Comments on "Ion adsorption components in liquid/solid systems"

Recently, Wu et al. (J Environ Sci 18(2006) 1167-1175) published a paper entitled as above. In the paper, the authors proposed a plotting method for describing adsorption isotherm, where adsorption density (q e) was plotted against the ratio of equilibrium concentration/particle concentration (Ce/W0) rather than (Ce) as traditionally defined. The authors claimed that this plot can eliminate the "particle concentration effect" (i.e., adsorption isotherm declines with increasing particle concentration), which may otherwise be inevasible with traditionally defined adsorption isotherms. We think that their conclusion is conceptually flawed and the plot may cause substantial inconstancy problems in practice.     

Ion adsorption components in liquid/solid systems

Experiments on Zn^2＋ and Cd^2＋ adsorptions on vermiculite in aqueous solutions were conducted to investigate the widely observed adsorbent concentration effect on the traditionally defined adsorption isotherm in the adsorbate range 25--500 mg/L and adsorbent range 10--150 g/L. The results showed that the equilibrium ion adsorption density did not correspond to a unique equilibrium ion concentration in liquid phase. Three adsorbate/adsorbent ratios, the equilibrium adsorption density, the ratio of equilibrium adsorbate concentration in liquid phase to adsorbent concentration, and the ratio of initial adsorbate concentration to adsorbent concentration, were found to be related with unique values in the tested range. Based on the assumption that the equilibrium state of a liquid/solid adsorption system is determined by four mutually related components： adsorbate in liquid phase, adsorbate in solid phase, uncovered adsorption site and covered adsorption site, and that the equilibrium chemical potentials of these components should be equalized, a new model was presented for describing ion adsorption isotherm in liquid/solid systems. The proposed model fit well the experimental data obtained from the examined samples.     

Adsorption–desorption behavior of atrazine on agricultural soils in China

Adsorption and desorption are important processes that affect atrazine transport,transformation,and bioavailability in soils.In this study,the adsorption–desorption characteristics of atrazine in three soils(laterite,paddy soil and alluvial soil) were evaluated using the batch equilibrium method.The results showed that the kinetics of atrazine in soils was completed in two steps:a"fast" adsorption and a "slow" adsorption and could be well described by pseudo-second-order model.In addition,the adsorption equilibrium isotherms were nonlinear and were well fitted by Freundlich and Langmuir models.It was found that the adsorption data on laterite,and paddy soil were better fitted by the Freundlich model;as for alluvial soil,the Langmuir model described it better.The maximum atrazine sorption capacities ranked as follows:paddy soil alluvial soil laterite.Results of thermodynamic calculations indicated that atrazine adsorption on three tested soils was spontaneous and endothermic.The desorption data showed that negative hysteresis occurred.Furthermore,lower solution pH value was conducive to the adsorption of atrazine in soils.The atrazine adsorption in these three tested soils was controlled by physical adsorption,including partition and surface adsorption.At lower equilibrium concentration,the atrazine adsorption process in soils was dominated by surface adsorption;while with the increase of equilibrium concentration,partition was predominant.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Synthesis of mesoporous Cu/Mg/Fe layered double hydroxide and its adsorption performance for arsenate in aqueous solutions

The mesoporous Cu/Mg/Fe layered double hydroxide(Cu/Mg/Fe-LDH) with carbonate intercalation was synthesized and used for the removal of arsenate from aqueous solutions.The Cu/Mg/Fe-LDH was characterized by Fourier transform infrared spectrometry,X-ray diffraction crystallography,scanning electron microscopy,X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller.Effects of various physico-chemical parameters such as pH,adsorbent dosage,contact time and initial arsenate concentration on the adsorption of arsenate onto Cu/Mg/Fe-LDH were investigated.Results showed that it was efficient for the removal of arsenate,and the removal efficiency of arsenate increased with the increment of the adsorbent dosage,while the arsenate adsorption capacity decreased with increase of initial pH from 3 to 11.The adsorption isotherms can be well described by the Langmuir model with R 2 > 0.99.Its adsorption kinetics followed the pseudo second-order kinetic model.Coexisting ions such as HPO42-,CO32-,SO42and NO3could compete with arsenate for adsorption sites on the Cu/Mg/Fe-LDH.The adsorption of arsenate on the adsorbent can be mainly attributed to the ion exchange process.It was found that the synthesized Cu/Mg/Fe-LDH can reduce the arsenate concentration down to a final level of < 10 μg/L under the experimental conditions,and makes it a potential material for the decontamination of arsenate polluted water.     

