It is well-known that the equilibrium isotope fractionation of mercury(Hg)includes classical massdependent fractionations(MDFs)and nuclear volume effect(NVE)induced mass-independent fractionations(MIFs).However,the ef...It is well-known that the equilibrium isotope fractionation of mercury(Hg)includes classical massdependent fractionations(MDFs)and nuclear volume effect(NVE)induced mass-independent fractionations(MIFs).However,the effect of the NVE on these kinetic processes is not known.The total fractionations(MDFs+NVEinduced MIFs)of several representative Hg-incorporated substances were selected and calculated with ab initio calculations in this work for both equilibrium and kinetic processes.NVE-induced MIFs were calculated with scaled contact electron densities at the nucleus through systematic evaluations of their accuracy and errors using the Gaussian09 and DIRAC19 packages(named the electron density scaling method).Additionally,the NVE-induced kinetic isotope effect(KIE)of Hg isotopes are also calculated with this method for several representative Hg oxidation reactions by chlorine species.Total KIEs for 202 Hg/^(198)Hg ranging from−2.27‰to 0.96‰are obtained.Three anomalous^(202)Hg-enriched KIEs(δ^(202)Hg/^(198)Hg=0.83‰,0.94‰,and 0.96‰,)caused by the NVE are observed,which are quite different from the classical view(i.e.,light isotopes react faster than the heavy ones).The electron density scaling method we developed in this study can provide an easier way to calculate the NVE-induced KIEs for heavy isotopes and serve to better understand the fractionation mechanisms of mercury isotope systems.展开更多
Isotope eff ects are pivotal in understanding silicate melt evaporation and planetary accretion processes.Based on the Hertz-Knudsen equation,the current theory often fails to predict observed isotope fractionations o...Isotope eff ects are pivotal in understanding silicate melt evaporation and planetary accretion processes.Based on the Hertz-Knudsen equation,the current theory often fails to predict observed isotope fractionations of laboratory experiments due to its oversimplified assumptions.Here,we point out that the Hertz-Knudsen-equation-based theory is incomplete for silicate melt evaporation cases and can only be used for situations where the vaporized species is identical to the one in the melt.We propose a new model designed for silicate melt evaporation under vacuum.Our model considers multiple steps including mass transfer,chemical reaction,and nucleation.Our derivations reveal a kinetic isotopic fractionation factor(KIFF orα)αour model=[m(^(1)species)/m(^(2)species)]^(0.5),where m(species)is the mass of the reactant of reaction/nucleation-limiting step or species of diffusion-limiting step and superscript 1 and 2 represent light and heavy isotopes,respectively.This model can eff ectively reproduce most reported KIFFs of laboratory experiments for various elements,i.e.,Mg,Si,K,Rb,Fe,Ca,and Ti.And,the KIFF-mixing model referring that an overall rate of evaporation can be determined by two steps jointly can account for the eff ects of low P_(H2)pressure,composition,and temperature.In addition,we find that chemical reactions,diffusion,and nucleation can control the overall rate of evaporation of silicate melts by using the fitting slope in ln(−ln f)versus ln(t).Notably,our model allows for the theoretical calculations of parameters like activation energy(E_(a)),providing a novel approach to studying compositional and environmental eff ects on evaporation processes,and shedding light on the formation and evolution of the proto-solar and Earth-Moon systems.展开更多
The kinetic fractionation of open-water evaporation against the stable water isotope H_2 ^(18)O is an important mechanism underlying many hydrologic studies that use ^(18)O as an isotopic tracer. A recent in-situ meas...The kinetic fractionation of open-water evaporation against the stable water isotope H_2 ^(18)O is an important mechanism underlying many hydrologic studies that use ^(18)O as an isotopic tracer. A recent in-situ measurement of the isotopic water vapor flux over a lake indicates that the kinetic effect is much weaker(kinetic factor 6.2‰) than assumed previously(kinetic factor14.2‰) by lake isotopic budget studies. This study investigates the implications of the weak kinetic effect for studies of deuterium excess-humidity relationships, regional moisture recycling, and global evapotranspiration partitioning. The results indicate that the low kinetic factor is consistent with the deuterium excess-humidity relationships observed over open oceans.The moisture recycling rate in the Great Lakes region derived from the isotopic tracer method with the low kinetic factor is a much better agreement with those from atmospheric modeling studies than if the default kinetic factor of 14.2‰ is used. The ratio of transpiration to evapotranspiration at global scale decreases from 84±9%(with the default kinetic factor) to 76±19%(with the low kinetic factor), the latter of which is in slightly better agreement with other non-isotopic partitioning results.展开更多
