Interaction of lead and chromium with chitin and chitosan

The interaction of the natural marine polymer chitin and its deacetylated derivative chitosan with lead and chromium has been investigated. The uptake of lead and chromium was determined from changes in concentration as measured by atomic absorption spectroscopy. A significant uptake of Pb(II) on both chitosan and chitin was observed. However, the uptake of Pb(II) on chitin was approximately 21% of that on chitosan. The number of Natoms in chitin and chitosan and per number of Pb(II) ions sorbed was 115 and 29, respectively. The number density of flakes observed in the scanning electron microscope and characterized by an intense Pb signal in energy dispersive analysis of x rays (EDAX) was greater on the surface of chitosan [containing 1.7 × 10^?4 mole Pb(II)/g chitosan] than chitin [containing 3.5 × 10^?5 mole Pb(II)/g chitin] after equilibration with Pb(II) solution. The bonding state of lead on chitosan as determined by electron spectroscopy for chemical analysis (ESCA) is similar to the bonding of lead in PbO based on the Pb 4f_7/2 binding energy. A significant shift in the O 1s binding energy from 532.2 to 531.4 eV was observed for chitosen after equilibration with Pb(II) solution. The caculated values of the N/Pb ratio from ESCA spectra were 0.5 and 11, for chitosan and chitin, respectively. A significant uptake of Cr(III) on chitosan was observed and a significant increase in the pH of solutions of Cr(III) on equilibration with chitosan occurred. A high number density of nodules characterized by an intense Cr signal in EDAX was observed in chitosan [containing 2.5 mole Cr(III)/g chitosan] after equilibration with Cr(III) solution. The calculated values of the N/Cr ratio from ESCA spectra was 18 for chitosan.     

Adsorption of humic acid onto chitin and chitosan

The adsorption of humic acid onto chitin and chitosan has been investigated. The uptake of humic acid from aqueous solution was determined from changes in concentration, as measured by ultraviolet-visible spectroscopy. The decrease in humic acid removal was observed with the increase in pH. A significant uptake of humic acid on both chitin and chitosan was observed. The uptake of humid acid on chitosan was greater than that on chitin. Adsorption isothermal data could be interpreted by the Langmuir and Freundlich equation. Langmuir and Freundlich constants have been determined. The experimental data of the adsorption equilibrium from humic acid solutions correlate well with the Langmuir isotherm equation, as compared to the Freundlich isotherm equation. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2305–2310, 1998     

Adsorption of Cr(III) ions by Turkish brown coals

The equilibrium and kinetic properties of Cr(III) ion adsorption by two brown coals from Anatolia, Turkey, have been investigated in batch stirred-tank experiments. The effects of adsorbent dose, initial sorbate concentration and contact time on the adsorption of Cr(III) by Isparta-Yalvaç-Yarikkaya (YK) and Kasikara (KK) brown coals were evaluated. The Cr(III) ions are able to form complex compounds with carboxylic and phenolic groups of brown coals and they were also bounded with phenolic groups even at low pH reaction of the solution (<3). Mechanisms including ion exchange, complexation and adsorption to the surface are possible in the sorption process. Our batch adsorption studies show the equilibrium adsorption data fit the linear Langmuir adsorption isotherm. Adsorption equilibrium was achieved in about 15–20 min for chromium(III). The Langmuir adsorption isotherm was used to describe the observed sorption phenomena. The maximum equilibrium uptake was 0.05 mmol of Cr(III)/g for KK, and 0.26 mmol of Cr(III)/g for YK, respectively, at a pH of 4.5. More than 90% of chromium(III) was removed by KK and YK from an aqueous solution after 60 min. In every experiment, the maximum Cr(III) was sequestered from the solution within 60 min. It is proposed that KK and YK brown coals can be used as potential sorbents for Cr(III) removal from aqueous solutions.     

