Fractionation Factors Research Articles

Uptake kinetics and distribution of flupyrimin by rice (Oryza sativa L.): Effects of subcellular fractionation and soil factors.

Flupyrimin is an emerging neonicotinoid insecticide primarily used to control rice planthoppers. However, knowledge gaps exist regarding its uptake and transport in rice planting systems. Elucidating the absorption and distribution properties of flupyrimin in rice will help assess the potential risks of human exposure to flupyrimin via the food chain. Here, we studied the uptake kinetics and transport mechanisms of flupyrimin in rice plants grown under hydroponic and soil conditions. The hydroponic experiment indicated that flupyrimin was easily taken up by rice roots via a symplastic passive diffusion process and was mainly distributed in the cell soluble fractions (50.6 %－88.0 %). Compared with transportation from the roots to the stems, flupyrimin was ultimately transported from the stems to the leaves with a greater translocation factor (TF) (TFLeave/Stem = 27.8 > TFStem/Root = 3.1). In rice-soil systems, the accumulation of flupyrimin by rice plants is influenced primarily by the soil organic matter content, which leads to increased adsorption of flupyrimin onto soils (R2 > 0.897, P < 0.014). Interestingly, the concentration of flupyrimin in rice was significantly positively correlated with its amount in the soil pore water (CIPW) (R2 > 0.967, P < 0.003), indicating that the uptake and accumulation of flupyrimin in rice planting systems can be estimated by CIPW. These findings enhance our knowledge of flupyrimin absorption and distribution in rice plants from treated soils and are important for guiding its field application and conducting environmental risk assessments.

An Evaluation of Secondary Mineral Formation/Dissolution and Phase Separation Based on Mg Isotopic Fractionation: The Shallow-Water Hydrothermal System in Milos, Greece

This study investigates Mg isotopes (δ26Mg) in vent fluids from Milos, Aegean Sea, to evaluate phase separation and secondary mineral formation. The δ26Mg vary significantly in Milos, exceeding 0.66‰, allowing for the classification of the fluids into three sub-groups based on chemical characteristics: seawater-like, cave fluids, and submarine-brines. The seawater-like fluids exhibit large δ26Mg variation, −0.64 to −1.18‰, and mostly follow a Rayleigh fractionation trend, with a fractionation factor α = 1.00020 ± 0.00011. The cave fluids are highly acidic, have low Cl, are vapor-rich, and display heavy δ26Mg compositions (−0.52 to −0.63‰). The submarine-brines are characterized by high Cl, high non-volatile metals, and light δ26Mg (−0.65 to −1.00‰). The latter two fluid types represent vapors and brines, respectively, which underwent phase separation at depth in Milos. These δ26Mg values were combined with major/trace elements, as well as Li and B isotopes, to explore possible controlling mechanisms. We report for the first time a shallow submarine hydrothermal system that has a vapor component enriched in heavy δ26Mg, but with no detectable isotopic changes in the brines. It is evident that δ26Mg in vent fluids is unique for separating effects of water/rock interaction and secondary mineral and phase separation at shallow-water systems.

Species-specific Antimony Isotope Analysis by High Performance Liquid Chromatography Coupled with Multicollector ICPMS Using Hydride Generation as an Interface.

A novel method has been developed for the simultaneous online determination of the isotopic compositions of different antimony (Sb) species in a single analytical run using high-performance liquid chromatography (HPLC) coupled with multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), with hydride generation (HG) serving as the interface. Various parameters affecting the precision of Sb isotope analysis including HG conditions, transient signal processing methods and peak integration windows, were optimized. The linear regression slope method and a 100% peak integration window provided the optimal precision. Under optimized conditions, our method achieved external 2SD precisions better than 0.05‰ for both Sb(III) and Sb(V), with minimal consumption of 0.5 ng for Sb(III) and 5 ng for Sb(V). Furthermore, flow injection (FI) coupled with HG-MC-ICPMS demonstrated precise Sb isotopic analysis with sample requirements as low as 0.25 ng. The proposed methods were validated by analyzing δ123Sb in synthetic solutions and reference materials. Additionally, it was applied to investigate isotopic fractionation during the reduction of Sb(V) by KI, revealing preferential reduction of the light Sb isotope(121Sb). The isotopic compositions of Sb(V) varied from -0.04- 1.18‰, fitting well with a Rayleigh fractionation model and yielding a fractionation factor (αSb(III)-Sb(V)) of 0.99831. In summary, this approach enables high precision isotopic analysis of Sb(III) and Sb(V) simultaneously with reduced sample consumption, providing a powerful tool for investigating Sb isotopic fractionation in various environmental processes and advancing our understanding of the Sb biogeochemical cycle.

