Based on geochemical data from natural gas samples across spring water systems and sedimentary basins,including Songliao,Bohai Bay,Sanshui,Sichuan,Ordos,Tarim and Ying-Qiong,this paper systematically compares the geoc...Based on geochemical data from natural gas samples across spring water systems and sedimentary basins,including Songliao,Bohai Bay,Sanshui,Sichuan,Ordos,Tarim and Ying-Qiong,this paper systematically compares the geochemical compositions of abiogenic versus biogenic gases.Emphasis is placed on the diagnostic signatures of abiogenic gases in terms of gas composition,and carbon,hydrogen and helium isotopes.The main findings are as follows.(1)In hydrothermal spring systems,abiogenic alkane gases are extremely scarce.Methane concentrations are typically less than 1%,with almost no detectable C^(2+)hydrocarbons.The gas is dominantly composed of CO_(2),while N_(2)is the major component in a few samples.(2)Abiogenic alkane gases display distinct isotopic signatures,including enriched methane carbon isotopic compositions(δ^(13)C_(1)>-25‰generally),complete carbon isotopic reversal(δ^(13)C_(1)>δ^(13)C_(2)>δ^(13)C_(3)>δ^(13)C_(4)),and enriched helium isotope(R/Ra>0.5,CH_(4)/^(3)He≤10^(6)generally).(3)The hydrogen isotopic composition of abiogenic alkane gases may be characterized by a positive sequence(δD_(1)<δD_(2)<δD_(3)),or a complete reversal(δD_(1)>δD_(2)>δD_(3)),or a V-shaped distribution(δD_(1)>δD_(2),δD_(2)<δD_(3)).The hydrogen isotopic compositions of methane generally show limited variation(about 9‰),possibly due to hydrogen isotopic exchange with connate water.(4)In terms of identifying gas origin,CH_(4)/^(3)He-R/Ra andδ^(13)CCO_(2)-R/Ra charts are more effective than CO_(2)/^(3)He-R/Ra chart.These new geological insights provide theoretical clues and diagnostic charts for the genetic identification of natural gas and further research on abiogenic gases.展开更多
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 i...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.展开更多
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 sign...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.展开更多
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 ...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.展开更多
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 rela...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.展开更多
Lack of information regarding lithium(Li)crystal chemistry in numerous minerals,especially those containing trace amounts of Li(ranging from a few to tens of ppm),limits our understanding of Li isotopic fractionation ...Lack of information regarding lithium(Li)crystal chemistry in numerous minerals,especially those containing trace amounts of Li(ranging from a few to tens of ppm),limits our understanding of Li isotopic fractionation in pegmatites.In this study,we examined the Li isotopic composition and Li content in various Li-poor(e.g.,quartz or feldspar)together with Li-rich(sopdumene or lepidolite)mineral phases within granitic pegmatites.We compiled a comprehensive dataset,encompassing a broad spectrum of Li contents(ranging from a few to tens of thousands of ppm)and Li isotopic values(-8‰to 41‰).The minerals exhibit distinct Li isotopic signatures.Specifically,elbaite and beryl show the highest values,while biotite displays a negative average.Compared to individual minerals,whole rocks demonstrate lower Li isotopic values,with pegmatites exhibiting the highest and non-granitic pegmatite wall rocks showing the lowest.Our study also uncovers a clear“V”shape relationship between Li isotopic values and logarithm of Li contents,with different mineral groups occupying specific regions within this shape.Furthermore,a significant correlation was observed between average Li isotopic values and Li-O(OH,F)bond lengths in various minerals.These discoveries underscore the crucial role of crystal chemistry in shaping the Li isotopic behavior in pegmatites from a statistical perspective.展开更多
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 i...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)).展开更多
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 ...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.展开更多
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, th...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.展开更多
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 δ...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.展开更多
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 character...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.展开更多
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 s...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.展开更多
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 ...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.展开更多
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 te...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.展开更多