Bacterial cellulose/PANi mat for Cr(VI) removal at acidic pH

Remediation of hexavalent chromium - Cr(VI) at acidic pH using polyaniline coated bacterial cellulose porous mat (BC/PANi) is presented and the possible mechanism is discussed. The efficacy of BC/PANi mats in remediation of Cr(VI) was studied by varying pH (pH 1, 2, 3, and 5) and initial Cr(VI) concentrations (250–1000 ppm) of the solution. The BC/PANi (50 mg) mat was able to completely reduce 2000 ppm Cr(VI) into Cr(III) in a 20 ml solution at pH ~ 1 in 24 h. An increasing chromium removal efficiency was observed with decreasing solution pH; reaching a maximum removal capacity of ~920 mg/g at pH 1. The proposed mechanism of negatively charged Cr(VI) ions removal by BC/PANi mat is adsorption and simultaneous reduction into Cr(III), followed by desorption of Cr(III) from the mat. The role of temperature and co-existing anions like sulphate, nitrate and chloride found in industrial sludge were also investigated for removal efficiency of Cr(VI) at acidic pH ~ 1. The adsorption kinetics of Cr(VI) on polyaniline surface followed a pseudo-second-order model with reduction of Cr(VI) into Cr(III) as rate-limiting step. The reduced Cr(III) from the media was further recovered by neutralizing the pH of the solution.     

壳聚糖处理含铬(Ⅵ)废液的研究

使用壳聚糖和改性壳聚糖吸附法分别处理含铬(Ⅵ)模拟废水。研究了吸附剂用量、吸附时间、废水酸度及铬(Ⅵ)离子初始浓度等对铬(Ⅵ)离子去除率的影响。并探讨不同壳聚糖的吸附效果。实验表明,Na2S改性后的壳聚糖对Cr(Ⅵ)吸附效果最为理想。该法简便,去除率高。     

一种新型吸附剂在痕量重金属分析中的应用

以二苯并18-冠-6交联席夫碱型壳聚糖作为新型吸附剂，用石墨炉原子吸收分光光度法测定了经过滤处理后的燃煤烟气中痕量铬、镉和铅的含量。经过滤处理后的燃煤烟气含铬1．42／μg／m3，其中三价铬占54．20％，为0．77μg／m3，镉0．256μg／m3，铅5．30μg/m3。     

Investigation of hydrogen reactivity and its use as a surface probe on high surface area copper-chromium-silver impregnated charcoal

ASC whetlerite is a copper/chromium/silver impregnated, activated charcoal which is used effectively to remove and hydrolyze vapor contaminants from gas streams. Its catalytic activity is known to decrease as the chromium oxidation state is reduced from +6 to +3. A thermal treatment process was used to systematically reduce the Cr(+6) species to Cr(+3)-containing species and a pulse technique was developed to nondestructively quantify this reduction using hydrogen. The data illustrated that hydrogen uptake can be correlated with the oxidation state(s) of the chromium metal impregnant. In addition, total uptake of hydrogen was determined in a static adsorption system. These data showed that total hydrogen uptake was independent of the oxidation state of chromium on the charcoal surface and was much greater than a one-to-one relationship between metal atoms and hydrogen atoms. These results suggested that hydrogen molecules are adsorbed and dissociated by the Cr(+3)-containing species and then diffuse away from the “Cr(+3) centers” to the activated charcoal support. Finally, the hydrogen pulse results together with ESCA data indicated that the deactivation of whetlerite involves not only the reduction of chromium, but most likely also the separation of the chromium/copper impregnants.     

Kinetics and mechanism of chromium electrodeposition from formate and oxalate solutions of Cr(III) compounds

Kinetics of multistep reaction of Cr(III) ions discharge to metal was studied on a stationary electrode and on a rotating disk electrode from the solutions containing formic acid or oxalic acid. The electroreduction of Cr(III) complex ions in aqueous solutions is shown to proceed via the formation of relatively stable intermediates—Cr(II) compounds which are partially removed into bulk solution. The effect of pH, organic ligand concentration and disk rotation velocity on the partial current density of chromium electroplating was demonstrated. The kinetic equations of the studied process were derived and compared with the experimental data. Kinetic parameters for the discharge of Cr(II) ions were calculated. The mechanism of chromium electrodeposition reaction was proposed. The electrodeposition of chromium from formate bath is suggested to proceed with the participation of hydroxocomplexes of bivalent chromium. The oxalate complexes of bivalent chromium directly discharge in the electrolytes containing oxalic acid. The partial polarization curves of chromium electrodeposition exhibit a current peak which may be caused by blocking the electrode surface with poorly soluble Cr(III) hydroxide.     

