enhance the rate of heat transmission. Also, a higher rate of heat transmission is observed for the hybrid nanofluid flow.

Magnesium geochemistry of authigenic carbonate at marine cold seep

Cold seeps, featured by their extremely methane-rich sedimentary environments, play a significant role in the geological history and are common in marine sediments across the seafloor. Primary dolomite, possibly mediated by microorganisms, can be widely discovered in methane-rich environments. Hence, cold seeps may provide new insights into the ‘dolomite problem’, which has confused geologists for decades. Magnesium isotope geochemistry of seep carbonates contributes to the understanding of the dolomite formation mechanism in marine environments. In this paper, magnesium geochemical characteristics of carbonates in modern sediments are summarized, along with rare researches on magnesium isotopes of seep carbonates. Methane vigorously interacts with sulfate by anaerobic oxidation of methane at cold seeps, producing vast amounts of dissolved sulfide which can significantly promote dolomitization of seep carbonates. Compared with temperature, alkalinity, mineralogy, etc., the competition between rapid carbonate precipitation rates and aqueous ligands may be the main factor of the magnesium fractionation at cold seeps, which is controlled by the kinetic effect. The range of magnesium isotopes of seep carbonates is narrow (from -3.46‰ to -2.36‰), and an upper limit of magnesium content seems to exist. This characteristic may be a good indicator for identifying dolomitization related to anaerobic oxidation of methane. Whereas, mechanisms of magnesium isotope fractionation and dolomitization at cold seeps remain unclear, necessitating more natural samples tested, stimulated calculation and laboratory experiment.

Rhenium Isotopes Record Oxidative Weathering Intensity in Sedimentary Rocks

AbstractOxidative weathering of organic carbon in sedimentary rocks is a major source of CO2 to the atmosphere over geological timescales, but the size of this emission pathway in Earth's past has not been directly quantified due to a lack of available proxy approaches. We have measured the rhenium isotope composition of organic‐rich rocks sampled from unweathered drill cores and weathered outcrops in south Texas, whose stratigraphic successions can be tightly correlated. Oxidative weathering of more than 90% of the organic carbon and ∼85% of the rhenium is accompanied by a shift to lower rhenium isotope compositions in the weathered outcrops. The calculated isotope composition of rhenium weathered from the initial bedrock for individual samples varies systematically by ∼0.7‰ with different fractions of rhenium loss. This variation can be empirically modeled with isotope fractionation factors of α = 1.0002–1.0008. Our results indicate that the isotope composition of rhenium delivered to the oceans can be altered by weathering intensity of rock organic matter and that the rhenium isotope composition of seawater is sensitive to past oxidative weathering and associated CO2 emissions.

Improved measurement of the semileptonic decay Ds+→K0e+νe

Analyzing e+e− collision data corresponding to an integrated luminosity of 7.33 fb−1 collected at center-of-mass energies between 4.128 and 4.226 GeV with the BESIII detector, we measure the branching fraction of the semileptonic decay Ds+→K0e+νe to be (2.98±0.23stat±0.12syst)×10−3. Based on fit to the partial decay rates in various q2 intervals, the product value of Ds+→K0 hadronic form factor and Cabibbo-Kobayashi-Maskawa element is measured to be f+K0(0)|Vcd|=0.143±0.011stat±0.003syst. With |Vcd|=0.22486±0.00067 as an input, the hadronic form factor is evaluated to be f+K0(0)=0.636±0.049stat±0.013syst. The branching fraction and form factor measurements are factors of 1.6 and 1.7 more precise than the previous world averages, respectively. Published by the American Physical Society 2024

Heavy iron isotopes reveal mantle oxidation in addition to pyroxenite sources for intraplate basalts