Significant progress has been made in exploring shale gas resources in the middle-upper Permian strata of western Hubei.However,the unclear geochemical characteristics and origins of the gas have hindered a comprehens...Significant progress has been made in exploring shale gas resources in the middle-upper Permian strata of western Hubei.However,the unclear geochemical characteristics and origins of the gas have hindered a comprehensive understanding of reservoir evolution and have constrained integrated resource development.This study involved a 28-h desorption experiment in which gases released from shales of the Dalong and Gufeng Formations were systematically collected for compositional and carbon—hydrogen isotope analyses.Comparing the compositional and geochemical characteristics of the desorbed gases and investigating their genetic origins resulted in four main findings:(1)Gas composition during the middle stage of desorption,excluding H_(2)S,best represents the original reservoir fluid,with component variations linked to adsorption and diffusion capacities.(2)Both shales display similar gas compositions with trace H_(2)S;the Dalong shale contains lower CH_(4),CO_(2),and H_(2)S but higher C_(2)H_(6)and N_(2).(3)Carbon and hydrogen isotopes indicate oil-type thermogenic gases,with carbon isotope reversal reflecting tectonic uplift,depressurization,and the mixing of primary kerogen-derived and secondary oil-/condensate-derived gases.(4)N_(2)likely originates from ammonium-bearing silicate decomposition,CO_(2)is mainly inorganic,from thermal carbonate decomposition with minor organic contribution,and H_(2)S may result from oil cracking or thermochemical sulfate reduction.This study provides a comprehensive record of the fluid characteristics of middle-upper Permian shale gas reservoirs and enhances the understanding of their formation and evolution.展开更多
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 ...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.展开更多
Prediction of production decline and evaluation of the adsorbed/free gas ratio are critical for determining the lifespan and production status of shale gas wells.Traditional production prediction methods have some sho...Prediction of production decline and evaluation of the adsorbed/free gas ratio are critical for determining the lifespan and production status of shale gas wells.Traditional production prediction methods have some shortcomings because of the low permeability and tightness of shale,complex gas flow behavior of multi-scale gas transport regions and multiple gas transport mechanism superpositions,and complex and variable production regimes of shale gas wells.Recent research has demonstrated the existence of a multi-stage isotope fractionation phenomenon during shale gas production,with the fractionation characteristics of each stage associated with the pore structure,gas in place(GIP),adsorption/desorption,and gas production process.This study presents a new approach for estimating shale gas well production and evaluating the adsorbed/free gas ratio throughout production using isotope fractionation techniques.A reservoir-scale carbon isotope fractionation(CIF)model applicable to the production process of shale gas wells was developed for the first time in this research.In contrast to the traditional model,this model improves production prediction accuracy by simultaneously fitting the gas production rate and δ^(13)C_(1) data and provides a new evaluation method of the adsorbed/free gas ratio during shale gas production.The results indicate that the diffusion and adsorption/desorption properties of rock,bottom-hole flowing pressure(BHP)of gas well,and multi-scale gas transport regions of the reservoir all affect isotope fractionation,with the diffusion and adsorption/desorption parameters of rock having the greatest effect on isotope fractionation being D∗/D,PL,VL,α,and others in that order.We effectively tested the universality of the four-stage isotope fractionation feature and revealed a unique isotope fractionation mechanism caused by the superimposed coupling of multi-scale gas transport regions during shale gas well production.Finally,we applied the established CIF model to a shale gas well in the Sichuan Basin,China,and calculated the estimated ultimate recovery(EUR)of the well to be 3.33×10^(8) m^(3);the adsorbed gas ratio during shale gas production was 1.65%,10.03%,and 23.44%in the first,fifth,and tenth years,respectively.The findings are significant for understanding the isotope fractionation mechanism during natural gas transport in complex systems and for formulating and optimizing unconventional natural gas development strategies.展开更多