Iron(III) ion removal from solution through adsorption on chitosan

The potential of different forms of chitosan to adsorb iron(III) ion from a Jectofer [an iron(III)–sorbitol–citric acid complex] solution was investigated. The working solution was chosen as Jectofer, to mimic the composition of excess iron(III) as may be found in biological systems. The equilibrium studies showed that chitosan powder has the highest sorption capacity for the iron(III) ion when compared to chitosan flakes and microspheres. The amount of iron(III) adsorbed onto chitosan was found to increase with the contact time to reach equilibrium within 3 h at 37°C. A higher initial concentration of a Jectofer solution resulted in a higher amount of iron(III) adsorbed. Higher pH values, in the range 2–7, also resulted in an increase in iron(III) uptake from the solution. The data of adsorption from the Jectofer solution were found to correlate well with the Freundlich isotherm equation. In vitro adsorption experiments showed that chitosan is capable of adsorbing excess iron, measured in terms of the ferritin level, in human blood. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1185–1192, 2002; DOI 10.1002/app.10416     

Coals as sorbents for the removal and reduction of hexavalent chromium from aqueous waste streams

The aim of this study is to demonstrate the potential of coals as a low-cost reactive barrier material for environmental protection applications, with the ability to prevent leaching of toxic Cr(VI) and other transition metals. Depending upon the type of ion and the surface functionalities, the uptake can involve ion sorption, ion exchange, chelation and redox mechanisms with the surface functionalities being considered as partners in electron transfer processes. The capacity for Cr(VI) uptake of low rank coals and oxidized bituminous coals has been found to lie within the range 0.2-0.6 mM g⁻¹. Air oxidation of bituminous coals can increase their Cr(VI) removal capacities. The effect of air oxidation of coals on uptake capacity was more pronounced for Cr(VI) than Cr(III), but less than for Hg(II) and the other ions (Ca²⁺, Ba²⁺, Zn²⁺, Cd²) investigated. As previously found for Hg(II), redox mechanisms play an important role in Cr(VI) uptake, with sorption of the resultant Cr(III) being aided by the functionalities arising from oxidation of the coal surface. In acidic media, much of the resultant Cr(III) is exchanged back into solution by hydrogen ions, but some of the sorbed chromium is irreversibly bound to the coal. The reduction of Cr(VI) alone is often considered a satisfactory solution in view of Cr(III) being essentially non-toxic.     

Removal of chromium(III) from tannery effluents,using a system of packed columns of zeolite and activated carbon

The removal of chromium(III) in packed columns of zeolite and activated carbon has been studied. The process of Cr(III) exchange in 13X zeolite was optimized using mass transference parameters. In addition, the effects of pH, the presence of interfering ions and the anion associated with the chromium in the solution were studied. It was found that particle diameter controls the Cr(III) exchange in the zeolite, indicating that particle diffusion predominantly controls the process of Cr(III) exchange in 13X zeolite. A mixed system of zeolite and activated carbon columns increased the efficiency of chromium removal from diluted wastewater. This effect occurred due to the reduction of the organic matter (chemical oxygen demand), adsorption of chromium, and interfering ions on the activated carbon column. The activated carbon + zeolite column system emerges as an alternative method in Cr(III) removal from tannery effluents. Copyright © 2005 Society of Chemical Industry     

Preparation and Characterization of Chitosan Coated Surgical Gauze Using Potassium Persulfate as Thermal Initiator

Chitosan powder was extracted from prawn shell via chitin formation by chemical treatment. Chitosan solution (2 wt.%) was prepared in aqueous solution containing ethanoic acid (2 wt.%) along with varying amounts of potassium persulphate as thermal initiator (10 to 50 mg). Surgical gauze was immersed in the chitosan solution for 10–45 min. Coating was carried out at 70–110°C and heating time varied from 30–180 min. Chitosan uptake and the mechanical properties of the chitosan coated surgical gauze, such as tensile strength (TS) and elongation at break (Eb), were measured. Soaking time, curing time, and curing temperature of the surgical gauze were optimized for the preparation of coated gauze over chitosan uptake and mechanical properties. Surgical gauze soaked for 20 min at 90°C for 120 min of curing showed the highest chitosan uptake and TS (9 MPa). Soil burial tests revealed that coated gauze became twisted and almost degraded within 6 weeks of ageing. Water uptake properties of the coated gauze were monitored. Scanning electron microscopic analysis of the surface of the coated gauze found that the coating of chitosan became brittle with the use of higher amounts (50 mg) of thermal initiator.     