The heavier iron isotopic composition of some oceanic island basalts (OIB) relative to primary mid-ocean ridge basalts (MORB) has commonly been interpreted to reflect the heavy bulk isotopic compositions of their sources (e.g., of a pyroxenite-dominated mantle region). Alternatively, comparable Fe isotopic signatures observed in continental intraplate basalts (CIB) may record enhanced isotope fractionation during partial melting of an oxidized source, offering valuable insights into mantle oxidation induced by subducted carbonate. To distinguish between these two independent contributions, here we present high-precision Fe isotopic data (δ57Fe) and Fe3+/∑Fe ratios for a suite of Cenozoic intraplate basalts from Inner Mongolia, East Asia. These basalts are distributed along a northwest-southeast (NW–SE) profile and associated with earlier subduction of the Paleo-Asian oceanic slab. Variations in Fe/Mn ratios and zinc isotopic compositions (δ66Zn) of these basalts reveal that altered oceanic crust has always contributed to their mantle sources but the amounts of recycled carbonate gradually vary. Together with existing data, we demonstrate that all of these basalts generally exhibit heavier δ57Fe (0.07 ‰ to 0.31 ‰), higher Fe3+/∑Femelt (0.08 to 0.39) and Fe/Mn (> 65) relative to primary MORB (δ57Fe ∼0.10 ‰; Fe3+/∑Femelt ∼0.10; Fe/Mn ∼60), pointing to a common origin of heavy Fe isotopes in intraplate basalts that may reflect those of pyroxenite sources (e.g., recycled crust). However, these basalts containing larger amounts of recycled carbonate in their sources (i.e., higher δ66Zn) have heavier δ57Fe at similar Fe/Mn ratios and proportions of pyroxenite melt. Such Fe isotopic signatures exceed the exclusive role of pyroxenite and are best attributed to partial melting at oxidizing conditions (i.e., high Fe3+/∑Fesource) with an inferred enlarged fractionation factor. This oxidized mantle source formed through the reduction of recycled carbonate to graphite/diamond at depths greater than 150 km. A global dataset of Fe isotopes in intraplate basalts is compiled in order to examine this interpretation further. Compared with OIB typically from a pyroxenite/eclogite-dominant source, CIB with similarly heavy δ57Fe and formed by similar melting degrees are commonly more silica-undersaturated, indicating a widespread carbonated mantle source. Thus, these observations highlight that heavy Fe isotopes can record carbonate-induced mantle oxidation in addition to source lithological heterogeneity for intraplate basalts.

Monitoring of stable isotope composition of precipitation reveals thunderstorm dynamics

ABSTRACT The summer of 2019 is particularly well known for the famous heatwaves that swept across the European continent, with its associated drought and record-breaking air temperatures. This was followed by powerful thunderstorms, characterised by hail and heavy rain that damaged the crops on a regional scale. Here, we investigated one of the largest storm cells, lasting more than 6 h, which struck southwestern Romania. High-temporal resolution sampling of storm precipitation was performed for stable isotope measurements, rainfall and air temperature, to follow the storm dynamics. Hydrogen and oxygen isotope measurements show an abrupt decreasing temporal trend followed by superimposed V-shaped patterns interpreted as reflecting moisture replenishment by successive rain bands. To model the stable isotope values of precipitation in relation to the general trend of decreasing air temperatures, we applied a numerical Rayleigh condensation model for a non-constant α isotopic fractionation factor between liquid water and water vapour. The storm is powered by four consecutive moisture fronts, each following a Rayleigh distribution. About 40 % of the water vapour condenses during the sampled storm due to adiabatic expansion and cooling, which lowers saturation. Condensation ceases when cooling and absolute humidity can no longer sustain the dew point, stopping the rain. The timing of the event, occurring late at night and early in the morning, its duration of over 6 h as well as its synoptic scale may indicate a mesoscale convective complex.

Exploring the influence of atmospheric CO2 and O2 levels on the utility of nitrogen isotopes as proxy for biological N2 fixation.