Taking deep coal-rock gas in the Yulin and Daning-Jixian areas of the Ordos Basin,NW China,as the research object,full-diameter coal rock samples with different cleat/fracture development degrees from the Carboniferou...Taking deep coal-rock gas in the Yulin and Daning-Jixian areas of the Ordos Basin,NW China,as the research object,full-diameter coal rock samples with different cleat/fracture development degrees from the Carboniferous Benxi Formation were selected to conduct physical simulation and isotope monitoring experiments of the full-life-cycle depletion development of coal-rock gas.Based on the experimental results,a dual-medium carbon isotope fractionation(CIF)model coupling cleats/fractures and matrix pores was constructed,and an evaluation method for free gas production patterns was established to elucidate the carbon isotope fractionation mechanism and adsorbed/free gas production characteristics during deep coal-rock gas development.The results show that the deep coal-rock gas development process exhibits a three-stage carbon isotope fractionation pattern:“Stable(Ⅰ)→Decrease(Ⅱ)→Increase(Ⅲ)”.A rapid decline in boundary pressure in stageⅢleads to fluctuations in isotope value,characterized by a“rapid decrease followed by continued increase”,with free gas being produced first and long-term supply of adsorbed gas.The CIF model can effectively match measured gas pressure,cumulative gas production,and δ^(13)C_(1) value of produced gas.During the first two stages of isotope fractionation,free gas dominated cumulative production.During the mid-late stages of slow depletion production,the staged pressure control development method can effectively increase the gas recovery.The production of adsorbed gas is primarily controlled by the rock's adsorption capacity and the presence of secondary flow channels.Effectively enhancing the recovery of adsorbed gas during the late stage remains crucial for maintaining stable production and improving the ultimate recovery factor of deep coal-rock gas.展开更多
Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not y...Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not yet fully understood.In this study,the V(V)reduction mechanisms with concomitant V isotope fractionation by the Gram-positive bacterium Bacillus subtilis(B.subtilis)and the Gramnegative bacterium Thauera humireducens(T.humireducens)were investigated.Both strains could effectively reduce V(V),removing(90.5%±1.6%)and(93.0%±1.8%)of V(V)respectively from an initial concentration of 50 mg L^(-1) during a 10-day incubation period.V(V)was bioreduced to insoluble vanadium(IV),which was distributed both inside and outside the cells.Electron transfer via cytochrome C,nicotinamide adenine dinucleotide,and glutathione played critical roles in V(V)reduction.Metabolomic analysis showed that differentially enriched metabolites(quinone,biotin,and riboflavin)mediated electron transfer in both strains.The aqueous V in the remaining solution became isotopically heavier as V(V)bioreduction proceeded.The obtained V isotope composition dynamics followed a Rayleigh fractionation model,and the isotope enrichment factor(e)was(–0.54‰±0.04‰)for B.subtilis and(–0.32‰±0.03‰)for T.humireducens,with an insignificant difference.This study provides molecular insights into electron transfer for V(V)bioreduction and reveals V isotope fractionation during this bioprocess,which is helpful for understanding V biogeochemistry and developing novel strategies for V remediation.展开更多
Stable Sr isotopic composition(δ^(88/86)Sr)can be used to study magmatic processes,but their fractionation mechanism during magmatic evolution remains unclear.To understand the fractionation behaviors of the stable S...Stable Sr isotopic composition(δ^(88/86)Sr)can be used to study magmatic processes,but their fractionation mechanism during magmatic evolution remains unclear.To understand the fractionation behaviors of the stable Sr isotopes during magmatism,we report theδ^(88/86)Sr values of the Huili granitic pluton,which was subjected to intensive crystal-melt separation.The Huili pluton consists of K-feldspar granite and more evolved albite granite,and the albite granite exhibits significantly higherδ^(88/86)Sr values(+0.36‰to+0.52‰)than that of K-feldspar granite(+0.11‰to+0.25‰).K-feldspar,which contributes most of the Sr budget of the K-feldspar granite,has slightly lowerδ^(88/86)Sr values(−0.01‰to+0.17‰)than the whole rock.Theδ^(88/86)Sr variation of the Huili granites can be explained by separation of melt from K-feldspar-dominated crystals,because crystallization of K-feldspar can result in heavy Sr isotopic composition of the extracted interstitial melt.Stable Sr and Ba isotopic ratios in the Huili granites are highly coupled toward the heavy direction,refl ecting their similar element partitioning and isotope fractionation behaviors between the crystalline K-feldspar and melt.This study indicates that melt extraction plays a key role in granitic magma evolution.展开更多
基金Supported by PetroChina Science and Technology Research and Technology Development Project(2021DJ0502)Open Research Project of Key Laboratory of Shale Gas Resources Exploration,Ministry of Natural Resources(Chongqing Institute of Geology and Mineral Resources)(KLSGE-2023).