Removal of cobalt(Ⅱ) ion from aqueous solution by chitosan-montmorillonite

Montmorillonite （MMT） modified with chitosan （CTS, molecular weight = S x 104） was applied to remove heavy metal cations by using Co2＋ as a model ion. An increase in MMT interlayer distance observed from X-ray diffraction indicates the intercalation of CTS into MMT. Together with the results of scanning electron microscopy and Fourier transform infrared spectroscopy, it was concluded that the composite material of CTS and MMT （CTS-- MMT） was prepared successfully. The mass ratio of CTS to MMT had a strong influence on the adsorption performance of CTS-MMT. The highest adsorption value of 150 mg/g was obtained over the composite material with CTS to MMT mass ratio of 0.25, which is much higher than those reported in other studies. The adsorption isotherms and kinetic results indicated that Co2＋ was adsorbed over CTS-MMT in a multilayer model, and the chemical sorption of Co2＋ was determined to be the rate-limiting step.     

Adsorption and desorption of herbicide monosulfuron-ester in Chinese soils

Monosulfuron-ester is a new, low rate, sulfonylurea herbicide that is being promoted for annual broadleaf and gramineal weed control; however, there is a lack of published information on its behavior in soils. The adsorption and desorption of monosulfuronester by seven type soils were measured using a batch equilibrium technique. The results showed that the Freundlich equation fitted its adsorption and desorption well, and the Freundlich constant values (Kf-ads) ranged from 0.88 to 5.66. Adsorption isotherms were nonlinear with 1/nf-ads values < 1. Soil pH, organic matter (OM), and clay content were the main factors influencing its adsorption and desorption. Adsorption and desorption were negatively correlated with pH 4.0–8.0 while positively correlated with OM and clay content. The adsorption of monosulfuron-ester was mainly a physical process, because its free energy (ΔG) in seven soils was less than 40 kJ/mol. Monosulfuron-ester adsorption by three soils increased with increasing CaCl2 concentration using CaCl2 as a background electrolyte. Monosulfuron-ester desorption was hysteretic in all tested soils.     

Pb(II) removal from water using Fe-coated bamboo charcoal with the assistance of microwaves

Bamboo charcoal(BC) was used as starting material to prepare iron-modified bamboo charcoal(Fe-MBC) by its impregnation in FeCl 3 and HNO 3 solutions simultaneously,followed by microwave heating.The material can be used as an adsorbent for Pb(Ⅱ) contaminants removal in water.The composites were prepared with Fe molar concentration of 0.5,1.0 and 2.0 mol/L and characterized by means of N 2 adsorption-desorption isotherms,X-ray diffraction spectroscopy(XRD),scanning electron microscopy coupled with energy dispersive X-ray spectrometry(SEM-EDS),Fourier transform infrared(FT-IR) and point of zero charge(pH pzc) measurements.Nitrogen adsorption analyses showed that the BET specific surface area and total pore volume increased with iron impregnation.The adsorbent with Fe molar concentration of 2 mol/L(2Fe-MBC) exhibited the highest surface area and produced the best pore structure.The Pb(Ⅱ) adsorption process of 2Fe-MBC and BC were evaluated in batch experiments and 2Fe-MBC showed an excellent adsorption capability for removal Pb(Ⅱ).The adsorption of Pb(Ⅱ) strongly depended on solution pH,with maximum values at pH 5.0.The ionic strength had a significant effect on the adsorption at pH < 6.0.The adsorption isotherms followed the Langmuir isotherm model well,and the maximum adsorption capacity for Pb(Ⅱ) was 200.38 mg/g for 2Fe-MBC.The adsorption processes were well fitted by a pseudo second-order kinetic model.Thermodynamic parameters showed that the adsorption of Pb(Ⅱ) onto Fe-MBC was feasible,spontaneous,and exothermic under the studied conditions,and the ion exchange mechanism played an significant role.These results have important implications for the design of low-cost and effective adsorbents in the removal of Pb(Ⅱ) from wastewater.     

