Recovery of gold by chicken egg shell membrane-conjugated chitosan beads

We have successfully prepared a bead-type adsorbent from two materials with different adsorption characteristics. Heavy metals were removed by greatly swollen egg shell membrane-conjugated chitosan beads. The egg shell membrane accumulated and removed precious metal ions from a dilute aqueous solution with a high affinity in a short contact time. Experiments suggested that chitosan beads could take up gold ions with great capacity and selectivity by conjugation with egg shell membrane. Under certain conditions, the selective removal of gold and copper in a mixture of gold and copper ions by egg shell membrane-conjugated chitosan beads was 100% and 2%, respectively. Egg shell membrane-conjugated chitosan beads can be seen as a promising material to recover gold in wastewater from various industries, such as electroplating.     

Renewable Resources and Enzymatic Processes to Create Functional Polymers: Adapting Materials and Reactions from Food Processing

We are exploiting materials and concepts from food science to create functionalized, environmentally friendly derivatives of the biopolymer chitosan, a byproduct of seafood processing. Functional groups are grafted onto chitosan using tyrosinase, the enzyme responsible for food browning. The functionalizing groups studied include low-molecular-weight phenols derived from natural sources and high-molecular-weight proteins. The approach of using low-molecular-weight phenols to functionalize chitosan is illustrated with arbutin, a natural phenol found in pears. Results demonstrate that tyrosinase initiates reactions that lead to the conversion of arbutin–chitosan solutions into gels. These gels can be rapidly broken by treatment with the chitosan-hydrolyzing enzyme chitosanase, demonstrating that the chitosan derivatives remain biodegradable. We briefly review other studies in which low-molecular-weight natural phenols are enzymatically grafted onto chitosan to confer functional properties. The creation of co-polymers is illustrated by results in which tyrosinase is used to couple gelatin onto chitosan. Gelatin is a proteinaceous byproduct of meat production. The tyrosinase-generated gelatin–chitosan conjugates have been observed to offer interesting rheological and thermal properties. These results demonstrate the potential for using renewable resources and enzymatic processing to create environmentally friendly polymers with useful functional properties.     

Arsenic Removal from Dilute Solutions by High Surface Area Mesoporous Iron Oxyhydroxide

Mesostructured iron oxyhydroxide (FeO _x ) and iron oxyhydroxide–phosphate (FeO _x P) composites were organized using dodecylsulfate surfactant as a template. X-ray diffraction studies depicted a lamellar structure of the product. Ion exchange and solvent extraction methods were employed for the removal of the surfactant. Carboxylate ions exchanged lamellar type mesostructured material reorganized to a wormhole-like mesoporous material when heated under N₂ atmosphere. Surfactant was completely removed by carboxylate ions as observed by the Fourier transform infrared spectra. High surface area acetate-exchanged FeO _x (230 m² g^?1) was obtained after the surfactant removal from the composite (2.8 m² g^?1). Surface area of acetate-exchanged FeO _x P was the highest (240 m²g^?1) after the removal of the surfactant. Local structure of iron species of FeO _x was investigated by X-ray absorption fine structure spectroscopy. Further, Fe···Fe bond appeared at 3.21–3.25 Å with coordination number 2–3, showing a high degree of un-saturation of Fe···Fe bonds. As compared with bulk iron oxyhydroxide and iron-intercalated montmorillonite, the mesoporous iron materials were highly effective for arsenic removal from low concentrations of aqueous solutions. Furthermore, mesoporous iron materials were stable in aqueous phase.     

Sunflower stalk, an agricultural waste, as an adsorbent for the removal of lead and cadmium from aqueous solutions

Sunflower residue, an agricultural waste material for the removal of lead (Pb) and cadmium (Cd) from aqueous solutions were investigated using a batch method. Adsorbent was prepared by washing sunflower residue with deionized water until the effluent was colorless. Batch mode experiments were carried out as a function of solution pH, adsorbent dosage, initial concentration and contact time. The results indicated that the adsorbent showed good sorption potential and maximum metal removal was observed at pH 5. Within 150 min of operation about 97 and 87 % of Pb and Cd ions were removed from the solutions, respectively. Lead and Cd sorption curves were well fitted to the modified two-site Langmuir model. The adsorption capacities for Pb and Cd at optimum conditions were 182 and 70 mg g^?1, respectively. The kinetics of Pb and Cd adsorption from aqueous solutions were analyzed by fitting the experimental data to a pseudo-second-order kinetic model and the rate constant was found to be 8.42 × 10^?2 and 8.95 × 10^?2 g mg^?1 min^?1 for Cd and Pb, respectively. The results revealed that sunflower can adsorb considerable amount of Pb and Cd ions and thus could be an economical method for the removal of Pb and Cd from aqueous systems.     