Thermochemical sulfate reduction (TSR) in geological deposits can account for the accumulation of H2S in deep sour gas reservoirs. In this paper, thermal simulation experiments on the reaction of CH4-CaSO4 were carri...Thermochemical sulfate reduction (TSR) in geological deposits can account for the accumulation of H2S in deep sour gas reservoirs. In this paper, thermal simulation experiments on the reaction of CH4-CaSO4 were carried out using an autoclave at high temperatures and high pressures. The products were characterized with analytical methods including carbon isotope analysis. It is found that the reaction can proceed to produce H2S, H2O and CaCO3 as the main products. Based on the experimental results, the carbon kinetic isotope fractionation was investigated, and the value of Ki (kinetic isotope effect) was calculated. The results obtained in this paper can provide useful information to explain the occurrence of H2S in deep carbonate gas reservoirs.展开更多
Several important equilibrium Si isotope fractionation factors among minerals,organic molecules and the H_4SiO_4 solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth'...Several important equilibrium Si isotope fractionation factors among minerals,organic molecules and the H_4SiO_4 solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth's surface environments.The results reveal that,in comparison to aqueous H_4SiO_4,heavy Si isotopes will be significantly enriched in secondary silicate minerals.On the contrary,quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution.The extent of ^(28)Si-enrichment in hyper-coordinated organosilicon complexes was found to be the largest.In addition,the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer was calculated,and the results support the previous statement that highly ^(28)Sienrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations.With the equilibrium Si isotope fractionation factors provided here,Si isotope distributions in many of Earth's surface systems can be explained.For example,the change of bulk soil δ^(30)Si can be predicted as a concave pattern with respect to the weathering degree,with the minimum value where allophane completely dissolves and the total amount of sesquioxides and poorly crystalline minerals reaches their maximum.When,under equilibrium conditions,the well-crystallized clays start to precipitate from the pore solutions,the bulk soil δ^(30)Si will increase again and reach a constant value.Similarly,the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain the δ^(30)Si variations in the ground water profile.The equilibrium Si isotope fractionations among the quadracoordinated organosilicon complexes and the H_4SiO_4solution may also shed light on the Si isotope distributions in the Si-accumulating plants.展开更多
Under Rayleigh equilibrium condition, stable isotopic ratio in residual water increases with the decrease of the residual water proportion f exponentially, and the fractionation rate of stable isotopes is inversely pr...Under Rayleigh equilibrium condition, stable isotopic ratio in residual water increases with the decrease of the residual water proportion f exponentially, and the fractionation rate of stable isotopes is inversely proportional to temperature. However, under kinetic evaporation condition, the fi'actionation of stable isotopes is not only related to the phase temperature but also influenced by the atmospheric humidity and the mass exchange between liquid and vapor phases. The ratio 6 in residual water will not change with f after undergoing evaporation of a long time for great relative humidity. The rate that the evaporating water body reaches isotopic steady state is mainly dependent on the relative humidity in atmosphere. The analysis shows that the actual mean linear variety rates, about -30.0, of the δ^18O in residual water versus the residual water proportion at Nagqu and Amdo stations are consistent with the simulated process under temperature of 20℃ and relative humidity of 50%. The distillation line simulated under Rayleigh equilibrium condition is analogous to the global meteoric water line (MWL) as the temperature is about 20℃. Under non-equilibrium condition, the slope and constant values of distillation line are directly proportional to temperature and relative humidity. According to the basic data, the simulated distillation line is very consistent with the actual distillation line of Qinghai Lake.展开更多
