Designing chitosan based magnetic beads with conocarpus waste-derived biochar for efficient sulfathiazole removal from contaminated water

The development of a simple method to synthesize highly efficient and stable magnetic microsphere beads for sulfathiazole (STZ) removal from contaminated aqueous media was demonstrated in this study. Conocarpus (Conocarpus erectus L.) tree waste (CW) derived biochar (BC) was modified to fabricate chitosan-BC (CBC) and magnetic CBC (CBC-Fe) microsphere beads. Proximate, chemical, and structural properties of the produced adsorbents were investigated. Kinetics, equilibrium, and pH adsorption batch trials were conducted to evaluate the effectiveness of the synthesized adsorbents for STZ removal. All adsorbents exhibited the highest STZ adsorption at pH 5.0. STZ adsorption kinetics data was best emulated using pseudo-second order and Elovich models. The equilibrium adsorption data was best emulated using Langmuir, Freundlich, Redlich–Peterson, and Temkin models. CBC-Fe demonstrated the highest Elovich, pseudo-second order, and power function rate constants, as well as the highest apparent diffusion rate constant. Additionally, Langmuir isotherm predicted maximum adsorption capacity was the highest for CBC-Fe (98.67 mg g⁻¹), followed by CBC (56.54 mg g⁻¹) and BC (48.63 mg g⁻¹). CBC-Fe and CBC removed 74.5%–108.8% and 16.2%–25.6% more STZ, respectively, than that of pristine BC. π-π electron-donor–acceptor interactions and Lewis acid-base reactions were the main mechanisms for STZ removal; however, intraparticle diffusion and H-bonding further contributed in the adsorption process. The higher efficiency of CBC-Fe for STZ adsorption could be due to its magnetic properties as well as stronger and conducting microsphere beads, which degraded the STZ molecules through generation of HO^• radicals.     

Fast and efficient adsorption/desorption of protein by a novel magnetic nano-adsorbent

A novel magnetic nano-adsorbent was prepared by covalently binding polyacrylic acid (PAA) on Fe₃O₄ superparamagnetic nanoparticles (13.2 nm) via carbodiimide activation. The maximum weight ratio of PAA to Fe₃O₄ was 0.12 (i.e., average of two PAA molecules on a magnetic nanoparticle). The magnetic nano-adsorbent possessed a high ionic exchange capacity of 1.64 meq g^–1 and was efficient for the recovery of lysozyme. The lysozyme could be completely adsorbed in 0.1 M phosphate buffer at pH 3–5 and completely desorbed in NaSCN solution (>1 M) within 1 min, and retained 95% activity after adsorption/desorption. In addition, the adsorption behavior followed the Langmuir adsorption isotherm with a maximum adsorption amount of 0.224 mg mg^–1 and a Langmuir adsorption equilibrium constant of 10 ml mg^–1 at 25 °C. The change of enthalpy at 15–35 °C was –4.2 kJ ml mol^–1 mg^–1.     

Enantioseparation of Mandelic Acid Enantiomers With Magnetic Nano‐Sorbent Modified by a Chiral Selector

In this study, R(+)‐α‐methylbenzylamine‐modified magnetic chiral sorbent was synthesized and assessed as a new enantioselective solid phase sorbent for separation of mandelic acid enantiomers from aqueous solutions. The chemical structures and magnetic properties of the new sorbent were characterized by vibrating sample magnetometry, transmission electron microscopy, Fourier transform infrared spectroscopy, and dynamic light scattering. The effects of different variables such as the initial concentration of racemic mandelic acid, dosage of sorbent, and contact time upon sorption characteristics of mandelic acid enantiomers on magnetic chiral sorbent were investigated. The sorption of mandelic acid enantiomers followed a pseudo‐second‐order reaction and equilibrium experiments were well fitted to a Langmuir isotherm model. The maximum adsorption capacity of racemic mandelic acid on to the magnetic chiral sorbent was found to be 405 mg g^?1. The magnetic chiral sorbent has a greater affinity for (S)‐(+)‐mandelic acid compared to (R)‐(?)‐mandelic acid. The optimum resolution was achieved with 10 mL 30 mM of racemic mandelic acid and 110 mg of magnetic chiral sorbent. The best percent enantiomeric excess values (up to 64%) were obtained by use of a chiralpak AD‐H column. Chirality 27:835–842, 2015. © 2015 Wiley Periodicals, Inc.     