Experimental and Modeling Studies for the Removal of Crystal Violet Dye from Aqueous Solutions using Eco-friendly <Emphasis Type="Italic">Gracilaria corticata</Emphasis> Seaweed Activated Carbon/Zn/Alginate Polymeric Composite Beads

This research article describes, an eco-friendly activated carbon prepared from the Gracilaria corticata seaweeds which was employed for the preparation of biodegradable polymeric beads for the efficient removal of crystal violet dye in an aqueous solution. The presence of chemical functional groups in the adsorbent material was detected using FTIR spectroscopy. The morphology and physical phases of the adsorbent materials were analyzed using SEM and XRD studies respectively. Batch mode dye adsorption behavior of the activated carbon/Zn/alginate polymeric beads was investigated as a function of dosage, solution pH, contact time, initial dye concentration and temperature. Maximum dye removal was observed at a pH of 5.0, 1 g of adsorbent dosage with 60 mg/L dye concentration, 50 min of contact time and at 30 °C. The equilibrium modeling studies were analyzed with Freundlich and Langmuir adsorption isotherms and the adsorption dynamics was predicted with Lagergren’s pseudo-first order, pseudo-second order equations and intra particle diffusion models. The process of dye removal followed a pseudo second-order kinetics rather than pseudo first order. The thermodynamic parameters like standard Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were determined and the results imply that the adsorption process was spontaneous, endothermic and increases the randomness between the adsorbent and adsorbate. The results from the experimental and correlation data reveal that the Gracilaria corticata activated carbon/Zn/alginate polymeric beads have proved to be an excellent adsorbent material for the removal of CV dye.     

Adsorption Kinetics of Dyes in Single and Binary Systems Using Cyanoguanidine-Crosslinked Chitosan of Different Deacetylation Degrees

The crosslinking of chitosan with cyanoguanidine shows some advantages, such as the improved the stability in acid solutions and the decrease of adsorbent cost. In this work, cyanoguanidine-crosslinked chitosan and pure chitosan were prepared to apply in the adsorption of Food Yellow 4 (FY4) and Food Blue 2 (FB2), in single and binary systems. Effects of pH and deacetylation degree (DD) of chitosan in adsorption were evaluated. The adsorbents were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The kinetic data were analyzed by pseudo-first order, pseudo-second order and Avrami models. The conditions of pH 3 and DD 95% were the more suitable to reach the highest adsorption capacities in all experimental assays. Under these conditions, the adsorption capacities for FY4 were approximately of 392 and 200 mg g^?1 and, for FB2 were approximately of 370 and 184 mg g^?1, respectively, in the single and binary systems. The Avrami model was suitable to represent the kinetic curves in all conditions, and the highest adsorption capacities were found for FY4 in binary aqueous system, being for the pure chitosan of 229 mg g^?1 and crosslinked chitosan of 218 mg g^?1. The Langmuir and extended Langmuir models presented a good fit to the equilibrium data in both systems. It was found that, the chitosan crosslinked with cyanoguanidine improved the chemical stability of chitosan as adsorbent.     

Clean Preparation Process of Chitosan Oligomers in Gly Series Ionic Liquids Homogeneous System

Chitosan oligomers because of its water solubility has some special physiological functions, such as binding lipid, affecting the mitogenic response, restraining the growth of tumors, and was widely used in cosmetics and health. H₂O₂/Gly (Glycine) series ionic liquids system, a new solvable-catalytic system, was an efficient clean process for preparation of chitosan oligomers. The effects of the anions of Gly series ionic liquids on the solubility and degradation for chitosan were investigated, and the results showed that [Gly]Cl aqueous solution was of good solubility and assistant degradation for chitosan. In additional, the mechanism for oxidative degradation of chitosan in ionic liquids (ILs) was studied. The effect on the property of chitosan oligomers catalyzed by H₂O₂, in two different kinds of solvents (HAc and [Gly]Cl) were compared. It was found that the performance of moisture absorption and retention of chitosan oligomers using ionic liquid aqueous solution as solvent was better than that using HAc aqueous solution as solvent, and even superior to that of hyaluronic acid. Furthermore, [Gly]Cl could be easily separated from the product and reused with only slight loss. It could provide an efficient and environmental friendly method for the preparation of chitosan oligomers in H₂O₂/ILs system.     