文摘Based on geochemical data from natural gas samples across spring water systems and sedimentary basins,including Songliao,Bohai Bay,Sanshui,Sichuan,Ordos,Tarim and Ying-Qiong,this paper systematically compares the geochemical compositions of abiogenic versus biogenic gases.Emphasis is placed on the diagnostic signatures of abiogenic gases in terms of gas composition,and carbon,hydrogen and helium isotopes.The main findings are as follows.(1)In hydrothermal spring systems,abiogenic alkane gases are extremely scarce.Methane concentrations are typically less than 1%,with almost no detectable C^(2+)hydrocarbons.The gas is dominantly composed of CO_(2),while N_(2)is the major component in a few samples.(2)Abiogenic alkane gases display distinct isotopic signatures,including enriched methane carbon isotopic compositions(δ^(13)C_(1)>-25‰generally),complete carbon isotopic reversal(δ^(13)C_(1)>δ^(13)C_(2)>δ^(13)C_(3)>δ^(13)C_(4)),and enriched helium isotope(R/Ra>0.5,CH_(4)/^(3)He≤10^(6)generally).(3)The hydrogen isotopic composition of abiogenic alkane gases may be characterized by a positive sequence(δD_(1)<δD_(2)<δD_(3)),or a complete reversal(δD_(1)>δD_(2)>δD_(3)),or a V-shaped distribution(δD_(1)>δD_(2),δD_(2)<δD_(3)).The hydrogen isotopic compositions of methane generally show limited variation(about 9‰),possibly due to hydrogen isotopic exchange with connate water.(4)In terms of identifying gas origin,CH_(4)/^(3)He-R/Ra andδ^(13)CCO_(2)-R/Ra charts are more effective than CO_(2)/^(3)He-R/Ra chart.These new geological insights provide theoretical clues and diagnostic charts for the genetic identification of natural gas and further research on abiogenic gases.
文摘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.
基金supported by the National Natural Science Foundation of China (Nos. 40973002, 41073002 and 41173049) the Fundamental Research Funds for the Central Universities (No. 020614330005)
文摘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.
基金The National Natural Science Foundation of China under contract No.41721005the COMRA Program of China under contract No.DY135-E2-2-03the Polar Environment Comprehensive Investigation&Assessment Program of China under contract Nos CHINARE2017-01-04-03 and CHINARE2017-04-01-06
文摘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.
基金supported by the National Natural Science Foundation of China (Grants No.50679024,40901015,and 41001011)the Fundamental Research Funds for the Central Universities (Grants No.B1020072 and B1020062)+2 种基金the Ph. D. Programs Foundation of the Ministry of Education of China (Grant No.20090094120008)the Special Fund of the State Key Laboratory of China (Grant No.2009586412)the Science Foundation of the HydroChina Chengdu Engineering Corporation (Grant No.P058)
文摘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.
