Pb（II） biosorption using chitosan and chitosan derivatives beads： Equilibrium, ion exchange and mechanism studies

The study examined the adsorption of Pb(II) ions from aqueous solution onto chitosan, chitosan-GLA and chitosan-alginate beads. Several important parameters influencing the adsorption of Pb(II) ions such as initial pH, adsorbent dosage and di erent initial concentration of Pb(II) ions were evaluated. The mechanism involved during the adsorption process was explored based on ion exchange study and using spectroscopic techniques. The adsorption capacities obtained based on non–linear Langmuir isotherm for chitosan, chitosan-GLA and chitosan-alginate beads in single metal system were 34.98, 14.24 and 60.27 mg/g, respectively. However, the adsorption capacity of Pb(II) ions were reduced in the binary metal system due to the competitive adsorption between Pb(II) and Cu(II) ions. Based on the ion exchange study, the release of Ca2+, Mg2+, K+ and Na+ ions played an important role in the adsorption of Pb(II) ions by all three adsorbents but only at lower concentrations of Pb(II) ions. Infrared spectra showed that the binding between Pb(II) ions and the adsorbents involved mostly the nitrogen and oxygen atoms. All three adsorbents showed satisfactory adsorption capacities and can be considered as an e cient adsorbent for the removal of Pb(II) ions from aqueous solutions.     

Preliminary investigation of phosphorus adsorption onto two types of iron oxide-organic matter complexes

Iron oxide(FeO)coated by natural organic matter(NOM)is ubiquitous.The associations of minerals with organic matter(OM)significantly changes their surface properties and reactivity,and thus affect the environmental fate of pollutants,including nutrients(e.g.,phosphorus(P)).In this study,ferrihydrite/goethite-humic acid(FH/GE–HA)complexes were prepared and their adsorption characteristics on P at various p H and ionic strength were investigated.The results indicated that the Fe O–OM complexes showed a decreased P adsorption capacity in comparison with bare Fe O.The maximum adsorption capacity(Q_(max))decreased in the order of FH(22.17 mg/g)FH-HA(5.43 mg/g)GE(4.67 mg/g)GE-HA(3.27 mg/g).After coating with HA,the amorphous FH–HA complex still showed higher P adsorption than the crystalline GE–HA complex.The decreased P adsorption observed might be attributed to changes of the Fe O surface charges caused by OM association.The dependence of P adsorption on the specific surface area of adsorbents suggests that the Fe O component in the complexes is still the main contributor for the adsorption surfaces.The P adsorptions on Fe O–HA complexes decreased with increasing initial p H or decreasing initial ionic strength.A strong dependence of P adsorption on ionic strength and p H may demonstrate that outer-sphere complexes between the OM component on the surface and P possibly coexist with inner-sphere surface complexes between the Fe O component and P.Therefore,previous over-emphasis on the contributions of original minerals to P immobilization possibly over-estimates the P loading capacity of soils,especially in humic-rich areas.     

Adsorption characteristics of copper, lead, zinc and cadmium ions by tourmaline

The adsorption characteristics of heavy metals： Cu（Ⅱ）, Pb（Ⅱ）, Zn（Ⅱ） and Cd（Ⅱ） ions on tourmaline were studied. Adsorption equilibrium was established. The adsorption isotherms of all the four metal ions followed well Langmuir equation. Tourmaline was found to remove heavy metal ions efficiently from aqueous solution with selectivity in the order of Pb（Ⅱ）〉Cu（Ⅱ）〉Cd（Ⅱ）〉Zn（Ⅱ）. The adsorption of metal ions by tourmaline increased with the initial concentration of metal ions increasing in the medium. Tourmaline could also increase pH value of metal solution.The maximum heavy metal ions adsorbed by tourmaline was found to be 78.86, 154.08, 67.25, and 66.67 mg/g for Cu（Ⅱ）, Pb（U）, Zn（Ⅱ） and Cd（U）, respectively. The temperature （25-55℃） had a small effect on the adsorption capacity of tourmaline. Competitive adsorption of Cu（Ⅱ）, Pb（Ⅱ）, Zn（Ⅱ） and Cd（Ⅱ） ions was also studied. The adsorption capacity of tourmaline for single metal decreased in the order of Pb〉Cu〉Zn 〉Cd and inhibition dominance observed in two metal systems was Pb〉Cu, Pb〉Zn, Pb〉Cd, Cu〉Zn, Cu〉Cd, and Cd〉Zn.     

