Removal of As(V) Using an Iron-Impregnated Ion Exchange Bead

The ability of an iron-impregnated ion exchange bead (PWX5) to remove As(V) from ground water was investigated. The effects of particle size, solution pH, As(V) concentration, competition, adsorbent concentration, temperature, iron content, and iron accessibility on removal kinetics and/or equilibrium were determined. PWX5's performance was compared to other iron-based adsorbents, primarily Bayoxide® E-33 (E-33), a granular ferric oxide, for arsenic removal performance. All of the factors cited impacted either the amount of As(V) adsorbed or the rate of adsorption. Stirred batch reactor data showed the rate of adsorption increased as particle size decreased and bottle point isotherm data showed As(V) adsorption maximum capacity increased with higher initial adsorbate concentration. The presence of phosphate and silicate reduced the amount of As(V) adsorbed as did a pH > 7.0. PWX5 is durable, rather homogeneous in size and effective at removing As(V). It is a viable alternative to E-33 which has a wider size distribution and wears more easily.     

Preparation and characterization of porous chitosan–tripolyphosphate beads for copper(II) ion adsorption

Porous chitosan–tripolyphosphate beads, prepared by the ionotropic crosslinking and freeze‐drying, were used for the adsorption of Cu(II) ion from aqueous solution. Batch studies, investigating bead adsorption capacity and adsorption isotherm for the Cu(II) ion, indicated that the Cu(II) ion adsorption equilibrium correlated well with Langmuir isotherm model. The maximum capacity for the adsorption of Cu(II) ion onto porous chitosan–tripolyphosphate beads, deduced from the use of the Langmuir isotherm equation, was 208.3 mg/g. The kinetics data were analyzed by pseudo‐first, pseudo‐second order kinetic, and intraparticle diffusion models. The experimental data fitted the pseudo‐second order kinetic model well, indicating that chemical sorption is the rate‐limiting step. The negative Gibbs free energy of adsorption indicated a spontaneous adsorption, while the positive enthalpy change indicated an endothermic adsorption process. This study explored the adsorption of Cu(II) ion onto porous chitosan–tripolyphosphate beads, and used SEM/EDS, TGA, and XRD to examine the properties of adsorbent. The use of porous chitosan–tripolyphosphate beads to adsorb Cu(II) ion produced better and faster results than were obtained for nonporous chitosan–tripolyphosphate beads. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Equilibrium and dynamic studies of the removal of As(III) and As(V) from contaminated aqueous systems using a functionalized biopolymer

BACKGROUND: A study of the removal of arsenic from a sample of actual groundwater using crosslinked xanthated chitosan is described. RESULTS: Removal of As(III) and As(V) was studied at pH 7.5 under equilibrium and dynamic conditions. The equilibrium data were fitted to Langmuir and Freundlich adsorption models and the various model parameters evaluated. The monolayer adsorption capacity from the Langmuir model for xanthated chitosan flakes (XCF) (As(V) 20.0 ± 0.56 mg g^?1; As(III) 33.0 ± 0.32 mg g^?1) were lower than obtained for xanthated chitosan granules (XCB) (As(V) 36.0 ± 0.52 mg g^?1; As(III) 48.0 ± 0.45 mg g^?1). Adsorption of As (V) was unaffected by the presence of other anions while in the case of As(III) the presence of sulfate and silicate caused a 26.5–50.9% decrease in adsorption. A sample (940 bed volumes) of a groundwater spiked with 200 µg L^?1 As(V) treated with XCF in column experiments reduced the arsenic concentration to < 10 µg L^?1. The adsorbent was also successfully applied for the removal of total inorganic arsenic down to < 10 µg L^?1 from real samples of arsenic‐contaminated groundwater. CONCLUSION: Xanthated chitosan was an efficient adsorbent for the removal of both forms of arsenic from groundwater under near neutral conditions. The presence of sulfur and the amino groups resulted in increased adsorption capacity of the sorbent. Copyright © 2012 Society of Chemical Industry     

Removal of copper(II) ions from aqueous solution onto chitosan and cross-linked chitosan beads

