Iron Isotopic Fractionation and Origin of Chromitites in the Paleo-Moho Transition Zone of the Kop Ophiolite, NE Turkey

The Kop ophiolite in NE Turkey is a fragment of Neo-Tethyan forearc.It can be mainly divided into a paleo-Moho transition zone(MTZ)in the North and a harzburgitic mantle sequence in the South.Dunites are predominant in the MTZ of the Kop ophiolite,and they are locally interlayered with chromitites and enclose minor bodies of harzburgites near the petrological Moho boundary.Large Fe isotopic variations were observed for magnesiochromite(-0.14‰to 0.06‰)and olivine(-0.12‰to 0.14‰)from the MTZ chromitites,dunites and harzburgites.In individual dunite samples,magnesiochromite usually has lighter Fe isotopic compositions than olivine,which was probably caused by subsolidus Mg-Fe exchange between the two mineral phases.Both magnesiochromite and olivine display an increasing trend ofδ56Fe along a profile from chromitite todunite.This trend reflects continuous fractional crystallization in a magma chamber,which resulted in heavier Fe isotopes concentrated in the evolved magmas.In each cumulative cycle of chromitite and dunite,dunite was formed from relatively evolved melts after massive precipitation of magnesiochromite.Mixing of more primitive and evolved melts in the magma chamber was a potential mechanism for triggering the crystallization of magnesiochromite,generating chromitite layers in the cumulate pile.Before mixing happened,the primitive melts had reacted with mantle harzburgites during their ascendance;whereas the evolved melts may lie on the olivine-chromite cotectic near the liquidus field of pyroxene.Variable degrees of magma mixing and differentiation are expected to generate melts with differentδ56Fe values,accounting for the Fe isotopic variations of the Kop MTZ.

Nitrogen isotopic fractionation of particulate organic matter production and remineralization in the Prydz Bay and its adjacent areas

During the 29 th Chinese National Antarctic Research Expedition,spatial variations in nitrogen isotopic composition of particulate nitrogen(δ15NPN)and their controlling factors were examined in detail with regard to nitrate drawdown by phytoplankton and particulate nitrogen(PN)remineralization in the Prydz Bay and its adjacent areas.To better constrain the nitrogen transformations,the physical and chemical parameters,including temperature,salinity,nutrients,PN andδ15NPN in seawater column were measured from surface to bottom.In addition,the nitrogen isotopic fractionation factor of nitrate assimilation by phytoplankton in the mixed layer,and the nitrogen isotopic fractionation factor of PN remineralization below the mixed layer were estimated using Rayleigh model and Steady State model,respectively.Our results showed that suspended particles had its lowestδ15NPN in the surface layer,which was due to the preferential assimilation of 14 N in nitrate by phytoplankton.Theδ15NPN in the mixed layer of the Prydz Bay and its adjacent areas decreased from the inner shelf to the outer basin,ascribing to the effect of isotope fractionation during phytoplankton assimilation.In mixed layer,the spatial distribution ofδ15NPN associated with particulate organic matter(POM)production can be well interpreted according to Rayleigh model and Steady State model.The nitrogen isotope fractionation factor during phytoplankton assimilating nitrate was estimated as 10.0‰by Steady State model,which was more reasonable than that calculated by Rayleigh model.These results validate the previous reports of fractionation factor during nitrate assimilation by phytoplankton.Increasingδ15NPN with depth below the euphotic zone correlated with the decreasing PN contents,and it was attributed to preferential remineralization of 14 N in PN by bacteria.In subsurface and deep layer,theδ15NPN distributions also conformed to Rayleigh model and Steady State model during PN remineralization,with a fractionation factor of about 3.6‰and 3.2‰,respectively.It is the first time to estimate the fractionation factor during POM production and remineralization in the Prydz Bay and its adjacent areas.Such fractionation may provide a useful tool for the follow-up study of the nitrogen dynamics in the Southern Ocean.