Biosorption of acid violet dye from aqueous solutions using native biomass of a new isolate of Penicillium sp.

Laboratory investigation of the potential use of Penicillium sp. as biosorbent for the removal of acid violet dye from aqueous solution was studied with respect to pH, temperature, biosorbent, initial dye concentrations. Penicillium sp. decolourizes acid violet (30 mg l⁻¹) within 12 h agitation of 150 rpm at pH 5.7 and temperature of 35 °C. The pellets exhibited a high dye adsorption capacity (5.88 mg g⁻¹) for acid violet dye over a pH range (4–9); the maximum adsorption was obtained at pH 5.7. The increase of temperature favored biosorption for acid violet, but the optimum temperature was 35 °C. Adsorption kinetic data were tested using pseudo-first-order, pseudo-second-order and kinetic studies showed that the biosorption process follows pseudo-first-order rate kinetics with an average rate constant of 0.312 min⁻¹. Isotherm experiments were conducted to determine the sorbent–desorption behavior of examined dye from aqueous solutions using Langmuir and Freundlich equations. Langmuir parameter indicated a maximum adsorption capacity of 4.32 mg g⁻¹ for acid violet and R_L value of 0.377. Linear plot of log q_e vs log C_e shows that applicability of Freundlich adsorption isotherm model. These results suggest that this fungus can be used in biotreatment process as biosorbent for acid dyes.     

Kinetic and equilibrium studies of copper biosorption onto <Emphasis Type="Italic">Pseudomonas aeruginosa</Emphasis> base using direct determination of copper by a voltammetric method

This paper provided information on the use of linear sweep anodic stripping voltammetry for evaluating the process of copper biosorption onto Pseudomonas aeruginosa. This technique was suited to determine the concentration of free copper ion on site on the mercaptoethane sulfonate modified gold electrode surface without any pretreatment. It was in favor of the study of kinetic process as the fast changing kinetic data characteristic just after the beginning of biosorption could be accurately depicted. Based on the electrochemical results, the kinetics and equilibrium of biosorption were systematically examined. The pseudo-second-order kinetic model was used to correlate the kinetic experimental data and the kinetic parameters were evaluated. The Langmuir and Freundlich models were applied to describe the biosorption equilibrium. It was found that the Langmuir isotherm fitted the experimental data better than the Freundlich isotherm. Maximum adsorption capacity of copper ion onto Pseudomonas aeruginosa was 0.9355 μmol mg⁻¹ (about 59.4417 mg g⁻¹).     

226Ra, 238U and Cd adsorption kinetics and binding capacity of two cyanobacterial strains isolated from highly radioactive springs and optimal conditions for maximal removal effects in contaminated water

Biomass-based decontamination methods are among the most interesting water treatment techniques. In this study, 2 cyanobacterial strains, Nostoc punctiforme A.S/S4 and Chroococcidiopsis thermalis S.M/S9, isolated from hot springs containing high concentrations of radium (²²⁶Ra), were studied to be associated with removal of radionuclides (²³⁸U and ²²⁶Ra) and heavy metal cadmium (Cd) from aqueous solutions. The adsorption equilibrium data was described by Langmuir and Freundlich isotherm models. Kinetic studies indicated that the sorption of 3 metals followed pseudo-second-order kinetics. Effects of biomass concentration, pH, contact time, and initial metal concentration on adsorption were also investigated. Fourier-transform infrared spectroscopy revealed active binding sites on the cyanobacterial biomass. The obtained maximum biosorption capacities were 630 mg g^?1 and 37 kBq g^?1 for ²³⁸U and ²²⁶Ra for N. punctiforme and 730 mg g^?1 and 55 kBq g^?1 for C. thermalis. These 2 strains showed maximum binding capacity 160 and 225 mg g^?1, respectively for Cd adsorption. These results suggest that radioactivity resistant cyanobacteria could be employed as an efficient adsorbent for decontamination of multi-component, radioactive and industrial wastewater.     