基金financially supported by the Second Tibetan Plateau Scientific Expedition and Research Program(STEP)(No.2019QZKK0802)。
文摘Lack of information regarding lithium(Li)crystal chemistry in numerous minerals,especially those containing trace amounts of Li(ranging from a few to tens of ppm),limits our understanding of Li isotopic fractionation in pegmatites.In this study,we examined the Li isotopic composition and Li content in various Li-poor(e.g.,quartz or feldspar)together with Li-rich(sopdumene or lepidolite)mineral phases within granitic pegmatites.We compiled a comprehensive dataset,encompassing a broad spectrum of Li contents(ranging from a few to tens of thousands of ppm)and Li isotopic values(-8‰to 41‰).The minerals exhibit distinct Li isotopic signatures.Specifically,elbaite and beryl show the highest values,while biotite displays a negative average.Compared to individual minerals,whole rocks demonstrate lower Li isotopic values,with pegmatites exhibiting the highest and non-granitic pegmatite wall rocks showing the lowest.Our study also uncovers a clear“V”shape relationship between Li isotopic values and logarithm of Li contents,with different mineral groups occupying specific regions within this shape.Furthermore,a significant correlation was observed between average Li isotopic values and Li-O(OH,F)bond lengths in various minerals.These discoveries underscore the crucial role of crystal chemistry in shaping the Li isotopic behavior in pegmatites from a statistical perspective.
基金financially supported by the Hebei Natural Sciences Foundation(Grant Nos.D2020402004 and D2021402020)Hebei Education Department Key Program(Grant No.ZD2018086)+1 种基金the State Natural Sciences Foundation(Grant No.41603011)Hebei University of Engineering Doctoral Special Program(Grant Nos.17129033019 and 17129033020)。
文摘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)).
基金financially supported by National Natural Science Foundation of China(Grant No.2013CB95670241573012+1 种基金4157113004141261058)
文摘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.
文摘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.
文摘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.
基金National Postdoctoral Innovative Talent Support Program(BX20220062)National Natural Science Foundation of China(41672130 and 41972123)SINOPEC Corp.(P17027-3)。
文摘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.
基金Supported by the Natural Science Foundation of Jiangsu Province,China(No.BK2010612)the Foundation of State Key Laboratory of Soil and Sustainable Agriculture(No.Y052010034)the Knowledge Innovation Program of the Institute of Soil Science,Chinese Academy of Sciences(No.ISSASIP0723)
文摘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.
基金financially supported by the National ‘‘863’’ Project (Grant No. 2012AA0611401)the program of the Chinese Academy of Sciences (Grant No. KZCX2-YW-JC103)
文摘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.
基金The paper was considerably improved as a result of reviews by H. G. M. Eggenkamp and A.Spivack, for which the authors were very grateful. Y. M. Zhou (Institute of Salt Lakes, Xining, China) kindly assisted with the chlorine isotopic measurements. This
文摘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.
基金supported by the Hubei Provincial Natural Science Foundation of China(Grant No.2022CFB490,2024AFD381)Science and Technology Project of Hubei Geological Bureau(Grant No.KJ2024-2,KJ2025-14)Open Fund of Technology Innovation Center for Shale oil and Gas Accumulation Theory and Engineering in Southern Complex Structural Area,China Geological Survey(Grant No.SOG-202410).
文摘Significant progress has been made in exploring shale gas resources in the middle-upper Permian strata of western Hubei.However,the unclear geochemical characteristics and origins of the gas have hindered a comprehensive understanding of reservoir evolution and have constrained integrated resource development.This study involved a 28-h desorption experiment in which gases released from shales of the Dalong and Gufeng Formations were systematically collected for compositional and carbon—hydrogen isotope analyses.Comparing the compositional and geochemical characteristics of the desorbed gases and investigating their genetic origins resulted in four main findings:(1)Gas composition during the middle stage of desorption,excluding H_(2)S,best represents the original reservoir fluid,with component variations linked to adsorption and diffusion capacities.(2)Both shales display similar gas compositions with trace H_(2)S;the Dalong shale contains lower CH_(4),CO_(2),and H_(2)S but higher C_(2)H_(6)and N_(2).(3)Carbon and hydrogen isotopes indicate oil-type thermogenic gases,with carbon isotope reversal reflecting tectonic uplift,depressurization,and the mixing of primary kerogen-derived and secondary oil-/condensate-derived gases.(4)N_(2)likely originates from ammonium-bearing silicate decomposition,CO_(2)is mainly inorganic,from thermal carbonate decomposition with minor organic contribution,and H_(2)S may result from oil cracking or thermochemical sulfate reduction.This study provides a comprehensive record of the fluid characteristics of middle-upper Permian shale gas reservoirs and enhances the understanding of their formation and evolution.