Simulation of Nitrogen Dynamics and Fluxes in Contrasting Catchments in Norway by Applying the Integrated Nitrogen Model for Catchments (INCA)

The process-based INCA model was applied to Dalelva Brook (3.2 km²) and the Bjerkreim River (685 km²) including several subcatchments, in order to test the model's ability to simulate streamwater nitrate (NO₃ ^-) dynamics and output fluxes under highly contrasting climatic conditions and nitrogen (N) loading. The simulated runoff volumes and mean NO₃ ^- concentrations at Dalelva and Bjerkreimwere within +2 to +10% of the measured average during 1993–1995 (–19 to +31% within individual years). INCA to a great extent also reproduced the observed streamwater flow dynamics at both study sites (coefficient of determination, r ² > 0.70). Temporal variation of streamwater NO₃ ^- during 1993–1995 was captured quite well by the model, especially at small catchments with a distinct seasonal NO₃ ^- pattern (r ² = 0.46–0.68). At the Bjerkreim River outlet, the relationship were somewhat weaker (r ² = 0.26, p < 0.01). Despite a few situations where the model failed to capturethe streamwater NO₃ ^- dynamics, INCA proved to be a quite robust tool for simulating NO₃ ^- dynamics and output fluxes in the two study catchments.     

Adsorption of Crystal Violet Dye from Aqueous Solution by Poly(Acrylamide-<Emphasis Type="Italic">co</Emphasis>-Maleic Acid)/Montmorillonite Nanocomposite

Poly(acrylamide-co-maleic acid)/montmorillonite nanocomposites, were synthesized via in situ polymerization with different maleic acid and MMT content. The capability of the hydrogel for adsorption of crystal violet (CV) was investigated in aqueous solutions at different pH values and temperatures. The pseudo-second-order kinetics model could fit successfully the adsorption kinetic data. The effects of maleic acid to acrylamide molar ratio (MA_R), weight percent of MMT (MMT%), the pH of medium and the solution temperature (T) on the CV adsorption capacity (q _e ) of adsorbents were studied by Taguchi experimental design approach. The results indicated that increasing the MMT% leads to a greater q _e . The q _e value of adsorbents increased also with increasing both MA_R and pH, while reduced when the temperature of medium increased. The relatively optimum conditions to achieve a maximum CV adsorption capacity for P(AAm/MA)/MMT adsorbents were found as: 0.06 for MA_R and 5 % of MMT%, medium pH = 7 and T = 20 °C.     

Eco-Friendly, Vascular Shape and Interpenetrating Poly (Acrylic Acid) Grafted Pectin Hydrogels; Biosorption and Desorption Investigations

The synthesis and characterization of poly (acrylic acid) grafted pectin hydrogel followed by biosorption and desorption characteristics of cadmium, as a model heavy metal, have been studied. The grafted eco-friendly pectin based interpenetrating hydrogel was prepared in the presence of gluteraldehyde crosslinker under N₂ atmosphere and characterized using ¹H-NMR, FTIR, TGA and SEM techniques. Gluteraldehyde was found to form one-arm and two-arm crosslinks in the copolymer. Upon grafting, two-dimensional sheet structures bounded to tubular and vascular cylindrical rods were observed. The biosorption and desorption data, determined experimentally, were fitted to pseudo-second order reaction kinetics. At higher ionic strength values, the maximum metal uptake value (q _max) was lowered and pseudo-second order rate constant (k ₂) was increased. Whereas, at higher pH values the maximum metal uptake value (q _max) was increased and Pseudo-second order rate constant (k ₂) was decreased. 0.1?M HCl solution was a suitable eluent to regenerate the hydrogel surface and recover the adsorbed cadmium metal ions. Pectin based copolymer could be used as an efficient candidature biosorbent for the recovery of cadmium metal ions from aqueous solutions.     