Equilibrium and Kinetics of Adsorption of Mn2+ by Haloarchaeon Halobacterium sp. GUSF (MTCC3265)

The coastal waters of countries bordering on an ocean show increases in manganese pollution due to runoff from mining activity and from industries dealing with production of ferroalloys, steel, iron, petrochemicals, and fertilizers. One gram of dried cells of haloarchaeon Halobacterium sp. GUSF (MTCC3265) adsorbed 99% Mn²⁺ in 60 min at pH 6.8 and 30ºC on contact with 109.54 mg Mn²⁺ per liter in saline solution. Adsorbed Mn²⁺ was quantified by atomic absorption spectrometry and demonstrated on the cell surface by SEM-EDX. Mn²⁺ adsorbed to functional groups of the adsorbent was studied by FTIR. The adsorption process of Mn²⁺ showed saturation and followed pseudo–second-order kinetics; was consistent with the homogeneity of the Langmuir model (R² of 0.99); exhibited a Q_max of 62.5 mg g^?1 and a binding energy of 0.018 L mg^?1. The Mn²⁺adsorption was also consistent with the heterogeneity of the Freundlich model by exhibiting a K_f of 1.0 mg g^?1 with an n value of 1.1. Adsorption efficiency of 99% was retained even after a third adsorption-desorption cycle. This is the first report on metal ion adsorption, using Mn²⁺ as an example, by the haloarchaeon Halobacterium sp. GUSF (MTCC3265) in the domain Archaea.     

A natural macroalgae consortium for biosorption of copper from aqueous solution: Optimization,modeling and design studies

In this study, the capacity of a natural macroalgae consortium consisting of Chaetomorpha sp., Polysiphonia sp., Ulva sp. and Cystoseira sp. species for the removal of copper ions from aqueous environment was investigated at different operating conditions, such as solution pH, copper ion concentration and contact time. These environmental parameters affecting the biosorption process were optimized on the basis of batch experiments. The experimentally obtained data for the biosorption of copper ions onto the macroalgae-based biosorbent were modeled using the isotherm models of Freundlich, Langmuir, Sips and Dubinin–Radushkevich and the kinetic models of pseudo-first-order, pseudo-second-order, Elovich and Weber and Morris. The pseudo-first-order and Sips equations were the most suitable models to describe the copper biosorption from aqueous solution. The thermodynamic data revealed the feasibility, spontaneity and physical nature of biosorption process. Based on the data of Sips isotherm model, the biosorption capacity of biosorbent for copper ions was calculated as 105.370 mg g^?1 under the optimum operating conditions. A single-stage batch biosorption system was developed to predict the real-scale-based copper removal performance of biosorbent. The results of this investigation showed the potential utility of macroalgae consortium for the biosorption of copper ions from aqueous medium.     

Bioremediation Potential of Chlorella: Spectroscopic,Kinetics, and Sem Studies

A dead dried alga, Chlorella sp., was used for the uptake of Cr⁺³, Cr₂O₇ ^?2, Cu⁺², and Ni⁺² from the aqueous solutions of these metal ions. The equilibrium data were fitted using the Langmuir and Freundlich isotherm model and the maximum uptakes for Cr⁺³, Cr₂O₇ ^?2, Ni⁺², and Cu⁺² were 98, 104, 108, and 183 mg/g, respectively. The Freundlich model, in comparison to the Langmuir model, better represented the sorption process. The kinetics of metal ions uptake by Chlorella sp. was best described by a pseudo-second order rate equation. Infrared spectroscopic data were employed to identify the site(s) of bonding in Chlorella sp. A scanning electron microscopic (SEM) study of pure dead Chlorella sp. and the species treated with different metal ions provided an idea of the extent of metal uptake by this species. The dead Chlorella sp took up maximum Cu(II). The size of the cell of the metal-treated Chlorella sp. obtained from SEM data is in agreement with the extent of metal uptake.     

