Effects of Phosphate Adsorption on Adsorption-Desorption and Availability of Cu and Zn Ions in Ultisols and Alfisols

Surface charge, secondary adsorption- desorption and form distribution of Cu2+ and Zn2+ in Ultisols and Alfisols having adsorbed phosphate were studied by potentiometric titration, adsorption equilibrium and sequential extraction method, respectively. The soil surface negative charges increased whereas the amount of positive charges decreased with increase of P adsorbed. The soil secondary adsorption capacity for Cu2+ and Zn2+ was positively significantly correlated with the amount of P adsorbed by the soils, which could be described by the Langmuir equation. The amounts of Cu2+ and Zn2+ desorption from soils were decreased after P adsorption by the soils and the relationship between them was linear. After the soils adsorbed P, form distribution of Cu2+ and Zn2+ in soils changed remarforbly.

Interaction Between Charge Characteristics and Cu^(2+) Adsorption-Desorption of Soils with Variable or Permanent Charge

Charge characteristics and Cu2+ adsorption-desorption of soils with variable charge (latosol) and permanent charge (brown soil) and the relationship between them were studied by means of back-titration and adsorption equilibrium respectively. The amount of variable negative charge was much less in variable-charge soil than in permanent-charge soil and increased with the pH in the system, but the opposite trend occurred in the points of zero charge (PZCs). The amount of Cu2+ ions sorbed by permanent-charge soil was more than that by variable-charge soil and increased with the increase of Cu2+ concentration within a certain range in the equilibrium solution. The amount of Cu2+ ions desorbed with KC1 from permanent-charge soil was more than that from variable-charge soil, but the amount of Cu2+ ions desorbed with de-ionized water from permanent-charge soil was extremely low whereas there was still a certain amount of desorption from variable-charge soil. The increase of PZC of soils with variable or permanent charge varied with the increment of Cu2+ ions added. When the same amount of Cu2+ ions was added, the increments of PZC and variable negative surface charge of permanent-charge soil were different from those of variable-charge soil.

Adsorption-Desorption Characteristics of Chlorimuron-Ethyl in Soils

The adsorption-desorption characteristics of chlorimuron-ethyl in soils were investigated to provide the basic data for evaluating the safety in field and the risk to water resource. The adsorption-desorption experiment was conducted by the batch equilibration and HPLC techniques; furthermore, data were analyzed with 5 mathematic models to describe the characteristics and mechanism of adsorption-desorption and translocation of the herbicide in soils. The results showed that the adsorption-desorption isotherms of chlorimuron-ethyl fitted for the Freundlich model well, and the physical reaction presents the main contribution during the adsorption-desorption process. The adsorption values （Kads-f） of chlorimuron-ethyl in 8 types of soil ranged from 0.798 to 6.891. The isotherms of 2# （Jiangxi clay） and 3# （Jiangxi sand loam） soils belong to the S-type curve, while the isotherms of another 6 type soils belong to the L-type isotherm. The results of desorption indicated that the hysteresis phenomena appeared during the desorption process, and the hysteresis coefficients （H） of the herbicides in 8 soils varied from 0.259-0.980. Furthermore, Kads-f and desorption values （Kads-f） increased with the OM （%） and the clay content increasing, while the values decreased with the soils pH increasing. The H values decreased with the OM and the clay content increasing, and increased with the soils pH increasing. It can be concluded that the low adsorption abilities of chlorimuron-ethyl in test soils and un-reversible adsorption existed in the process, which will induce the great translocation of the herbicide after application in field. It can be transported to ground or groundwater causing risk to environments. The physical and chemical properties of soils, including the OM, the clay content, and the pH of soil were the dominating factors during the adsorption-desorption.