Biological N2 fixation (BNF) is traced to the Archean. The nitrogen isotopic fractionation composition (δ15N) of sedimentary rocks is commonly used to reconstruct the presence of ancient diazotrophic ecosystems. While δ15N has been validated mostly using organisms grown under present-day conditions; it has not under the pre-Cambrian conditions, when atmospheric pO2 was lower and pCO2 was higher. Here, we explore δ15N signatures under three atmospheres with (i) elevated CO2 and no O2 (Archean), (ii) present-day CO2, and O2 and (iii) future elevated CO2, in marine and freshwater, heterocytous cyanobacteria. Additionally, we augment our data set from literature for more generalized dependencies of δ15N and the associated fractionation factor epsilon (ε = δ15Nbiomass - δ15NN2) during BNF in Archaea and Bacteria, including cyanobacteria, and habitats. The ε ranges between 3.70‰ and -4.96‰ with a mean ε value of -1.38 ± 0.95‰, for all bacteria, including cyanobacteria, across all tested conditions. The expanded data set revealed correlations of isotopic fractionation of BNF with CO2 concentrations, toxin production, and light, although within 1‰. Moreover, correlation showed significant dependency of ε to species type, C/N ratios and toxin production in cyanobacteria, albeit it within a small range (-1.44 ± 0.89‰). We therefore conclude that δ15N is likely robust when applied to the pre-Cambrian-like atmosphere, stressing the strong cyanobacterial bias. Interestingly, the increased fractionation (lower ε) observed in the toxin-producing Nodularia and Nostoc spp. suggests a heretofore unknown role of toxins in modulating nitrogen isotopic signals that warrants further investigation.IMPORTANCENitrogen is an essential element of life on Earth; however, despite its abundance, it is not biologically accessible. Biological nitrogen fixation is an essential process whereby microbes fix N2 into biologically usable NH3. During this process, the enzyme nitrogenase preferentially uses light 14N, resulting in 15N depleted biomass. This signature can be traced back in time in sediments on Earth, and possibly other planets. In this paper, we explore the influence of pO2 and pCO2 on this fractionation signal. We find the signal is stable, especially for the primary producers, cyanobacteria, with correlations to CO2, light, and toxin-producing status, within a small range. Unexpectedly, we identified higher fractionation signals in toxin-producing Nodularia and Nostoc species that offer insight into why some organisms produce these N-rich toxic secondary metabolites.

Bending Analysis of Multiwall Carbon Nanotube Reinforced Functionally Graded Composite Cylindrical Shell

The curved structural components of aircraft, automobiles, and marine vessels, such as cylindrical panels, are primarily exposed to loading, which can result in bending failure, particularly in lightweight structures. The bending analysis of cylindrical panels made of functionally graded multiwall carbon nanotube (FG-MWCNT) epoxy composites is subjective in this study. In the first section, FG-MWCNT composite cylindrical panels are simulated in the ANSYS software. There are three methods for distributing uniaxially aligned reinforcements. The material properties of the carbon nanotubes uniformly distributed and functionally graded over the thickness of the shell structure are estimated using an extended rule of mixture micromechanical model that incorporates certain useful characteristics. To demonstrate the effectiveness and applicability of the proposed finite element approach, deflection data are presented. The analysis of the shell structure's bending includes an investigation of the impact of CNT volume fraction, boundary condition, lengthto-thickness ratio, and other geometrical factors

Increasing the Measured Effective Quantum Volume with Zero Noise Extrapolation

Quantum volume is a full-stack benchmark for near-term quantum computers. It quantifies the largest size of a square circuit which can be executed on the target device with reasonable fidelity. Error mitigation is a set of techniques intended to remove the effects of noise present in the computation of noisy quantum computers when computing an expectation value of interest. Effective quantum volume is a proposed metric that applies error mitigation to the quantum volume protocol to evaluate the effectiveness not only of the target device but also of the error mitigation algorithm. Digital zero-noise extrapolation is an error mitigation technique that estimates the noiseless expectation value using circuit folding to amplify errors by known scale factors and then extrapolating computed expectation values to the zero-noise limit. Here we demonstrate that zero-noise extrapolation, with global and local unitary folding with fractional scale factors, in conjunction with dynamical decoupling, can increase the effective quantum volume over the vendor-measured quantum volume. Specifically, we measure the effective quantum volume of four IBM Quantum superconducting processor units, obtaining values that are larger than the vendor-measured quantum volume on each device. This is the first such increase reported.

Fractional factors and component factors in graphs with isolated toughness smaller than 1

AbstractLet be a simple graph and let be two integers with . We prove that for every if and only if has a ‐factor, where denotes the number of isolated vertices of and is a special family of trees. Furthermore, we characterize the trees in in terms of their bipartition.