Particle concentration effect in adsorption/desorption of Zn(Ⅱ) on anatase type nano TiO_2

Adsorption/desorption in a new Zn(Ⅱ)-TiO_2 adsorption system was investigated at different particle concentrations(C_p).TEM,SEM and XRD analyses revealed that the TiO_2 particles were an aggregation of nano-sized(approximately 10 nm)pure anatase-type TiO_2. Adsorption experiments were carried out with particle concentrations of 100,400 and 1000 mg/L,and their adsorption isotherms were found to decline successively,showing an obvious C_p effect.Desorption experiments indicated that adsorption in this system was irreversible,and the irreversibility increased with increasing C_p.These phenomena could be explained by the MEA(metastable equilibrium adsorption)theory and the C_p effect could be modeled well with an MEA-Freundlich-type C_p effect isotherm equation. This study may help understand environmental behavior of contaminants on ultrafine natural particles.     

Size distribution of the secondary organic aerosol particles from the photooxidation of toluene

In a smog chamber, the photooxidation of toluene was initiated by hydroxyl radical （OH.） under different experimental conditions. The size distribution of secondary organic aerosol（SOA） particles from the above reaction was measured using aerodynamic particle sizer spectrometer. It was found from our experimental results that the number of SOA particles increased with increasing the concentration of toluene. As the reaction time prolonged, the sum of SOA particles was also increased. After a reaction time of 130 min, the concentration of secondary organic aerosol particles would be kept constant at 2300 particles/cm^3. Increasing illumination power of blacklamps could significantly induce a higher concentration of secondary organic aerosol particle. The density of SOA particles would also be increased with increasing concentration of CH30NO, however, it would be decreased as soon as the concentration of CH30NO was larger than 225.2 ppm. Nitrogen oxide with initial concentration higher than 30. 1 ppm was also found to have little effect on the formation of secondary organic aerosol.     

Study of cyanide removal from contaminated water using zinc peroxide nanomaterial

The present study highlights the potential application of zinc peroxide(ZnO_2)nanomaterial as an efficient material for the decontamination of cyanide from contaminated water. A process patent for ZnO_2 synthesis has been granted in United States of America(US Patent number 8,715,612; May 2014),South Africa,Bangladesh,and India. The ZnO_2 nanomaterial was capped with polyvinylpyrrolidone(PVP)to control the particle size. The PVP capped ZnO_2nanomaterial(PVP-ZnO_2)before and after adsorption of cyanide was characterized by scanning electron microscope,transmission electron microscope,X-ray diffractometer,Fourier transform infrared spectroscopy and time of flight-secondary ion mass spectrometry. The remaining concentration of cyanide after adsorption by PVP-ZnO_2 was determined using ion chromatograph. The adsorption of cyanide over PVP-ZnO_2 was also studied as a function of p H,adsorbent dose,time and concentration of cyanide. The maximum removal of cyanide was observed in p H range 5.8–7.8 within 15 min. The adsorption data was fitted to Langmuir and Fruendlich isotherm and it has been observed that data follows both the isotherms and also follows second order kinetics.     

Effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils

Glyphosate （GPS） is a non-selective, post-mergence herbicide that is widely used throughout the world. Due to the similar molecular structures of glyphosate and phosphate, adsorption of glyphosate on soil is easily affected by coexisting phosphate, especially when phosphate is applied at a significant rate in farmland. This paper studied the effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils including two variable charge soils and one permanent charge soil. The results indicated that Freundlich equations used to simulate glyphosate adsorption isotherms gave high correlation coefficients（0.990-0.998） with K values of 2751, 2451 and 166 for the zhuanhong soil（ZH soil, Laterite）, red soil（ RS, Udic Ferrisol） and Wushan paddy soil（WS soil, Anthrosol）, respectively. The more the soil iron and aluminum oxides and clay contained, the more glyphosate adsorbed. The presence of phosphate significantly decreased the adsorption of glyphosate to the soils by competing with glyphosate for adsorption sites of soils. Meanwhile, the effects of phosphate on adsorption of glyphosate on the two variable charge soils were more significant than that on the permanent charge soil. When phosphate and glyphosate were added in the soils in different orders, the adsorption quantities of glyphosate on the soils were different, which followed GPS-soil 〉 GPS-P-soil = GPS-Soil-P 〉 P-soil-GPS, meaning a complex interaction occurred among glyphosate, phosphate and the soils.     

Metal composition of layered double hydroxides (LDHs) regulating ClO4- adsorption to calcined LDHs via the memory effect and hydrogen bonding

A series of calcined carbonate layered double hydroxides （CLDHs） with various metal compositions and different M^2＋/M^3＋ ratios were prepared as adsorbents for perchlorate. Adsorption isotherms fit Langmuir model well, and the adsorption amount followed the order of MgA1-CLDHs 1〉 MgFeCLDHs 〉〉 ZnA1-CLDHs. The isotherms of MgA1-CLDHs and MgFe-CLDHs displayed a two-step shape at low and high concentration ranges and increased with an increase in the M^2＋/M^3＋ ratio from 2 to 4. The two-step isotherm was not observed for ZnA1-CLDHs, and the adsorption was minimally affected by the M^2＋/M^3＋ ratio. The LDHs, CLDHs and the reconstructed samples were characterized by X-ray diffraction, SEM, FT-IR and Raman spectra to delineate the analysis of perchlorate adsorption mechanisms. The perchlorate adsorption of MgA1-CLDHs and MgFe-CLDHs was dominated by the structural memory effect and the hydrogen bonds between the free hydroxyl groups on the reconstructed-LDHs and the oxygen atoms of the perchlorates. For ZnAI-CLDHs, the perchlorate adsorption was controlled by the structural memory effect only, as the hydroxyl groups on the hydroxide layers preferred to form strong hydrogen bonds with carbonate over perchlorate, which locked the intercalated perchlorate into a more confined nano-interlayer. Several distinct binding mechanisms of perchlorate by CLDHs with unique M^2＋ ions were proposed.     

A comparative study and evaluation of sulfamethoxazole adsorption onto organo-montmorillonites

Three organo-montmorillonites were prepared using surfactants, and their adsorption behaviors toward sulfamethoxazole（SMX） were investigated. The surfactants used were cetyltrimethyl ammonium bromide（CTMAB）, 3-（N,N-dimethylhexadecylammonio） propane sulfonate（HDAPS） and 1,3-bis（hexadecyldimethylammonio）-propane dibromide（BHDAP）. The properties of the organo-montmorillonites were characterized by X-ray diffraction, scanning electron microscopy and N2adsorption–desorption isotherm measurements. Results showed that the interlayer spacing of montmorillonite was increased and the surface area as well as the morphology were changed. Batch adsorption experiments showed that the surfactant loading amount had a great effect on the adsorption of SMX. The adsorption process was p H dependent and the maximum adsorption capacity was obtained at p H 3 for HDAPS-Mt, while CTMAB-Mt and BHDAP-Mt showed a high removal efficiency at 3–11. The adsorption capacity increased with the initial SMX concentration and contact time but decreased with increasing solution ionic strength.Kinetic data were best described by the pseudo second-order model. Equilibrium data were best represented by the Langmuir model, and the Freundlich constant（n） indicated a favorable adsorption process. The maximum adsorption capacity of SMX was 235.29 mg/g for CTMAB-Mt, 155.28 mg/g for HDAPS-Mt and 242.72 mg/g for BHDAP-Mt. Thermodynamic parameters were calculated to evaluate the spontaneity and endothermic or exothermic nature. The adsorption mechanism was found to be dominated by electrostatic interaction,while hydrophobic interaction played a secondary role.     