A Study of the Photocatalytic Oxidation of Humic Acid on Anatase and Mixed-phase Anatase–Rutile TiO2 Nanoparticles

In this study, slurry photocatalytic oxidation process was investigated for natural organic matter removal from aqueous humic acid solutions by using different titanium dioxide (TiO₂) under UV-A irradiation. Bench scale experimental studies were conducted at different humic acid concentration at the range of 10–50 mg/L and different pH. Anatase and mixed-phase anatase–rutile TiO₂ nano particles used in the photocatalytic reactor. The results were evaluated in terms of the parameters that are specific to organic matter content such as dissolved organic carbon concentration, ultraviolet absorbance at 254 nm (UV₂₅₄), specific ultaviolet absorbance at 254 nm, and color (VIS₄₀₀). It was observed that increasing humic acid concentration decreases photocatalytic degradation efficiency. The reactivity of the mixed-phase anatase–rutile (Degussa P-25) TiO₂ was greater than individual anatase particles and the highest efficiency was observed at pH 3 for anatase TiO₂.     

Multi-response optimization of Fenton process for applicability assessment in landfill leachate treatment

Fenton process, as a pretreatment method, was found to be effective in the primary treatment of mature/medium landfill leachate. However, the main problem of the process is the large amount of produced sludge that requires an accurate feasibility evaluation for operational applications. In this study, the response surface methodology was applied for the modeling and optimization of Fenton process in three target responses, (1) overall COD removal, (2) sludge to iron ratio (SIR) and (3) organics removal to sludge ratio (ORSR), where the latter two were new self-defined responses for prediction of sludge generation and applicability assessment of the process, respectively. The effective variables included the initial pH, [H₂O₂]/[Fe²⁺] ratio and Fe²⁺ dosage. According to the statistical analysis, all the proposed models were adequate (with adjusted R² of 0.9116–0.9512) and had considerable predictive capability (with prediction R² up to 0.9092 and appropriate adequate precision). It was found that all the variables had significant effects on the responses, specifically by their observed role in dominant oxidation mechanism. The optimum operational conditions obtained by overlay plot, were found to be initial pH of 5.7, [H₂O₂]/[Fe²⁺] ratio of 17.72 and [Fe²⁺] of 195 mM, which led to 69% COD removal, 2.4 (l sludge/consumed mole Fe²⁺) of SIR and 16.5 (gCOD removed/l produced sludge) for ORSR in verification test, in accordance with models-predicted values. Finally, it was observed that [H₂O₂]/[Fe²⁺] ratio and Fe²⁺ dosage had significant influence on COD removal, while Fe²⁺ dosage and [H₂O₂]/[Fe²⁺] ratio had remarkable effects on SIR and ORSR responses, respectively.     

Study of Bulk and Sub-Event Wet Deposition in Gebze,Turkey

This study presents the chemical composition of bulk deposition during the period of February 1996–May 1997 and the chemical composition of sub-event wet deposition on 13 August 1997 in Gebze. Samples were analyzed for SO₄ ^2-, NO₃ ^-, Cl^-,Ca²⁺, Mg²⁺, K⁺, Na⁺, and NH₄ ⁺ in addition to pH. The source of some ionic components in the bulk deposition such as K⁺ and Ca²⁺ were found to be the terrestrial regions, as expected. The (non-sea Cl^-)/Cl^- ratio of 0.05 suggests that the very large portion of Cl^- in the bulkdeposition was of marine origin. The ratio of (non-sea SO₄ ^2-)/SO₄ ^2- varied between 0.86 and 0.99,indicating that the main source of sulfate was not the sea. It is found that the sulfate and calcium concentrations were highest in summer and lowest in fall. The analysis of bulk deposition also indicated that nearly 24% of the events were acidic (pH < 5.6). During sub-event wet deposition collectedon the same site pH decreased continually, and during the passageof cold front concentrations of Cl^-, SO₄ ^2- and NO₃ ^- increased.     