Preparation and characterization of organic polymer modified composite polyaluminum chloride

Compared with traditional aluminum salts, polyaluminum chloride （PACI） has better coagulation-flocculation performance in turbidity removal. However, it is still inferior to organic polymers in terms of bridging function. In order to improve the aggregating property of PACl, different composite PACl flocculants were prepared with various organic polymers. The effect of organic polymer on the distribution or Al（Ⅲ） species in composite flocculants was studied using ^27TAl NMR and Al-ferron complexation methods. The charge neutralization and surface adsorption characteristics of composite flocculants were also investigated. Jar tests were conducted to evaluate the turbidity removal efficacy of organic polymer modified composite flocculants. The study shows that cationic polymer and anionic polymer have significant influences on the coagulation-flocculation behaviors of PACl. Both cationic and anionic polymers can improve the turbidity removal performancc of PACl but the mechanisms arc much different： cationic organic polymer mainly increases the charge neutralization ability, but anionic polymer mainly enhances the bridging function.     

Ethyl thiosemicarbazide intercalated organophilic calcined hydrotalcite as a potential sorbent for the removal of uranium(VI) and thorium(IV) ions from aqueous solutions

This work was conducted to determine the practicability of using a new adsorbent 4-ethyl thiosemicarbazide intercalated,organophilic calcined hydrotalcite(ETSC-OHTC) for the removal of uranium(U(VI)),and thorium(Th(IV)) from water and wastewater.The FTIR analysis helped in realizing the involvement of nitrogen and sulphur atoms of ETSC in binding the metal ions through complex formation.Parameters like adsorbent dosage,solution pH,initial metal ions concentration,contact time and ionic strength,that influence adsorption phenomenon,were studied.The optimum pH for maximum adsorption of U(VI) and Th(IV) was found to be in the range 4.0-6.0.The contact time required for reaching equilibrium was 4 hr.The pseudo second-order kinetic model was the best fit to represent the kinetic data.Analysis of the equilibrium adsorption data using Langmuir,Freundlich and Sips models showed that the Freundlich model was well suited to describe the metal ions adsorption.The K F values were 25.43 and 29.11mg/g for U(VI) and Th(IV),respectively,at 30°C.The adsorbent can be regenerated effectively from U(VI) and Th(IV) loaded ones using 0.01mol/L HCl.The new adsorbent was quite stable for many cycles,without much reduction in its adsorption capacity towards the metals.     

Effect of environmental factors on the complexation of iron and humic acid

A method of size exclusion chromatography coupled with ultraviolet spectrophotometry and off-line graphite furnace atomic absorption spectrometry was developed to assess the complexation properties of iron(Fe) and humic acid(HA) in a water environment. The factors affecting the complexation of Fe and HA, such as ionic strength, p H, temperature and UV radiation, were investigated. The Fe–HA complex residence time was also studied. Experimental results showed that p H could influence the deprotonation of HA and hydrolysis of Fe, and thus affected the complexation of Fe and HA. The complexation was greatly disrupted by the presence of Na Cl. Temperature had some influence on the complexation. The yield of Fe–HA complexes showed a small decrease at high levels of UV radiation, but the effect of UV radiation on Fe–HA complex formation at natural levels could be neglected. It took about 10 hr for the complexation to reach equilibrium, and the Fe–HA complex residence time was about 20 hr.Complexation of Fe and HA reached a maximum level under the conditions of p H 6, very low ionic strength, in the dark and at a water temperature of about 25°C, for 10 hr. It was suggested that the Fe–HA complex could form mainly in freshwater bodies and reach high levels in the warm season with mild sunlight radiation. With changing environmental parameters, such as at lower temperature in winter or higher p H and ionic strength in an estuary, the concentration of the Fe–HA complex would decrease.     