Partitioning of the high-level radioactive waste from the purex process by 40% TBF in isoparaffin using magnesium nitrate as a salting-out agent

Centrifugal contactor rig trials of the partitioning flowsheet were carried out using simulated and real high level waste solutions obtained by reprocessing of WWER-100 spent nuclear fuel with burn-up of 47 MW day/t. 40% TBP in Isopar M was used as a solvent with magnesium nitrate as a salting-out agent. Complete removal of Cs, Sr, Zr and Mo to raffinate was achieved. Rare earth elements, Am and Cm were totally concentrated in TPE and REE product. Comparison of the results of this work with previous trials with iron (III) nitrate as a salting-out agent [1] demonstrated that using magnesium nitrate as a salting-out agent resulted in higher decontamination factors of TPE and REE fraction from Cs (~10000) than using iron (III) nitrate (7500).

Diatom silicon isotope ratios in Quaternary research: Where do we stand?

Silicon stable isotope ratios (expressed as δ30Si) in biogenic silica have been widely used as a proxy for past and present biogeochemical cycling in both marine and lacustrine settings, in particular for nutrient utilization reconstructions. Yet an analysis of publication trends suggests a significant decline in the application of δ30Si to Quaternary science questions in the last five years. At the same time as δ30Si proxy applications have decreased, we are learning more about its complexities: an expanding body of work is highlighting biases, caveats or complications involved in the application of δ30Si-based approaches to the sediment record. These include the demonstration of species-specific silicon isotope fractionation factors (i.e. ‘vital effects’) or the potential for Fe or other trace metals to influence silicon isotope fractionation. Others have inferred the potential of biogenic silica dissolution to alter an initial δ30Si value, or questioned the preservation of the initial δ30Si through early diagenetic processes more generally. Another challenge receiving more attention is centered around deconvolving a δ30Si-value into a signal reflecting biological productivity and a signal reflecting changes in the δ30Si of dissolved silicon driven by whole-system and/or circulation changes. Finally, a number of studies focus on analytical difficulties, especially during sample preparation related to achieving and demonstrating a contaminant free biogenic silica. These challenges lead us to posit that the Quaternary science community is moving away from silicon isotope proxies because they are losing confidence in their reliability and usefulness. Here, focusing on the diatoms – the dominant biosilicifiers in both lakes and the ocean – we synthesize progress in understanding nuances and caveats of δ30Si-based proxies in order to answer whether the fall-off in δ30Si-based Quaternary research is warranted. We suggest that with some simple steps that can be readily implemented, and with the closing of key knowledge gaps, there is no reason to believe silicon isotopes do not have a promising future in the Quaternary sciences.

Effect of Stromal Vascular Fraction in the Rat Model of Pharyngocutaneous Fistulas.

A pharyngocutaneous fistula is one of the complications after laryngeal and pharyngeal surgery. It may also contribute to wound healing due to adipose tissue-derived stem cells and the growth factors in the stromal vascular fraction. The aim of this study was to investigate the effects of the adipose tissue-derived stromal vascular fraction on wound healing in the pharyngocutaneous fistula model induced in rats. Approval was received from the Animal Experiments Local Ethics Committee before starting the study (29.01.2016-2016/09). Eleven male Sprague-Dawley rats weighing approximately 300 g were included in the study. The animals were randomly divided into the study and control groups so that each group would include five animals. An animal was assigned as a donor for the removal of omental adipose tissue. Among the animals in which the pharyngocutaneous fistula model was created under general anesthesia, 1 ml of the stromal vascular fraction was injected into the study group on postoperative day 1. In postoperative week 2, all the animals were sacrificed and examined histologically (epithelialization-cell infiltration - mucosal injury). IBM SPSS Statistics for Windows, version 15, was used in the analyses. A p-value <0.05 was considered significant. Epithelialization was higher in the study group compared to the control group. However, no statistically significant difference was found between the two groups (p = 0.08). The cell infiltration was found to be statistically higher in the control group compared to the study group (p = 0.03). The mucosal injury was found to be significantly higher in the control group compared to the study group (p = 0.03). According to the Pearson correlation test, a negative correlation was found between epithelialization and cell infiltration and mucosal injury (p = 0.019 and p = 0.001). A positive correlation was found between cell infiltration and mucosal injury (p = 0.009). It was shown that stromal vascular fraction had a positive effect on wound healing in the pharyngocutaneous fistula model. According to the data we have obtained, we think that it can be effective in the treatment of pharyngocutaneous fistulas after more extensive preclinical and clinical studies are carried out.