This work aims to investigate the intrinsic kinetics of thermal dimerization of C_5 fraction in the reactive distillation process. Experiments are conducted in an 1000-m L stainless steel autoclave under some selected...This work aims to investigate the intrinsic kinetics of thermal dimerization of C_5 fraction in the reactive distillation process. Experiments are conducted in an 1000-m L stainless steel autoclave under some selected design conditions. By means of the weighted least squares method, the intrinsic kinetics of thermal dimerization of C_5 fraction is established, and the corresponding pre-exponential factor as well as the activation energy are determined. For example, the pre-exponential factor A is equal to 4.39×105 and the activation energy E4 a is equal to 6.58×10J/mol for the cyclopentadiene dimerization reaction. The comparison between the experimental and calculated results shows that the kinetics model derived in this work is accurate and reliable, which can be used in the design of reactive distillation columns.展开更多
The Triassic and Jurassic tight sandstone gas in the western Sichuan depression,Sichuan Basin has attracted much attention in recent years,and the Upper Triassic coal-bearing Xujiahe Formation is believed to be the ma...The Triassic and Jurassic tight sandstone gas in the western Sichuan depression,Sichuan Basin has attracted much attention in recent years,and the Upper Triassic coal-bearing Xujiahe Formation is believed to be the major source rock.However,there are relatively few studies on the carbon isotopic heterogeneity of methane generated from coal-measure source rocks and the origin of the natural gases in Xinchang Gas Field is still controversial.In this study,one coal-measure mudstone sample and one coal sample of the Xujiahe Formation in western Sichuan Basin were selected for gold tube pyrolysis experiment to determine their gas generation characteristics.Geological extrapolation of gas generation and methane carbon isotope fractionation parameters reveals that the main gas generation stage of Xujiahe Formation ranges from Late Jurassic to Cretaceous in the Xinchang Gas Field.The natural gas in the 5th member of Xujiahe Formation in Xinchang Gas Field is mainly derived from the 5th member of Xujiahe Formation itself,i.e.,self-generation and self-reservoir,however,the gas in the Jurassic gas pools is mainly derived from the source rocks of the 3rd member of Xujiahe Formation rather than the 5th member of Xujiahe Formation.展开更多
The capacity of humic acid extracted from organic waste (HAw) to reduce Cr(Ⅵ) was tested at pH 2.5,4 and 6 and compared with coal-derived humic acid (HAc).HAw was more effective than HAc in reducing Cr(Ⅵ).Th...The capacity of humic acid extracted from organic waste (HAw) to reduce Cr(Ⅵ) was tested at pH 2.5,4 and 6 and compared with coal-derived humic acid (HAc).HAw was more effective than HAc in reducing Cr(Ⅵ).The kinetics of Cr(Ⅵ) reductions depended strongly on pH.The calculation of the apparent rate coefficients indicated that HAw was more efficient at reducing Cr(Ⅵ) than HAc,but was also more efficient than HAs from soil and peat.The reduction capability of HAs depends on the type of functional groups (i.e.,thiols and phenols) present,rather than the free radicals.HAw was more efficient at reducing Cr(Ⅵ) than HAc because more reactive phenols were present,i.e.,methoxy-and methyl-phenols.展开更多