Comparison study of phosphorus adsorption on different waste solids: Fly ash, red mud and ferric–alum water treatment residues

The adsorption of phosphorus(P) onto three industrial solid wastes(fly ash, red mud and ferric–alum water treatment residual(FAR)) and their modified materials was studied systematically via batch experiments. Compared with two natural adsorbents(zeolite and diatomite), three solid wastes possessed a higher adsorption capacity for P because of the higher Fe, Al and Ca contents. After modification(i.e., the fly ash and red mud modified by FeCl_3 and FARs modified by HCl), the adsorption capacity increased, especially for the modified red mud, where more Fe bonded P was observed. The P adsorption kinetics can be satisfactorily fitted using the pseudo-second-order model. The Langmuir model can describe well the P adsorption on all of the samples in our study. p H and dissolved organic matter(DOM) are two important factors for P adsorption. Under neutral conditions, the maximum adsorption amount on the modified materials was observed. With the deviation from pH 7, the adsorption amount decreased, which resulted from the change of P species in water and surface charges of the adsorbents. The DOM in water can promote P adsorption, which may be due to the promotion effects of humic-Fe(Al) complexes and the pH buffer function exceeds the depression of competitive adsorption.     

Competitive and cooperative adsorption of arsenate and citrate on goethite

The fate of arsenic in natural environments is influenced by adsorption onto metal (hydr)oxides. The extent of arsenic adsorption is strongly a ected by coexisting dissolved natural organic acids. Recently, some studies reported that there existed competitive adsorption between arsenate and citrate on goethite. Humic acid is known to interact strongly with arsenate by forming complexes in aqueous solution, hence it is necessary to undertake a comprehensive study of the adsorption of arsenate/citrate onto goethite in the presence of one another. The results showed that at the arsenate concentrations used in this study (0.006–0.27 mmol/L), citrate decreased arsenate adsorption at acidic pH but no e ect was observed at alkaline pH. In comparison, citrate adsorption was inhibited at acidic pH, but enhanced at alkaline pH by arsenate. This was probably due to the formation of complex between arsenate and citrate like the case of arsenate with humic acid. These results implied that the mechanism of the adsorption of arsenate and citrate onto goethite in the presence of one another involved not only competition for binding sites, but the cooperation between the two species at the watergoethite interface as well.     

Insight into selective removal of copper from high-concentration nickel solutions with XPS and DFT: New technique to prepare 5N-nickel with chelating resin

An efficient and profitable separation process was proposed to prepare 5N(the purity of the metal solution reaches 99.999%) high-purity nickel from 3N nickel-solutions using Purolite S984. The adsorption performance of this superior resin, especially its selectivity for metal ions,was explored quantitatively. The maximum adsorption capacity for copper was 2.286 mmol/g calculated by the Langmuir model, which was twice as large as that for nickel. In the binary systems, the adsorption capacity for nickel was decreased by 45%, indicating direct competition for the active sites. The infinite separation factor for copper versus nickel exceeded 300, revealing the feasibility of preparing5N-level high-purity nickel solutions, which was further verified using the 800 BV(bed volume) effluent in the column dynamic process.According to the cost–benefit analysis, purification contributed to a profit of approximately 60,000 USD per cycle, and the investment return period was less than 1/3 years. Density functional theory analysis confirmed that four nitrogen atoms would be involved in the coordination complex and thus a structure involving two five-membered rings could be achieved. The X-ray photoelectron spectra confirmed the involvement of nitrogen atoms,implying a coordination ratio of approximately 1:1.     

Removal of heavy metals from aqueous solution by sawdust adsorption

The adsorption of lead, cadmium and nicel from aqueous solution by sawdust of walnut was investigated. The effect of contact time, initial metal ion concentration and temperature on metal ions removal has been studied. The equilibrium time was found to be of the order of 60 min. Kinetics fit pseudo first-order, second-order and intraparticle diffusion models, hence adsorption rate constants were calculated. The adsorption data of metal ions at temperatures of 25, 45 and 60~C have been described by the Freundlich and Langmuir isotherm models. The thermodynamic parameters such as energy, entropy and enthalpy changes for the adsorption of heavy metal ions have also been computed and discussed. Ion exchange is probably one of the major adsorption mechanisms for binding divalent metal ions to the walnut sawdust. The selectivity order of the adsorbent is Pb（I1）~Cd（II）〉Ni（I1）. From these results, it can be concluded that the sawdust of walnut could be a good adsorbent for the metal ions from aqueous solutions.     