Ni (II) adsorption onto Chrysanthemum indicum: Influencing factors,isotherms, kinetics,and thermodynamics

The study explores the adsorption potential of Chrysanthemum indicum biomass for nickel ion removal from aqueous solution. C. indicum flowers in raw (CIF-I) and biochar (CIF-II) forms were used as adsorbents in this study. Batch experiments were conducted to ascertain the optimum conditions of solution pH, adsorbent dosage, contact time, and temperature for varying initial Ni(II) ion concentrations. Surface area, surface morphology, and functionality of the adsorbents were characterized by Brunauer, Emmett, and Teller (BET) surface analysis, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier transform infrared spectroscopy (FTIR). Adsorption kinetics were modeled using pseudo-first order, pseudo-second order, Elovich, intraparticle diffusion, Bangham's, and Boyd's plot. The equilibrium data were modeled using Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich (D-R) isotherm models. Experimental data provided the best fit to pseudo-second-order kinetic model and Langmuir isotherm model for the adsorption of Ni(II) ion on both CIF-I and CIF-II with maximum adsorption capacities of 23.97 and 44.02 mg g^?1, respectively. Thermodynamic analysis of the data proved the process to be spontaneous and endothermic in nature. Desorption studies were conducted to evaluate the possibility of reusing the adsorbents. Findings of the present study provide substantial evidence for the use of C. indicum flower as an eco-friendly and potential adsorbent for the removal of Ni(II) ions from aqueous solution.     

Adsorptive removal of Pb(II) by activated carbon prepared from Spartina alterniflora: Equilibrium,kinetics and thermodynamics

Low-cost activated carbon was prepared from Spartina alterniflora by phosphoric acid activation for the removal of Pb(II) from dilute aqueous solution. The effect of experimental parameters such as pH, initial concentration, contact time and temperature on the adsorption was studied. The obtained data were fitted with the Langmuir and Freundlich equations to describe the equilibrium isotherms. The kinetic data were fitted with the Lagergren-first-order, pseudo-second-order and Elovich models. It was found that pH played a major role in the adsorption process. The maximum adsorption capacity for Pb(II) on S. alterniflora activated carbon (SAAC) calculated from Langmuir isotherm was more than 99 mg g⁻¹. The optimum pH range for the removal of Pb(II) was 4.8–5.6. The Freundlich isotherm model was found to best describe the experimental data. The kinetic rates were best fitted to the pseudo-second-order model. Thermodynamic study showed the adsorption was a spontaneous exothermic process.     

Optimum Sorption Isotherm by Linear and Nonlinear Methods for Safranin onto Alkali-Treated Rice Husk

Rice husk, a lignocellulosic by-product of the agroindustry, was treated with alkali and used as a low-cost adsorbent for the removal of safranin from aqueous solution in batch adsorption procedure. In order to estimate the equilibrium parameters, the equilibrium adsorption data were analyzed using the following two-parameter isotherms: Freundlich, Langmuir, and Temkin. A comparison of linear and nonlinear regression methods in selecting the optimum adsorption isotherm was applied on the experimental data. Six linearized isotherm models (including four linearized Langmuir models) and three nonlinear isotherm models are thus discussed in this paper. In order to determine the best-fit isotherm predicted by each method, seven error functions namely, coefficient of determination (r ²), the sum of the squares of the errors (SSE), sum of the absolute errors (SAE), average relative error (ARE), hybrid fractional error-function (HYBRID), Marquardt's percent standard deviation (MPSD), and the chi-square test (χ²) were used. It was concluded that the nonlinear method is a better way to obtain the isotherm parameters and the data were in good agreement with the Langmuir isotherm model.     

Arsenic and fluoride removal by potato peel and rice husk (PPRH) ash in aqueous environments

Finding appropriate adsorbent may improve the quality of drinking water in those regions where arsenic (As) and fluoride (F^?) are present in geological formations. In this study, we evaluated the efficiency of potato peel and rice husk ash (PPRH-ash)-derived adsorbent for the removal of As and F from contaminated water. Evaluation was done in batch adsorption experiments, and the effect of pH, initial adsorbate concentration, contact time, and adsorbent dose were studied. Characteristics of adsorbents were analyzed using scanning electron micropcope (SEM) and Fourier transform infrared (FTIR) spectroscopy. Both the Langmuir and Freundlich isotherm models fitted well for F^? and As sorption process. The maximum adsorption capacity of adsorbent for As and F^? was 2.17 μg g^?1 and 2.91 mg g^?1, respectively. The As and Fi removal was observed between pH 7 and 9. The sorption process was well explained with pseudo-second order kinetic model. Arsenic adsorption was not decreased in the presence of carbonate and sulfate. Results from this study demonstrated potential utility of this agricultural biowaste, which could be developed into a viable filtration technology for As and F^? removal in As- and F-contaminated water streams.     