Optical and EPR Studies of Redox Interactions of Polyvalent Ions (Cr, Cu) in Glass

Chromium centers in isolated Cr ions and Cr(III)-Cu(II) redox interactions were investigated by optical and EPR spectra. Line shapes and intensities of high-field Cr(III)-Cu(II) superimposed EPR absorption lines were sensitive to alkali content of host glasses. High-field chromium g values (1.94 to 1.99) and intensities (190 to 3600) were calculated. The increase in g values from 1.96 to 1.98 is related to an increase in Cr(V) and to a conversion from Cu(I) to Cu(II) with increased alkali content. Two components of Cr powder spectra near g = 2.0 and g = 5.0 correspond to isolated octahedral Cr centers described by Landry et al. Cr-Cr pair structure was not observed for low Cr₂O₃ concentrations. Three components of optical absorption bands near 340 nm, 430 to 460 nm, and 600 nm were measured in Cr(III)-Cu(II) redox systems. Electronic interactions of Cr(III)-Cu(II) redox systems and the structure of Cr centers are discussed.     

Effect of Cr(III) solution chemistry on electrodeposition of chromium

This work provides a new insight into the interaction of urea with formate during the chromium electrodeposition from a sulphate-based Cr(III) solution. The influence of solution chemistry on chromium electrodeposition in a Cr(III) bath containing sodium formate and urea as complexing agents was studied by FT-IR, XPS and AFM. The results show that good quality Cr coatings may be obtained only in those cases when the secondary ligand with the carbamidic group predominates over urea in the electrolyte. This suggests that electrodeposition of good quality chromium deposit is possible due to the formation of active chromium–carbamid complexes [Cr(carbamid)_n(H₂O)_6-n ]³⁺. These complexes delay the formation of the stable oligomeric species, and thus provide a prolonged working lifetime in the Cr(III) formate-urea electrolyte.     

微波条件下甲壳素脱乙酰反应的条件研究

研究了微波处理条件下,甲壳素脱乙酰反应条件对壳聚糖脱乙酰度的影响。结果表明:微波甲壳素颗粒大小选择为0.18～0.3mm(过60～80目筛)较利于反应。在料液比小于1∶12(质量∶体积)时,壳聚糖脱乙酰度几乎不变,粘度逐渐增大,之后脱乙酰度随料液比的增大而下降。脱乙酰度随碱液浓度的增大而增大。随微波处理时间的延长,脱乙酰度上升、特性粘度下降。微波功率越高,相同时间下,产品的脱乙酰度越高。经正交试验得出:粒度为0.18～0.3mm的甲壳素原料,按料液比1∶12(质量∶体积)加入浓度为50%(质量分数)的NaOH溶液,在微波功率320W下处理21min,所得产品的脱乙酰度可达85.65%,特性粘度为394.07mL/g,灰分为0.05%。     

Biosorption of chromium (III) by orange (Citrus cinensis) waste: Batch and continuous studies

The present study explores the ability of orange waste biomass to remove Cr (III) from aqueous solutions. Batch kinetic and isotherm studies were carried out on a laboratory scale to evaluate the adsorption capacity of orange waste. The effects of particle size, adsorbent dose and solution pH on Cr (III) removal were also studied. The results showed that the higher the adsorbent dosage and the pH, the higher the percentage of metal removal. No significant influence of particle size on sorption capacity was observed in the experimental conditions studied. A kinetic study revealed that the adsorption of Cr (III) onto orange waste was a gradual process and equilibrium was reached within 3 days. A pseudo-second order model was the most appropriate to describe the kinetic experimental data. Equilibrium assays displayed a maximum sorption capacity ranging from 0.57 mmol/g to 1.44 mmol/g when the pH increased from 3 to 5, according to the Sips model, which along with the Redlich–Peterson equation, is very suitable for correlating equilibrium data. The use of the studied adsorbent in the removal of chromium in continuous mode was successful and the breakthrough curves were adequately represented by BDST model. Due to the slow kinetics of chromium sorption onto orange waste, the sorption capacity in batch assays was higher than that in continuous assays.     