Stereotactic radiosurgery vs. fractionated radiotherapy for large vestibular schwannomas: should FSRT be the preferred treatment?

To evaluate the effect of fractionation and prognostic factors on local control (LC) in the treatment of vestibular schwannoma (VS). The medical records of 104 patients with vestibular schwannoma who were treated with stereotactic radiosurgery (SRS) from January 2015 to September 2023 were retrospectively collected. SRS was performed using Cyberknife® robotic lineer accelerator. The primary endpoint of this study was LC rates. The chi-square test or Fischer's exact test, where appropriate, was used to compare progression rates in patients with small (< 20cc) and large tumors (≥ 20cc) which were treated in different fractionation schemes. The median total prescribed dose was 18Gy (range, 12-30Gy). With a median 54.8month follow-up period (range, 3.4-111.9month), 12 (12%) patients had progressive disease. Regression in tumor size, and stable disease was observed in 49 (47%) and 43 (41%) patients, respectively. The 3-y LC rate was 89% in all cohort and similar between patients who received SRS in 1, 3, and 5 fractions (p = 0.074). LC rates were slightly lower in patients with large tumors than those with small tumors (83% vs 94%, p = 0.200). Patients with large tumors (≥ 20cc) which was treated with SRS in 1 fraction had a higher rate of progression compared to patients with small tumors (< 20cc) (100% vs 0%, p = 0.006). But there was no difference between progression rates in large and small tumors, which were treated in 3, and 5 fractions (p = 0.100 and p = 1.000, respectively). No prognostic factors were found to predict tumor progression. Both SRS and fractionated stereotactic radiotherapy (FSRT) provides high LC in patients with VS, however, FSRT may be preferred for large tumors due to higher LC rates compared to single fraction SRS.

Research on vertical vibration characteristics of rolling mill based on magnetorheological fluid damper absorber

The study of rolling mill vibration theory has always been a scientific frontier in the field of rolling forming, which is very important to the quality of sheet metal and the stable operation of equipment. A magnetorheological fluid damper absorber is designed to control the nonlinear vertical vibration of rolling mill. Considering the fractional order and delay factors in the control effect of magnetorheological fluid, the fractional order delay nonlinear vertical vibration equation with magnetorheological damping damper is established. The amplitude-frequency characteristic equations of the main resonance and sub-resonance of the system are solved by multi-scale method. The effects of stiffness coefficient, damping coefficient, time delay, fractional order, and exciting force on the vibration characteristics of roller system are analyzed by comparing the amplitude-frequency curve, time-domain curve and phase diagram. The transition set of the steady-state response of the system and the corresponding bifurcation topology structure are analyzed by using the singularity theory. A magnetorheological fluid damper absorber platform of rolling mill is built based on modern test technology, and the influence laws of the control threshold, control current, type of magnetorheological fluid and reduction rate are analyzed. The correctness and feasibility of the design of the magnetorheological fluid damper absorber are verified, which provided theoretical guidance and technical support for the nonlinear dynamic analysis and stability control of the rolling mill.

Objective Bayesian Model Selection for Spatial Hierarchical Models with Intrinsic Conditional Autoregressive Priors

We develop Bayesian model selection via fractional Bayes factors to simultaneously assess spatial dependence and select regressors in Gaussian hierarchical models with intrinsic conditional autoregressive (ICAR) spatial random effects. Selection of covariates and spatial model structure is difficult, as spatial confounding creates a tension between fixed and spatial random effects. Researchers have commonly performed selection separately for fixed and random effects in spatial hierarchical models. Simultaneous selection methods relieve the researcher from arbitrarily fixing one of these types of effects while selecting the other. Notably, Bayesian approaches to simultaneously select covariates and spatial model structure are limited. Our use of fractional Bayes factors allows for selection of fixed effects and spatial model structure under automatic reference priors for model parameters, which obviates the need to specify hyperparameters for priors. We also show the equivalence between two ICAR specifications and derive the minimal training size for the fractional Bayes factor applied to the ICAR model under the reference prior. We perform a simulation study to assess the performance of our approach and we compare results to the Deviance Information Criterion and Widely Applicable Information Criterion. We demonstrate that our fractional Bayes factor approach assigns low posterior model probability to spatial models when data is truly independent and reliably selects the correct covariate structure with highest probability within the model space. Finally, we demonstrate our Bayesian model selection approach with applications to county-level median household income in the contiguous United States and residential crime rates in the neighborhoods of Columbus, Ohio.

