Ferrihydrite, prepared in the presence of different amount of As and Cd in the solution, was used to study the combined effect of As and Cd coexisted in the same system on the transformation of ferrihydrite into crys...Ferrihydrite, prepared in the presence of different amount of As and Cd in the solution, was used to study the combined effect of As and Cd coexisted in the same system on the transformation of ferrihydrite into crystalline products at pH & and pH 12. The data showed that there was apparent interaction between As and Cd in the transformation process. At pH 8, the transformation product was hematite with 1% As and different percent Cd (mole fraction, so as the follows), but the size of particles formed with different amount of Cd was different. At pH 12, the transformation products varied from sole hematite with 1% As and less than 2% Cd to a mixture of hematite and goethite with more than and equal to 2% Cd, and the percentage of goethite in the transformation products increased with the increasing level of Cd in the system. XRD (X-ray diffraction) and chemical analysis data showed that almost all As and part of Cd initially present in the system were retained in the crystalline products. The presence of As increased the amount of Cd retained in the structure of iron oxide. SEM (Scanning Electron Microscope) examination showed that the presence of As and Cd also altered the morphology of cry stalline products.展开更多
The reduction of less stable ferric hydroxides and formation of ferrous phases is critical for the fate of phosphorus in anaerobic soils and sediments. The interaction between ferrous iron and phosphate was investigat...The reduction of less stable ferric hydroxides and formation of ferrous phases is critical for the fate of phosphorus in anaerobic soils and sediments. The interaction between ferrous iron and phosphate was investigated experimentally during the reduction of synthetic ferrihydrite with natural organic materials as carbon source. Ferrihydrite was readily reduced by dissimilatory iron reducing bacteria (DIRB) with between 52% and 73% Fe(III) converted to Fe(II) after 31 days, higher than without DIRB. Formation of ferrous phases was linearly coupled to almost complete removal of both aqueous and exchangeable phosphate. Simple model calculations based on the incubation data suggested ferrous phases bound phosphate with a molar ratio of Fe(II):P between 1.14 - 2.25 or a capacity of 246 - 485 mg·P·g-1 Fe(II). XRD analysis indicated that the ratio of Fe(II): P was responsible for the precipitation of vivianite (Fe3(PO4)2·8H2O), a dominant Fe(II) phosphate mineral in incubation systems. When the ratio of Fe(II):P was more than 1.5, the precipitation of Fe(II) phosphate was soundly crystallized to vivianite. Thus, reduction of ferric iron provides a mechanism for the further removal of available phosphate via the production of ferrous phases, with anaerobic soils and sediments potentially exhibiting a higher capacity to bind phosphate than some aerobic systems.展开更多
Now LiCoO2 is the most widely used electrode material in commercial rechargeable lithium-based batteries; however, the toxicity of cobalt and the scarcity of cobalt sources, as well as the limited charge/discharge cap...Now LiCoO2 is the most widely used electrode material in commercial rechargeable lithium-based batteries; however, the toxicity of cobalt and the scarcity of cobalt sources, as well as the limited charge/discharge capacity（130-140 mA.h.g-1） of LiCoO2 electrode drive many efforts to develop various alternative electrode materials, including diverse transition metal oxides and their lithiated counterparts. Amongst them, iron oxides,展开更多
The coexistence of cadmium(Cd(Ⅱ))and arsenate(As(Ⅴ))pollution has long been an environmental problem.Biochar,a porous carbonaceous material with tunable functionality,has been used for the remediation of contaminate...The coexistence of cadmium(Cd(Ⅱ))and arsenate(As(Ⅴ))pollution has long been an environmental problem.Biochar,a porous carbonaceous material with tunable functionality,has been used for the remediation of contaminated soils.However,it is still challenging for the dynamic quantification and mechanistic understanding of the simultaneous sequestration of multi-metals in biochar-engineered environment,especially in the presence of anions.In this study,ferrihydrite was coprecipitated with biochar to investigate how ferrihydritebiochar composite affects the fate of heavy metals,especially