An Experimental Study on the Conductivity Changes in Coal during Methane Adsorption-Desorption and their Influencing Factors

During the processes of methane adsorption and desorption,the internal structure of coal changes,accordingly leading to changes in electrical conductivity.In this paper,using low rank coal seams of the Yan'an Formation in the Dafbsi field as the research subject,the relationship between coal resistivity,methane adsorption quantity,and equilibrium pressure is analyzed through proximate analysis,mercury injection tests,low temperature liquid nitrogen adsorption tests,and coal resistivity measurements during methane adsorption and desorption.The results show that during the process of pressure rise and methane adsorption,the conductivity of coal increases,resulting from heat release from methane adsorption,coal matrix swelling and adsorbed water molecules replaced by methane,but the resistivity reduction gradually decreases.The relationship between coal resistivity and methane adsorption quantity and equilibrium pressure can be described by a quadratic function.During the processes of depressurization and desorption,the resistivity of coal rebounds slightly,due to decalescence of methane desorption,coal matrix shrinkage and water-gas displacement,and the relationship coincides with a linear function.Methane adsorption leads to irreversible changes in coal internal structure and enhances the coal conductivity,and resistivity can not be restored to the initial level even after methane desorption.The resistivity and reduction rate of durain are higher than those of vitrain,with relatively greater homogeneous pore throat structure and fewer charged particles in the double electric layer.In addition,moisture can enhance the conductivity of coal and makes it change more complexly during methane adsorption and desorption.

Temperature Effect on Boron Adsorption-Desorption Kinetics in Soils

The effect of temperature on the properties of boron adsorption-desorption in brown-red soil, yellowbrown soil and calcareous alluvial soil of Hubei Province was investigated with the mobile displacement technique. The experimental data of B adsorption-desorption amounts and reaction t line at 25 and 40℃ were fitted by the zero-order, first-order and parabolic diffusion kinetic equations. The adsorption process was in conformity with the parabolic diffusion law at both the temperatures, and the values of rate constant of the parabolic diffusion equation in B adsorption were 0.138, 0.124 and 0.105 mg kg-1 min-1/2 at 25℃, and 0.147, 0.146 and 0.135 mg kg-1 min-1/2 at 40℃ for the brown-red soil, yellow-brown soil, and calcareous alluvial soil, respectively. The relationship between amount of B desorption and reaction time could be well described by the first-order kinetic equation, and the corresponding values of rate constant were 0.0422, 0.0563 and 0.0384 min-1 at 25℃, and 0.0408, 0.042 3 and 0.0401 min-1 at 40℃ for the brown-red soil, the yellow-brown soil and the calcareous alluvial soil, respectively. Therefore, the desorption process of B might be related to the amount of B adsorbed in soil. The higher the temperature, the lower the amount of B adsorption for the same soil in the same reaction time. The values of the apparent activation energy of B adsorption in the three soils calculated with the rate constants of parabolic diffusion equation were 3.27, 8.44 and 12.99 kJ mol-1, respectively, based on the experimental data of B adsorption amounts and reaction time at 25 and 40℃.

MOLECULAR BEAM STUDIES ON ADSORPTION-DESORPTION KINETICS OF CO AND H_2 ON Ni SURFACE

Adsorption-desorption kinetics of CO and H_2 on Ni surface were studied with molecular beam relaxation spectrometry. It is found that there are two adsorbed states in the substrate temperature range 330K<T<480K and 720K<T<900K respectively for CO/Ni system. These results can be explained by a precursor state model. Their kinetic parameters: E_(aα)=14.6kJ/mol, E_(dx)=49.3kJ/mol; E_(aβ)= 68.6kJ/mol, E_(dβ)=200.6kJ/mol. It is shown that there are two adsorbed states in the low (350K<T<430K) and high (550K<T<625K) temperature range respectively for H_2/Ni system. These results can be explained by a direct dissociative model. Their kinetic parameters:E_(dl)=26.3kJ/mol, E_(dh)=103.7kJ/mol.

Laboratory test on moisture adsorption-desorption of wall paintings at Mogao Grottoes, China

Moisture adsorption-desorption tests (MATs) were conducted on simulated mural plaster specimens under different air temperatures (ATs) and relative humidity (RH) to investigate the possible effect of seasonal alteration and visitors’ breath on the deterioration of Mogao Grottoes, Dunhuang, China. Saturated salt solutions were used to maintain a constant RH, and plant growth cabinets were used to maintain a constant or varying temperature in the simulation test. The weight of specimen was periodically measured to determine the adsorbed or desorbed moisture. Test data illustrate that the desorption process is far quicker than the adsorption one, indicating that it is possible to inhibit the disadvantage effect from visitors, such as shortening the staying time in caves. In case of high humidity, an accumulated moisture adsorption was found to correspond to the varying temperature. On the other hand, in case of low humidity, accumulated moisture desorption corresponded. Test data imply that opening caves more often to visitors in humid seasons should be avoided so as to prevent continuous wetting of wall paintings.