Iron isotope fractionation during granite weathering under different climates

Climate controls chemical weathering of silicate rocks on the transport of iron (Fe) and its isotopes from continent to the ocean, impacting the global Fe geochemical cycle. However, it's elusive if Fe isotope fractionation during silicate weathering reflects variations in climate factors. This study examines two granite-derived regolith profiles; one in Beijing (BJ), representing a temperate climate, and the other in Guangdong (GD), representing a tropical climate, to investigate their mineralogy, Fe-bearing phases, element concentrations, and Fe isotope compositions. Our results show that, despite climate differences, the two granite weathering profiles have average δ56Febulk regolith values within analytical uncertainty (0.09 ± 0.02 ‰ vs. 0.12 ± 0.04 ‰, 2SD). The δ56Febulk regolith values of temperate and tropical regolith are similar to or slightly higher than those of their respective bedrocks and remain steady along the entire weathering profile. The limited variation of Fe isotope composition in weakly weathered temperate regolith likely reflects the dissolution of primary minerals rather than the formation of secondary minerals. The Rayleigh fractionation calculations also show a Δ56Fepore solution-regolith value of ∼0 ‰ between pore solution and regolith. In contrast, in the tropical profile, despite the abundance of secondary minerals and the differences in δ56Fe values among the extracted Fe-pools exceeding 0.68 ‰, only limited Fe isotope fractionation is observed in the bulk regolith (0.01 ‰ to 0.24 ‰). These variations are likely driven by the formation of Fe oxides, relying on the atomic distribution of Fe in hematite and goethite. The linear regression analysis estimates the apparent Fe isotope fractionation factor between hematite and goethite as 0.46 ± 0.07 ‰ (Δ56Fehematite-goethite, 1SE). These findings indicate that the sensitivity of Fe isotope fractionation in bulk regolith to variations in climate factors is relatively limited. However, combined with results from other weathering profiles in different climate zones, two models suggest that changes in δ56Fe values of easily leachable and silicate-bound Fe pools are likely influenced by climate factors such as temperature and precipitation. This work advances our understanding of the Fe isotope fractionation during silicate weathering and its potential climate connection on Earth's surface.

Reaction-controlled triple O-isotope exchange trajectories during experimental alteration of olivine

The measurements and application of triple O-isotope system is a relatively new and powerful tool in tracing water-rock interaction, allowing to distinguish the temperature-dependent fractionation from the water amount that interacted with the rock. While the use of 18O/16O fractionation between minerals and fluids is well-established, most natural mineral-water reactions remain uncharacterized in terms of the triple isotope fractionation (17O/16O and18O/16O). The triple O-isotope approach is especially promising when it comes to natural samples, where an array of exchanged samples constrains the fluid endmembers. However, multiple exchange mechanisms are likely to occur between the reacting rock and water, which has not been investigated for triple O-isotopes. This study examines the triple O-isotope exchange between fluid and olivine experimentally, as this is a common reaction in nature and mechanisms/rates of reaction are societally important for CO2 sequestration. Water-olivine reaction in batch experiments was investigated at 275 °C at the saturated water vapor pressure of 59.5 bar. Reactants were loaded at mass ratios 0.6 to 2 and exchanged for periods of time between 44 and 1048 h. Local meteoric water and mantle olivine were taken as the initial reactants. The mineral products are brucite, serpentine and minor magnetite that occur as coatings on unreacted olivine as well as individual crystals. The progress of this dissolution-precipitation reaction was traced with the δD-δ′18O-Δ′17O values of reacted fluids and mineral products. After 1048 h of reaction, ∼50 wt% of unreacted olivine remained. In general, experimental data conforms with the triple O-isotope fractionation factors calculated for the co-existing secondary minerals forming in equilibrium with fluid. However, there is scatter and deviations in the reacted fluid compositions likely driven by the difference in relative rates of secondary mineral formation and changing modal and chemical mineral composition. We observe that brucite and magnetite form abundant aggregates early in the progress of the reaction, while chrysotile forms fine-grained coatings that become abundant later. Since individual mineral-water fractionation 103ln18/16α range over 10 ‰ with θ ranging between 0.51 and 0.53, the dynamic behavior of dissolution-precipitation mechanism during alteration of olivine is the main factor to the “wandering” triple O-isotope trajectories in our relatively short experiments.