Experimental study of relationship between average isotopic fractionation factor and evaporation rate

Isotopic fractionation is the basis of tracing the water cycle using hydrogen and oxygen isotopes. Isotopic fractionation factors in water evaporating from free water bodies are mainly affected by temperature and relative humidity, and vary significantly with these atmospheric factors over the course of a day. The evaporation rate （E） can reveal the effects of atmospheric factors. Therefore, there should be a certain functional relationship between isotopic fractionation factors and E. An average isotopic fractionation factor （ t~＊ ） was defined to describe isotopic differences between vapor and liquid phases in evaporation with time intervals of days. The relationship between or＊ and E based on the isotopic mass balance was investigated through an evaporation pan experiment with no inflow. The experimental results showed that the isotopic compositions of residual water were more enriched with time; tr＊ was affected by air temperature, relative humidity, and other atmospheric factors, and had a strong functional relation with E. The values of 0~＊ can be easily calculated with the known values of E, the initial volume of water in the pan, and isotopic compositions of residual water.

First-principle study of Ba isotopic fractionation during ion exchange processes

The potential utilization and development of the Ba isotope tool depend on an accurateδ^(137/134)Ba determination of the samples.During the chemical purification,whether the adsorption process on the surface of the ionexchange resin could lead to the Ba isotopic fractionation and the degree of fractionation directly influence the accurateδ^(137/134)Ba determination.In the present work,first-principles calculations based on the density functional theory were used to quantify the Ba isotopic equilibrium fractionation factor between the aqueous solution and the resin in the acid leaching process.By constructing and optimizing the geometric configurations of Ba-containing species,Ba(H_(2)O)_(n)^(2+),Ba(H_(2)O)_(n)Cl_(2),Ba(H_(2)O)_(n)(NO_(3))2,and the adsorbed Ba^(2+)on the surface of the resin,extracting the harmonic vibrational frequencies,we finally at 298 K obtained the fractionations,Δ^(137/134)Ba_(soln-ads)=0.07‰,Δ^(137/134)Ba_(Ba(H_(2)O)_(n)Cl_(2)-ads)=0.05‰,andΔ^(137/134)-Ba^(Ba(H_(2)O)_(n)(NO_(3))2-ads)=0.02‰.Overall,there were almost no Ba isotope fractionations during leaching.Although the Ba isotope fractionation can be magnified by the Rayleigh fractionation process in purification,the difference inδ137/134Ba between the initial and final stages did not exceed0.060‰(or 0.045‰)when leaching the standard sample with HCl or HNO_(3),which is equal to or less than the accuracy of Ba isotopic analysis.At a common yield of89.75%,Ba isotopic fractionation induced by incomplete recovery was 0.015‰for HCl(or 0.011‰for HNO_(3)).Finally,if the influence of an incomplete recovery on theδ137/134Ba determination needs to be ignored,the recovery is suggested to be not less than 67%for HCl(or 46%for HNO_(3)).

Soil organic carbon dynamics study bias deduced from isotopic fractionation in corn plant

Carbon stable isotope techniques were extensively employed to trace the dynamics of soil organic carbon(SOC)across a land-use change involving a shift to vegetation with different photosynthetic pathways.Based on the isotopic mass balance equation,relative contributions of new versus old SOC,and SOC turnover rate in corn fields were evaluated world-wide.However,most previous research had not analyzed corn debris left in the field,instead using an average corn plant δ^(13)C value or a measured value to calculate the proportion of corn-derived SOC,either of which could bias results.This paper carried out a detailed analysis of isotopic fractionation in corn plants and deduced the maximum possible bias of SOC dynamics study.The results show approximately 3‰ isotopic fractionation from top to bottom of the corn leaf.The ^(13)C enrichment sequence in corn plant was tassel﹥stalk or cob﹥root﹥leaves.Individual parts accounting for the total dry mass of corn returned distinct values.Consequently,the average δ^(13)C value of corn does not represent the actual isotopic composition of corn debris.Furthermore,we deduced that the greater the fractionation in corn plant,the greater the possible bias.To alleviate bias of SOC dynamics study,we suggest two measures:analyze isotopic compositions and proportions of each part of the corn and determine which parts of the corn plant are left in the field and incorporated into SOC.

