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Isosteric heats of sorption and desorption of phenanthrene in soils and carbonaceous materials
2013
Wang, Guohui | Grathwohl, Peter
Isosteric heats (ΔH) of sorption/desorption of phenanthrene were determined for carbonaceous materials (Pahokee peat, lignite, and high-volatile bituminous coal) and two soils based on reported equilibrium sorption/desorption isotherms at four different temperatures (4, 20, 46 and 77 °C). In addition, ΔH for desorption of native phenanthrene was determined to elucidate the “aging” effect by equilibrating samples with water at six temperatures (20, 40, 53, 61, 73, and 86 °C). Isosteric heats decreased with increasing solute concentration and were in a range of 19–35 kJ mol−1. Values higher than the heat of octanol–water phase transfer for phenanthrene (19 kJ mol−1) imply that both partitioning and adsorption processes are involved for these materials, where the sorptive contributions from both processes were estimated based on the phenanthrene thermodynamic data. Moreover, on the basis of ΔH values of desorption, release of native and spiked phenanthrene from our samples was similar.
Показать больше [+] Меньше [-]Kinetic control of contaminant release from NAPLs – Experimental evidence
2013
Wehrer, Markus | Rennert, Thilo | Totsche, Kai Uwe
Mass transfer processes of pollutants from non-aqueous phase liquids (NAPL) may control groundwater pollution at abandoned industrial sites. We studied release kinetics of polycyclic aromatic hydrocarbons (PAHs) from fresh and aged tar phases using a dialysis tubing technique. Time for equilibration ranged from several days to more than three years. For fresh tar materials the release seems to be limited by retarded pore diffusion, while for two of three aged tars diffusion limited release influenced by dissolved organic matter (DOM) was assumed. The equilibration process was driven by solubilization thermodynamics expressed by Raoult's law. Yet, solubility enhancement was observed potentially due to the presence of organic mobile sorbents. The results show that the release of PAHs from tar phases is generally rate limited and partitioning according to Raoult's law is the driving mechanism of the exchanges process.
Показать больше [+] Меньше [-]Filling the gap: Estimating physicochemical properties of the full array of polybrominated diphenyl ethers (PBDEs)
2013
Yue, Chaoyang | Li, Loretta Y.
Physicochemical properties of PBDE congeners are important for modeling their transport, but data are often missing. The quantitative structure–property relationship (QSPR) approach is utilized to fill this gap. Individual research groups often report piecemeal properties through experimental measurements or estimation techniques, but these data seldom satisfy fundamental thermodynamic relationships because of errors. The data then lack internal consistency and cannot be used directly in environmental modeling. This paper critically reviews published experimental data to select the best QSPR models, which are then extended to all 209 PBDE congeners. Properties include aqueous solubility, vapor pressure, Henry's law constant, octanol–water partition coefficient and octanol–air partition coefficient. Their values are next adjusted to satisfy fundamental thermodynamic equations. The resulting values then take advantage of all measurements and provide quick references for modeling and PBDE-contaminated site assessment and remediation. PCBs are also compared with respect to their properties and estimation methods.
Показать больше [+] Меньше [-]Kinetics and equilibrium models for the sorption of tributyltin to nZnO, activated carbon and nZnO/activated carbon composite in artificial seawater
2013
Ayanda, Olushola S. | Fatoki, Olalekan S. | Adekola, Folahan A. | Ximba, Bhekumusa J.
The removal of tributyltin (TBT) from artificial seawater using nZnO, activated carbon and nZnO/activated carbon composite was systematically studied. The equilibrium and kinetics of adsorption were investigated in a batch adsorption system. Equilibrium adsorption data were analyzed using Langmuir, Freundlich, Temkin and Dubinin–Radushkevich (D–R) isotherm models. Pseudo first- and second-order, Elovich, fractional power and intraparticle diffusion models were applied to test the kinetic data. Thermodynamic parameters such as ΔG°, ΔS° and ΔH° were also calculated to understand the mechanisms of adsorption. Optimal conditions for the adsorption of TBT from artificial seawater were then applied to TBT removal from natural seawater. A higher removal efficiency of TBT (>99%) was obtained for the nZnO/activated carbon composite material and for activated carbon but not for nZnO.