The adsorption of Cu(II) ions onto chitosan and cross-linked chitosan beads has been investigated. Chitosan beads were cross-linked with glutaraldehyde (GLA), epichlorohydrin (ECH) and ethylene glycol diglycidyl ether (EGDE) in order to obtain sorbents that are insoluble in aqueous acidic and basic solution. Batch adsorption experiments were carried out as a function of pH, agitation period, agitation rate and concentration of Cu(II) ions. A pH of 6.0 was found to be a optimum for Cu(II) adsorption on chitosan and cross-linked chitosan beads. Isotherm studies indicate Cu(II) can be effectively removed by chitosan and cross-linked chitosan beads. Adsorption isothermal data could be well interpreted by the Langmuir equation. Langmuir constants have been determined for chitosan and cross-linked chitosan beads. The experimental data of the adsorption equilibrium from Cu(II) solution correlated well with the Langmuir isotherm equation. The uptakes of Cu(II) ions on chitosan beads were 80.71 mg Cu(II)/g chitosan, on chitosan-GLA beads were 59.67 mg Cu(II)/g chitosan-GLA, on chitosan-ECH beads were 62.47 mg Cu(II)/g chitosan-ECH and on chitosan-EGDE beads were 45.94 mg Cu(II)/g chitosan-EGDE. The Cu(II) ions can be removed from the chitosan and cross-linked chitosan beads rapidly by treatment with an aqueous EDTA solution and at the same time the chitosan and cross-linked chitosan beads can be regenerated and also can be used again to adsorb heavy metal ions.     

利用电解锰渣制备As(Ⅲ)吸附材料及其性能研究

通过对工业废弃物电解锰渣(electrolytic manganese residues, EMRs)进行改性制备As(Ⅲ)吸附材料（改性EMRs），探究了NaOH用量、超声及微波对其表面结构及吸附性能的影响。结果表明：该工业废渣在固液比M(EMRs)∶V(NaOH, aq) = 1∶10(C _NaOH，aq = 2.0 mol·L^-1)条件下，经超声反应（200 W）2 h脱除大部分Si、S、Ca后，再微波（700 W）反应5 min以使Fe、Mn等活性吸附基团在其表面沉积，最后经105℃烘干制得改性EMRs。SEM结果表明，EMRs改性后表面形成片层纳米结构，对砷具有良好的吸附性能，可将初始As(Ⅲ)浓度为50 mg·L^-1废水出水中砷降至0.042 mg·L^-1，符合国家地表水环境质量标准Ⅰ类水质量要求(GB 3838—2002)；同时，经3% NaOH溶液再生处理后可继续使用。XPS结果表明，改性EMRs吸附砷性能与其表面Fe₃O₄、FeOOH、MnO₂等对As(Ⅲ)具有吸附作用或氧化作用的活性物种的增多密切相关。     

Adsorption of indomethacin onto chemically modified chitosan beads

Macroporous chitosan beads used for the immobilization of an anti-inflammatory drug were prepared by the wet phase-inversion method. There are two stages of phase-inversion observed from the cast of chitosan droplet in tripolyphosphate (TPP) aqueous solution. The first stage of phase-inversion is dominated by liquid-liquid demixing and the morphology of the freeze-dried chitosan bead shows a bundle-like porous structure. The following stage of phase-inversion is attributed to the solid-liquid demixing and the morphology of the freeze-dried chitosan bead changes to an interconnected porous structure comprising particulates around the pores. The pore size and porosity of the bead can be varied by altering synthesis conditions, such as initial polymer concentration, and the pH value and concentration of the casting agent (TPP aqueous solution). Quaternary ammonium, and aliphatic and aromatic acyl groups were introduced into the porous chitosan beads to interact with an anti-inflammatory drug, indomethacin, through the electrostatic interaction and hydrophobic interaction. The results indicated that chemical modification of the porous chitosan beads have obvious effect on the adsorption of indomethacin.     