Study on sulfur migration in activated carbon adsorption-desorption cycle: Effect of alkali/alkaline earth metals

Activated carbon(AC)has been widely used in the removal of SO_(2) from flue gas owing to its well-developed pore structure and abundant functional groups.Herein,the effect of alkali/alkaline earth metals on sulfur migration was investigated based on the dynamic adsorption and temperature programmed desorption experiment.The adsorption and desorption properties of six types of AC(three commercial and three laboratory-made)were carried out on a fixed-bed experimental device,and the physical and chemical properties of samples were determined by X-ray fluorescence,X-ray diffraction,scanning electron microscopy/energy dispersive X-ray,and X-ray photoelectron spectroscopy analysis.The experimental results showed that the adsorbed SO_(2) cannot be completely desorbed by increasing the regeneration temperature(350-850℃),while the SO_(2) fixed in the AC combines with the Ca-based minerals in the ash to form a stable sulfate.For different samples,higher ash content,higher CaO content in the ash and a more developed pore structure lead to a higher SO_(2) fixation rate.Moreover,the multiple adsorption-desorption cycles experiment showed that the effect of SO_(2) fixation is mainly reflected in the first cycle,after which the adsorption and desorption amount are approximately the same.This study elucidates the effect of alkali/alkaline earth metals on the adsorption-desorption cycle of AC,which provides a deeper understanding of sulfur migration in the AC flue gas desulfurization process.

Adsorption-desorption of Silica Nanoparticles on Poly（ethylene glycol） Brushes Grafted onto Au Substrate Studied by Quartz Crystal Microbalance

The adsorption-desorption of silica nanoparticles（NPs） on poly（ethylene glycol）（PEG） grafted onto gold（Au） substrate was studied by quartz crystal microbalance with dissipation monitoring（QCM-D） technique. The results of frequency and dissipation show that SiO2 NPs can be adsorbed strongly on PEG-SH brushes at pH of 9.6, and a new dense and rigid construction is formed. Adjusting the pH from 9.6 to 12.3 resulted in the desorption of si- lica NPs from the PEG brushes because of a significant weakening of the hydrogen bond between the silica NPs and PEG chains. In addition, the viscoelastic properties of the system during the adsorption-desorption process were also analyzed via the relationship between the normalized frequency（Af/n） and mass. And the corresponding atomic force microscopy（AFM） images also exhibit morphological changes during the above process, consistent with the changes in viscoelasticity.

Accumulation and exploration enlightenment of shallow normal-pressure shale gas in southeastern Sichuan Basin, SW China

Based on the drilling, logging, experimental and testing data of Well PD1, a shallow normal-pressure shale gas well in the Laochangping anticline in southeastern Sichuan Basin, the shallow shale gas reservoirs of the Ordovician Wufeng Formation to Silurian Longmaxi Formation (Wufeng-Longmaxi) were investigated in terms of geological characteristics, occurrence mechanism, and adsorption-desorption characteristics, to reveal the enrichment laws and high-yield mechanism of shallow normal-pressure shale gas in complex structure areas. First, the shallow shale gas reservoirs are similar to the medium-deep shale gas reservoirs in static indicators such as high-quality shale thickness, geochemistry, physical properties and mineral composition, but the former is geologically characterized by low formation pressure coefficient, low gas content, high proportion of adsorbed gas, low in-situ stress, and big difference between principal stresses. Second, shallow shales in the complex structure areas have the gas occurrence characteristics including low total gas content (1.1-4.8 m3/t), high adsorbed gas content (2.5-2.8 m3/t), low sensitive desorption pressure (1.7-2.5 MPa), and good self-sealing. Third, the adsorbed gas enrichment of shales is mainly controlled by organic matter abundance, formation temperature and formation pressure: the higher the organic matter abundance and formation pressure, the lower the formation temperature and the higher the adsorption capacity, which is more beneficial for the adsorbed gas occurrence. Fourth, the shallow normal-pressure shale gas corresponds to low sensitive desorption pressure. The adsorbed gas can be rapidly desorbed and recovered when the flowing pressure is reduced below the sensitive desorption pressure. Fifth, the exploration breakthrough of Well PD1 demonstrates that the shallow complex structure areas with adsorbed gas in dominance can form large-scale shale reservoirs, and confirms the good exploration potential of shallow normal-pressure shale gas in the margin of the Sichuan Basin.