Effect of calcium on adsorption capacity of powdered activated carbon

We investigated the effect of calcium ion on the adsorption of humic acid (HA) (as a target pollutant) by powered activated carbon. The HA adsorption isotherms at different pH and kinetics of two different solutions including HA alone and HA doped Ca²⁺, were performed. It was showed that the adsorption capacity of powdered activated carbon (PAC) for HA was markedly enhanced when Ca²⁺ was doped into HA. Also, HA and Ca²⁺ taken as nitrate were tested on the uptake of each other respectively and it was showed that the adsorbed amounts of both of them were significantly promoted when HA and calcium co-existed. Furthermore, the adsorbed amount of HA slightly decreased with the increasing of Ca²⁺ concentration, whereas the amount of calcium increased with the increasing of HA concentration, but all above the amounts without addition. Finally, the change of pH before and after adsorption process is studied. In the two different solutions including HA alone and HA doped Ca²⁺, pH had a small rise, but the extent of pH of later solution was bigger.     

Rapid adsorption of toxic Pb(Ⅱ) ions from aqueous solution using multiwall carbon nanotubes synthesized by microwave chemical vapor deposition technique

Multiwall carbon nanotubes(MWCNTs) were synthesized using a tubular microwave chemical vapor deposition technique, using acetylene and hydrogen as the precursor gases and ferrocene as catalyst. The novel MWCNT samples were tested for their performance in terms of Pb(Ⅱ)binding. The synthesized MWCNT samples were characterized using Fourier Transform Infrared(FT-IR), Brunauer, Emmett and Teller(BET), Field Emission Scanning Electron Microscopy(FESEM) analysis, and the adsorption of Pb(Ⅱ) was studied as a function of p H,initial Pb(Ⅱ) concentration, MWCNT dosage, agitation speed, and adsorption time, and process parameters were optimized. The adsorption data followed both Freundlich and Langmuir isotherms. On the basis of the Langmuir model, Qmaxwas calculated to be 104.2 mg/g for the microwave-synthesized MWCNTs. In order to investigate the dynamic behavior of MWCNTs as an adsorbent, the kinetic data were modeled using pseudo first-order and pseudo second-order equations. Different thermodynamic parameters, viz., ΔH0, ΔS0and ΔG0were evaluated and it was found that the adsorption was feasible, spontaneous and endothermic in nature. The statistical analysis revealed that the optimum conditions for the highest removal(99.9%) of Pb(Ⅱ) are at p H 5, MWCNT dosage 0.1 g, agitation speed 160 r/min and time of 22.5 min with the initial concentration of 10 mg/L. Our results proved that microwave-synthesized MWCNTs can be used as an effective Pb(Ⅱ) adsorbent due to their high adsorption capacity as well as the short adsorption time needed to achieve equilibrium.     