Magmatic differentiation of peralkaline granites: Constraints from iron isotope fractionation between Fe-bearing minerals

Iron isotopes have been found useful in tracing magmatic processes of calc-alkaline granitic magmas, but its application in peralkaline granitic systems is hampered by the lack of information regarding the Fe isotope fractionation factors between alkali-rich ferromagnesian silicate minerals and FeTi oxides. To better understand the behavior of Fe isotopes during peralkaline magma differentiation, we carried out high-precision Fe isotope analyses on peralkaline and associated metaluminous high-silica granite rocks and Fe-bearing minerals separated from the rocks in Zhoushan archipelago, southeast China. The Fe-bearing mineral show a large dispersion in Fe isotope compositions, with δ56Fe ranging from 0.03 ‰ to 0.70 ‰, following the sequence of K-feldspar ≥ magnetite > aegirine > arfvedsonite > ilmenite. The δ56Fe differences between the mineral pairs are relatively consistent. Based on the magmatic temperatures defined by quartz-zircon oxygen isotopic geothermometer, the temperature-dependent equilibrium Fe isotope fractionation functions between following mineral pairs are obtained: Δ56Feaegirine-arfvedsonite = 0.20 (± 0.07) × 106/T2, Δ56Femagnetite-arfvedsonite = 0.38 (± 0.06) × 106/T2, and Δ56Femagnetite-aegirine = 0.16 (± 0.04) × 106/T2. The bulk peralkaline granites have variable but generally high δ56Fe values ranging from 0.28 ± 0.03 ‰ to 0.62 ± 0.04 ‰, with a mean of 0.42 ± 0.09 ‰ (1SD), which are higher than those of the associated metaluminous granitic samples (δ56Fe = 0.22 ± 0.05 ‰, 1SD). Furthermore, δ56Fe values of the peralkaline granites are negatively correlated with Sm/Yb and MnO, consistent with removal of isotopically light Fe-enriched arfvedsonite, implying that peralkaline granites experienced extensive magma differentiation regardless whether they were derived from differentiation of mantle-derived basaltic melts or partial melting of curst sources. Our results highlight a large Fe isotope fractionation between alkali ferromagnesian silicates and oxides, confirming Fe isotopes as a potential tool in tracking the differentiation processes of peralkaline magmas.

Influencing factors of hydrogen isotopic fractionation of light hydrocarbons during evaporation and implications

The isotopic fractionation of organic compounds during evaporation is one of the most critical issues in the field of stable isotopes. The hydrogen (H) isotopic compositions of light hydrocarbons (LHs) in oil have gained increasing interest in the research of oil genesis in recent years. However, compared to carbon (C) isotopes, our understanding of H isotopic fractionation patterns and influences for various types of LHs during evaporation is limited. In this study, we performed evaporation experiments at a constant temperature on LHs in three systems: single compound, alkane mixture, and light oil. We assessed the contents and H isotopic compositions of individual LHs in the residual liquid phase. The degree of H isotopic fractionation and influencing factors are studied combined with C isotopes. The H isotopic fractionation of LHs exhibits “inverse isotope fractionation” characteristics (a depletion in D in the residual LHs) with progressive evaporation, which is opposite to the C isotopic fractionation. The degree of isotopic fractionation is influenced by the evaporation system, the compounds’ molecular weight, and their structure. (1) The isotopic fractionation degree of H and C decreases in the following order: light oil > alkane mixture > single compound system. This difference may be related to the unsaturation level of the evaporative system and the evaporation matrix. (2) For LHs with the similar structure in the same evaporation system, the degree of H isotopic fractionation increases with increasing molecular weight due to the buffering effect of the sample pool, while the magnitude of C isotopic fractionation decreases. (3) For LHs with the same C number, methylcyclohexane (MCH) has a lower evaporation rate and less isotopic fractionation than the other C7 compounds like 3-methylhexane (3-MH), n-heptane (nC7), and toluene (Tol).The distinctive fractionation characteristics of H isotopes make them very useful in geological applications. Combining H and C isotopic compositions of the same compound with the commonly used molecular ratios of LHs (e.g., nC7/MCH, Tol/nC7) enables full differentiation of three critical processes controlling oil formation: evaporation, thermal maturation, and biodegradation. Furthermore, the differences in H isotopic compositions between C7 LHs (3-MH, nC7, and Tol) may be changed by evaporation, but the variation range is much smaller than that caused by source differences. Therefore, combining H and C isotopes may have great potential for oil source characterizations.

