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Remediation of organic and inorganic arsenic contaminated groundwater using a nanocrystalline TiO2-based adsorbent
2009
Jing, Chuanyong | Meng, Xiaoguang | Calvache, Edwin | Jiang, Guibin
A nanocrystalline TiO₂-based adsorbent was evaluated for the simultaneous removal of As(V), As(III), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in contaminated groundwater. Batch experimental results show that As adsorption followed pseudo-second order rate kinetics. The competitive adsorption was described with the charge distribution multi-site surface complexation model (CD-MUSIC). The groundwater containing an average of 329 μg L⁻¹ As(III), 246 μg L⁻¹ As(V), 151 μg L⁻¹ MMA, and 202 μg L⁻¹ DMA was continuously passed through a TiO₂ filter at an empty bed contact time of 6 min for 4 months. Approximately 11 000, 14 000, and 9900 bed volumes of water had been treated before the As(III), As(V), and MMA concentration in the effluent increased to 10 μg L⁻¹. However, very little DMA was removed. The EXAFS results demonstrate the existence of a bidentate binuclear As(V) surface complex on spent adsorbent, indicating the oxidation of adsorbed As(III). A nanocrystalline TiO₂-based adsorbent could be used for the simultaneous removal of As(V), As(III), MMA, and DMA in contaminated groundwater.
Show more [+] Less [-]Quantification of activated carbon contents in soils and sediments using chemothermal and wet oxidation methods
2009
Brändli, Rahel C. | Bergsli, Anders | Ghosh, Upal | Hartnik, Thomas | Breedveld, Gijs D. | Cornelissen, Gerard
Activated carbon (AC) strongly sorbs organic pollutants and can be used for remediation of soils and sediments. A method for AC quantification is essential to monitor AC (re)distribution. Since AC is black carbon (BC), two methods for BC quantification were tested for AC mixed in different soils and sediments: i) chemothermal oxidation (CTO) at a range of temperatures and ii) wet-chemical oxidation with a potassium dichromate/sulfuric acid solution. For three soils, the amount of AC was accurately determined by CTO at 375 °C. For two sediments, however, much of the AC disappeared during combustion at 375 °C, which could probably be explained by catalytic effects by sediment constituents. CTO at lower temperatures (325–350 °C) was a feasible alternative for one of the sediments. Wet oxidation effectively functioned for AC quantification in sediments, with almost complete AC recovery (81–92%) and low remaining amounts of native organic carbon (5–16%). Activated carbon quantification is best performed for soils with chemothermal oxidation at 375 °C, and for sediments with wet oxidation with potassium dichromate/sulfuric acid.
Show more [+] Less [-]Sorption behavior of bensulfuron-methyl on andisols and ultisols volcanic ash-derived soils: Contribution of humic fractions and mineral–organic complexes
2009
Espinoza, Jeannette | Fuentes, Edwar | Báez, Maria E.
Bensulfuron-methyl sorption was studied in Andisol and Ultisol soils in view of their characteristic physical and chemical properties, presenting acidic pH and variable charge. Humic and fulvic acids (HA and FA) and humin (HUM) contributions were established. Sorption was studied by using two synthetic sorbents, an aluminum-silicate with iron oxide coverage and the same sorbent coated with humic acid. Freundlich model described Bensulfuron-methyl behavior in all sorbents (R2 0.969–0.998). Kf for soils (8.3–20.7 μg1−1/n mL1/n g−1) were higher than those reported in the literature. Organic matter, halloysite or kaolinite, and specific surface area contributed to the global process. The highest Kf for HA, FA and HUM were 539.5, 82.9, and 98.7 μg1−1/n mL1/n g−1. Model sorbents described the participation of variable charge materials with high adsorption capacity. The constant capacitance model was used to assess effects of Bensulfuron-methyl adsorption on the distribution of SOH, SOH2+ and SO− sites of sorbents. Organic matter, phyllosilicates, variable charge minerals and organo-mineral complexes contribute to bensulfuron-methyl sorption on volcanic ash-derived soils.
Show more [+] Less [-]Preparation, Characterization, and Adsorption Behavior of Cu(II) Ions onto Alkali-Treated Weed (Imperata cylindrica) Leaf Powder
2009
Hanafiah, M. A. K. M. | Zakaria, H. | Wan Ngah, W. S.