UV Photolysis of N2O Isotopomers： Isotopic Fractionations and Product Rotational Quantum State Distributions

The time-dependent quantum wave packet method is used to study the dynamics of the pho- todissociation processes for the isotopomers 14N14N16O, 14N15N16O, 15N14N16O, 15N15N16O, 14N14N17O, and 14N14N18O. In general, the computed isotopic fractionation factors derived from the absorption cross sections of five heavy isotopomers are in good agreement with the experimental results. Relative to the 14NI4N16O isotopomer, the N2 rotational state distributions for the isotopically nitrogen substituted N2O are found to be entirely shifted to higher rotational states. Similar to its isotopic fractionation factors, the N2 rotational state distributions for the asymmetric isotopomers 14N15N16O and 15N14N16O are found to be observably different.

Simulations of an isotopic fractionation by freezing in an open system

This paper presents a model of isotopic fractionation by freezing under near equilibrium conditions in an open system and uses the model to predict the fractionation curve and slope gradient of δ 18 O versus δD. The simulation results show that 1) the fractionation curve and slope gradient are determined by the ratio of freezing rate to input rate, 2) the isotopic value in the initial stage of freezing is determined by the isotopic value of initial water; 3) in the latter half of freezing in an open system, the isotopic value converges to a certain value determined by that of input water. These results suggest that the shape of the fractionation curve is the method to distinguish whether freezing occurred in a closed or open system. This analysis is applied to an isotopic curve observed in basal ice of Hamna Glacier, Sya drainage, East Antarctica. The isotopic curve indicates formation by regelation in an open system with a ratio of freezing/input rates of about 10/4.

Research progress on isotopic fractionation in the process of shale gas/coalbed methane migration

The research progress of isotopic fractionation in the process of shale gas/coalbed methane migration has been reviewed from three aspects: characteristics and influencing factors, mechanism and quantitative characterization model, and geological application. It is found that the isotopic fractionation during the complete production of shale gas/coalbed methane shows a four-stage characteristic of “stable-lighter-heavier-lighter again”, which is related to the complex gas migration modes in the pores of shale/coal. The gas migration mechanisms in shale/coal include seepage, diffusion, and adsorption/desorption. Among them, seepage driven by pressure difference does not induce isotopic fractionation, while diffusion and adsorption/desorption lead to significant isotope fractionation. The existing characterization models of isotopic fractionation include diffusion fractionation model, diffusion-adsorption/desorption coupled model, and multi-scale and multi-mechanism coupled model. Results of model calculations show that the isotopic fractionation during natural gas migration is mainly controlled by pore structure, adsorption capacity, and initial/boundary conditions of the reservoir rock. So far, the isotope fractionation model has been successfully used to evaluate critical parameters, such as gas-in-place content and ratio of adsorbed/free gas in shale/coal etc. Furthermore, it has shown promising application potential in production status identification and decline trend prediction of gas well. Future research should focus on:(1) the co-evolution of carbon and hydrogen isotopes of different components during natural gas migration,(2) the characterization of isotopic fractionation during the whole process of gas generation-expulsion-migration-accumulation-dispersion, and(3) quantitative characterization of isotopic fractionation during natural gas migration in complex pore-fracture systems and its application.

Carbon isotopic fractionation during vaporization of low molecular weight hydrocarbons(C6–C12)

Three series of laboratory vaporization experiments were conducted to investigate the carbon isotope fractionation of low molecular weight hydrocarbons（LMWHs）during their progressive vaporization.In addition to the analysis of a synthetic oil mixture,individual compounds were also studied either as pure single phases or mixed with soil.This allowed influences of mixing effects and diffusion though soil on the fractionation to be elucidated.The LMWHs volatilized in two broad behavior patterns that depended on their molecular weight and boiling point.Vaporization significantly enriched the ^13C present in the remaining components of the C6–C9 fraction,indicating that the vaporization is mainly kinetically controlled;the observed variations could be described with a Rayleigh fractionation model.In contrast,the heavier compounds（n-C10–n-C12）showed less mass loss and almost no significant isotopic fractionation during vaporization,indicating that the isotope characteristics remained sufficiently constant for these hydrocarbons to be used to identify the source of an oil sample,e.g.,the specific oil field or the origin of a spill.Furthermore,comparative studies suggested that matrix effects should be considered when the carbon isotope ratios of hydrocarbons are applied in the field.