Reduction of hexavalent chromium using polyaniline films. Effect of film thickness, potential and flow velocity on the reaction rate and polymer stability

Reduction of very toxic hexavalent chromium (Cr(VI)) to its trivalent state (Cr(III)) is necessary to facilitate the treatment of wastewater by precipitation or adsorption. The present study proposes the use of thin films of polyaniline on a conducting substrate for this purpose. The reduction rate of hexavalent chromium and the degree of degradation of the polyaniline film were studied as a function of the solution flow velocity, applied potential and film thickness. The reduction rate was significantly affected by the flow velocity, while the film thickness was observed to have little effect. The potential had no effect on the reduction rate within the range studied. The current efficiency was 100% in all experiments and no significant degradation of polyaniline was observed.     

Immobilization of chromium (VI) evaluated by binding isotherms for ground granulated blast furnace slag and ordinary Portland cement

The interaction mechanisms of the Cr(VI) ion in presence of GGBFS and OPC were evaluated by chromium binding isotherms and by pore solution analysis. The chromium in the final leaching solution was measured and the solid samples were investigated by SEM and by XRD. GGBFS was more efficient than OPC in fixing Cr ions at lower initial concentrations. However, from an initial Cr(VI) concentration of 2000 and 5000 mg/L, OPC was more efficient.

For an initial Cr(VI) concentration of 50 000 mg/L, around 145 mg Cr/g was fixed by OPC and only 8 and 55 mg Cr/g were fixed by GGBFS in alkaline and water-based immersion solutions, respectively. The Cr-bearing phases identified by XRD and SEM are: CaCrO₄ and CaCrO₄·2H₂O, C–S–H and calcium aluminate phases. The pore solution chemistry indicates that a value around 92% of chromium was retained by GGBFS and 87% by OPC.     

Chitosan from Muga silkworms (Antheraea assamensis) and its influence on thermal degradation behavior of poly(lactic acid) based biocomposite films

The research work is focused on extraction of chitin from Muga silkworms (MS) and its conversion into chitosan by chemical treatment process. The extracted amount of chitin and chitosan from MS were obtained ～8 wt % and ～7 wt %, respectively. Potentiometric titrations, conductometric titrations, elemental analysis, ¹H‐NMR and FTIR analyses were employed to calculate the degree of deacetylation of chitosan (extracted at 80 ºC after 10 h) and found as 77% ± 2, 81% ± 1.8, 82% ± 2.4, 97.77% ± 0.3, and 82% ± 1.8, respectively. The deacetylation process of chitin showed pseudo‐first order reaction kinetics and activation energy was estimated as ～15.5 kJ/mole. The extracted chitosan (at 80 ºC after 10 h) showed higher crystallinity and improved thermal stability with respect to chitosan extracted from other marine sources. Subsequently, poly(lactic acid) (PLA) and extracted chitosan dispersed biocomposite films were prepared by solution casting method. Significant dispersion of chitosan (extracted at 80 ºC after 10 h) micro‐particles were observed in biocomposite films using FESEM analysis. Due to chitosan interaction with PLA, significant reduction in thermal degradation and activation energy was observed during nonisothermal degradation scan of such films using Flynn‐Wall‐Ozawa and Kissinger‐Akahira‐Sunose models. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43710.     

Adsorption of hexavalent chromium by chitosan‐based polymeric surfactants

Chitosan‐based polymeric surfactants (CBPSs) were prepared by the partial N‐acylation of amine groups on chitosan with acid anhydrides. To apply the CBPSs for the removal of Cr(VI) commonly found in wastewater, a batch test was conducted to evaluate the adsorption capacity. The removal efficiency of Cr(VI) by the CBPS depended on several factors, including the solution pH, CBPS dose, and ionic strength. Our results show that the CBPSs exhibited a greater adsorption capacity for Cr(VI) than have other modified chitosans reported in the literature. The maximum adsorption capacity of Cr(VI) was 180 mg/g of CBPS at a final pH of 5.3. From the results of dynamic light scattering, we propose that the removal mechanism of Cr(VI) by the CBPSs was mainly through the adsorption of negatively charged chromium ions by positively charged amine groups on the CBPSs followed by colloidal precipitation because of its lower solubility. Conclusively, we found that the CBPS was significantly effective for the removal of Cr(VI). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 44–50, 2005