Показать больше [+] Меньше [-]Kinetics and Thermodynamics of Sorption for As(V) on the Porous Biomorph-Genetic Composite of α-Fe2O3/Fe3O4/C with Eucalyptus Wood Hierarchical Microstructure
2013
Zhu, Yinian | Zhu, Zongqiang | Chen, Yudao | Yang, Feng | Qin, Hui | Xie, Liwei
A novel porous biomorph-genetic composite of α-Fe₂O₃/Fe₃O₄/C (PBGC-Fe/C) with eucalyptus wood template was prepared, characterized and tested for its sorption capacity of As(V) from aqueous solution. The result indicated that the PBGC-Fe/C material retained the hierarchical porous structure of eucalyptus wood with three different types of pores (widths 70∼120, 4.1∼6.4 and 0.1∼1.3 μm) originating from vessels, fibres and pits of the wood, respectively. Its surface area was measured to be 59.2 m²/g. With increasing initial As(V) concentration from 5 to 100 mg/L, the amounts of As(V) sorbed on the pulverized PBGC-Fe/C sorbent (<0.149 mm) increased from 0.50 to 4.01 mg/g at 25 °C, from 0.50 to 4.83 mg/g at 35 °C and from 0.50 to 4.19 mg/g at 45 °C, and the corresponding removal rates decreased from 99.97 to 40.10 % at 25 °C, 99.95 to 48.40 % at 35 °C and 99.92 to 42.05 % at 45 °C. At the initial concentrations of 5, 10 and 50 mg/L, the sorption capacities for the unpulverized PBGC-Fe/C sorbent (>3 mm) were determined to be 0.50, 0.99 and 2.49 mg/g, respectively, which exhibited a similar average value to those of fine particles or nanoparticles of iron oxides. The sorption could well be described by the pseudo-second-order kinetic equation. The equilibrium data were found to follow Freundlich as well as Langmuir isotherms.
Показать больше [+] Меньше [-]Adsorptive removal of Pb²⁺ form aqueous solution by macrocyclic calix[4]naphthalene: kinetic, thermodynamic, and isotherm analysis
2013
Ahmad, Rais | Kumar, Rajeev | Laskar, Mohammad Asaduddin
BACKGROUND: The adsorption characteristics of Pb²⁺ ions from aqueous solutions onto calix[4]naphthalene have been investigated. METHOD: Calix[4]naphthalene was prepared by the condensation of 1-naphthol and formaldehyde (1:2) in presence of hydrochloric acid at 80°C. The effect of various operation parameters, such as solution pH, initial metal ion concentration, contact time, and temperature, on the adsorption capacity of calix[4]naphthalene for Pb²⁺ have been investigated. RESULT: Experimental results showed that the adsorption of Pb²⁺ ions increased with the increase in solution pH and temperature. Langmuir and Freundlich isotherms models were used to describe the adsorption behavior of Pb²⁺ by calix[4]naphthalene. Equilibrium data fitted well with the Langmuir isotherm model and the maximum adsorption capacity of calix[4]naphthalene for Pb²⁺ at 30°C was found to be 29.15 mg g⁻¹. Kinetic studies indicated that the adsorption followed pseudo-second order model and the thermodynamic studies revealed that the adsorption process was spontaneous and endothermic in nature. The obtained results demonstrated that calix[4]naphthalene can be used as an effective adsorbent for Pb²⁺ ions removal from water.
Показать больше [+] Меньше [-]Sorption and desorption studies of a reactive azo dye on effective disposal of redundant material
2013
Çelekli, Abuzer | Bozkurt, Hüseyin
The effective disposal of redundant elephant dung (ED) is important for environmental protection and utilization of resource. The aim of this study was to remove a toxic-azo dye, Reactive Red (RR) 120, using this relatively cheap material as a new adsorbent. The FTIR-ATR spectra of ED powders before and after the sorption of RR 120 and zero point charge (pHzpc) of ED were determined. The sorption capacity of ED for removing of RR 120 were carried out as functions of particle size, adsorbent dose, pH, temperature, ionic strength, initial dye concentration, and contact time. Sorption isotherm, kinetic, activation energy, thermodynamic, and desorption parameters of RR 120 on ED were studied. The sorption process was found to be dependent on particle size, adsorbent dose, pH, temperature, ionic strength, initial dye concentration, and contact time. FTIR-ATR spectroscopy indicated that amine and amide groups have significant role on the sorption of RR 120 on ED. The pHzpc of ED was found to be 7.3. Sorption kinetic of RR 120 on ED was well described by sigmoidal Logistic model. The Langmuir isotherm was well fitted to the equilibrium data. The maximum sorption capacity was 95.71 mg g(-1). The sorption of RR 120 on ED was mainly physical and exothermic according to results of D-R isotherm, Arrhenius equation, thermodynamic, and desorption studies. The thermodynamic parameters showed that this process was feasible and spontaneous. This study showed that ED as a low-cost adsorbent had a great potential for the removal of RR 120 as an alternative eco-friendly process.