Adsorption of lanthanum by magnetic alginate‐chitosan gel beads

BACKGROUND: The risk of environmental pollution is aggravated by the increasing application of considerable amounts of rare earth elements in advanced materials. This paper reports the preparation of novel magnetic alginate–chitosan gel beads and their application for adsorption of lanthanum ions from aqueous solution. RESULTS: Stable magnetic alginate–chitosan gel beads with average diameter 0.85 ± 0.05 mm were prepared by loading iron oxide nanoparticles onto a combined alginate and chitosan absorbent. The performance of the prepared beads for the adsorption of lanthanum ions from aqueous solution was tested. It was found that various parameters, such as aqueous pH, contact time, metal ion concentration, ion strength and temperature, have an effect on the adsorption. Adsorption equilibrium was reached in 10 h and the maximum uptake capacity was 97.1 mg g^?1. From the analysis of pH, FTIR and XPS data, it is proposed that lanthanum adsorption proceeds through mechanisms of cation exchange, electrostatic interaction and surface complexation, with the oxygen atoms the main binding sites. In addition, lanthanum ions could be selectively separated from coexisting base metal ions such as Pb (II), Cd (II), Co (II), Ni (II) and Cu (II) in the aqueous solution. CONCLUSION: The prepared magnetic alginate–chitosan gel beads exhibit high uptake capacity and selectivity for lanthanum sorption, and thus can be used for adsorptive recovery of lanthanum from aqueous solutions. Copyright © 2010 Society of Chemical Industry     

Effects of Acylation and Crosslinking on the Material Properties and Cadmium Ion Adsorption Capacity of Porous Chitosan Beads

Abstract

Chitosan is a novel glucosamine biopolymer derived from the shells of marine organisms. This biopolymer is very attractive for heavy metal ion separations from wastewater because it is selective for toxic transition metal ions over less toxic alkali or alkane earth metal ions. Highly porous, 3-mm chitosan beads were prepared by an aqueous phase-inversion technique for casting gel beads followed by freeze drying. In the attempt to simultaneously improve material properties and adsorption capacity, chitosan was chemically modified by 1) homogeneous acylation of amine groups with nonanoyl chloride before bead casting, and 2) heterogeneous crosslinking of linear chitosan chains with the bifunctional reagent glutaric dialdehyde (GA) after bead casting but before freeze drying. The random addition of C₈ hydrocarbon side chains to about 7% of the amine groups on uncrosslinked chitosan beads via N-acylation improved the saturation adsorption capacity from 169 to 216 mg Cd²⁺/g-bead at saturation (pH 6.5, 25°C) but only slightly reduced solubility in acid solution. Crosslinking of the N-acylated chitosan beads with 0.125 to 2.5 wt% GA in the crosslinking bath increased the internal surface area from 40 to 224 m²/g and rendered the beads insoluble in 1 M acetic acid (pH 2.36). However, crosslinking of the N-acylated chitosan beads reduced the saturation adsorption capacity to 136 mg Cd²⁺/g-bead at 0.75 wt% GA and 86 mg Cd²⁺/g-bead at 2.5 wt% GA. Crosslinking also significantly reduced the compression strength. There was no clear relationship between internal surface area and adsorption capacity, suggesting that the adsorbed cadmium was not uniformly loaded into the bead.     

Synthesis of the cotton cellulose based Fe(III)-loaded adsorbent for arsenic(V) removal from drinking water

A novel macroporous bead adsorbent, Fe(III)-loaded ligand exchange cotton cellulose adsorbent [Fe(III)LECCA], is synthesized for selective adsorption of arsenate anions [As(V)] from drinking water in batch and column systems. As(V) adsorption on Fe(III)LECCA was independent of pH, especially in drinking water pH range. Film diffusive control mechanism will benefit As(V) exchange with Fe(III)LECCA whether in batch or in column experiments. When treating the tap water at 26.0 BV/h, the column still preserves 83% of the original saturation adsorption capacity of the As(V) aqueous solution. These results have indicated that Fe(III)LECCA has the potential to act as an adsorbent for the removal of As(V) from drinking water considering its availability, nontoxicity and cost-effectiveness.     