Phosphorus Speciation in Wetland Sediments of Zhujiang (Pearl) River Estuary,China

Phosphorus fractions and adsorption-release characteristics of sediments in the Zhujiang （Pearl） River estuary wetland were investigated. Results showed that the total phosphorus （TP） content in surface sediments ranged from 648.9 mg/kg to 1064.0 mg/kg; inorganic phosphorus （IP） was the major fraction of TP and ranged from 422.5 mg/kg to 643.9 mg/kg. Among the inorganic phosphorus, the main fractions were phosphorus bound to A1 and Fe （Fe/A1-P）, and calcium-bound phosphorus （Ca-P）, accounting for 23%-42% and 21%-67% of IP, respectively. The vertical distribution of TP contents were significantly positive correlated with organic phosphorus （Org-P） and Fe/A1-P contents. The bio-available phosphorus contents in vertical sediments varied from 128.6 mg/kg to 442.9 mg/kg, mainly existed in Fe-AI/P fraction, and increased from the bottom to top sediments. The transport of phosphorus in sediment-water in- terface was controlled by the soil characteristics. The active Fe and A1 content was considered as the main factor that determines adsorp- tion capacity in vegetated marsh wetland. The P buffering capacity of the sediments in vegetated marsh wetland was greater than that in mudflat wetland. The potential risk of eutrophication in the study area is high. Reducing terrestrial phosphorus discharge and preventing the sediment Fe/A1-P release to the interstitial water are the possible solutions to reduce the risk of eutrophication in estuary wetlands, and planting vegetation in estuary wetland can also reduce the release of phosphorus in surface sediment.

Seepage law and permeability calculation of coal gas based on Klinkenberg effect

Focused on the Klinkenberg effect on gas seepage, the independently developed triaxial experimental system of gas seepage was applied to conduct research on the seepage characteristics of coal seam gas. By means of experimental data analysis and theoretical derivation, a calculation method of coal seam gas permeability was proposed, which synthesized the respective influences of gas dynamic viscosity, compressibility factor and Klinkenberg effect. The study results show that the Klinkenberg effect has a significant influence on the coal seam gas seepage, the permeability estimated with the method considering the Klinkenberg effect is correct, and this permeability can fully reflect the true seepage state of the gas. For the gas around the standard conditions, the influences of dynamic viscosity and compressibility factor on the permeability may be ignored. For the gas deviating far away from the standard conditions, the influences of dynamic viscosity and compressibility factor on the permeability must be considered. The research results have certain guiding significance in forming a correct understanding of the Klinkenberg effect and selecting a more accurate calculation method for the permeability of coal containing gas.

Alkali metal cation doping of metal-organic framework for enhancing carbon dioxide adsorption capacity

Metal-organic frameworks （MOFs） have attracted much attention as adsorbents for the separation of CO2 from flue gas or natural gas. Here, a typical metal-organic framework HKUST-I（also named Cu-BTC or MOF-199） was chemically reduced by doping it with alkali metals （Li, Na and K） and they were further used to investigate their CO2 adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction （XRD）, thermo-gravimetric analysis （TGA） and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO2 storage capacity of HKUST-1 doped with moderate quantities of Li＋, Na＋ and K＋, individually, was greater than that of unmodified HKUST-1. The highest CO2 adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11% increase in adsorption capacity at 298 K and 18 bar as compared with HKUST- 1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO2 than those of N2. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO2 after 10 cycles.