The static recrystallization behavior of SA508-III steel was investigated by isothermal double-hit hot compression tests at the deformation temperature of 950-1 250 ℃,the strain rate of 0. 01-1 s^(-1),and the inter...The static recrystallization behavior of SA508-III steel was investigated by isothermal double-hit hot compression tests at the deformation temperature of 950-1 250 ℃,the strain rate of 0. 01-1 s^(-1),and the inter-pass time of 1-300 s.The effects of deformation parameters,including forming temperature,strain rate,degree of deformation( pre-strain) and initial austenite grain size,on the softening kinetics were analyzed. Experimental results show that static recrystallization kinetics is strongly dependent on deformation temperature and degree of deformation,while less affected by the strain rate and initial grain size. The kinetics and microstructural evolution equations of static recrystallization for SA508-III steel were developed to predict the softening behavior and the statically recrystallized grain size,respectively. Based on the comparison between the experimental and predicted results,it is found that the established equations can give a reasonable estimate of the static softening behavior for SA508-III steel.展开更多
Finding alternative local sources of plant nutrients is a practical, low-cost, and long-term strategy. In this study, laboratory column experiments were conducted in a completely randomized design to evaluate the feas...Finding alternative local sources of plant nutrients is a practical, low-cost, and long-term strategy. In this study, laboratory column experiments were conducted in a completely randomized design to evaluate the feasibility of using phosphate rock and dolostone as fertilizers or acid-neutralizing agents for application in tropical acid soils. The dissolution rates of different particle-size fractions(0.063–0.25, 0.25–0.5, and 0.5–2 mm) of both rocks were studied by citric acid solution at p H 4 and 2 and water, with extraction times of 1, 3, 5, 7, 12, 24, 72, 144, 240, and 360 h. The results showed that the dissolution of both rocks depended on the particle size,leaching solution, and extraction time. The dissolution rate of rock-forming minerals increased as the specific surface area increased,corresponding to a decrease in particle size. In all cases, the release kinetics was characterized by two phases: 1) a first stage of rapid release that lasted 24 h and would ensure short-term nutrient release, and 2) a second stage of slow release after 24 h, representing the long-term nutrient release efficiency. Both rocks were suitable as slow-release fertilizers in strongly acid soils and would ensure the replenishment of P, Ca, and Mg. A combination of fine and medium particle-size fractions should be used to ensure high nutrient-release efficiency. Much work could remain to determine the overall impact of considerable amounts of fresh rocks in soils.展开更多
基金This paper is supported by Chinese NSF project(42130114)the strategic priority research program(B)of CAS(XDB41000000)the pre-research Project on Civil Aerospace Technologies No.D020202 funded by Chinese National Space Administration(CNSA)。
文摘It is well-known that the equilibrium isotope fractionation of mercury(Hg)includes classical massdependent fractionations(MDFs)and nuclear volume effect(NVE)induced mass-independent fractionations(MIFs).However,the effect of the NVE on these kinetic processes is not known.The total fractionations(MDFs+NVEinduced MIFs)of several representative Hg-incorporated substances were selected and calculated with ab initio calculations in this work for both equilibrium and kinetic processes.NVE-induced MIFs were calculated with scaled contact electron densities at the nucleus through systematic evaluations of their accuracy and errors using the Gaussian09 and DIRAC19 packages(named the electron density scaling method).Additionally,the NVE-induced kinetic isotope effect(KIE)of Hg isotopes are also calculated with this method for several representative Hg oxidation reactions by chlorine species.Total KIEs for 202 Hg/^(198)Hg ranging from−2.27‰to 0.96‰are obtained.Three anomalous^(202)Hg-enriched KIEs(δ^(202)Hg/^(198)Hg=0.83‰,0.94‰,and 0.96‰,)caused by the NVE are observed,which are quite different from the classical view(i.e.,light isotopes react faster than the heavy ones).The electron density scaling method we developed in this study can provide an easier way to calculate the NVE-induced KIEs for heavy isotopes and serve to better understand the fractionation mechanisms of mercury isotope systems.
基金supported by Chinese NSF project(42,130,114)the strategic priority research program(B)of CAS(XDB41000000)the pre-research Project on Civil Aerospace Technologies No.D020202 funded by Chinese National Space Administration(CNSA)and Guizhou Provincial 2021 Science and Technology Subsidies(No.GZ2021SIG).