Coagulation of Sericin Protein in Silk Degumming Wastewater Using Quaternized Chitosan

The evaluation of 2-hydroxypropyltrimethyl ammonium chloride chitosan (HACC), a biodegradable cationic polymer, for the coagulation of sericin in silk degumming waste solution was carried out using jar-test coagulation experiments. The coagulation efficiency was assessed by the factors of residual turbidity, sericin removal and COD_Cr. The results indicated that the efficiency were dependent on the operational parameters of pH, coagulant dosage and settling time. The optimal pH value was found to be around 8, while a 1 g/L HACC dosage was sufficient in providing more than 98 % turbidity removal and 76 % sericin removal. The results were comparable to those got by the use of conventional coagulants. The coagulation of sericin by HACC may be involved in a dual mechanism including charge neutralization and bridging mechanism. Moreover, the sludge cake from the coagulation, mainly containing sericin protein and modified chitosan, might be used as finishing agent for polyester fabric or food additive for animals after fundamental purified.     

Leachate treatment before injection into a bioreactor landfill: Clogging potential reduction and benefits of using methanogenesis

In this study, an anaerobic sequencing batch reactor (ASBR) was operated with leachate from Brady Road Municipal Landfill in Winnipeg, Manitoba, Canada. Leachate was collected twice from the same cell at the landfill, during the first and 70th day of the study, and then fed into the ASBR. The ASBR was seeded at the start-up with biosolids from the anaerobic digester from Winnipeg’s North End Water Pollution Control Center (NEWPCC). Due to the higher COD and VFA removal rates measured with the second batch of leachate, an increase of approximately 0.3 pH units was observed during each cycle (from pH 7.2 to 7.5). In addition, CO₂ was produced between cycles at constant temperature where a fraction of the CO₂ became dissolved, shifting the CO₂/bicarbonate/carbonate equilibrium. Concurrent with the increase in pH and carbonate, an accumulation of fixed suspend solids (FSS) was observed within the ASBR, indicating a buildup of inorganic material over time. From it, Ca²⁺ and Mg²⁺ were measured within the reactor on day 140, indicating that most of the dissolved Ca²⁺ was removed within cycles. There is precedence from past researches of clogging in leachate-collection systems (Rowe et al., 2004) that changes in pH and carbonate content combined with high concentrations of metals such as Ca²⁺ and Mg²⁺ result in carbonate mineral precipitants. A parallel study investigated this observation, indicating that leachate with high concentration of Ca²⁺ under CO₂ saturation conditions can precipitate out CaCO₃ at the pH values obtained between digestion cycles. These studies presented show that methanogenesis of leachate impacts the removal of organic (COD, VFA) as well as inorganic (FSS, Ca²⁺) clog constituents from the leachate, that otherwise will accumulate inside of the recirculation pipe in bioreactor landfills. In addition, a robust methanogenesis of leachate was achieved, averaging rates of 0.35 L CH₄ produced/g COD removed which is similar to the theoretical removal of 0.4 L CH₄/g COD. Therefore, using methanogenesis of leachate prior to recirculation in bioreactor landfills will help to (1) control clog formation within leachate pipes and (2) produce an important additional source of energy on-site.     

Investigation of pH-Sensitive Swelling and Curcumin Release Behavior of Chitglc Hydrogel

Hydrogels are in use for encapsulation of curcumin for possible use in wound healing. Encapsulation helps in targeted delivery and enhanced activity of curcumin. We report here a pH sensitive hydrogel developed from chitosan. The hydrogel was prepared by reaction of chitosan and d-glucose, facilitated by the reducing agent Na-cyanoborohydride. The maximum yield of the hydrogel was obtained at pH 4.5 with the amount of chitosan, d-glucose and Na-cyanoborohydride as 0.3, 2.0 and 2.0 g respectively. A maximum curcumin loading efficiency of 74% was observed with curcumin amount in the feed at 0.15 g. The release study revealed a sustained release pattern over a period of 80 h with an initial burst release. Curcumin loaded hydrogel showed mild antibacterial activity against Proteus mirabilis and Enterobacter aerogenes.     

