Effect of Sulfate on Adsorption of Zinc and Cadmium by Variable Charge Soils *1

SO 4 2- and Zn 2+ or Cd 2+ were added to three variable charge soils in different sequences. In one sequence sulfate was added first, and in the other, Zn 2+ or Cd 2+ first. The addition of sulfate to the system invariably caused an increase in adsorption of the heavy metal added, with the effect more remarkable when the soil reacted with the sulfate prior to the metal. The shift in pH 50 for both Zn and Cd adsorption was also comparatively larger in the first sequence of reactions. It was suggested that the increase in negative charge density and the resultant negative potential of the soil were the primary cause of the pronounced effect of sulfate on adsorption of Zn or Cd, and the formation of the ternary surface complex S SO 4 M might also play a role in the effect.

Effect of Crop-Straw Derived Biochars on Pb(Ⅱ) Adsorption in Two Variable Charge Soils

Two variable charge soils were incubated with biochars derived from straws of peanut, soybean, canola, and rice to investigate the effect of the biochars on their chemical properties and Pb（II） adsorption using batch experiments. The results showed soil cation exchange capacity （CEC） and pH significantly increased after 30 d of incubation with the biochars added. The incorporation of the biochars markedly increased the adsorption of Pb（II）, and both the electrostatic and non-electrostatic adsorption mechanisms contributed to Pb（II） adsorption by the variable charge soils. Adsorption isotherms illustrated legume- straw derived biochars more greatly increased Pb（II） adsorption on soils through the non-electrostatic mechanism via the formation of surface complexes between Pb（II） and acid functional groups of the biochars than did non-legume straw biochars. The adsorption capacity of Pb（II） increased, while the desorption amount slightly decreased with the increasing suspension pH for the studied soils, especially in a high suspension pH, indicating that precipitation also plays an important role in immobilizing Pb（II） to the soils.

Effect of Zn Adsorption on Charge of Variable Charge Soils

The variation in apparent charge of two typical variable charge soils resulting from Zn adsorption were studied by KC1 saturation and NH4NO3 replacement methods. Results showed that zinc were adsorbed specifically to those sites with negative charge. As in different pH ranges, the percentages of specific and electrostatic adsorptions of zinc and the mechanisms of specific adsorption were different, the effects of Zn adsorption on apparent charge were varied and could be characterized as: when 1 mmol Zn2+ was adsorbed, a change about 1 mmol in the apparent charge was observed in the low pH range (Ⅰ), 1.4 to 1.5 mmol in the moderate pH range (Ⅱ) and 0.55 to 0.6 mmol in the high pH range (Ⅲ). These experimental data, in terms of soil charge, proved once more author's conclusion in the preceding paper (Sun, 1993) that in accordance with the behaviors of Zn adsorption by the variable charge soils in relation to pH, three pH ranges with different adsorption mechanisms were delineated; that is, in Range Ⅰ, specific adsorption was the predominant mechanism, in Ranges Ⅱ and Ⅲ, specific and electrostatic adsorptions co-existed, but their specific adsorption mechanisms were not identical.

Adsorption of Chloride, Nitrate and Perchlorate by Variable Charge Soils

Two cells consisting of a chloride-selective electrode and a nitrate-selective electrode or of a chloride-selective electrode and a perchlorate-selective electrode were directly put in the soil suspension to determine the concentration ratios Cl-/ NO3- or Cl-/ ClO4- for studying the adsorption of the three anions by variable charge soils. It was found that all the concentration ratios CCl- / CNO3- and CCl- / CClO4- in suspension were smaller than unity when soil samples were in equilibrium with mixed KCl and KNO3 or KCl and KClO4 solutions of equal concentration. The order of the amount of chloride, nitrate and perchlorate adsorbed by variable charge soils was Cl-> NO3-> ClO4- when the soils adsorbed these anions from the solution containing equal concentrations of Cl-, NO3- and ClO4-. Such factors as the pH of the suspension, the iron oxide content of the soil etc. could affect the amounts and the ratios of anions adsorbed. The adsorption was chiefly caused by coulombic attraction, but a covalent force between the anion and the metal atom on the surface of soil particles may also be involved, at least for Cl- ions, even for NO3- ions.

Effect of Low-Molecular-Weight Organic Acids on Cl-Adsorption by Variable Charge Soils

Low-molecular-weight (LMW) organic acids exist widely in soils and have beenimplicated in many soil processes. The objective of the present paper was to evaluate effect of twoLMW organic acids, citric acid and oxalic acid, on Cl^-adsorption by three variable charge soils, alatosol, a lateritic red soil and a red soil, using a batch method. The results showed that thepresence of citric acid and oxalic acid led to a decrease in Cl^- adsorption with larger decreasesfor citric acid. Among the different soils Cl^- adsorption in the lateritic red soil and the redsoil was more affected by both the LMW organic acids than that in the latosol.