Deciphering Paleocene‐Eocene Thermal Maximum Climatic Dynamics: Insights From Oxygen and Hydrogen Isotopes in Clay Minerals of Paleosols From the Southern Pyrenees

AbstractThis study focuses on the Paleocene‐Eocene Thermal Maximum (PETM), a hyperthermal event characterized by a rapid increase in global temperature (5–8°C) over 20 ka, in the Southern Pyrenean Foreland Basin. Although there is evidence of increased flood discharge and erosion in the Southern Pyrenees, how paleoclimatic conditions and weathering evolved remains to be assessed. This study focuses on the catchment scale climatological changes recorded in the clay minerals of floodplain paleosols, giving insights into how rainfall affected the weathering regime during and after the hyperthermal event. The oxygen (δ18O) and hydrogen (δD) isotope compositions were analyzed in two clay fractions in paleosols of the Esplugafreda continental section. The clay minerals comprise a dominant smectite‐rich assemblage, which indicates a predominantly seasonal, semi‐arid climate throughout the section. Two positive excursions in the δ18O record during the Pre‐Onset Excursion (POE) and the Syn‐PETM support an increase in air near‐surface temperature. Using the δD and δ18O smectite fractionation factors, we estimate a Mean Annual Air Temperature (MAAT) of 24.2 ± 1.0°C for the POE and 27.0 ± 0.8°C for the Syn‐PETM. The δD values show a relatively stable composition during the climatic disturbance, which suggests that this mid‐latitude catchment was overall characterized by low yearly rainfall, with a peak in extreme events during the body of the PETM and a trend toward aridification during the recovery phase of the PETM, supported by the paleosol morphotype. These climatic conditions suggest a kinetically controlled weathering regime, where physical transport of the sediments played a primary role as a denudation mechanism.

Boron diffusion, related isotope fractionation and the structural role of B in pegmatite forming melts

In this study, we experimentally investigate the diffusion of B in flux-rich (1.7 % Li2O, 2.5 % B2O3, 2.7 % P2O5 and 3.5 % F) pegmatite forming melts in order to assess the transport mechanisms of B in rare-element pegmatite deposits. Glasses were synthesized with either different B isotope compositions or with different B concentrations (up to 2.45 wt% B2O3). In order to explore the effect of water on transport properties, nominally dry and hydrous glasses (3.1–3.9 wt% H2O) were investigated. The produced glasses were combined to diffusion couples to study self-diffusion and chemical diffusion of B in the same chemical system. Experiments were conducted using an internally heated pressure vessel and a rapid-heat and rapid-quench cold-seal pressure vessel at 100 MPa Ar pressure in the temperature range of 850–1250 °C for 1.6–97.3 h. In chemical diffusion experiments, the flow of B is compensated by a combined opposing flow of all other cations and F, without changing their element ratios. Thus, effective binary diffusion coefficients are obtained. Similar activation energies were determined for B self-diffusion and chemical diffusion under nominally dry conditions (196 ± 6 kJ/mol and 200 ± 17kJ/mol, respectively). Many hydrous experiments show a tilted to strongly deformed interface after the run, which was probably formed by advective flow of the low-viscosity melts during heating under pressure. Based on the successful experiments, an activation energy of 138 ± 8 kJ/mol was estimated for chemical diffusion of B in hydrous melts. We show that B diffusivity correlates with the Eyring diffusivity and, therefore, with the melt viscosity. The stable isotopes of B fractionate kinetically along the diffusion profiles due to the faster diffusivity of 10B over 11B. This isotope fractionation can be quantified with an empirical isotope fractionation factor (β) of 0.032 ± 0.002. This effect is small, but significant and was previously not observed in experimental studies. While it is insensitive to the water contents used in our study, it seems to be strongly dependent on the experimental boundary conditions, such as the ratios of B between the diffusion couple halves and the B enrichment in the melt. Solid-state NMR experiments reveal that the majority of B is in trigonal coordination in our melts, which effectively weakens the melt structure. This further suggests that coordination differences are unlikely to be the driving force for B isotope fractionation between melt and fluid during late-stage fluid exsolution in pegmatitic systems.