Rebuilding the theory of isotope fractionation for evaporation of silicate melts under vacuum condition

Isotope eff ects are pivotal in understanding silicate melt evaporation and planetary accretion processes.Based on the Hertz-Knudsen equation,the current theory often fails to predict observed isotope fractionations of laboratory experiments due to its oversimplified assumptions.Here,we point out that the Hertz-Knudsen-equation-based theory is incomplete for silicate melt evaporation cases and can only be used for situations where the vaporized species is identical to the one in the melt.We propose a new model designed for silicate melt evaporation under vacuum.Our model considers multiple steps including mass transfer,chemical reaction,and nucleation.Our derivations reveal a kinetic isotopic fractionation factor(KIFF orα)αour model=[m(^(1)species)/m(^(2)species)]^(0.5),where m(species)is the mass of the reactant of reaction/nucleation-limiting step or species of diffusion-limiting step and superscript 1 and 2 represent light and heavy isotopes,respectively.This model can eff ectively reproduce most reported KIFFs of laboratory experiments for various elements,i.e.,Mg,Si,K,Rb,Fe,Ca,and Ti.And,the KIFF-mixing model referring that an overall rate of evaporation can be determined by two steps jointly can account for the eff ects of low P_(H2)pressure,composition,and temperature.In addition,we find that chemical reactions,diffusion,and nucleation can control the overall rate of evaporation of silicate melts by using the fitting slope in ln(−ln f)versus ln(t).Notably,our model allows for the theoretical calculations of parameters like activation energy(E_(a)),providing a novel approach to studying compositional and environmental eff ects on evaporation processes,and shedding light on the formation and evolution of the proto-solar and Earth-Moon systems.

A preliminary experimental study of the boron concentration in vapor and the isotopic fractionation of boron between seawater and vapor during evaporation of seawater

A laboratory experiment was undertaken to investigate the behaviour of boron at the seawater-air interface under air flow conditions. Dried air at 25 and 35℃ was passed over or bubbled through seawater at the same temperature. A combination of ice-chilled condensers and KOH impregnated cellulose fibre filters was used to collect boron from the reacted air. When air stripped of boron was passed over the seawater, boron was found in the reacted air, and its concentration was higher in the higher temperature test. In the tests where air was bubbled through seawater the concentration of boron in the reacted air was directly proportional to the air flow rate. In this situation the boron in the reacted air was mainly introduced as a spray of microdroplets. Isotopic analysis of the collected boron in the non-bubbled tests yields fractionation factors which demonstrate that the lighter isotope, 10B, is enriched in the reacted air. The size of the fractionation changes with temperature, ruling out a purely kinetic effect.

Boron Isotopic Fractionation and Trace Element Incorporation in Various Species of Modern Corals in Sanya Bay, South China Sea

The boron isotope paleo-pH proxy has been extensively studied due to its potential for understanding past climate change, and further calibrations were considered for accurate applications of the proxy because of significant variability related to biocarbonate microstructure. In this work, we studied the boron isotopic fractionation between modern marine corals and their coexisting seawater collected along shallow area in Sanya Bay, South China Sea. The apparent partition coefficient of boron（KD） ranged from 0.83×10-3 to 1.69×10-3, which are in good agreement with previous studies. As the analyzed coral skeleton（~5 g） spanned the growth time period of 1–2 years, we discussed the boron isotopic fractionation between pristine corals and modern seawater using the annual mean seawater pH of 8.12 in this sea area. Without taking the vital effect into account,（11B/10B）coral values of all living corals spread over the curves of（11B/10B）borate vs.（11B/10B）sw with the α4-3 values ranging from 0.974 to 0.982. After calibrating the biological effect on the calcifying fluid pH, the field-based calcification on calcifying fluid pH（i.e., Δ（pHbiol-pHsw）） for coral species of Acropora, Pavona, Pocillopora, Faviidae, and others including Proites are 0.42, 0.33, 0.36, 0.19, respectively, and it is necessary to be validated by coral culturing experiment in the future. Correlations in B/Ca vs. Sr/Ca and B/Ca vs. pHbiol approve temperature and calcifying fluid pH influence on skeletal B/Ca. Fundamental understanding of the thermodynamic basis of the boron isotopes in marine carbonates and seawater will strengthen the confidence in the use of paleo-pH proxy as a powerful tool to monitor atmospheric CO2 variations in the past.