Adsorption of Potassium and Sodium Ions by Variable Charge Soils

Adsorption of potassium and sodium ions by four typical variable charge soils of South China was studied. The results indicated that the variable charge soils saturated with H and Al showed a much higher preference for potassium ions relative to sodium ions, and this tendency could not be changed by such factors as the pH, the concentration of the cations, the dielectric constant of solvent, the accompanying anions and the iron oxide content etc., suggesting that this difference in affinity is caused by the difference in the nature of the two cations. It was observed that a negative adsorption of sodium ions by latosol and lateritic red soil in a mixed system containing equal amount of potassium and sodium ions at low pH, which is caused by a competitive adsorption of potassium and sodium ions and repulsion of positive charge on the surfaces of soil particles for cations. The adsorption of potassium and sodium ions increased with the decreases in the dielectric constant of solvent and the iron oxide content. Sulfate affected the adsorption of potassium and sodium ions through changing the surface properties of the soils.

Effect of Specific Adsorption of Ions on Electrokinetic Properties of Variable Charge Soils

Studies were carried out by using electrophoretic method on the effects of the specific adsorption of the anions,such as SO4^2-,PO4^3-,and F^- ions,the cations,such as Ca^2+,Mn^2+,Zn^2+,and Cu^2+,ions,and the anions and cations coexisting,such as Zn^2+ and SO4^2= ions,on electrokinetic properties of the red soils as typical variable charge soils in China concerning variation in the specific ion species and concentrations,with an emphasis on the interaction between soil colloid surfaces and the ions in soil solutions.The results showed that the adsorption of specific ions led to a very pronounced decrease in zeta potentials of the soil colloids and a shift of the IEPs to lower values for specific anions,and an obvious increase in zeta potentials of the soil colloids and a shift of the IEPs to higher values for specific cations.Under circumstances of the specific anions and cations coexisting,for instance,Zn^2+ and SO4^2- ions,the zeta potentials changed with values higher than the value for SO4^2- alone and lower than that for Zn^2+ alone,and the IEP was between that for Zn^2+ and that for SO4^2-.The adsorption of Zn^2+ and Cu^2+ ions resulted in a reversal of the zeta potentials,and appearance of two IEPs for Zn^2+ and no IEP for Cu^2+,exhibiting interesting special effects of these kinds of metal ions.The higher the concentrations of the ions,the greater the change of the electrokinetic properties.

Adsorption Kinetics of Pb^(2+) and Cu^(2+) on Variable Charge Soils and Minerals: Ⅱ. Equations for Describing Experimental Data

Different mathematical methods, including linearization, differential, integration and nonlinear least squares approximation (Newton-Marquardt method), were used to fit different kinetic equations, such as zero-order, first-order (i. e, membrane diffusion), second-order, parabolic-diffusion, Elovich, two-constant equations, to the experimental data of Pb2+ and Cu2+ adsorption on variable charge soils and kaolinite. Assuming each M2+ occupied two adsorption sites, two more equations, the so-called surface second-order equation and third-order equation were derived and compared with the above equations according to the fitting results, which showed that the second-order equation and surface second-order equation, being one equation in different expressions under some conditions, were better than the other equations in describing the Pb2+ and Cu2+ adsorption kinetics, and the latter was the best.

Adsorption of Potassium and Calcium Ions by Variable Charge Soils

Interactions of potassium and calcium ions with four typical variable charge soils in South China were examined by measuring pK-0.5pCa value with a potassium ion-selective electrode and a calcium ion-selective electrode,and pK value with a potassium ion-selective electrode.The results showed that adsorption of potassium and calcium ions increased with soil suspension pH,and the tendency of the pK-0.5pCa value changing with pH differed with respect to pH range and potassium to calcium ratio.Adsorption of equal amount of calcium and potassium ions led to release of an identical number of protons,suggesting similar adsorption characteristics of these two ions when adsorbed by variable charge soils.Compared with red soil,latosol and lateritic red soil had higher adsorption selectivities for calcium ion.The red soil had a greater affinity for potassium ion than that for calcium ion at low concentration,which seems to result from its possession of 2:1 type minerals,such as vermiculite and mica with a high affinity for potassium ion.The results indicated that adsorption of potassium and calcium ions by the variable charge soils was chiefly caused by the electrostatic attraction between the cations and the soil surfaces.Moreover,it was found that sulfate could affect the adsorption by changing soil surface properties and by forming ion-pair.