in the coexistence of Cd(Ⅱ)and As(Ⅴ).In the solution system containing both Cd(Ⅱ)and As(Ⅴ),the maximum adsorption capacities of ferrihydrite-biochar composite for Cd(Ⅱ)and As(Ⅴ)reached 82.03μmol/g and 531.53μmol/g,respectively,much higher than those of the pure biochar(26.90μmol/g for Cd(Ⅱ),and 40.24μmol/g for As(Ⅴ))and ferrihydrite(42.26μmol/g for Cd(Ⅱ),and 248.25μmol/g for As(Ⅴ)).Cd(Ⅱ)adsorption increased in the presence of As(Ⅴ),possibly due to the changes in composite surface charge in the presence of As(Ⅴ),and the increased dispersion of ferrihydrite by biochar.Further microscopic and mechanistic results showed that Cd(Ⅱ)complexed with both biochar and ferrihydrite,while As(Ⅴ)was mainly complexed by ferrihydrite in the Cd(Ⅱ)and As(Ⅴ)coexistence system.Ferrihydrite posed vital importance for the co-adsorption of Cd(Ⅱ)and As(Ⅴ).The different distribution patterns revealed by this study help to a deeper understanding of the behaviors of cations and anions in the natural environment.展开更多
Hexavalent chromium[Cr(Ⅵ)]causes serious harm to the environment due to its high toxicity,solubility,and mobility.Ferrihydrites(Fh)are the main adsorbent and trapping agent of Cr(Ⅵ)in soils and aquifers,and they usu...Hexavalent chromium[Cr(Ⅵ)]causes serious harm to the environment due to its high toxicity,solubility,and mobility.Ferrihydrites(Fh)are the main adsorbent and trapping agent of Cr(Ⅵ)in soils and aquifers,and they usually coexist with silicate(Si),forming Si-containing ferrihydrite(Si-Fh)mixtures.However,the mechanism of Cr(Ⅵ)retention by Si-Fh mixtures is poorly understood.In this study,the behaviors and mechanisms of Cr(Ⅵ)adsorption onto Si-Fh with different Si/Fe molar ratios was investigated.Transmission electron microscope,Fourier transform infrared spectroscopy,X-ray diffraction,X-ray photoelectron spectroscopy,and other techniques were used to characterize Si-Fh and Cr(Ⅵ)-loading of Si-Fh.The results show that specific surface area of Si-Fh increases gradually with increasing Si/Fe ratios,but Cr(Ⅵ)adsorption on Si-Fh decreases with increasing Si/Fe ratios.This is because with an increase in Si/Fe molar ratio,the point of zero charge of Si-Fh gradually decreases and electrostatic repulsion between Si-Fh and Cr(Ⅵ)increases.However,the complexation of Cr(Ⅵ)is enhanced due to the increase in adsorbed hydroxyl(A-OH-)on Si-Fh with increasing Si/Fe molar ratio,which partly counteracts the effect of the electrostatic repulsion.Overall,the increase in the electrostatic repulsion has a greater impact on adsorption than the additional complexation with Si-Fh.Density functional theory calculation further supports this observation,showing the increases in electron variation of bonding atoms and reaction energies of inner spherical complexes with the increase in Si/Fe ratio.展开更多
Sulfate-reducing bacteria play an important role in the geochemistry of iron(oxyhydr)oxide and arsenic(As)in natural environments;however,the associated reaction processes are yet to be fully understood.In this study,...Sulfate-reducing bacteria play an important role in the geochemistry of iron(oxyhydr)oxide and arsenic(As)in natural environments;however,the associated reaction processes are yet to be fully understood.In this study,batch experiments coupled with geochemical,spectroscopic,microscopic,and thermodynamic analyses were conducted to investigate the dynamic coupling of ferrihydrite transformation and the associated As desorption/redistribution mediated by Desulfovibrio vulgaris(D.vulgaris).The results indicated that D.vulgaris could induce ferrihydrite transformation via S^(2-)-driven and direct reduction processes.In the absence of SO_(4)^(2-),D.vulgaris directly reduced ferrihydrite,and As desorption and re-sorption occurred simultaneously during the partial transformation of ferrihydrite to magnetite.The increase in SO_(4)^(2-)loading promoted the S^(2-)-driven reduction of ferrihydrite and accelerated the subsequent mineralogical transformation.In the low and medium SO_(4)^(2-)treatments,ferrihydrite was completely transformed to a mixture of magnetite and mackinawite,which increased the fraction of As in the residual phase and stabilized As.In the high SO_(4)^(2-)treatment,although the replacement of ferrihydrite by only mackinawite also increased the fraction of As in the residual phase,22.1%of the total As was released into the solution due to the poor adsorption affinity of As to mackinawite and the conversion of As^(5+)to As^(3+).The mechanisms of ferrihydrite reduction,mineralogy transformation,and As mobilization and redistribution mediated by sulfate-reducing bacteria are closely related to the surrounding SO_(4)^(2-)loadings.These results advance our understanding of the biogeochemical behavior of Fe,S,and As,and are helpful for the risk assessment and remediation of As contamination.展开更多