Evaluation of chitosan tripolyphosphate gel beads as bioadsorbents for iron in aqueous solution and in human blood in vitro

Nonimprinted and Fe³⁺ imprinted chitosan tripolyphosphate gel beads were prepared via physical gel formation. A method based on in situ crosslinking using ethylene glycol diglycidyl ether was developed to imprint the chitosan tripolyphosphate gels with Fe³⁺ ion without deteriorating the gel beads. The beads were characterized by FTIR, SEM, XRD, and DSC with respect to the chemical structure, surface morphology, crystallinity, and thermal behavior. Swelling kinetics and Fe³⁺ ion adsorption behavior from aqueous solution were studied. The Fe³⁺ imprinted and in situ crosslinked beads proved to be durable and effective adsorbents for Fe³⁺ in solution. The bead prepared by in situ crosslinking and in the presence of 10 mM template ion had an equilibrium iron adsorption capacity of 53.9 mg/g after 3-hour contact with 5 mM Fe³⁺ solution. The pros and cons of the beads as biomedical iron adsorbents were tested by evaluating their serum iron removal capacities from human blood. The preliminary tests carried out showed that Fe³⁺ imprinted beads were more effective in decreasing serum iron in human blood when compared to the nonimprinted beads. The decrease in serum iron level accompanied a parallel decrease in the hemoglobin level. The calcium level was also affected upon contact with the beads. The Fe³⁺ imprinted beads were less effective than the nonimprinted ones in decreasing the calcium level indicating selectivity towards iron containing species. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

麦饭石负载壳聚糖对As(V)的吸附性能研究

利用麦饭石负载壳聚糖制备一种复合吸附剂。研究了复合壳聚糖对As(V)的吸附。结果表明:在pH值为4～7,吸附时间为40min,复合壳聚糖对As(V)的去除率达99%以上,残余As(V)浓度低于国家综合排放标准(0.5mg/L)。通过对实验数据运用相关数学模型拟合,表明复合壳聚糖对As(V)的吸附符合Langmuir和Freundlich吸附等温式,最大吸附量qmax为39.1850mg/g,n为4.7902,相关系数分别为:0.9967、0.9489。吸附过程动力学适合二级动力学方程。     

Biosorption of As(III) and As(V) from Aqueous Solution by Lichen (Xanthoria parietina) Biomass

The biosorption of As(III) and As(V) from aqueous solution on lichen (Xanthoria parietina) biomass were investigated using different experimental parameters such as solution pH, biomass concentration, contact time, and temperature. The equilibrium data were evaluated by Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) isotherm models. The biosorption capacity of X. parietina for As(III) and As(V) was found to be 63.8 mg/g and 60.3 mg/g. The mean sorption energy values calculated from D–R model indicated that the biosorption of As(III) and As(V) onto X. parietina biomass took place by chemical ion-exchange. The thermodynamic parameters showed that the biosorption of As(III) and As(V) ions onto X. parietina biomass was feasible, spontaneous, and exothermic in nature. Kinetic examination of the sorption data revealed that the biosorption processes of both As(III) and As(V) followed well the pseudo-second-order kinetics. The arsenic ions were desorbed from X. parietina using both 1 M HCl and 1 M HNO₃. The recovery yield of arsenic ions was found to be 80-90% and the biosorbent had good reusability after consecutive seven sorption-desorption cycles.     

Preparation of Silk Sericin/Lignin Blend Beads for the Removal of Hexavalent Chromium Ions

In the present study, novel adsorbents having high adsorption capability and reusability were prepared using agricultural by-products: silk sericin and lignin. Silk sericin and lignin blend beads were successfully prepared using simple coagulation methods for the removal of hexavalent chromium (Cr(VI)) from aqueous solution. A 1 M lithium chloride (LiCl)/dimethyl sulfoxide (DMSO) solvent system successfully dissolved both sericin and lignin and had sufficient viscosity for bead preparation. Compared to the conventional sericin bead adsorbent, sericin/lignin blend beads showed higher Cr(VI) adsorption capacity. The amount of lignin added to the adsorbent greatly affected the adsorption capacity of the beads, and a 50:50 sericin/lignin blend ratio was optimal. Adsorption behavior followed the Freundlich isotherm, which means the adsorption of Cr(VI) occurred on the heterogeneous surface. Cr(VI) adsorption capability increased with temperature because of thermodynamic-kinetic effects. In addition, over 90% of Cr(VI) ions were recovered from the Cr(VI) adsorbed sericin/lignin beads in a 1 M NaOH solution. The adsorption-desorption recycling process was stable for more than seven cycles, and the recycling efficiency was 82%. It is expected that the sericin/lignin beads could be successfully applied in wastewater remediation especially for hazardous Cr(VI) ions in industrial wastewater.     