基金co-supported by the Chinese Academy of Sciences (Grant No. XDB03020100)the National Basic Research Program of China (Grant No. 2013CB956400)the National Natural Science Foudation of China (Grant Nos. 41321061, 41571014 & 41371022)
文摘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.
基金supported by the Natural Science Foundation of China(Grant No.42302170)National Postdoctoral Innovative Talent Support Program(Grant No.BX20220062)+3 种基金CNPC Innovation Found(Grant No.2022DQ02-0104)National Science Foundation of Heilongjiang Province of China(Grant No.YQ2023D001)Postdoctoral Science Foundation of Heilongjiang Province of China(Grant No.LBH-Z22091)the Natural Science Foundation of Shandong Province(Grant No.ZR2022YQ30).
文摘Prediction of production decline and evaluation of the adsorbed/free gas ratio are critical for determining the lifespan and production status of shale gas wells.Traditional production prediction methods have some shortcomings because of the low permeability and tightness of shale,complex gas flow behavior of multi-scale gas transport regions and multiple gas transport mechanism superpositions,and complex and variable production regimes of shale gas wells.Recent research has demonstrated the existence of a multi-stage isotope fractionation phenomenon during shale gas production,with the fractionation characteristics of each stage associated with the pore structure,gas in place(GIP),adsorption/desorption,and gas production process.This study presents a new approach for estimating shale gas well production and evaluating the adsorbed/free gas ratio throughout production using isotope fractionation techniques.A reservoir-scale carbon isotope fractionation(CIF)model applicable to the production process of shale gas wells was developed for the first time in this research.In contrast to the traditional model,this model improves production prediction accuracy by simultaneously fitting the gas production rate and δ^(13)C_(1) data and provides a new evaluation method of the adsorbed/free gas ratio during shale gas production.The results indicate that the diffusion and adsorption/desorption properties of rock,bottom-hole flowing pressure(BHP)of gas well,and multi-scale gas transport regions of the reservoir all affect isotope fractionation,with the diffusion and adsorption/desorption parameters of rock having the greatest effect on isotope fractionation being D∗/D,PL,VL,α,and others in that order.We effectively tested the universality of the four-stage isotope fractionation feature and revealed a unique isotope fractionation mechanism caused by the superimposed coupling of multi-scale gas transport regions during shale gas well production.Finally,we applied the established CIF model to a shale gas well in the Sichuan Basin,China,and calculated the estimated ultimate recovery(EUR)of the well to be 3.33×10^(8) m^(3);the adsorbed gas ratio during shale gas production was 1.65%,10.03%,and 23.44%in the first,fifth,and tenth years,respectively.The findings are significant for understanding the isotope fractionation mechanism during natural gas transport in complex systems and for formulating and optimizing unconventional natural gas development strategies.
基金Youth Fund of National Natural Science Foundation of China(42302170)CNPC Scientific and Technological Innovation Fund(2022DQ02-0104)RIPED Open Project Fund(2024-KFKT-31).