Nitrogen Isotopic Fractionation Related to Nitrification Capacity in Agricultural Soils

A laboratory-based aerobic incubation was conducted to investigate nitrogen （N） isotopic fractionation related to nitrification in five agricultural soils after application of ammonium sulfate （（NH4）2804）. The soil samples were collected from a subtropical barren land soil derived from granite （RGB）, three subtropical upland soils derived from granite （RQU）, Quaternary red earth （RGU）, Quaternary Xiashu loess （YQU） and a temperate upland soil generated from alluvial deposit （FAU）. The five soils varied in nitrification potential, being in the order of FAU 〉 YQU 〉 RGU 〉 RQU 〉 RGB. Significant N isotopic fractionation accompanied nitrification of NH4＋. 615N values of NH4＋ increased with enhanced nitrification over time in the four upland soils with NH4＋ addition, while those of NO3 decreased consistently to the minimum and thereafter increased. 515N values of NH4＋ showed a significantly negative linear relationship with NH4＋-N concentration, but a positive linear relationship with NO3-N concentration. The apparent isotopic fractionation factor calculated based on the loss of NH4＋ was 1.036 for RQU, 1.022 for RGU, 1.016 for YQU, and 1.020 for FAU, respectively. Zero- and first-order reaction kinetics seemed to have their limitations in describing the nitrification process affected by NH4＋ input in the studied soils. In contrast, N kinetic isotope fractionation was closely related to the nitrifying activity, and might serve as an alternative tool for estimating the nitrification capacity of agricultural soils.

Altitudinal effect of soil n-alkane δD values on the eastern Tibetan Plateau and their increasing isotopic fractionation with altitude

Stable isotope paleoaltimetry has provided unprecedented insights into the topographic histories of many of the world's highest mountain ranges. However, on the Tibetan Plateau(TP), stable isotopes from paleosols generally yield much higher paleoaltitudes than those based on fossils. It is therefore essential when attempting to interpret accurately this region's paleoaltitudes that the empirical calibrations of local stable isotopes and the relations between them are established. Additionally,it is vital that careful estimations be made when estimate how different isotopes sourced from different areas may have been influenced by different controls. We present here 29 hydrogen isotopic values for leaf wax-derived n-alkanes(i.e., δD_(wax) values,and abundance-weighted average δD values of C_(29) and C_(31)) in surface soils, as well as the δD values of soil water(δD_(sw)) samples(totaling 22) from Mount Longmen(LM), on the eastern TP(altitude ~0.8–4.0 km above sea level(asl), a region climatically affected by the East Asian Monsoon(EAM). We compared our results with published data from Mount Gongga(GG). In addition,47 river water samples, 55 spring water samples, and the daily and monthly summer precipitation records(from May to October,2015) from two precipitation observation stations were collected along the GG transect for δD analysis. LM soil δD_(wax) values showed regional differences and responded strongly to altitude, varying from.160‰ to.219‰, with an altitudinal lapse rate(ALR) of.18‰ km^(-1)(R^2=0.83; p<0.0001; n=29). These δD_(wax) values appeared more enriched than those from the GG transect by ~40‰. We found that both the climate and moisture sources led to the differences observed in soil δD_(wax) values between the LM and GG transects. We found that, as a general rule, ε_(wax/rw), ε_(wax/p) and εwax/sw values(i.e., the isotopic fractionation of δD_(wax) corresponding to δD_(rw), δD_p and δD_(sw)) increased with increasing altitude along both the LM and GG transects(up to 34‰ and 50‰, respectively). Basing its research on a comparative study of δD_(wax), δD_p, δD_(rw)(δD_(springw)) and δD_(sw), this paper discusses the effects of moisture recycling, glacier-fed meltwater, relative humidity(RH), evapotranspiration(ET), vegetation cover, latitude,topography and/or other factors on ε_(wax/p) values. Clearly, if ε_(wax-p) values at higher altitudes are calculated using smaller ε_(wax-p) values from lower altitudes, the calculated paleowaterδD_p values are going to be more depleted than the actual δD values, and any paleoaltitude would therefore be overestimated.

How to estimate isotope fractionations of a Rayleigh-like but diffusion-limited disequilibrium process?