Effect of Organic Manure on Phosphorus Adsorption－Desorption and Availability in Paddy Soil Derived from Red Earth

A field test with the traditional rotation of paddy rice/upland crop (wheat) was carried out on a paddysoil derived from red earth to elucidate the effect of organic manure on the phosphorus adsorption-desorptionby soil and its P availability Soil samples were taken from different treatments at rice harvesting stage andanalysed. The isothermal adsorption of P by the samples fitted very well with Langmuir equation, and hence,the parameters in the equation, i.e., maximum adsoaption (qm), constant related to bonding energy (k) andtheir product (k x qm) could be used as a comprehensive index to characterize the potential P adsorptivityof the soil.Organo-inorganic fertilization and organic manuring conld decrease qm and k, while mineral P appli-cation had little effect on them. The isothermal desorption of P was significantly correlated with initiallyadded and isothermally adsorbed P. Part of P added was fixed, which represented the P fixation capacityof soil, and organic manuring could obviously lower the P fixation. The content of soil available P had asignificant negative correlation with qm, k and fixed P. It is concluded that organic manure could increase theP availability of paddy soil derived from red earth by decreasing qm, k, maximum buffering capacity (MBC=k x qm) and fixation capacity.

Influence of Clay Minerals on Some Soil Fertility Attributes: A Review

Clay minerals constitute an important component of the soil system and knowledge of their role in soil fertility is imperative for sustainable soil management and productivity. The aim of this work is to overview the influence of clay minerals on some major soil fertility attributes. The rationale for carrying out this work is that most soil fertility studies rarely incorporate soil mineralogy. Clay minerals, through their physical and chemical properties, affect soil fertility by controlling nutrient supplies and availability, through the sequestration and stabilization of soil organic matter, by controlling soil physical properties through microaggregate formation, by influencing soil acidity and controlling soil microbial population and activity. The main processes involved in these relationships are dissolution-precipitation and adsorption-desorption processes, alongside mechanisms involving the formation of short-range-ordered phases. Although the determination of soil mineralogical properties is very costly and time-consuming, information about a soil’s mineralogy is imperative for a holistic understanding and proper management of soil fertility. Therefore, the development of rapid, low-cost, reliable and efficient techniques of soil mineralogical analysis, directly applicable to soil fertility investigations, constitutes a major challenge. Also, future research should investigate the relationships between clay minerals and soil nitrogen vis-à-vis sequestration and stabilization. Lastly, clay minerals should be considered in studies dealing with soil quality assessment, especially in the choice of soil quality indicators.

Superficial performance and pore structure of palygorskite treated by hydrochloric acid

In order to amend the superficial performance of palygorskite and improve its application, the natural palygorskite(NP) was treated in the dipping and ionic exchanging experiments using 6mol/L hydrochloric acid treatment. The performance and pore structure of the treated palygorskite(TP) were investigated by means of microscope analyses, FT-IR, XRF, BET-SSA and full hole distribution analytical techniques. The results show that the hydrochloric acid treatment can make the gracile and aggregating compact crystal bundles inside palygorskite clay broken and dispersed, the roughness of microcrystalline surface increases, which not only can dissolve or remove dolomite but vary the superficial performance of palygorskite to some degree. The specific surface area and pore volume increase a lot, while the mean pore size decreases. The pore structure of TP changes remarkably compared with that of NP after 6mol/L hydrochloric acid treatment, and the relevant physicochemical performance can be improved.

Emergence of carbonaceous material for hydrogen storage:an overview

Hydrogen has gained enormous relevance due to its lower carbon footprint and its potential role in balancing energy supply and demand.It is being considered as a sustainable substitute for conventional fuels.The generation of hydrogen using renewable energy sources is still in development,with a significant challenge lying in the efficient and safe storage of hydrogen due to its low energy density.This challenge hinders the widespread adoption of hydrogen.Compression and liquefaction methods of storage face issues of losses that reduce their effectiveness.The technology for hydrogen storage has advanced significantly in the past few years,driven by recent enhancements in synthesizing carbonaceous materials with hydrogen storage capabilities.This article critically reviews novel carbonaceous materials for hydrogen storage,including biochar,activated carbon,carbon nanotubes,carbon nanocomposites,carbon aerogel,fullerenes,MXenes,graphite,graphene and its derivatives.Effective hydrogen adsorption using microporous materials,such as activated carbons,is crucial,sparking interest in economically viable options for hydrogen storage.Despite this,a significant amount of work still needs to be accomplished before the potential and advantages of the hydrogen economy can be fully realized and utilized by manufacturers and academics.