文摘Taking deep coal-rock gas in the Yulin and Daning-Jixian areas of the Ordos Basin,NW China,as the research object,full-diameter coal rock samples with different cleat/fracture development degrees from the Carboniferous Benxi Formation were selected to conduct physical simulation and isotope monitoring experiments of the full-life-cycle depletion development of coal-rock gas.Based on the experimental results,a dual-medium carbon isotope fractionation(CIF)model coupling cleats/fractures and matrix pores was constructed,and an evaluation method for free gas production patterns was established to elucidate the carbon isotope fractionation mechanism and adsorbed/free gas production characteristics during deep coal-rock gas development.The results show that the deep coal-rock gas development process exhibits a three-stage carbon isotope fractionation pattern:“Stable(Ⅰ)→Decrease(Ⅱ)→Increase(Ⅲ)”.A rapid decline in boundary pressure in stageⅢleads to fluctuations in isotope value,characterized by a“rapid decrease followed by continued increase”,with free gas being produced first and long-term supply of adsorbed gas.The CIF model can effectively match measured gas pressure,cumulative gas production,and δ^(13)C_(1) value of produced gas.During the first two stages of isotope fractionation,free gas dominated cumulative production.During the mid-late stages of slow depletion production,the staged pressure control development method can effectively increase the gas recovery.The production of adsorbed gas is primarily controlled by the rock's adsorption capacity and the presence of secondary flow channels.Effectively enhancing the recovery of adsorbed gas during the late stage remains crucial for maintaining stable production and improving the ultimate recovery factor of deep coal-rock gas.
基金supported by the National Natural Science Foundation of China(U21A2033)the Fundamental Research Funds for the Central Universities(2652022103).
文摘Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not yet fully understood.In this study,the V(V)reduction mechanisms with concomitant V isotope fractionation by the Gram-positive bacterium Bacillus subtilis(B.subtilis)and the Gramnegative bacterium Thauera humireducens(T.humireducens)were investigated.Both strains could effectively reduce V(V),removing(90.5%±1.6%)and(93.0%±1.8%)of V(V)respectively from an initial concentration of 50 mg L^(-1) during a 10-day incubation period.V(V)was bioreduced to insoluble vanadium(IV),which was distributed both inside and outside the cells.Electron transfer via cytochrome C,nicotinamide adenine dinucleotide,and glutathione played critical roles in V(V)reduction.Metabolomic analysis showed that differentially enriched metabolites(quinone,biotin,and riboflavin)mediated electron transfer in both strains.The aqueous V in the remaining solution became isotopically heavier as V(V)bioreduction proceeded.The obtained V isotope composition dynamics followed a Rayleigh fractionation model,and the isotope enrichment factor(e)was(–0.54‰±0.04‰)for B.subtilis and(–0.32‰±0.03‰)for T.humireducens,with an insignificant difference.This study provides molecular insights into electron transfer for V(V)bioreduction and reveals V isotope fractionation during this bioprocess,which is helpful for understanding V biogeochemistry and developing novel strategies for V remediation.
基金supported by National Natural Science Foundation of China(42473009).
文摘Stable Sr isotopic composition(δ^(88/86)Sr)can be used to study magmatic processes,but their fractionation mechanism during magmatic evolution remains unclear.To understand the fractionation behaviors of the stable Sr isotopes during magmatism,we report theδ^(88/86)Sr values of the Huili granitic pluton,which was subjected to intensive crystal-melt separation.The Huili pluton consists of K-feldspar granite and more evolved albite granite,and the albite granite exhibits significantly higherδ^(88/86)Sr values(+0.36‰to+0.52‰)than that of K-feldspar granite(+0.11‰to+0.25‰).K-feldspar,which contributes most of the Sr budget of the K-feldspar granite,has slightly lowerδ^(88/86)Sr values(−0.01‰to+0.17‰)than the whole rock.Theδ^(88/86)Sr variation of the Huili granites can be explained by separation of melt from K-feldspar-dominated crystals,because crystallization of K-feldspar can result in heavy Sr isotopic composition of the extracted interstitial melt.Stable Sr and Ba isotopic ratios in the Huili granites are highly coupled toward the heavy direction,refl ecting their similar element partitioning and isotope fractionation behaviors between the crystalline K-feldspar and melt.This study indicates that melt extraction plays a key role in granitic magma evolution.