文摘Isotope eff ects are pivotal in understanding silicate melt evaporation and planetary accretion processes.Based on the Hertz-Knudsen equation,the current theory often fails to predict observed isotope fractionations of laboratory experiments due to its oversimplified assumptions.Here,we point out that the Hertz-Knudsen-equation-based theory is incomplete for silicate melt evaporation cases and can only be used for situations where the vaporized species is identical to the one in the melt.We propose a new model designed for silicate melt evaporation under vacuum.Our model considers multiple steps including mass transfer,chemical reaction,and nucleation.Our derivations reveal a kinetic isotopic fractionation factor(KIFF orα)αour model=[m(^(1)species)/m(^(2)species)]^(0.5),where m(species)is the mass of the reactant of reaction/nucleation-limiting step or species of diffusion-limiting step and superscript 1 and 2 represent light and heavy isotopes,respectively.This model can eff ectively reproduce most reported KIFFs of laboratory experiments for various elements,i.e.,Mg,Si,K,Rb,Fe,Ca,and Ti.And,the KIFF-mixing model referring that an overall rate of evaporation can be determined by two steps jointly can account for the eff ects of low P_(H2)pressure,composition,and temperature.In addition,we find that chemical reactions,diffusion,and nucleation can control the overall rate of evaporation of silicate melts by using the fitting slope in ln(−ln f)versus ln(t).Notably,our model allows for the theoretical calculations of parameters like activation energy(E_(a)),providing a novel approach to studying compositional and environmental eff ects on evaporation processes,and shedding light on the formation and evolution of the proto-solar and Earth-Moon systems.
基金supported by the National Natural Science Foundation of China (Grant Nos. 41475141, 41830860, 41575147 & 41505005)the National Key Research and Development Program of China (Grant No. 2016YFC0500102)+5 种基金the U. S. National Science Foundation (Grant No. 1520684)the Science and Technology Department of Ningxia (Grant No. 2015KJHM34)the China Special Fund for Meteorological Research in the Public Interest (Major projects, Grant No. GYHY201506001-6)the NUIST Scientific Foundation (Grant No. KLME1415)the Priority Academic Program Development of Jiangsu Higher Education Institutions (Grant No. PAPD)the Ministry of Education of the People’s Republic of China (Grant No. PCSIRT)
文摘The kinetic fractionation of open-water evaporation against the stable water isotope H_2 ^(18)O is an important mechanism underlying many hydrologic studies that use ^(18)O as an isotopic tracer. A recent in-situ measurement of the isotopic water vapor flux over a lake indicates that the kinetic effect is much weaker(kinetic factor 6.2‰) than assumed previously(kinetic factor14.2‰) by lake isotopic budget studies. This study investigates the implications of the weak kinetic effect for studies of deuterium excess-humidity relationships, regional moisture recycling, and global evapotranspiration partitioning. The results indicate that the low kinetic factor is consistent with the deuterium excess-humidity relationships observed over open oceans.The moisture recycling rate in the Great Lakes region derived from the isotopic tracer method with the low kinetic factor is a much better agreement with those from atmospheric modeling studies than if the default kinetic factor of 14.2‰ is used. The ratio of transpiration to evapotranspiration at global scale decreases from 84±9%(with the default kinetic factor) to 76±19%(with the low kinetic factor), the latter of which is in slightly better agreement with other non-isotopic partitioning results.
文摘Thermochemical sulfate reduction (TSR) in geological deposits can account for the accumulation of H2S in deep sour gas reservoirs. In this paper, thermal simulation experiments on the reaction of CH4-CaSO4 were carried out using an autoclave at high temperatures and high pressures. The products were characterized with analytical methods including carbon isotope analysis. It is found that the reaction can proceed to produce H2S, H2O and CaCO3 as the main products. Based on the experimental results, the carbon kinetic isotope fractionation was investigated, and the value of Ki (kinetic isotope effect) was calculated. The results obtained in this paper can provide useful information to explain the occurrence of H2S in deep carbonate gas reservoirs.