Adsorption and desorption behavior under coal–water–gas coupling conditions of high- and low-rank coal samples

High-and low-rank coalbed methane(CBM)are both important fields of CBM development in China,but their formation and production mechanisms differ considerably.The adsorption/desorption behavior of high-and low-rank coals under the coupling of coal–water–gas was investigated using two series of samples.Coal samples from Zhangjiamao(ZJM)coal mine,Ordos basin,and Sihe(SH)coal mine,Qinshui basin,were tested by isothermal adsorption–desorption experiment,natural imbibition experiment,nuclear magnetic resonance,mercury injection porosimetry,contact angle test,and permeability test.Isothermal adsorption and desorption experiments under dry,equilibrium water,and saturated water,were performed to explore the differences between the adsorption and desorption characteristics.The results show that the wettability and permeability of the ZJM low-rank coal sample was considerably higher than that of the SH high-rank coal sample.The imbibition process of the ZJM sample exhibited a high imbibition rate and high total-imbibition volume,whereas the SH sample exhibited a slow imbibition rate and low total-imbibition volume.The ZJM sample had a complex pore structure and diverse pore-size distribution with a lower mercury withdrawal efficiency at 59.60%,whereas the SH sample had a relatively uniform pore-size distribution with a higher mercury withdrawal efficiency at 97.62%.The response of adsorption and desorption of the ZJM sample to water was more significant than that of the SH sample.The desorption hysteresis of the ZJM sample was stronger than that of the SH sample and was more prominently affected by water,which was consistent with its strong wettability and complex pore-throat configuration.A comprehensive adsorption and desorption mode was constructed for high-and low-rank coal samples under coal–water–gas coupling condition.The research results are important to enrich the geological theory of high-and low-rank CBM and to guide efficient CBM recovery.

Zirconia prepared from UIO-66 as a support of Ru catalyst for ammonia synthesis

The development of effective Ru catalyst for ammonia synthesis is of important practical value and scientific significance because of the wide application of ammonia as a fertilizer and its promising applications in the renewable energy.Generally,ZrO_(2) was regarded as an inferior support for Ru catalyst used in ammonia synthesis.Here we prepare ZrO_(2) with monoclinic phase and carbon species from ZrCl_(4) following the preparation route of UiO-66 as well as ammonia treatment.Owing to the presence of a larger amount of hydrogen adsorption as well as the easier desorption of hydrogen species,the ill effect of hydrogen species on the nitrogen adsorption-desorption and ammonia synthesis can be effectively alleviated.The resulting ZrO_(2)-supported Ru catalyst showed 4 times higher ammonia synthesis activity than the conventional Ru/ZrO_(2) obtained from zirconium nitrate.

Carbon isotope fractionation during shale gas transport: Mechanism, characterization and significance

The gas in-place(GIP)content and the ratio of adsorbed/free gas are two key parameters for the assessment of shale gas resources and have thus received extensive attention.A variety of methods have been proposed to solve these issues,however none have gained widespread acceptance.Carbon isotope fractionation during the methane transport process provides abundant information,serving as an effective method for differentiating the gas transport processes of adsorbed gas and free gas and ultimately evaluating the two key parameters.In this study,four stages of methane carbon isotope fractionation were documented during a laboratory experiment that simulated gas transport through shale.The four stages reflect different transport processes:the free gas seepage stage(Ⅰ),transition stage(Ⅱ),adsorbed gas desorption stage(Ⅲ)and concentration diffusion stage(Ⅳ).Combined with the results of decoupling experiments,the isotope fractionation characteristics donated by the single effect(seepage,adsorption-desorption and diffusion)were clearly revealed.We further propose a technique integrating the Amoco curve fit(ACF)method and carbon isotope fractionation(CIF)to determine the dynamic change in adsorbed and free gas ratios during gas production.We find that the gases produced in stage Ⅰ are primarily composed of free gas and that carbon isotope ratios of methane(δ13C1)are stable and equal to the ratios of source gas(13C 10).In stage Ⅱ,the contribution of free gas decreases,while the proportion of adsorbed gas increases,and the δ13C1 gradually becomes lighter.With the depletion of free gas,the adsorbed gas contribution in stage Ⅲ reaches 100%,and the δ13C1 becomes heavier.Finally,in stage Ⅳ,the desorbed gas remaining in the pore spaces diffuses out under the concentration difference,and the δ13C1 becomes lighter again and finally stabilizes.In addition,a kinetic model for the quantitative description of isotope fractionation during desorption and diffusion was established.