Vieta–Lucas polynomials-based collocation simulation to analyze the solvent fraction factor in active and passive control flow induced by torsional motion

The present research explores the Boger fluid flow past a stretching cylinder with torsional motion in the presence of the magnetic field. It is assumed that the cylinder rotates continuously around its axis and that the starting point's position along the axis correlates with the cylinder wall's expansion rate. Additionally, the consequence of active and passive control of nanoparticles, activation energy, thermophoresis, and Brownian motion effects are considered. Similarity variables transform the governing partial differential equations into non-dimensional ordinary differential equations (ODEs). Furthermore, the Vieta–Lucas polynomials-based collocation method (V-LPBCM) is employed to solve the resulting ODEs. The V-LPBCM outcomes of Nusselt and Sherwood numbers are compared with Runge–Kutta Fehlberg's fourth-fifth-order scheme for validation purposes. The impact of various dimensionless parameters on the different profiles is depicted in the graphical representation. The increase in values of the magnetic parameter, the ratio of relaxation time, and the Reynolds number decline the velocity profile. The velocity profile increases as the values of the solvent fraction parameter rise. The thermal profile increases as the heat source/sink, and thermophoretic parameters rise. The increase in values of activation energy parameter increases the thermal profile.

Iron isotopic fractionation by magmatic-hydrothermal fluid-melt interaction in the Himalayan leucogranites

Iron (Fe) isotopes have been used to trace magmatic evolution (e.g., mineral fractional crystallization, partial melting degree, and fluid exsolution), but the behavior of Fe isotopes in magmatic-hydrothermal processes remains poorly constrained. Here we report Fe isotope compositions of the Kampa leucogranites from the Himalayan orogenic belt to understand the fluid-melt interaction and rare metal enrichment in highly-evolved granites. The Nb/Ta ratio divides samples into two groups: group 1 with high Nb/Ta ratios while group 2 with low Nb/Ta ratios. The δ56Fe of group 1 leucogranites range from 0.14‰ to 0.23‰, isotopically heavier than the average upper continental crust value, indicative of the residues from fractional crystallization. On the contrary, the group 2 leucogranites exhibit large range of δ56Fe from -0.21‰ to 0.21‰. The correlations between fluid-mobile/fluid-immobile element ratios, and iron isotope, and tetrad effect were attributed to the effect of magmatic-hydrothermal fluid-melt interaction during magma evolution. A fluid-melt interaction model with an initial δ56Fe of -0.4‰ for the fluid and a fractionation factor Δ56Fefluid-melt of -0.35‰ successfully explains the observed Fe isotope data. It is likely that these magmatic-hydrothermal fluids are derived from exsolution from the underlying magma reservoirs in the middle crust, which can modify the Fe isotope compositions and bring abundant rare metal elements into the leucogranites. Therefore, Fe isotope data can reveal the properties of magmatic-hydrothermal fluids and serve as an indicator for ore-forming processes.

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.

Stable carbon isotopic composition of particulate organic matter in the Cosmonaut and Cooperation Seas in summer

This study examined particulate organic carbon (POC) and its isotopic composition (δ13CPOC) in the Cosmonaut and Cooperation Seas in the Antarctica during the summer of 2019. Our results show that the spatial variation of POC concentration in summer surface water generally mirrors that of δ13CPOC, with higher POC and δ13CPOC values in the Cosmonaut Sea compared to the Cooperation Sea. The δ13CPOC values in both seas were positively correlated with the proportion of Chl-a in smaller particles (< 20 μm). However, the relationship with the proportion of biogenic POC in smaller particles (< 20 μm) differed between the two seas. This discrepancy is attributed to differences in the dominant phytoplankton species. In the Cosmonaut Sea, smaller phytoplankton (nano- and pico-phytoplankton) were dominated by Phaeocystis antarctica, whereas in the Cooperation Sea, they were dominated by pennate diatoms. The δ13CPOC in deep waters of both seas increased with depth, reflecting the effects of organic remineralization. The carbon isotope fractionation factors during remineralization, estimated using Rayleigh model, were 1.5 ± 0.2‰ and 1.6 ± 0.2‰ in the Cosmonaut Sea and the Cooperation Sea, respectively. These small isotope effects indicate that the isotope signals of organic matter exported from the upper layer are well preserved in the deep ocean. Additionally, anomalously high δ13CPOC values were observed in the bottom water outside the Cape Darnley polynya in the Cooperation Sea, reflecting the input of ice algae-derived organic matter from the shelf during AABW formation. A simple isotopic mass balance estimate suggests that 6–19% of the POC in the AABW of the Cooperation Sea is contributed by ice algae. Our study highlights the complexity of factors affecting δ13CPOC in the Southern Ocean, emphasizing the importance of phytoplankton community composition.

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.