Adsorption Kinetics of Pb^(2+) and Cu^(2+) on Variable Charge Soils and Minerals: Ⅲ. Adsorption Kinetics of Pb^(2+) Within 30 Minutes

The adsorption kinetics of Pb^2+ on different soils and minerals with variable charges was studied by the two ion-selective electrode technique at different pH and concentrations.The results showed that more than 95% of adsorption on all the samples occurred during the first 5 minutes.All adsorption time-dependent data could fit the surface second-order equation very well.The values of Xm were goethite>kaolinite,and latosol>red soil at the same initial reaction concentration.The values of k were kaolinite>>goethite,and latosol>red soil at the same reaction pH and initial concentration.The higher the suspension pH,the faster the adsorption occurred.The meaning of Xm got by the two ion-selective electrode technique(one kind of batch technique) was different from that by the miscible displacement technique in that the former was only the equilibrium adsorption amount at a definite concentration and pH,but the latter was almost equal to the adsorption capacity at a definite pH with much less influence of concentration.One Pb^2+ was supposed to occupy two adsorption sites as the adsorption mechanism is concerned.

Release of Hydroxyl Ions Associated with Chloride Adsorption in Electrodialyzed Variable Charge Soils

The release of hydroxyl ions from two variable charge soils associated with the adsorption of chloride in NaClO4 solutions was examined. The complete release required about 10 minutes. The release decreased with the increase in the NaClO4 concentration at first and eventually was little affected by the latter. The adsorption of Cl- was almost linearly related with the quantity of NaCl added to the system, while the OHrelease-NaCl curve varied with the soil type and the concentration of NaClO4. The logarithm of the quantity of released OH- was linearly related with the pH. The ratio of released OH- to adsorbed Cl- was larger in dilute NaClO4 solutions than in concentrated solutions and decreased with increasing NaCl.

Construction of a Pillared-layer Framework Based on Charge Balance:CO2 Adsorption and Luminescence

Via the strategy of charge balance,one new pillared layered metal-organic framework [Zn2（TNB）（2-nim）]（H3TNB = 4,4？,4？？-nitrilotribenzoicacid,2-nim = 2-nitroimidazole）（1） was successfully synthesized based on mixed ligands,where binuclear [Zn2（CO2）3]~＋ cluster-based cationic layers [Zn2（TNB）]~＋ are connected by deprotonated 2-nitroimidazole.Meanwhile,CO2 adsorption bahaviors and luminescent property of compound 1 were investigated.

Zn Adsorption by Variable Charge Soils in Relation to pH

Zn adsorption by pure oxides or in the presence of a high concentration of inner electrolyte has been extensively studied. But, in studies on Zn adsorption in the complicated soil system, especially in variable charge soils, profound knowledge about the adsorption mechanism still lacks. In this paper, taking Zn ion adsorption by two typical variable charge soils as the object of the study, author discusses the relation between Zn adsorption and pH and possible adsorption mechanisms. The results showed that in the low pH range where the amount of Zn adsorbed did not exceed 50% of Zn added, the specific adsorption was the dominant mechanism. The species of Zn specifically adsorbed was free Zn2+ ion. In the middle and high pH ranges, the mechanisms of specific and electrostatic adsorptions, co-existed, accounting for about 70% and 30% , respectively. Noteworthily, in the high pH range, the hydroxyl Zn ion (ZnOH +) from Zn2+ hydrolysis probably was a preferable species for specific adsorption.

Adsorption of Phosphate on Variable Charge Soils

The study about the adsorption of phosphate on four variable charge soils and some minerals revealed that two stage adsorption appeared in the adsorption isotherms of phosphate on 4 soils and there was a maximum adsorption on Al-oxide-typed surfaces between pH 3.5 to pH 5.5 as suspension pH changed from 2 to 9, but the adsorption amount of phosphate decreased continually as pH rose on Fe-oxide typed surfaces. The adsorption amount of phosphate and the maximum phosphate adsorption pH decreased in the order of yellow-red soil > lateritic red soil > red soil > paddy soil, which was coincided with the content order of amorphous Al oxide. The removement of organic matter and Fe oxide made the maximum phosphate adsorption pH rise from 4.0 to 5.0 and 4.5, respectively. The desorption curves with pH of four soils showed that phosphate desorbed least at pH 5. Generally the desorption was contrary to the adsorption with pH changing. There was a good accordance between adsorption or desorption and the concentration of Al in the suspension. The possible mechanisms of phosphate adsorption are discussed.

Cu Secondary Adsorption by Some Variable Charge Soils After Adsorbing SO_4^(2-)

Cu secondary adsorption by three variable charge soils collected from hubei Province and Hunan Province was investigated.The amount of Cu secondary adsorption increased with that of SO4^2- elementary adsorption and conformed with the Langmuir,freundlich and Temkin isotherms.Desorption of secondary-adsorbed Cu indicated that the hysteresis ratio decreased as Cu secondary adsorption increased,which meant that secondry-adsorbed Cu existed not only in the exchangeable form but also in the bridge form and specifically adsorbed form.The amount of Cu secondary adsorption increased with the temperature.