Lignin is a common soil organic matter that is present in soils,but its effect on the transformation of ferrihydrite(Fh)remains unclear.Organic matter is generally assumed to inhibit Fh transformation.However,lignin c...Lignin is a common soil organic matter that is present in soils,but its effect on the transformation of ferrihydrite(Fh)remains unclear.Organic matter is generally assumed to inhibit Fh transformation.However,lignin can reduce Fh to Fe(Ⅱ),in which Fe(Ⅱ)-catalyzed Fh transformation occurs.Herein,the effects of lignin on Fh transformation were investigated at 75℃ as a function of the lignin/Fh mass ratio(0-0.2),pH(4-8)and aging time(0-96 hr).The results of Fh-lignin samples(mass ratios=0.1)aged at different pH values showed that for Fh-lignin the time of Fh transformation into secondary crystalline minerals was significantly shortened at pH 6 when compared with pure Fh,and the Fe(Ⅱ)-accelerated transformation of Fh was strongly dependent on pH.Under pH 6,at low lignin/Fh mass ratios(0.05-0.1),the time of secondary mineral formation decreased with increasing lignin content.For high lignosulfonate-content material(lignin:Fh=0.2),Fh did not transform into secondary minerals,indicating that lignin content plays a major role in Fh transformation.In addition,lignin affected the pathway of Fh transformation by inhibiting goethite formation and facilitating hematite formation.The effect of coprecipitation of lignin on Fh transformation should be useful in understanding the complex iron and carbon cycles in a soil environment.展开更多
文摘Ferrihydrite, prepared in the presence of different amount of As and Cd in the solution, was used to study the combined effect of As and Cd coexisted in the same system on the transformation of ferrihydrite into crystalline products at pH & and pH 12. The data showed that there was apparent interaction between As and Cd in the transformation process. At pH 8, the transformation product was hematite with 1% As and different percent Cd (mole fraction, so as the follows), but the size of particles formed with different amount of Cd was different. At pH 12, the transformation products varied from sole hematite with 1% As and less than 2% Cd to a mixture of hematite and goethite with more than and equal to 2% Cd, and the percentage of goethite in the transformation products increased with the increasing level of Cd in the system. XRD (X-ray diffraction) and chemical analysis data showed that almost all As and part of Cd initially present in the system were retained in the crystalline products. The presence of As increased the amount of Cd retained in the structure of iron oxide. SEM (Scanning Electron Microscope) examination showed that the presence of As and Cd also altered the morphology of cry stalline products.
文摘The reduction of less stable ferric hydroxides and formation of ferrous phases is critical for the fate of phosphorus in anaerobic soils and sediments. The interaction between ferrous iron and phosphate was investigated experimentally during the reduction of synthetic ferrihydrite with natural organic materials as carbon source. Ferrihydrite was readily reduced by dissimilatory iron reducing bacteria (DIRB) with between 52% and 73% Fe(III) converted to Fe(II) after 31 days, higher than without DIRB. Formation of ferrous phases was linearly coupled to almost complete removal of both aqueous and exchangeable phosphate. Simple model calculations based on the incubation data suggested ferrous phases bound phosphate with a molar ratio of Fe(II):P between 1.14 - 2.25 or a capacity of 246 - 485 mg·P·g-1 Fe(II). XRD analysis indicated that the ratio of Fe(II): P was responsible for the precipitation of vivianite (Fe3(PO4)2·8H2O), a dominant Fe(II) phosphate mineral in incubation systems. When the ratio of Fe(II):P was more than 1.5, the precipitation of Fe(II) phosphate was soundly crystallized to vivianite. Thus, reduction of ferric iron provides a mechanism for the further removal of available phosphate via the production of ferrous phases, with anaerobic soils and sediments potentially exhibiting a higher capacity to bind phosphate than some aerobic systems.