Removal of chromium (VI) using poly(methylacrylate) functionalized guar gum

Using persulfate/ascorbic acid redox pair, poly(methylacrylate) was grafted on to guar gum and the conditions for the grafting were optimized. The copolymer sample having maximum %G was evaluated for the removal of Cr(VI) and the sorption conditions were optimized. The sorption was found pH dependent, pH 1.0 being the optimum value. Sorption data at pH 1.0 were modeled using both the Langmuir and Freundlich isotherms where the data fitted better to Freundlich isotherm. The equilibrium sorption capacity of 29.67 mg/g was determined from the Langmuir isotherm. The sorption followed a pseudo-second-order kinetics with a rate constant 2.5 × 10^?4 g mg^?1 min^?1. The grafted product was also evaluated for Cr(VI) removal from local electroplating industrial waste water. The regeneration experiments revealed that the guar-graft-poly(methylacrylate) could be successfully reused for five cycles. In the present study conductivity measurements were used instead of conventional photometric method for determining Cr(VI) concentration in the equilibrium solutions and the results obtained have been compared with photometric method. Optimum Cr(VI) binding under highly acidic conditions indicated significant contribution of non electrostatic forces in the adsorption process.     

Biosorption of Pb<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript> by Non-Living Biomass of <Emphasis Type="Italic">Spirulina</Emphasis> sp.

Removal of heavy metals (Pb²⁺, Zn²⁺) from aqueous solution by dried biomass of Spirulina sp. was investigated. Spirulina rapidly adsorbed appreciable amount of lead and zinc from the aqueous solutions within 15 min of initial contact with the metal solution and exhibited high sequestration of lead and zinc at low equilibrium concentrations. The specific adsorption of both Pb²⁺ and Zn²⁺ increased at low concentration and decreased when biomass concentration exceeded 0.1 g l⁻¹. The binding of lead followed Freundlich model of kinetics where as zinc supported Langmuir isotherm for adsorption with their r ² values of 0.9659 and 0.8723 respectively. The adsorption was strongly pH dependent as the maximum lead biosorption occurred at pH 4 and 10 whereas Zn²⁺ adsorption was at pH 8 and 10.     

Scavenging Rhodamine B dye using moringa oleifera seed pod

Moringa oliferia seed pod was modified using orthophosphoric acid (H₃PO₄) and used as adsorbent for sequestering Rhodamine B (Rh-B) dye from aqueous solution. The acid-modified adsorbent (MOSPAC) was characterized using Scanning Electron microscopy (SEM), Fourier Transform Infra Red (FTIR), Energy Dispersive X-ray (EDX), pH point of zero charge (pH_pzc) and Boehm Titration (BT) techniques, respectively. Operational parameters such as contact time, initial dye concentration, adsorbent dosage, pH and solution temperature were studied in batch process. Optimum dye adsorption was observed at pH 3.01. Equilibrium adsorption data was tested data using four different isotherm models: Langmuir, Freundlich, Temkin and Dubinin-Radushkevich. Langmuir isotherm model fitted most with maximum monolayer adsorption capacity of 1250 mg g^–1. Pseudo-second-order kinetic model provided the best correlation for the experimental data. Thermodynamic study showed that the process is endothermic, spontaneous and feasible. MOSPAC is an effective adsorbent for the removal of RhB dye from aqueous solutions.     

Sensitivity analysis of amino acids in simulated moving bed chromatography

We conducted a sensitivity analysis of the simulated moving bed (SMB) chromatography with the case model of the separation of two amino acids phenylalanine and tryptophan. We consider a four-zone SMB chromatography where the triangle theory is used to determine the operating conditions. Competitive Langmuir isotherm model was used to determine the adsorption isotherm. The finite difference method is used to solve nonlinear partial differential equation (PDE) systems numerically. We examined the effects of alterations in the operating conditions (feed-extract, feed-raffinate, eluent-extract, eluent-raffinate, recycle, and switching time) and the adsorption isotherm parameters (Langmuir isotherm parametersa andb) on SMB efficiency. The variation range of operating conditions and Langmuir isotherma was between −50 and 50% of original value and the variation range of the Langmuir isothermb was between 2.25⁻⁵ and 2.25⁵ times of original value.     