The Rayleigh distillation isotope fractionation(RDIF) model is one of the most popular methods used in isotope geochemistry. Numerous isotope signals observed in geologic processes have been interpreted with this model. The RDIF model provides a simple mathematic solution for the reservoir-limited equilibrium isotope fractionation effect. Due to the reservoir effect, tremendously large isotope fractionations will always be produced if the reservoir is close to being depleted. However, in real situations, many prerequisites assumed in the RDIF model are often difficult to meet. For instance, it requires the relocated materials, which are removed step by step from one reservoir to another with different isotope compositions(i.e., with isotope fractionation), to be isotopically equilibrated with materials in the first reservoir simultaneously. This ‘‘quick equilibrium requirement’’ is indeed hard to meet if the first reservoir is sufficiently large or the removal step is fast. The whole first reservoir will often fail to re-attain equilibrium in time before the next removal starts.This problem led the RDIF model to fail to interpret isotope signals of many real situations. Here a diffusion-coupled and Rayleigh-like(i.e., reservoir-effect included) separation process is chosen to investigate this problem. We find that the final isotope fractionations are controlled by both the diffusion process and the reservoir effects via the disequilibrium separation process. Due to its complexity, we choose to use a numerical simulation method to solve this problem by developing specific computing codes for the working model.According to our simulation results, the classical RDIF model only governs isotope fractionations correctly at the final stages of separation when the reservoir scale(or thickness of the system) is reduced to the order of magnitude of the quotient of the diffusivity and the separation rate. The RDIF model fails in other situations and the isotope fractionations will be diffusion-limited when the reservoir is relatively large, or the separation rate is fast. We find that the effect of internal isotope distribution inhomogeneity caused by diffusion on the Rayleigh-like separation process is significant and cannot be ignored. This method can be applied to study numerous geologic and planetary processes involving diffusion-limited disequilibrium separation processes including partial melting,evaporation, mineral precipitation, core segregation, etc.Importantly, we find that far more information can be extracted through analyzing isotopic signals of such ‘‘disequilibrium’’processes than those of fully equilibrated ones, e.g., reservoir size and the separation rate. Such information may provide a key to correctly interpreting many isotope signals observed from geochemical and cosmochemical processes.

Water Role and Its Influence on Hydrogen Isotopic Composition of Natural Gas during Gas Generation

In order to discuss the role and influence of water during the generation of natural gas,the participation mechanism of water during the evolution of organic matter and its influences were summarized.In addition,we carried out an anhydrous cracking experiment of oil extracted from the Feixianguan Formation source rock in a closed system,which led to the establishment of the kinetic models for describing carbon and hydrogen isotopic fractionation during gas generation from organic matter.The models were calibrated and then applied to the northeastern Sichuan Basin.By combining a series of gas generation experiments from octadecane pyrolysis without water or with distilled water in varying mass proportions,several results were proved:(1) the hydrogen isotopic composition of natural gas becomes lighter with the participation of formation water;(2) we can quantitatively study the hydrogen isotopic fractionation with the kinetic model for describing carbon isotopic fractionation; (3) more abundant and reliable geological information can be obtained through the combined application of carbon and hydrogen isotopic indices.

Isotopic Geochemistry of Cadmium:A Review

Cadmium（Cd） is a scarce, but not an extremely rare element in the Earth＇s crust（crustal average： 0.2 ppm Cd）. Geochemically, Cd exhibits thiophile, lithophile, and volatile behavior in different geologic processes. Biologically, it is a nutrient-like element that is closely related to P and Zn and is toxic element to organisms. Presently, Cd isotopes have been successfully utilized to trace Cd sources and nutrient cycling in marine systems in addition to unearthing other geochemical processes. Using published studies and our recent work, this survey summarizes the chemical preparation and mass spectrometry of Cd isotopes. It also reviews Cd isotopic compositions and fractionation mechanisms in nature as well as experiments.