Показать больше [+] Меньше [-]Biosorption of synthetic dyes (Direct Red 89 and Reactive Green 12) as an ecological refining step in textile effluent treatment
2013
Guendouz, Samira | Khellaf, Nabila | Zerdaoui, Mostefa | Ouchefoun, Moussa
With the use of cost-effective natural materials, biosorption is considered as an ecological tool that is applied worldwide for the remediation of pollution. In this study, we proposed Lemna gibba biomass (LGB), a lignocellulosic sorbent material, for the removal of two textile dyes, Direct Red 89 (DR-89) and Reactive Green 12 (RG-12). These azo dyes commonly used in dying operations of natural and synthetic fibres are the most important pollutants produced in textile industry effluents. For this purpose, batch biosorption experiments were carried out to assess the efficacy of LGB on dye treatment by evaluating the effect of contact time, biomass dosage, and initial dye concentration. The results indicated that the bioremoval efficiency of 5 mg L⁻¹ DR-89 and RG-12 reached approximately 100 % after 20 min of the exposure time; however, the maximum biosorption of 50 mg L⁻¹ DR-89 and 15 mg L⁻¹ RG-12 was determined to be about 60 and 47 %, respectively. Fourier transform infrared spectroscopy used to explain the sorption mechanism showed that the functional groups of carboxylic acid and hydroxyl played a major role in the retention of these pollutants on the biomass surface. The modelling results using Freundlich, Langmuir, Temkin, Elovich, and Dubini Radushkevich (D-R) isotherms demonstrated that the DR-89 biosorption process was better described with the Langmuir theory (R ² = 0.992) while the RG-12 biosorption process fitted well by the D-R isotherm equation (R ² = 0.988). The maximum biosorption capacity was found to be 20.0 and 115.5 mg g⁻¹ for DR-89 and RG-12, respectively, showing a higher ability of duckweed biomass for the bioremoval of the green dye. The thermodynamic study showed that the dye biosorption was a spontaneous and endothermic process. The efficacy of using duckweed biomass for the bioremoval of the two dyes was limited to concentrations ≤50 mg L⁻¹, indicating that L. gibba biomass may be suitable in the refining step of textile effluent treatment.
Показать больше [+] Меньше [-]Preparation of char from lotus seed biomass and the exploration of its dye removal capacity through batch and column adsorption studies
2013
Nethaji, S. | Sivasamy, A. | Kumar, R Vimal | Mandal, A. B.
Char was obtained from lotus seed biomass by a simple single-step acid treatment process. It was used as an adsorbent for the removal of malachite green dye (MG) from simulated dye bath effluent. The adsorbent was characterized for its surface morphology, surface functionalities, and zero point charge. Batch studies were carried out by varying the parameters such as initial aqueous pH, adsorbent dosage, adsorbent particle size, and initial adsorbate concentration. Langmuir and Freundlich isotherms were used to test the isotherm data and the Freundlich isotherm best fitted the data. Thermodynamic studies were carried out and the thermodynamic parameters such as ∆G, ∆H, and ∆S were evaluated. Adsorption kinetics was carried out and the data were tested with pseudofirst-order model, pseudosecond-order model, and intraparticle diffusion model. Adsorption of MG was not solely by intraparticle diffusion but film diffusion also played a major role. Continuous column experiments were also conducted using microcolumn and the spent adsorbent was regenerated using ethanol and was repeatedly used for three cycles in the column to determine the reusability of the regenerated adsorbent. The column data were modeled with the modeling equations such as Adam-Bohart model, Bed Depth Service Time (BDST) model, and Yoon-Nelson model for all the three cycles.
Показать больше [+] Меньше [-]Nanoporous activated carbon fluidized bed catalytic oxidations of aqueous o, p and m-cresols: kinetic and thermodynamic studies
2013
Karthikeyan, S. | Sekaran, G. | Gupta, V. K.
Nanoporous activated carbon prepared from rice husk through precarbonisation at 400 °C and phosphoric acid activation at 800 °C was used as fluidized bed in Fenton oxidation of the o, p and m-cresols in aqueous solution. The efficiencies of homogeneous Fenton oxidation, fluidized Fenton oxidation and aerobic biological oxidation systems for the removal of o, p and m-cresols in aqueous solution have been compared. The kinetic constants and the thermodynamic parameters for the homogeneous Fenton, heterogeneous Fenton and aerobic biological oxidations of o, p and m-cresols in synthetic wastewater were determined. The degradation of cresols in synthetic wastewater was confirmed using FT-IR,¹H-NMR and UV–visible spectroscopy.
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