Preparation,Characterization and Application of Magnetic Fe3O4-CS for the Adsorption of Orange I from Aqueous Solutions

Fe₃O₄ (Fe₃O₄-CS) coated with magnetic chitosan was prepared as an adsorbent for the removal of Orange I from aqueous solutions and characterized by FTIR, XRD, SEM, TEM and TGA measurements. The effects of pH, initial concentration and contact time on the adsorption of Orange I from aqueous solutions were investigated. The decoloration rate was higher than 94% in the initial concentration range of 50–150 mg L⁻¹ at pH 2.0. The maximum adsorption amount was 183.2 mg g⁻¹ and was obtained at an initial concentration of 400 mg L⁻¹ at pH 2.0. The adsorption equilibrium was reached in 30 minutes, demonstrating that the obtained adsorbent has the potential for practical application. The equilibrium adsorption isotherm was analyzed by the Freundlich and Langmuir models, and the adsorption kinetics were analyzed by the pseudo-first-order and pseudo-second-order kinetic models. The higher linear correlation coefficients showed that the Langmuir model (R² = 0.9995) and pseudo-second-order model (R² = 0.9561) offered the better fits.     

Copper adsorption kinetics of cultured algal cells and freshwater phytoplankton with emphasis on cell surface characteristics

Comparative studies were carried out on the adsorption of copper by a range of laboratory-cultured algae and freshwater phytoplankton samples. The level of surface mucilage associated with the cultured algae ranged from high (Anabaena spiroides, Eudorina elegans) to moderate (Anabaena cylindrica, Microcystis aeruginosa) to complete absence (Chlorella vulgaris, Asterionella formosa, Aulacoseira varians, Ceratium hirundinella). With laboratory cultures, the rapid uptake, EDTA release and quantitative similarity between living and dead (glutaraldehyde-fixed) algae were consistent with physical binding of Cu at the cell surface. The higher Cu adsorption per unit surface area and longer adsorption time of mucilaginous algae in the time-course study, and the relatively high level of Cu bound to mucilage found by X-ray microanalysis suggest that mucilage played an important role in metal binding. For all species examined, Cu adsorption kinetics (external Cu concentrations 1 to 1000 mg L⁻¹) showed a clear fit to the Freundlich, but not the Langmuir isotherm, indicating a monolayer adsorption model with heterogenous binding sites. The Freundlich adsorption capacity constant (K_f) was higher in mucilaginous (3.96–12.62) compared to nonmucilaginous (0.36–3.63) species, but binding intensity (Freundlich constant 1/n) did not differ between the two cell types. The results suggest that mucilaginous algal species may have potential as biosorbents for treatment of industrial effluents containing heavy metals. Investigation of the Cu adsorption behavior of four mixed phytoplankton samples also revealed a good fit to the Freundlich, but not the Langmuir, isotherm. Freundlich constants were in the range 2.3–3.2 for samples dominated by Chlorophyta, Bacillariophyta and Cyanophyta, but recorded a value of 7.4 in the sample dominated by Dinophyta. Comparison with data from laboratory monocultures suggested that the adsorption kinetics of mixed environmental phytoplankton samples cannot be predicted simply in terms of the major algal species.     

Evaluation of mucoadhesive properties of chitosan microspheres prepared by different methods

The mucoadhesive properties of chitosan microspheres prepared by different method were evaluated by studying the interaction between mucin and microspheres in aqueous solution. The interaction was determined by the measurement of mucin adsorbed on the microspheres. A strong interaction between chitosan microspheres and mucin was detected. The intensity of the interaction was dependent upon the method of preparation of chitosan microspheres and the amount of mucin added. The extent of mucus adsorption was proportional to the absolute values of the positive zeta potential of chitosan microspheres. The zeta potential in turn was found to be dependent upon the method of preparation of microspheres. The adsorption of type III mucin (1% sialic acid content) was interpreted using Freundlich or Langmuir adsorption isotherms. The values ofr ² were greater for Langmuir isotherm as compared with Freundlich isotherm. The adsorption of a suspension of chitosan microspheres in the rat small intestine indicated that chitosan microspheres prepared by tripolyphosphate cross-linking and emulsification ionotropic gelation can be used as an excellent mucoadhesive delivery system. The microspheres prepared by glutaraldehyde and thermal cross-linking showed good stability in HC1 as compared with microspheres prepared by tripolyphosphate and emulsification ionotropic gelation.