Exfoliated Mg–Al–Fe layered double hydroxides/polyether sulfone mixed matrix membranes for adsorption of phosphate and fluoride from aqueous solutions

Mg–Al–Fe layered double hydroxides(LDHs) were exfoliated and incorporated in polyether sulfone membranes for the removal of phosphate and fluoride for the first time. The exfoliation methods, coagulation bath, LDH amount, interfering ions, adsorption isotherm,desorption and reuse of the membranes were investigated. It was found that LDHs could be quickly exfoliated in formamide/N,N-dimethylformamide(DMF) solvent mixtures with sodium carboxymethyl cellulose as a stabilizer. The membranes displayed much higher adsorption capacity for phosphate(5.61 mg/g) and faster adsorption rate than the unexfoliated materials. With increased DMF content in the coagulation bath, the static and dynamic adsorption capacity rose. Interference from Cl-and SO_4~(2-)(50 mg/L) on adsorption of phosphates was not apparent. The membranes displayed excellent reusability in dynamic adsorption/desorption. The membranes also showed high adsorption capacity for fluorides(1.61 mg/g).     

Immobilization of Cu~(2+) and Cd~(2+) by earthworm manure derived biochar in acidic circumstance

Earthworm manure, the by-product obtained from the disposing of biowastes by earthworm breeding, is largely produced and employed as a feedstock for biochar preparation through pyrolysis. For repairing acidic soil or acidic electroplating effluent,biochar physicochemical properties would suffer from some changes like an acidic washing process, which hence affected its application functions. Pristine biochar(UBC)from pyrolysis of earthworm manure at 700°C and biochar treated by HCl(WBC) were comparatively investigated regarding their physicochemical properties, adsorption capability and adsorption mechanism of Cu~(2+) and Cd~(2+) from aqueous solution to explore the immobilization characteristics of biochar in acidic environment. After HCl treatment,the soluble ash content and phenolic-OH in the WBC sample was notably decreased against the increase of the carboxyl C_O, aromatic C_C and Si–O–Si, compared to that of UBC. All adsorption processes can be well described by Langmuir isotherm model. The calculated maximum adsorption capacity of Cu~(2+) and Cd~(2+) adsorption on UBC were 36.56 and 29.31 mg/g, respectively, which were higher than that of WBC(8.64 and 12.81 mg/g,respectively), indicating that HCl treatment significantly decreased biochar adsorption ability. Mechanism analysis revealed that alkali and alkaline earth metallic, salts(carbonates, phosphates and silicates), and surface functional groups were responsible for UBC adsorption, corresponding to ion exchange, precipitation and complexation,respectively. However, ion exchange made little contributions to WBC adsorption due to the great loss of soluble ash content. WBC adsorption was mainly attributed to the abundant exposure of silicates and surface functional groups(carboxyl C_O and aromatic C_C).     

Zeolite (Na) modified by nano-Fe particles adsorbing phosphate in rainwater runoff

Zeolite (Na) modified by self-synthesized nano-Fe particles was used as infiltration media to adsorb phosphate in rainwater runoff. The adsorption capacities increased up to 75 times that of natural zeolite at a saturated equilibrium phosphate concentration of 0.42 mg/L. The correlation of capacity and material-specific surface area indicated that specific surface area was not the key factor contributing to the capacity improvement. SEM and XRD analysis showed that chemical reaction between Fe and P to form new products like cacoxenite is the main reason for the increased capacity, and that the method of adding metal ions or particles to improve the adsorption capacity for phosphate is feasible.     