The adsorption of Cu(II) ions by sodium-hydroxide-treated Imperata cylindrica (SoHIC) leaf powder was investigated under batch mode. The influence of solution pH, adsorbent dosage, shaking rate, copper concentration, contact time, and temperature was studied. Copper adsorption was considered fast as the time to reach equilibrium was 40-90 min. Several kinetic models were applied and it was found that pseudo-second-order fitted well the adsorption data. In order to understand the mechanism of adsorption, spectroscopic analyses involving scanning electron microscope (SEM) coupled with energy-dispersive spectroscopy (EDS) and Fourier transform infrared (FTIR) spectrophotometer were carried out. Ion exchange was proven the main mechanism involved as indicated by EDS spectra and as there was a release of light metal ions (K⁺, Na⁺, Mg²⁺, and Ca²⁺) during copper adsorption. Complexation also occurred as demonstrated by FTIR spectra involving hydroxyl, carboxylate, phosphate, ether, and amino functional groups. The equilibrium data were correlated with Langmuir, Freundlich, and Dubinin-Radushkevich isotherm models. Based on Langmuir model, the maximum adsorption capacity was recorded at the highest temperature of 310 K, which was 11.64 mg g⁻¹.
Show more [+] Less [-]Cadmium, Copper and Zinc Biosorption Study by Non-Living Egeria densa Biomass
2009
Pietrobelli, Juliana M. T. de A. | Módenes, Aparecido N. | Fagundes-Klen, Márcia R. | Espinoza-Quiñones, Fernando R.
In this work, the potential removal of Cd, Cu, and Zn ions by non-living macrophytes Egeria densa has been studied. The adsorption kinetic and equilibrium experiments of these three metals on E. densa were performed in batch systems with controlled temperature and constant shaking. It was observed that all metal adsorption rates have increased when the pH was increasing. A pH threshold of 5 was established for use in adsorption experiments in order to avoid the metal precipitation. For adsorption kinetic tests, the equilibrium times for all metals were around 45 to 60 min. The equilibrium data at pH 5 were better described by the Langmuir isotherm than the Freundlich one, with the adsorption rate and maximum metal content values of 0.43 L g⁻¹ and 1.25 mequiv g⁻¹ for Cd, 4.11 L g⁻⁻¹ and 1.43 mequiv g⁻¹ for Cu, and 0.83 L g⁻¹ and 0.93 mequiv g⁻¹ for Zn. These adsorption parameters for E. densa resemble or are better than those for other biosorbents already studied, suggesting that the macrophytes E. densa as a biosorbent has a good metal removal potential for applications in effluent treatment systems.
Show more [+] Less [-]Vermicompost for Tinted Organic Cationic Dyes Retention
2009
de Godoi Pereira, Madson | Korn, Mauro | Santos, Bruno Barros | Ramos, Marcia Guia
The use of vermicompost was expanded as natural adsorbent for cationic dyes retention. The adsorption profiles in batch and flow modes for crystal violet and methylene blue on vermicompost material were evaluated. In batch mode, a retention index higher than 97% was obtained for both compounds, while in flow condition, 40 g of dried adsorbent material were enough to remove 100 mg of crystal violet or methylene blue at column flow rates of 5 and 20 mL min⁻¹. Adsorption isotherms showed adsorptive maximum capacities for vermicompost of 0.78 and 5.47 mg g⁻¹, respectively, which were compatible with the literature. Due to this good efficiency capacity, incineration steps can be considered as acceptable disposal procedures for enriched vermicompost. From these characteristics, economical and environmental advantages of the proposed material for the evaluated cationic dyes retention were evidenced.