基金the funding support from the 973 Program(2014CB440904)CAS/SAFEA International Partnership Program for Creative Research Teams(Intraplate Mineralization Research Team,KZZD-EW-TZ-20)Chinese NSF projects(41173023,41225012,41490635,41530210)
文摘Several important equilibrium Si isotope fractionation factors among minerals,organic molecules and the H_4SiO_4 solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth's surface environments.The results reveal that,in comparison to aqueous H_4SiO_4,heavy Si isotopes will be significantly enriched in secondary silicate minerals.On the contrary,quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution.The extent of ^(28)Si-enrichment in hyper-coordinated organosilicon complexes was found to be the largest.In addition,the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer was calculated,and the results support the previous statement that highly ^(28)Sienrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations.With the equilibrium Si isotope fractionation factors provided here,Si isotope distributions in many of Earth's surface systems can be explained.For example,the change of bulk soil δ^(30)Si can be predicted as a concave pattern with respect to the weathering degree,with the minimum value where allophane completely dissolves and the total amount of sesquioxides and poorly crystalline minerals reaches their maximum.When,under equilibrium conditions,the well-crystallized clays start to precipitate from the pore solutions,the bulk soil δ^(30)Si will increase again and reach a constant value.Similarly,the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain the δ^(30)Si variations in the ground water profile.The equilibrium Si isotope fractionations among the quadracoordinated organosilicon complexes and the H_4SiO_4solution may also shed light on the Si isotope distributions in the Si-accumulating plants.
基金N ational N atural Science Foundation of China, N o.40271025 the N ational H igh Technology Research andD evelopm ent Program of China (863 Program ), N o.2002A A 135360+1 种基金 the Program of Education D epartm ent ofH unan Province,N o.03C210the CA S Tianshan G laciologicalStation Foundation,N o.TZ2000-02
文摘Under Rayleigh equilibrium condition, stable isotopic ratio in residual water increases with the decrease of the residual water proportion f exponentially, and the fractionation rate of stable isotopes is inversely proportional to temperature. However, under kinetic evaporation condition, the fi'actionation of stable isotopes is not only related to the phase temperature but also influenced by the atmospheric humidity and the mass exchange between liquid and vapor phases. The ratio 6 in residual water will not change with f after undergoing evaporation of a long time for great relative humidity. The rate that the evaporating water body reaches isotopic steady state is mainly dependent on the relative humidity in atmosphere. The analysis shows that the actual mean linear variety rates, about -30.0, of the δ^18O in residual water versus the residual water proportion at Nagqu and Amdo stations are consistent with the simulated process under temperature of 20℃ and relative humidity of 50%. The distillation line simulated under Rayleigh equilibrium condition is analogous to the global meteoric water line (MWL) as the temperature is about 20℃. Under non-equilibrium condition, the slope and constant values of distillation line are directly proportional to temperature and relative humidity. According to the basic data, the simulated distillation line is very consistent with the actual distillation line of Qinghai Lake.
文摘This work aims to investigate the intrinsic kinetics of thermal dimerization of C_5 fraction in the reactive distillation process. Experiments are conducted in an 1000-m L stainless steel autoclave under some selected design conditions. By means of the weighted least squares method, the intrinsic kinetics of thermal dimerization of C_5 fraction is established, and the corresponding pre-exponential factor as well as the activation energy are determined. For example, the pre-exponential factor A is equal to 4.39×105 and the activation energy E4 a is equal to 6.58×10J/mol for the cyclopentadiene dimerization reaction. The comparison between the experimental and calculated results shows that the kinetics model derived in this work is accurate and reliable, which can be used in the design of reactive distillation columns.