Preparation,characterization and application of iron (III)-loaded chitosan hollow fiber membranes as a new bio-based As (V) sorbent

Fe (III)-loaded chitosan (CS) hollow fibers (CS-Fe (III) HF) were successfully prepared according to the dry-wet spinning technique. The CS-Fe (III) HFs were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and thermal gravimetric analysis (TGA). Removal of pentavalent arsenic was studied through biosorption on CS-Fe (III) HF adsorptive membranes. The response surface methodology (RSM) was applied to investigate the influence of the main operating parameters such as contact time, pH, initial As (V) concentration and HFs dosage on the adsorption capacity of As (V). From the Pareto analysis, pH, [As (V)]_o, [CS-Fe (III) HF membranes] and squared effect of [As(V)]_o were found to produce the largest effect on biosorption of As (V). Kinetic studies showed that the pseudo-second-order kinetic model provides the best correlation to the experimental results. Equilibrium data fitted well with the Langmuir model with maximum adsorption capacity of 3,703 μg g^?1. A laboratory scale glass membrane module consisting of three CS-Fe(III) HFs has also been prepared and tested for biosorption of As (V) at a real scale. Permeability of As (V) ions through the CS-Fe (III) HF membranes was 0.145 μmol m^?2 h^?1 bar ^?1.     

A low-cost and environment friendly chitosan/aluminum hydroxide bead adsorbent for fluoride removal from aqueous solutions

A novel low-cost adsorbent named chitosan/Al(OH)₃·(CS/Al(OH)₃) bead was successfully prepared by employing AlCl₃·6H₂O aqueous solution as the solvent for CS. The CS/Al(OH)₃ beads were used for fluoride removal from water. The beads were synthesized using the chitosan and aluminum chloride with the mass ratio of 2:1 as the precursor and in situ generation of aluminum hydroxide sorbents in sodium hydroxide solution. Then, the beads were washed with distilled water to neutral and freeze dried. The sorbents were characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX), Fourier transform infrared spectrometry (FTIR), and X-ray diffractometry (XRD), respectively. Batch adsorption experiments were conducted to evaluate the parameters that affected the defluoridation capacity. The influencing parameters including pH, co-existing ions in water and initial temperature of the adsorption process were studied. The influence of temperature confirmed that the adsorption was spontaneous and endothermic. The adsorption isotherm of fluoride followed Langmuir isotherm model and the sorption kinetics was more suitable for pseudo-second-order kinetic model. The defluoridation capacity of chitosan/Al(OH)₃ calculated using Langmuir model was 23.06 mg/g (293 K, pH 4). The experimental results showed that the CS/Al(OH)₃ bead adsorbent is promising for the fluoride adsorption.     

Selective sorption of Fe(III) using modified forms of chitosan beads

Modified chitosan beads (CB) were prepared and used for the removal of Fe(III) ions from aqueous solution. The advantages of modified CB than raw CB have been explored. The sorption capacity (SC) of the modified forms of CB namely, protonated CB, carboxylated CB, and grafted CB were found to be 3533, 3905, and 4203 mg kg^?1, respectively, while the raw CB showed the SC of 2913 mg kg^?1 only. Batch adsorption studies were conducted to optimize various equilibrating conditions like contact time, pH, and coions. The sorbents were characterized by FTIR, WDXRF, and SEM with EDAX analysis. The sorption process has been explained with Freundlich and Langmuir isotherms. Thermodynamic parameters such as ΔG°, ΔH°, and ΔS° were calculated to understand the nature of sorption. Modified CB are more selective for Fe(III) than Cu(II), which inturn higher than Cr(VI). A suitable mechanism for iron sorption onto modified CB was established. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Removal of As(V) and Cr(VI) in aqueous solution by sand media simultaneously coated with Fe and Mn oxides