Oxygen isotope fractionation during amorphous to crystalline calcium carbonate transformation at varying relative humidity and temperature

Crystalline calcium carbonate isotope compositions have been widely used to reconstruct past environments. However, if their isotopic compositions are modified because of crystallization from an amorphous precursor, their reliability as paleo-geochemical proxies can be compromised. This study explored the changes in the oxygen isotope compositions during the transformation of amorphous calcium carbonate (ACC) into crystalline carbonate under different conditions of relative humidity (RH of 33–95 %), temperature (T of 5 °C and 20 °C) and in the presence/absence of atmospheric CO2. The data showed that at low RH and T (e.g., RH ≤ 45 % and 5 °C) when a complete ACC-crystalline carbonate transformation did not take place then the original ACC δ18O values (δ18OCaCO3 = −15.9 ± 1.0 ‰, VPDB) were preserved throughout the experimental runtime (up to 144 days). In contrast, in fully crystallized CaCO3 (e.g., at RH ≥ 60 %) the δ18OCaCO3 values increased rapidly over the first few days, followed by a slower and gradual increase. By the end of the experiments (i.e., after 103–144 days) the crystalline δ18OCaCO3 values ranged from −10.4 ‰ to −8.1 ‰ in the presence of atmospheric CO2 and from −12.6 ‰ to −9.5 ‰ in the CO2-free experiments. These changes in oxygen isotope compositions of the CaCO3 reaction products (calcite and/or vaterite) were mainly driven by exchange with H2O from the hydrated ACC i.e. the synthesis fluid. In CO2-present experiments, oxygen isotope fractionation factors between the CaCO3 reaction products and the synthesis fluid (18αc–w) approached or exceeded oxygen isotope equilibrium values. This could be explained by a decrease in the initially high pH of the aqueous fluid released from ACC dissolution during CO2 hydration/hydroxylation, which would have increased the oxygen isotope exchange kinetics between H2O and dissolved inorganic carbon (DIC). In some experiments, the hydration/hydroxylation of 18O-enriched CO2, due to isotopic salt-effects, might have also resulted in 18O-enriched calcium carbonates and calculated fractionation factors that exceeded equilibrium values. In the CO2-free experiments, isotopic equilibrium between the crystalline phase and the synthesis fluid was not reached. This oxygen isotope disequilibrium suggests that without the pH lowering effect of the hydroxylation/hydration of CO2, the CO32− released during ACC/calcite dissolution-reprecipitation may have not isotopically equilibrated with the high pH synthesis fluid due to the long equilibration times required to reach isotope equilibrium at high pH values, leading to the self-buffering of δ18OCaCO3 values. The results suggest that the oxygen isotopic compositions of natural carbonates formed from ACC transformation in air and at low water/solid ratio (e.g., biominerals or carbonates formed in caves) are complex and cannot be used as simple proxies if the reaction kinetics (RH/CO2/T) and H2O sources are not known and quantified.

Deep regolith weathering controls δ30Si composition of groundwater under contrasting landuse in tropical watersheds