Immobilization study of biosorption of heavy metal ions onto activated sludge

Activated sludge was immobilized into Ca-alginate beads via entrapment, and biosorption of three heavy metal ions, copper(Ⅱ), zinc(Ⅱ), and chromimum(Ⅱ), from aqueous solution in the concentration range of 10-100 mg/L was studied by using both entrapped activated sludge and inactivated free biomass at pH≤5. A biphasic metal adsorption pattern was observed in all immobilized biomass experiments. The biosorption of metal ions by the biosorbents increased with the initial concentration increased in the medium. The adsorption rate of immobilized pre-treated activated sludge(PAS) was much lower than that of free PAS due to the increase in mass transfer resistance resulting from the polymeric matrix. Biosorption equilibrium of beads was established in about 20 h and the adsorbed heavy metal ions did not change further with time. No significant effect of temperature was observed in the test for free biomass while immobilized PAS appeared to be strong temperature dependent in the test range of 10 and 40℃.Besides, the content of activated sludge in the calcium alginate bead has an influence on the uptake of heavy metals. The sorption equilibrium was well modeled by Langmuir isotherm, implying monomolecular adsorption mechanism. Carboxyl group in cell wall played an important role in surface adsorption of heavy metal ions on PAS.     

Insight into the adsorption of tetracycline onto amino and amino–Fe~(3+) gunctionalized mesoporous silica: Effect of functionalized groups

In order to study the influences of functionalized groups onto the adsorption of tetracycline,we prepared a series of amino and amino–Fe~(3+)complex mesoporous silica adsorbents with diverse content of amino and Fe~(3+)groups(named N,N-SBA15 and Fe-N,N-SBA15).The resulting mesoporous silica adsorbents were fully characterized by X-ray powder diffraction(XRD),Fourier transform infrared spectrometer(FTIR)and N_2adsorption/desorption isotherms.Furthermore,the effects of functionalized groups on the removal of TC were investigated.The results showed that the periodic ordered structure of SBA-15 was maintained after modification of amino/Fe~(3+)groups.The functionalized amino groups decreased the adsorption capacity while the coordinated Fe~(3+)increased the adsorption capacity.The adsorption kinetics of TC fitted pseudo-second-order model well and the equilibrium was achieved quickly.The adsorption isotherms fitted the Langmuir model well and with the Fe~(3+)content increased from 3.93%to 8.26%,the Q_(max)of the adsorbents increased from 102 to 188 mmol/kg.The solution p H affected the adsorption of TC onto amino complex adsorbents slightly while influenced the adsorption onto Fe-amine complex adsorbents greatly.The adsorption of TC on SBA15 and N,N-SBA15 may be related to the formation of outer-sphere surface complexes,while the adsorption of TC onto Fe-N,N-SBA15 was mainly attributed to the inner-sphere surface complexes.This study could offer potential materials that have excellent adsorption behavior for environmental remediation and suggested useful information for the preparing other adsorbents in environmental applications.     

Preparation of Fe–Co based MOF-74 and its effective adsorption of arsenic from aqueous solution

To obtain a cost-effective adsorbent for the removal of arsenic in water,a novel nanostructured Fe–Co based metal organic framework(MOF-74)adsorbent was successfully prepared via a simple solvothermal method.The adsorption experiments showed that the optimal molar ratio of Fe/Co in the adsorbent was 2:1.The Fe_2Co_1MOF-74 was characterized by various techniques and the results showed that the nanoparticle diameter ranged from60 to 80 nm and the specific surface area was 147.82 m~2/g.The isotherm and kinetic parameters of arsenic removal on Fe_2Co_1MOF-74 were well-fitted by the Langmuir and pseudo-second-order models.The maximum adsorption capacities toward As(III)and As(V)were 266.52 and 292.29 mg/g,respectively.The presence of sulfate,carbonate and humic acid had no obvious effect on arsenic adsorption.However,coexisting phosphate significantly hindered the removal of arsenic,especially at high concentrations(10 mmol/L).Electrostatic interaction and hydroxyl and metal–oxygen groups played important roles in the adsorption of arsenic.Furthermore,the prepared adsorbent had stable adsorption ability after regeneration and when used in a real-water matrix.The excellent adsorption performance of Fe_2Co_1MOF-74 material makes it a potentially promising adsorbent for the removal of arsenic.     