In this research, sand media simultaneously coated with iron and manganese (iron and manganese coated sand, IMCS) were applied to treat synthetic wastewater contaminated with both Cr(VI) and As(V). Scanning electron microscopy (SEM) and X-ray diffraction spectroscopy (XRD) were used to characterize the surface properties of the coated layer of IMCS. Adsorption of Cr(VI) and As(V) onto IMCS followed a typical anionic type, showing a gradual decrease of adsorption as the solution pH increased. In a single system, IMCS showed a greater adsorption capacity for As(V) than that for Cr(VI) over the entire solution pH range. In a binary system, As(V) preferentially occupied the limited adsorption sites on IMCS and therefore Cr(VI) adsorption was suppressed. This result indicates that As(V) adsorption onto the surface of IMCS occurs through a strong chemical bonding such as an inner-sphere complex. As(V) adsorption onto the IMCS was well described by second-order kinetics. From the adsorption isotherm experiments at pH 4, the maximum adsorbed amount of Cr(VI) and As(V) onto IMCS in a single system was 102 mg/kg and 455 mg/kg, respectively.     

Modeling As(III) and As(V) Removal by an Iron Oxide Impregnated Activated Carbon in a Binary Adsorbate System

The adsorption behavior of As(III) as a function of pH on an iron oxide impregnated activated carbon (FeAC) at different adsorbate/adsorbent concentrations was modeled using the surface complexation modeling approach (SCM). The surface complexation constants developed from single sorbate experiments successfully predicted competition between As(V) and As(III) and the SCM predictions were verified experimentally. The monoprotic surface site representation described the experimental data better than the diprotic representation. Based on surface complexation modeling simulations, the effect of As(V) on As(III) removal was greater than As(III) on As(V) removal. As(III) → (As(V) was observed for the FeAC and the virgin carbon beginning at pH = 8.     

Removal of Hg2+ from aqueous solution using a novel composite carbon adsorbent

A novel composite carbon adsorbent (GCA) has been prepared by immobilizing activated carbon and genipin‐crosslinked chitosan into calcium alginate gel beads via entrapment and applied to the removal of mercury (Hg²⁺) ions from aqueous solution (e.g., drinking water). Two bead sizes and two mixing ratios of components were obtained and characterized. Batch experiments were performed to study the uptake equilibrium and kinetics of Hg²⁺ ions by the GCA. The Hg²⁺ adsorption capacity of GCA was found to be dependent of pH and independent of size of the adsorbent. The Hg²⁺ adsorption rate of GCA increases with decreasing its bead size. However, both adsorption capacity and rate of GCA for Hg²⁺ increase with increasing its chitosan content. Otherwise, it was shown that the GCA has higher Hg²⁺ adsorption capacity and rate than activated carbon, which might be caused by the incorporation of chitosan into the GCA. The maximum Hg²⁺ adsorption capacity of GCA was found to be 576 mg/g, which is over seven times higher than that of activated carbon. Our results reveal the uniform distribution of activated carbon and chitosan within the alginate gel bead and that Hg²⁺ ions can diffuse inside the bead. It also demonstrated the feasibility of using this GCA for Hg²⁺ removal at low pH values. The Hg²⁺ absorbed beads of the GCA can be effectively regenerated and reused using H₂SO₄. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Selective Separation of Arsenic(III) and (V) Ions with Ferric Complex of Chelating Ion-Exchange Resin

Abstract

Trace levels of aqueous arsenic(III) and (V) ions were adsorbed selectively onto the ferric complex of a chelating resin, Uniselec UR-10. The adsorption was markedly dependent upon the pH of the aqueous phase. The distribution ratio and the specific adsorption capacity of arsenic(III) were 23,000 and 0.47 mmole/g, respectively, at the optimum pH for the adsorption, 9.2. The corresponding values of arsenic(V) were 22,000 and 0.53 mmole/g at the optimum pH 5.5. In the column operation the adsorption of the arsenic ions was also dependent upon the flow velocity and the size of the resin particle. A velocity of 60 cm/hr and 100 to 200 mesh size afforded satisfactory results. Adsorbed arsenic was recovered quantitatively by eluting the resin with 2 N hydrochloric acid, where the complexed iron was also eluted. A trace level of arsenic in wastewater from a geothermal power plant was successfully separated in the presence of a large excess of diverse cations and anions. Trace arsenic in natural seawater was also successfully preconcentrated 100 to 200 times over the original level by adsorption onto the ferric resin followed by elution with hydrochloric acid.