Show more [+] Less [-]Adsorption of Geosmin and MIB on Activated Carbon Fibers-Single and Binary Solute System
2009
Srinivasan, Rangesh | Sorial, George A
The adsorption of two taste- and odor-causing compounds, namely MIB (2-methyl isoborneol—C₁₁H₂₀O) and geosmin (C₁₂H₂₂O) on activated carbon was investigated in this study. The impact of adsorbent pore size distribution on adsorption of MIB and geosmin was evaluated through single solute and multicomponent adsorption of these compounds on three types of activated carbon fibers (ACFs) and one granular activated carbon (GAC). The ACFs (ACC-15, ACC-20, and ACC-25) with different degrees of activation had narrow pore size distributions and specific critical pore diameters whereas the GAC (F-400) had a wider pore size distribution and lesser microporosity. The effect of the presence of natural organic matter (NOM) on MIB and geosmin adsorption was also studied for both the single solute and binary systems. The Myers equation was used to evaluate the single solute isotherms as it converges to Henry's law at low coverage and also serves as an input for predicting multicomponent adsorption. The single solute adsorption isotherms fit the Myers equation well and pore size distribution significantly influenced adsorption on the ACFs and GAC. The ideal adsorbed solute theory (IAST), which is a well-established thermodynamic model for multicomponent adsorption, was used to predict the binary adsorption of MIB and geosmin. The IAST predicted well the binary adsorption on the ACFs and GAC. Binary adsorption isotherms were also conducted in the presence of oxygen (oxic) and absence of oxygen (anoxic). There were no significant differences in the binary isotherm between the oxic and anoxic conditions, indicating that adsorption was purely through physical adsorption and no oligomerization was taking place. Binary adsorptions for the four adsorbents were also conducted in the presence of humic acid to determine the effect of NOM and to compare with IAST predictions. The presence of NOM interestingly resulted in deviation from IAST behavior in case of two adsorbents, ACC-15 and F-400.
Show more [+] Less [-]Two-stage Batch Adsorber Design: A Time-Dependent Langmuir Model for Adsorption of Pb²⁺ and Cd²⁺ onto Modified Kaolinite Clay
2009
Unuabonah, E. I. | Adebowale, K. O. | Ofomaja, A. E.
The kinetics of the adsorption of Pb²⁺ and Cd²⁺ by sodium tetraborate (NTB)-modified kaolinite clay adsorbent was studied. A one-stage and two-stage optimization of equilibrium data were carried out using the Langmuir and time-dependent Langmuir models, respectively. Increasing temperature was found to increase the pseudo-second order kinetic rate constant and kinetic data for Pb²⁺ adsorption were found to fit well with the pseudo-second order kinetic model (PSOM) while that for Cd²⁺ were found to show very good fit to the modified pseudo-first order kinetic model (MPFOM). Binary solutions of Pb²⁺ and Cd²⁺ reduced the adsorption capacity of the modified adsorbent for either metal ion with increased initial sorption rate due to competition of metal ions for available adsorption sites. The use of NTB-modified kaolinite clay adsorbent reduces by approximately 72.2% and 96.3% the amount of kaolinite clay needed to adsorb Pb²⁺ and Cd²⁺ from wastewater solutions. From the two-stage batch adsorber design study, the minimum operating time to determine a specified amount of Pb²⁺ and Cd²⁺ removal was developed. The two-stage batch adsorption process predicted less than half the minimum contact time to reach equilibrium in the one-stage process for the adsorption of Pb²⁺ and Cd²⁺ by NTB-modified kaolinite clay adsorbent and requires 0.05 times the mass of the adsorbent for the single-stage batch adsorption at the same operating conditions.
Show more [+] Less [-]Preparation of calcium oxalate--bromopyrogallol red inclusion sorbent and application to treatment of cationic dye and heavy metal wastewaters
2009
Wang, Hong-Yan | Gao, Hong-Wen
Background, aim, and scope Dye pollutants are a major class of environmental contaminants. Over 100,000 dyes have been synthesized worldwide and more than 700,000 tons are produced annually and over 5% are discharged into aquatic environments. The adsorption or sorption is one of the most efficient methods to remove dye and heavy metal pollutants from wastewater. However, most of the present sorbents often bear some disadvantages, e.g. low sorption capacity, difficult separation of spoil, complex reproduction, or secondary pollution. Development of novel sorbents that can overcome these limitations is desirable. Materials and methods On the basis of the chemical coprecipitation of calcium oxalate (CaC₂O₄), bromopyrogallol red (BPR) was embedded during the growing of CaC₂O₄ particles. The ternary C₂O₄ ²⁻-BPR-Ca²⁺ sorbent was yielded by the centrifugation. Its composition was determined by spectrophotometry and AAS, and its structure and morphology were characterized by powder X-ray diffraction (XRD), laser particle-size analysis, and scanning electron microscopy (SEM). The adsorption of ethyl violet (EV) and heavy metals, e.g. Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) were carried out and their removal rate determined by spectrophotometry and ICP-OES. The adsorption performance of the sorbent was compared with powder activated carbon. The Langmuir isothermal model was applied to fit the embedment of BPR and adsorption of EV. Results The saturation number of BPR binding to CaC₂O₄ reached 0.0105 mol/mol and the adsorption constant of the complex was 4.70 x 10⁵ M⁻¹. Over 80% of the sorbent particles are between 0.7 and 1.02 μm, formed by the aggregation of the global CaC₂O₄/BPR inclusion grains of 30-50 nm size. Such a material was found to adsorb cationic dyes selectively and sensitively. Ethyl violet (EV) was used to investigate the adsorption mechanism of the material. One BPR molecule may just bind with one EV molecule. The CaC₂O₄/BPR inclusion material adsorbed EV over two times more efficiently than the activated carbon. The adsorption of EV on the CaC₂O₄/BPR inclusion sorbent was complete in only 5 min and the sedimentation complete in 1 h. However, those of EV onto activated carbon took more than 1.5 and 5 h, respectively. The treatment of methylene blue and malachite green dye wastewaters indicated that only 0.4% of the sorbent adsorbed over 80% of color substances. Besides, the material can also adsorb heavy metals by complexation with BPR. Over 90% of Pb²⁺, and approximately 50% of Cd²⁺ and Cu²⁺, were removed in a high Zn²⁺-electroplating wastewater when 3% of the material was added. Eighty-six percent of Cu²⁺, and 60% of Ni²⁺ and Cd²⁺, were removed in a high Cd²⁺-electroplating wastewater. Discussion The embedment of BPR into CaC₂O₄ particles responded to the Langmuir isothermal adsorption. As the affinity ligand of Ca²⁺, BPR with sulfonic groups may be adsorbed into the temporary electric double layer during the growing of CaC₂O₄ particles. Immediately, C₂O₄ ²⁻ captured the Ca²⁺ to form the CaC₂O₄ outer enclosed sphere. Thus, BPR may be released and embedded as a sandwich between CaC₂O₄ layers. The adsorption of EV on the sorbent obeyed the Langmuir isothermal equation and adsorption is mainly due to the ion-pair attraction between EV and BPR. Different from the inclusion sorbent, the activated carbon depended on the specific surface area to adsorb organic substances. Therefore, the adsorption capacity, equilibrium, and sedimentation time of the sorbent are much better than activated carbon. The interaction of heavy metals with the inclusion sorbent responded to their coordination. Conclusions By characterizing the C₂O₄ ²⁻-BPR-Ca²⁺ inclusion material using various modern instruments, the ternary in situ embedment particle, [(CaC₂O₄)₉₅(BPR)] n ²n⁻, an electronegative, micron-sized adsorbent was synthesized. It is selective, rapid, and highly effective for adsorbing cationic dyes and heavy metals. Moreover, the adsorption is hardly subject to the impact of electrolytes. Recommendations and perspectives The present work provides a simple and valuable method for preparing the highly effective adsorbent. If a concentrated BPR wastewater was reused as the inclusion reactant, the sorbent will be low cost. By selecting the inclusion ligand with a special structure, we may prepare some particular functional materials to recover the valuable substances from seriously polluted wastewaters. The recommended method will play a significant role in development of advanced adsorption materials.
Show more [+] Less [-]Removal of Cu++ ions from aqueous solution by bisorbent based on Lagenaria vulgaris shell | Uklanjanje Cu++ jona iz vodenih rastvora biosorbentom na bazi kore Lagenaria vulgaris
2009
Bojic, A., Univerzitet u Nisu, Nis (Serbia). Prirodno-matematicki fakultet, Odsek za hemiju | Mitic-Stojanovic, D.L., JP Vodovod, Vranje (Serbia) | Bojic, d., Univerzitet u Nisu, Nis (Serbia). Prirodno-matematicki fakultet, Odsek za hemiju | Andjelkovic, T., Univerzitet u Nisu, Nis (Serbia). Prirodno-matematicki fakultet, Odsek za hemiju
This study investigates the effect of pH, temperature, contact time and initial metal concentration on Cu++ ions removal from water solutions, using biomass of Lagenaria vulgaris skin (LV). With higher pH, the efficiency of copper sorption increases and reaches its maximum at pH 7.0. Temperature has negative effect on sorption process due to its exothermic properties. Biosorption efficiency increases with time and reaches equilibium after 40 min. Increasing initial copper concentration gives an increase in biosorbent sorption capacity, and a proportional decrease in treatment efficiency. Obtained results have shown that LV based biosorbent is an efficient and available mean for toxic metal removal from natural and waste waters.
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