基金the National Natural Science Foundation of China(Nos.20401015 and 50574082)Beijing Nova Pro-gram(No.2005B20)Program for New Century Excellent Talents in Universities of China
文摘Now LiCoO2 is the most widely used electrode material in commercial rechargeable lithium-based batteries; however, the toxicity of cobalt and the scarcity of cobalt sources, as well as the limited charge/discharge capacity（130-140 mA.h.g-1） of LiCoO2 electrode drive many efforts to develop various alternative electrode materials, including diverse transition metal oxides and their lithiated counterparts. Amongst them, iron oxides,
基金supported by the National Key R&D Program of China(No.2019YFC1803900)the National Natural Science Foundation of China(No.42107264)+1 种基金Guangdong Basic and Applied Basic Research Foundation(No.2020A1515110610)Guangzhou Basic and Applied Basic Research Foundation(No.202002030364)。
文摘The coexistence of cadmium(Cd(Ⅱ))and arsenate(As(Ⅴ))pollution has long been an environmental problem.Biochar,a porous carbonaceous material with tunable functionality,has been used for the remediation of contaminated soils.However,it is still challenging for the dynamic quantification and mechanistic understanding of the simultaneous sequestration of multi-metals in biochar-engineered environment,especially in the presence of anions.In this study,ferrihydrite was coprecipitated with biochar to investigate how ferrihydritebiochar composite affects the fate of heavy metals,especially in the coexistence of Cd(Ⅱ)and As(Ⅴ).In the solution system containing both Cd(Ⅱ)and As(Ⅴ),the maximum adsorption capacities of ferrihydrite-biochar composite for Cd(Ⅱ)and As(Ⅴ)reached 82.03μmol/g and 531.53μmol/g,respectively,much higher than those of the pure biochar(26.90μmol/g for Cd(Ⅱ),and 40.24μmol/g for As(Ⅴ))and ferrihydrite(42.26μmol/g for Cd(Ⅱ),and 248.25μmol/g for As(Ⅴ)).Cd(Ⅱ)adsorption increased in the presence of As(Ⅴ),possibly due to the changes in composite surface charge in the presence of As(Ⅴ),and the increased dispersion of ferrihydrite by biochar.Further microscopic and mechanistic results showed that Cd(Ⅱ)complexed with both biochar and ferrihydrite,while As(Ⅴ)was mainly complexed by ferrihydrite in the Cd(Ⅱ)and As(Ⅴ)coexistence system.Ferrihydrite posed vital importance for the co-adsorption of Cd(Ⅱ)and As(Ⅴ).The different distribution patterns revealed by this study help to a deeper understanding of the behaviors of cations and anions in the natural environment.
基金supported by the National Natural Science Foundation of China(Nos.42130509 and 42177061)the National Key Research and Development Program of China(No.2020YFC1808300)Jilin Province Science and Technology Development Projects(No.20190303056SF)。
文摘Hexavalent chromium[Cr(Ⅵ)]causes serious harm to the environment due to its high toxicity,solubility,and mobility.Ferrihydrites(Fh)are the main adsorbent and trapping agent of Cr(Ⅵ)in soils and aquifers,and they usually coexist with silicate(Si),forming Si-containing ferrihydrite(Si-Fh)mixtures.However,the mechanism of Cr(Ⅵ)retention by Si-Fh mixtures is poorly understood.In this study,the behaviors and mechanisms of Cr(Ⅵ)adsorption onto Si-Fh with different Si/Fe molar ratios was investigated.Transmission electron microscope,Fourier transform infrared spectroscopy,X-ray diffraction,X-ray photoelectron spectroscopy,and other techniques were used to characterize Si-Fh and Cr(Ⅵ)-loading of Si-Fh.The results show that specific surface area of Si-Fh increases gradually with increasing Si/Fe ratios,but Cr(Ⅵ)adsorption on Si-Fh decreases with increasing Si/Fe ratios.This is because with an increase in Si/Fe molar ratio,the point of zero charge of Si-Fh gradually decreases and electrostatic repulsion between Si-Fh and Cr(Ⅵ)increases.However,the complexation of Cr(Ⅵ)is enhanced due to the increase in adsorbed hydroxyl(A-OH-)on Si-Fh with increasing Si/Fe molar ratio,which partly counteracts the effect of the electrostatic repulsion.Overall,the increase in the electrostatic repulsion has a greater impact on adsorption than the additional complexation with Si-Fh.Density functional theory calculation further supports this observation,showing the increases in electron variation of bonding atoms and reaction energies of inner spherical complexes with the increase in Si/Fe ratio.