A mathematical diffusion model of carbon isotopic reversals inside ultra-tight Longmaxi shale matrixes

Developing mathematical models for high Knudsen number(Kn)flow for isotopic gas fractionation in tight sedimentary rocks is still challenging.In this study,carbon isotopic reversals(δ^(13)C_(1)>δ^(13)C_(2))were found for four Longmaxi shale samples based on gas degassing experiments.Gas in shale with higher gas content exhibits larger reversal.Then,a mathematical model was developed to simulate the carbon isotopic reversals of methane and ethane.This model is based on these hypotheses:(i)diffusion flow is dominating during gas transport process;(ii)diffusion coefficients are nonlinear depending on concentration gradient.Our model not only shows a good agreement with isotopic reversals,but also well predicts gas production rates by selecting appropriate exponents m and m^(*) of gas pressure gradient,where m is for ^(12)C and m^(*)is for ^(13)C.Moreover,the(m−m^(*))value has a positive correlation with fractionation level.(m1−m1^(*))of methane are much higher than that of ethane.Finally,the predicted carbon isotopic reversal magnitude(δ^(13)C_(1)−δ^(13)C_(2))exhibits a positive relationship with total gas content since gas in shale with higher gas content experiences a more extensive high Kn number diffusion flow.As a result,our model demonstrates an impressive agreement with the experimental carbon isotopic reversal data.

Processes involving soil CO_(2)dynamic in a sector of Chaco-Pampean plain,Argentina:An isotope geochemical approach

The magnitude and spatial variability of CO_(2)surface emissions and processes involving CO_(2)released to the atmosphere from the soils are relevant issues in the context of climate change.This work evaluated CO_(2)fluxes and^(13)C/^(12)C ratio of vegetation,organic matter,and soil gases from no disturbed soils of Chaco Pampean Plain(Argentina)with different soil properties and environmental conditions(PL and PA units).Soil organic decomposition from individual layers was accompanied byδ^(13)C of total organic carbon(δ^(13)C-TOC)values more enriched to depth.δ^(13)C-TOC values in the upper soil profile~ca.0–15 cm were like the plant community of this area(~−33 to−29‰)whileδ^(13)CTOC varied stronger bellow horizon A,till~−24‰.Bothδ^(13)C-TOC and soilδ^(13)C-CO_(2)were similar(~−24 to 26‰)at deeper horizons(~50–60 cm).Toward the superficial layers,δ^(13)C-TOC andδ^(13)C-CO_(2)showed more differences(till~4‰),due influence of the diffusion process.Horizon A layer(~0–20 cm)from both PL and PA units contained the most enrichedδ^(13)C-CO_(2)values(~−15–17‰)because atmospheric CO_(2)permeated the soil air.A simple two-component mixing model between sources(atmosphericδ^(13)C-CO_(2)and soil CO_(2))confirmed that process.Isotopically,CO_(2)fluxes reflected the biodegradation of C3 plants(source),diffusive transport,and CO_(2)exchange(atmosphere/soil).Soil moisture content appeared as a determining factor in the diffusion process and the magnitude of CO_(2)surface emissions(12–60 g·m^(−2)·d^(−1)).That condition was confirmed by CO_(2)diffusion coefficients estimated by air-filled porosity parameters and soil radon gradient model.

Vital effects of K isotope fractionation in organisms： observations and a hypothesis

Compared with the measureable but limited K isotope variation in geological samples,biological samples have much larger variations in δ^41 values：from-1.3‰ to＋1.1‰ relative to the international K standard NIST SRM 3141a.Notably,higher plants generally have δ^41 values that are lower than igneous rocks,whereas sea plants（algae）have δ^41 values that are higher than seawater;the range in δ^41K values of plants encompasses the δ^41 values of both igneous rocks and seawater.Plant cells utilize different K uptake mechanisms in response to highand low-K conditions.In a low-K environment,plant cells use energy-consuming ion pumps for active uptake of K;plant cells in high-K environments use non-energy-consuming ion channels.Based on these facts and on K isotope data from sea and land plants,it is hypothesized that the different K uptake mechanisms are accompanied by distinct K isotope fractionation behaviors or vital effects.The enrichment of light K isotopes in terrestrial plants could be attributed to preferential transport of isotopically light K in the energy-consuming active uptake process by K ion pumps in the membranes of plant root cells.On the other hand,the enrichment of heavy K isotopes in algae may be caused by a combination of the lack of K isotope fractionation during K uptake from seawater via ion channels and the preferential efflux of light K isotopes across the cell membrane back to the seawater.The large variation of K isotope compositions in biological samples therefore may reflect the diversity of isotopic vital effects for K in organisms,which implies the great potential of K isotopes in biogeochemical studies.