Regulated adsorption-diffusion and enhanced charge transfer in expanded graphite cohered with N,B bridge-doping carbon patches to boost K-ion storage

The great challenges are remained in constructing graphite-based anode with well built-in structures to accelerate kinetics and enhance stability in the advanced K-ion batteries(KIBs).Here,we firstly report the design of expanded graphite cohered by N,B bridge-doping carbon patches(NBEG)for efficient K-ion adsorption/diffusion and long-term durability.It is the B co-doping that plays a crucial role in maximizing doping-site utilization of N atoms,balancing the adsorption-diffusion kinetics,and promoting the charge transfer between NBEG and K ions.Especially,the robust lamellar structure,suitable interlayer distance,and rich active sites of the designed NBEG favor the rapid ion/electron transfer pathways and high K-ion storage capacity.Consequently,even at a low N,B doping concentration(4.36 at%,2.07 at%),NBEG anode shows prominent electrochemical performance for KIBs,surpassing most of the advanced carbon-based anodes.Kinetic studies,density functional theory simulations,and in-situ Raman spectroscopy are further performed to reveal the K-ion storage mechanism and confirm the critical actions of co-doping B.This work offers the new methods for graphite-electrode design and the deeper insights into their energy storage mechanisms in KIBs.

A Model for Anion Electric Adsorption on Variable Charge Soils

A model was established for anion electric adsorption on variable charge surfaces and an equation to describe the relationship of adsorption amount with equalibrium concentration and suspension pH was derived according to the principles of surface reaction between variable charge surface and anions.The adsorption behaviours of nitrate and chloride on variable charge soils were modelled and the results showed that the model could describe the adsorption of nitrate very well.

Optical Properties of Neutral and Charged Low Band Gap Alternating Copolyfluorenes： TD-DFT Investigation

Electronic structure and optical properties of neutral and charged low band gap alternating copolyfluorenes （Green 1, which is based on alternating repeating units consisting of alkyl-substituted fluorene and a thiophene-[1,2,5]thiadiazolo-[3,4]quinoxaline-thiophene （T-TDQ-T） unit were investigated theoretically with time-dependent density functional theory （TD-DFT） method, and their excited state properties were further analyzed with 2D site and 3D cube representations. For neutral Green 1, the band gap, binding energy, exciton binding energy, and nuclear relaxation energy were obtained. The transition dipole moments of neutral and charged Green 1 are compared using 3D transition density, which reveals the orientation and strength of transition dipole moments. The charge redistribution of neutral and charged Green 1 upon excitation are displayed and compared with 3D charge difference density. The electron-hole coherences of neutral and charged Green 1 upon excitation are investigated with 2D site representation （transition density matrix）. The excited state properties of neutral Green 1 calculated with TD-DFT method are compared with that calculated with ZINDO method, which reveals the importance of electron-electron interaction （in TD-DFT） in the excited state properties.

Kinetics and isotherms of Neutral Red adsorption on peanut husk

Adsorption of Neutral Red (NR) onto peanut husk in aqueous solutions was investigated at 295 K. Experiments were carried out as function of pH, adsorbent dosage, contact time, and initial concentration. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, and Toth isotherm models. The results indicated that the Toth and Langmuir models provided the best correlation of the experimental data. The adsorption capacity of peanut husk for the removal of NR was deter...

Discharge mode and particle transport in radio frequency capacitively coupled Ar/O_(2) plasma discharges

Simulations are conducted on capacitively coupled Ar/O_(2)mixed gas discharges employing a one-dimensional fluid coupled with an electron Monte Carlo(MC)model.The research explores the impact of different O_(2)ratio and pressures on the discharge characteristics of Ar/O_(2)plasma.At a fixed Ar/O_(2)gas ratio,with the increasing pressure,higher ion densities,as well as a slight increase in electron density in the bulk region can be observed.The discharge remains dominated by the drift-ambipolar(DA)mode,and the flux of O(3P)at the electrode increases with the increasing pressure due to higher background gas density,while the fluxes of O(1D)and Ardecrease due to the pronounced loss rate.With the increasing proportion of O_(2),a change in the dominant discharge mode from a mode to DA mode can be detected,and the O_(2)-associated charged particle densities are significantly increased.However,Ar+density shows a trend of increasing and then decreasing,while for neutral fluxes at the electrode,Arflux decreases,and O(3P)flux increases with the reduced Ar gas proportion,while trends in O(1D)flux show slight differences.The evolution of the densities of the charged particle and the neutral fluxes under different discharge parameters are discussed in detail using the ionization characteristics as well as the transport properties.Hopefully,more comprehensive understanding of Ar/O_(2)discharge characteristics in this work will provide a valuable reference for the industry.