基金supported by the National Key Research and Development Plan of China (No.2019YFC1805300)Postdoctoral Science Foundation (No.2022M711476)+1 种基金the National Nature Science Foundation of China (No.41830861)the Program for Guangdong Introducing Innovative and Entrepreneurial Teams (No.2017ZT07Z479)。
文摘Sulfate-reducing bacteria play an important role in the geochemistry of iron(oxyhydr)oxide and arsenic(As)in natural environments;however,the associated reaction processes are yet to be fully understood.In this study,batch experiments coupled with geochemical,spectroscopic,microscopic,and thermodynamic analyses were conducted to investigate the dynamic coupling of ferrihydrite transformation and the associated As desorption/redistribution mediated by Desulfovibrio vulgaris(D.vulgaris).The results indicated that D.vulgaris could induce ferrihydrite transformation via S^(2-)-driven and direct reduction processes.In the absence of SO_(4)^(2-),D.vulgaris directly reduced ferrihydrite,and As desorption and re-sorption occurred simultaneously during the partial transformation of ferrihydrite to magnetite.The increase in SO_(4)^(2-)loading promoted the S^(2-)-driven reduction of ferrihydrite and accelerated the subsequent mineralogical transformation.In the low and medium SO_(4)^(2-)treatments,ferrihydrite was completely transformed to a mixture of magnetite and mackinawite,which increased the fraction of As in the residual phase and stabilized As.In the high SO_(4)^(2-)treatment,although the replacement of ferrihydrite by only mackinawite also increased the fraction of As in the residual phase,22.1%of the total As was released into the solution due to the poor adsorption affinity of As to mackinawite and the conversion of As^(5+)to As^(3+).The mechanisms of ferrihydrite reduction,mineralogy transformation,and As mobilization and redistribution mediated by sulfate-reducing bacteria are closely related to the surrounding SO_(4)^(2-)loadings.These results advance our understanding of the biogeochemical behavior of Fe,S,and As,and are helpful for the risk assessment and remediation of As contamination.
基金supported by the National Key Research and Development Program of China(No.2020YFC1808002)the National Natural Science Foundation of China(Nos.52104406,and U20A20267)the Natural Science Foundation of Hunan Province(Nos.2022JJ20074,and 2020JJ4740)。
文摘Lignin is a common soil organic matter that is present in soils,but its effect on the transformation of ferrihydrite(Fh)remains unclear.Organic matter is generally assumed to inhibit Fh transformation.However,lignin can reduce Fh to Fe(Ⅱ),in which Fe(Ⅱ)-catalyzed Fh transformation occurs.Herein,the effects of lignin on Fh transformation were investigated at 75℃ as a function of the lignin/Fh mass ratio(0-0.2),pH(4-8)and aging time(0-96 hr).The results of Fh-lignin samples(mass ratios=0.1)aged at different pH values showed that for Fh-lignin the time of Fh transformation into secondary crystalline minerals was significantly shortened at pH 6 when compared with pure Fh,and the Fe(Ⅱ)-accelerated transformation of Fh was strongly dependent on pH.Under pH 6,at low lignin/Fh mass ratios(0.05-0.1),the time of secondary mineral formation decreased with increasing lignin content.For high lignosulfonate-content material(lignin:Fh=0.2),Fh did not transform into secondary minerals,indicating that lignin content plays a major role in Fh transformation.In addition,lignin affected the pathway of Fh transformation by inhibiting goethite formation and facilitating hematite formation.The effect of coprecipitation of lignin on Fh transformation should be useful in understanding the complex iron and carbon cycles in a soil environment.