Land use changes are known to alter terrestrial silicon cycling and the export of dissolved silicon from soil to fluvial systems, but the impact of such changes on groundwater systems remain unclear. In order to identify the processes responsible for groundwater geochemistry and to assess the impact of agricultural processes, we examined multiple isotopic tracers (δ30Si, oxygen (δ18O) and hydrogen (δ2H) isotopes) in groundwater, soil porewater and surface water from two contrasted watersheds having the same gneissic lithology, one forested (Mule Hole) and one intensely cultivated (Berambadi) in the Kabini basin in South India. In the cultivated watershed, groundwater exhibits high Cl− and NO3− concentrations indicative of fertilizer inputs and solute enrichment from evapotranspiration due to multiple groundwater pumping/recharge cycles. The DSi concentration in groundwater is significantly higher in the cultivated watershed (980 ± 313 μM) than in the forested one (711 ± 154 μM), indicating more intense evapotranspiration due to irrigation cycles. The groundwater δ30Si values ranged from 0.6 ‰ to 3.4 ‰ and exhibit no significant differences between cultivated (1.2 ± 0.5 ‰) and forested (1.0 ± 0.2 ‰) watersheds, indicating limited impact of land use and land cover. Groundwater also shows no significant seasonal differences in DSi and δ30Si within watersheds, indicating a buffer to seasonal recharge during wet season. The δ30Si of a majority of groundwater samples fits a steady-state open flow through system, with an isotopic fractionation factor (30ε) between precipitating phase and groundwater ranging from −1.0 ‰ and − 2.0 ‰, consistent with precipitation of kaolinite-type clays, dominant in the study area. The steady-state flow through system in groundwater can be interpreted as a continuous DSi input from mineral weathering reactions with a dynamic equilibrium between Si supply and precipitation of secondary phases. We also observe, in both watersheds, similar DSi and δ30Si values in local surface water that includes small streams and a river (406 ± 194 μM, 1.6 ± 0.3 ‰) and in soil porewater (514 ± 119 μM, 1.6 ± 0.2 ‰). Compared to soil porewater, groundwater exhibits significantly lower δ30Si signatures and higher DSi, reflecting the contribution of an isotopically light silicon source, resulting from water-rock interaction during percolation through the unsaturated zone. We assign this steady input of DSi to the weathering of primary silicate minerals in the regolith, such as Na-plagioclase, biotite and chlorite, with formation of kaolinite and smectites type clays. A simple isotopic mass balance suggests that deep regolith weathering can contribute to almost half of the DSi in groundwater. We conclude that silicon cycling in soil porewaters, and surface waters are directly impacted by land use, while the isotopic composition of groundwater remains unaffected. Our results indicate that Si isotopic signatures of weathering, adsorption, and plant uptake occurring in the shallow soil and saprolite horizons are partly overprinted and homogenized by the regolith weathering in the deep critical zone, irrespective of land use and seasonality.

Tight isolated toughness bound for fractional (a,b,m)-deleted graphs

A graph [Formula: see text] is a fractional [Formula: see text]-deleted graph if deleting any [Formula: see text] edges from [Formula: see text], the resulting subgraph still admits a fractional [Formula: see text]-factor. As an exclusive graph-based parameter, isolated toughness and its variant are utilized to measure the vulnerability of networks which are modelled by graph topology structures. Early studies have shown the inherent connection between isolated toughness and the existence of fractional factors in specific settings. This paper provides a theoretical perspective on the sufficient conditions for fractional [Formula: see text]-deleted graphs with respect to isolated toughness and its variant. The sharpness of the given isolated toughness bounds is explained by counterexamples.

Spatial effect of urban morphology on land surface tempature from the perspective of local climate zone

Urban expansion results in the intrusion of artificial surfaces into natural environments, giving rise to phenomena such as urban heat islands and heightened temperatures within inhabited areas. This study examined the dynamic evolution of urban morphology and land surface temperature through the lens of local climate zone. Furthermore, the spatial relationship between urban morphology indices and land surface temperature was analyzed within the context of loops. The investigation yielded several noteworthy findings: (1) LCZ8, LCZ6, and LCZD were the most significant transfer-in and transfer-out classes within the study area. (2) The heat contribution of residential LCZs (LCZ 2,3,5) decreased over time, ranging from 0.415 to 0.171, while that of industrial LCZs (LCZ 8,10) increased within the range of 0.348–0.553. (3) Urban heat island mitigation can be achieved by regulating building height and surface fraction. Establishing a judicious threshold for reducing LST is imperative for sky view factor and impervious surface fraction factors. Surface albedo exhibited a substantial inhibitory effect in 2020. The observation of urban morphological changes and long-term local climate zone considerations integrate the responsibility of mitigating urban heat islands into urban planning.