Chemodynamics of heavy metals in long-term contaminated soils：Metal speciation in soil solution

The concentration and speciation of heavy metals in soil solution isolated from long-term contaminated soils were investigated. The soil solution was extracted at 70% maximum water holding capacity (MWHC) after equilibration for 24 h. The free metal concentrations (Cd2+, Cu2+, Pb2+, and Zn2+) in soil solution were determined using the Donnan membrane technique (DMT). Initially the DMT was validated using artificial solutions where the percentage of free metal ions were significantly correlated with the percentages predicted using MINTEQA2. However, there was a significant difference between the absolute free ion concentrations predicted by MINTEQA2 and the values determined by the DMT. This was due to the significant metal adsorption onto the cation exchange membrane used in the DMT with 20%, 28%, 44%, and 8% mass loss of the initial total concentration of Cd, Cu, Pb, and Zn in solution, respectively. This could result in a significant error in the determination of free metal ions when using DMT if no allowance for membrane cation adsorption was made. Relative to the total soluble metal concentrations the amounts of free Cd2+ (3%–52%) and Zn2+ (11%–72%) in soil solutions were generally higher than those of Cu2+ (0.2%–30%) and Pb2+ (0.6%–10%). Among the key soil solution properties, dissolved heavy metal concentrations were the most significant factor governing free metal ion concentrations. Soil solution pH showed only a weak relationship with free metal ion partitioning coefficients (Kp) and dissolved organic carbon did not show any significant influence on Kp.     

Sequestration of toxic Pb（II） ions by chemically treated rubber （Hevea brasiliensis ） leaf powder

Rubber leaf powder (an agricultural waste) was treated with potassium permanganate followed by sodium carbonate and its performance in the removal of Pb(II) ions from aqueous solution was evaluated. The interactions between Pb(II) ions and functional groups on the adsorbent surface were confirmed by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) coupled with X-ray energy dispersive spectroscopy (EDX). The effects of several important parameters which can affect adsorption capacity such as pH, adsorbent dosage, initial lead concentration and contact time were studied. The optimum pH range for lead adsorption was 4–5. Even at very low adsorbent dosage of 0.02 g, almost 100% of Pb(II) ions (23 mg/L) could be removed. The adsorption capacity was also dependent on lead concentration and contact time, and relatively a short period of time (60–90 min) was required to reach equilibrium. The equilibrium data were analyzed with Langmuir, Freundlich and Dubinin-Radushkevich isotherms. Based on Langmuir model, the maximum adsorption capacity of lead was 95.3 mg/g. Three kinetic models including pseudo first-order, pseudo second-order and Boyd were used to analyze the lead adsorption process, and the results showed that the pseudo second-order fitted well with correlation coefficients greater than 0.99.     

Recent advances on porous organic frameworks for the adsorptive removal of hazardous materials

Environmental pollution is one of the most serious problems facing mankind today,and has attracted widespread attention worldwide. The burgeoning class of crystalline porous organic framework materials, metal–organic frameworks and covalent organic frameworks present promising application potential in areas related to pollution control due to their interesting surface properties. In this review, the literature of the past five years on the adsorptive removal of various hazardous materials, mainly including heavy metal ions, harmful gases, organic dyes, pharmaceutical and personal care products, and radionuclides from the environment by using COFs and MOFs, is summarized. The adsorption mechanisms are also discussed to help understand their adsorption performance and selectivity. Additionally, some insightful suggestions are given to enhance the performance of MOFs and COFs in the adsorptive removal of various hazardous materials.     

New insight into adsorption characteristics and mechanisms of the biosorbent from waste activated sludge for heavy metals

The adsorption characteristics and mechanisms of the biosorbent from waste activated sludge were investigated by adsorbing Pb2+and Zn2+in aqueous single-metal solutions. A p H value of the metal solutions at 6.0 was beneficial to the high adsorption quantity of the biosorbent. The optimal mass ratio of the biosorbent to metal ions was found to be 2. A higher adsorption quantity of the biosorbent was achieved by keeping the reaction temperature below 55°C. Response surface methodology was applied to optimize the biosorption processes, and the developed mathematical equations showed high determination coefficients(above 0.99 for both metal ions) and insignificant lack of fit(p = 0.0838 and 0.0782 for Pb2+and Zn2+, respectively). Atomic force microscopy analyses suggested that the metal elements were adsorbed onto the biosorbent surface via electrostatic interaction. X-ray photoelectron spectroscopy analyses indicated the presence of complexation(between –NH2,-CN and metal ions) and ion-exchange(between –COOH and metal ions). The adsorption mechanisms could be the combined action of electrostatic interaction, complexation and ion-exchange between functional groups and metal ions.