基金supported by the XDA special program of Chinese Academy of Science (No.XDA14010104)the Natural Science Foundation of China (No.41925014)。
文摘The Triassic and Jurassic tight sandstone gas in the western Sichuan depression,Sichuan Basin has attracted much attention in recent years,and the Upper Triassic coal-bearing Xujiahe Formation is believed to be the major source rock.However,there are relatively few studies on the carbon isotopic heterogeneity of methane generated from coal-measure source rocks and the origin of the natural gases in Xinchang Gas Field is still controversial.In this study,one coal-measure mudstone sample and one coal sample of the Xujiahe Formation in western Sichuan Basin were selected for gold tube pyrolysis experiment to determine their gas generation characteristics.Geological extrapolation of gas generation and methane carbon isotope fractionation parameters reveals that the main gas generation stage of Xujiahe Formation ranges from Late Jurassic to Cretaceous in the Xinchang Gas Field.The natural gas in the 5th member of Xujiahe Formation in Xinchang Gas Field is mainly derived from the 5th member of Xujiahe Formation itself,i.e.,self-generation and self-reservoir,however,the gas in the Jurassic gas pools is mainly derived from the source rocks of the 3rd member of Xujiahe Formation rather than the 5th member of Xujiahe Formation.
文摘The capacity of humic acid extracted from organic waste (HAw) to reduce Cr(Ⅵ) was tested at pH 2.5,4 and 6 and compared with coal-derived humic acid (HAc).HAw was more effective than HAc in reducing Cr(Ⅵ).The kinetics of Cr(Ⅵ) reductions depended strongly on pH.The calculation of the apparent rate coefficients indicated that HAw was more efficient at reducing Cr(Ⅵ) than HAc,but was also more efficient than HAs from soil and peat.The reduction capability of HAs depends on the type of functional groups (i.e.,thiols and phenols) present,rather than the free radicals.HAw was more efficient at reducing Cr(Ⅵ) than HAc because more reactive phenols were present,i.e.,methoxy-and methyl-phenols.
基金Item Sponsored by National Basic Research Program of China(2011CB012903)National Science and Technology Major Project of China(2012ZX04012-011)
文摘The static recrystallization behavior of SA508-III steel was investigated by isothermal double-hit hot compression tests at the deformation temperature of 950-1 250 ℃,the strain rate of 0. 01-1 s^(-1),and the inter-pass time of 1-300 s.The effects of deformation parameters,including forming temperature,strain rate,degree of deformation( pre-strain) and initial austenite grain size,on the softening kinetics were analyzed. Experimental results show that static recrystallization kinetics is strongly dependent on deformation temperature and degree of deformation,while less affected by the strain rate and initial grain size. The kinetics and microstructural evolution equations of static recrystallization for SA508-III steel were developed to predict the softening behavior and the statically recrystallized grain size,respectively. Based on the comparison between the experimental and predicted results,it is found that the established equations can give a reasonable estimate of the static softening behavior for SA508-III steel.
基金supported by the "Applied Research and Multi-sectorial Program" (FIAM) (No. 5.2.1) granted by the Italian Cooperation and Development Agency (ICDA) to the Universidade Eduardo Mondlanethe Polytechnic University of Marche, Italy for the PhD scholarship provided to the first author as well as research funding for this work
文摘Finding alternative local sources of plant nutrients is a practical, low-cost, and long-term strategy. In this study, laboratory column experiments were conducted in a completely randomized design to evaluate the feasibility of using phosphate rock and dolostone as fertilizers or acid-neutralizing agents for application in tropical acid soils. The dissolution rates of different particle-size fractions(0.063–0.25, 0.25–0.5, and 0.5–2 mm) of both rocks were studied by citric acid solution at p H 4 and 2 and water, with extraction times of 1, 3, 5, 7, 12, 24, 72, 144, 240, and 360 h. The results showed that the dissolution of both rocks depended on the particle size,leaching solution, and extraction time. The dissolution rate of rock-forming minerals increased as the specific surface area increased,corresponding to a decrease in particle size. In all cases, the release kinetics was characterized by two phases: 1) a first stage of rapid release that lasted 24 h and would ensure short-term nutrient release, and 2) a second stage of slow release after 24 h, representing the long-term nutrient release efficiency. Both rocks were suitable as slow-release fertilizers in strongly acid soils and would ensure the replenishment of P, Ca, and Mg. A combination of fine and medium particle-size fractions should be used to ensure high nutrient-release efficiency. Much work could remain to determine the overall impact of considerable amounts of fresh rocks in soils.