Biosorption of clofibric acid and carbamazepine in aqueous solution by agricultural waste rice straw

Due to their widespread use, clofibric acid （CA） and carbamazepine （CBZ） have been frequently detected simultaneously at relatively high concentrations in aquatic environments. In this study, agricultural waste rice straw was employed as a potentially low-cost, effective and easy-to-operate biosorbent （RSB） to remove CA and CBZ. The adsorption of both pharmaceuticals followed pseudo second-order kinetics, and intraparticle diffusion was an important rate-limiting step. The adsorption isotherms of both drugs were fit well with Freundlich model. The adsorption of CA onto RSB was exothermic and was more likely to be dominated by physical processes, while the adsorption of CBZ was endothermic. Solution pH was determined to be the most important factor for CA adsorption, such that the adsorption capacity of CA onto RSB increased with the decline of solution pH. In the lower range of solution pH below 3. l, the CA removal efficiency was enhanced with the increase of biosorbent dosage. The CBZ removal efficiency was enhanced with the increase of RSB dosage without pH control. The maximum adsorption capacities were 126.3 mg/g for CA and 40.0 mg/g for CBZ.     

Effect of sorbed and desorbed Zn（II） on the growth of a green alga （ Chlorella pyrenoidosa）

Toxic effect of Zn（II） on a green alga （Chlorella pyrenoidosa） in the presence of sepiolite and kaolinite was investigated. The Zn-free clays were found to have a negative impact on the growth of C. pyrenoidosa in comparison with control samples （without adding any clay or Zn（II））. When Zn（II） was added, the algae in the presence of clays could be better survived than the control samples, which was actually caused by a decrease in Zn（II） concentration in the solution owing to the adsorption of Zn（II） on the clays. When the solution system was diluted, the growth of algae could be further inhibited as compared to that in a system which had the same initial Zn（II） concentration as in the diluted system. This in fact resulted from desorption of Zn（II） from the zinc-contaminated clays, although the effect varied according to the different desorption capabilities of sepiolite and kaolinite. Therefore the adsorption and desorption processes of Zn（H） played an important part in its toxicity, and adsorption and desorption of pollutants on soils/sediments should be well considered in natural eco-environmental systems before their risk of toxicity to aquatic organisms was assessed objectively.     

Adsorption of zinc on manganite(γ-MnOOH): particle concentration effect and adsorption reversibility

The adsorption and desorption processes of Zn(Ⅱ) on τ-MnOOH as a function of particle concentrations (Cp) were studied. An obvious Cp effect was observed in this adsorption system. The degree of adsorption hysteresis increased greatly with the increasing of Cp, indicating that the extent of the real metastable-equilibrium states deviating from the ideal equilibrium state was enhanced with the increasing of Cp. The Cp-reversibility relationship confirmed the metastable-equilibrium adsorption (MEA) inequality (Pan, 1998a), which was the core formulation of the MEA theory. Because the MEA inequality was based on the basic hypothesis of MEA theory that adsorption densitιy ι is not a state variable, the Cp-reversibility relationship gave indirect evidence to the basic hypothesis of MEA theory.     

A laboratory scale study on arsenic（Ⅴ） removal from aqueous medium using calcined bauxite ore

The present work deals with the As（Ⅴ） removal from an aqueous medium by calcined refractory grade bauxite （CRB） as a function of solution pH, time, As（Ⅴ） concentration and temperature. The residual As（Ⅴ） was lowered from 2 mg/L to below 0.01 mg/L in the optimum pH range 4.0-7.0 using a 5 g/L CRB within 3 h contact time. The adsorption data fits well with Langmuir isotherm and yielded Langmuir monolayer capacity of 1.78 mg As（Ⅴ）/g of CRB at pH 7.0. Presence of anions such as silicate and phosphate decreased As（Ⅴ） adsorption efficiency. An increase temperature resulted a decrease in the amount of As（Ⅴ） adsorbed by 6%. The continuous fixed bed column study showed that at the adsorbent bed depth of 30 cm and residence time of 168 min, the CRB was capable of treating 340 bed volumes of As（V） spiked water （C0 = 2 mg/L） before breakthrough （Ce = 0.01 mg/L）. This solid adsorbent, although not reusable, can be considered for design of adsorption columns as an efficiency arsenic adsorption media.