A Synthetic Filter Material Containing Nutrients for Biofilter

In this study, a synthetic filter material with nutrients (PVA/peat/KNO₃ composite bead) was developed for biofilteration. The optimal preparing condition was each of the peat and PVA aqueous solutions mixed with 6.4 g KNO_3, and the minimum nitrogen content in the boric and phosphate aqueous solutions was 3.94 and 1.52 g-N/l, respectively. The equilibrium amount of inorganic nitrogen extracted by leaching from the prepared composite bead was between 7.95 and 8.21 mg N/g dry solid. The path of inorganic nitrogen extracted by leaching was the inorganic nitrogen dispersed in the peat phase firstly diffused into the outer PVA phase and then it diffused out of the bead surface for the A-type bead; and that was the inorganic nitrogen dispersed in both the peat and PVA phases simultaneously diffuses into the outer PVA phase and out of the bead surface, respectively, for the H-type bead. The microbial growth rate k _g of the H-type composite bead was higher than that of the A-type composite bead about 1.09–1.58 times, and the maximum value of k _g was at the H-type composite bead immersed in 0.384 M KNO₃ aqueous solution. The percentage of removed VOCs retained at more than 98% during the biofilter operating 230 days as the composite bead immersed in KNO₃ aqueous solution before packing. This composite bead bed was without the further addition of nutrients during the operating period.     

Adsorptive Separation of Lysozyme from Aqueous Solutions Using Sulphonyl and Carboxyl Functionalized Stearyl Alcohol Grafted Epichlorohydrin

In the present work ability of the two novel adsorbents, sulphonyl and carboxyl functionalized stearyl alcohol-grafted epichlorohydrin, SA-g-E-SO₃H, SA-g-E-COOH; to remove lysozyme (LYZ) from aqueous solution was assessed. The adsorbent characterization was done using FTIR, XRD, SEM and TGA analyses. The adsorption efficiency was influenced by solution pH and the optimum operating pH was found to be 4.0 for SA-g-E-SO₃H and 5.0 for SA-g-E-COOH and their adsorption efficiency was evaluated using the various isotherm and kinetics models. The Sips isotherm model and pseudo-second-order kinetic model were found to be the best for describing the equilibrium and kinetic behaviors of the adsorption process. Batch adsorption/desorption studies in acidic medium, for over six cycles showed excellent regeneration capability of the adsorbents and could lead to the development of viable and promising technology for the adsorptive recovery of LYZ from aqueous solutions. The efficiency of the adsorbents for the LYZ adsorption was verified using egg white. The result obtained from this study revealed that adsorption ability of 25 mg of SA-g-E-COOH is 98.4 % which is more than that of SA-g-E-SO₃H (96.2 %). The efficiency of SA-g-E-SO₃H to remove LYZ from aqueous solution was found to be higher compared to SA-g-E-COOH.     

Chemical Composition and Acidity of Rain at the Gulf of Iskenderun,North-East Mediterranean

The purpose of the present work was to investigate the chemistry of rain in the Gulf of Iskenderun, North East Mediterranean, Turkey. The Gulf region has a large number of industries. Main industries existing in the region are iron and steel works, fertilizer plants, a cement plant, and several medium and mini size steel mills in addition to the international pipe line terminals. This study aims to apportion the local sources contributing to the overall pollution of the region. To this end a precipitation sampling program was started in January 2000, and over 48 precipitation samples were collected from each of 5 stations located at Iskenderun city center, Iskenderun industrial zone, Payas city center, the campus of Iskenderun Technical College and the campus of Mustafa Kemal University. Samples were analysed for pH, NO₃ ⁺, Cl^-. Ca, Al, Ba, Na, Cd, Co, Cr, Cu, Pb, Li, Mg, Mn, Ni, Zn, Fe, K. Concentrations of metal ions were determined by ICP-AES. NO₃ ^- ions and pH were determined by using NO₃ ^- selective electrode and pH meter, respectively.pH values of the collected samples at the industrial zone and at Payas city center, ranged between 5.02 and 7.38, respectively. NO₃ ^- and metal ions concentrations were highly variable. Concentrations of Ca and Fe ions were higher in the industrial zone and Payas city center. In the other three stations, concentrations of metal ions and NO₃ ^- ion were lower than that of industrial zone and the values of pH ranged between 6 and 7.4. The average pH values at Iskenderun Gulf showed that the precipitation was not acidic, because of the high concentration of Ca. The highest concentrations of Na and Cl ions were recorded in the University campus because the campus is located by the Mediterranean Sea.