Degradation of Adsorbed Sarin on Activated Carbons: A 31P‐MAS‐NMR Study

The fate of the OP nerve agent isopropyl methylphosphonofluoridate (sarin) on granular activated and metal‐impregnated activated carbons that are used in gas‐mask filters was investigated by means of ³¹P magic‐angle‐spinning (MAS) NMR spectroscopy. The results show that most of the adsorbed sarin on extensively dried carbons decomposes with a half‐life of 5–12 days. A MAS‐NMR signal of the degradation product isopropyl methylphosphonic acid (IMPA) appears in the spectra of sarin on non‐impregnated carbons. The IMPA signal is not visible in the spectra from metal‐impregnated carbons, probably due to strong binding of the acid molecule to paramagnetic Cr³⁺ and Cu²⁺ ions. Exposure of BPL and ASC carbons to air of 53% relative humidity shortens the degradation time by approximately an order of magnitude. Wetting shortens the half‐life of sarin on BPL carbon to approximately 2 hours.     

Evaluation of Two Low‐Cost–High‐Performance Adsorbent Materials in the Waste‐to‐Product Approach for the Removal of Pesticides from Drinking Water

This study evaluates the performance of two low cost and high performance adsorption materials, i.e., activated carbon produced from two natural waste products: Bamboo and coconut shell, in the removal of three pesticides from drinking water sources. Due to the fact that bamboo and coconut shell are abundant and inexpensive materials in many parts of the world, they respond to the “low‐cost” aspect. The adsorption capacities of two local adsorbents have been compared with commercial activated carbon to explore their potential to respond to the “high quality” aspect. Two pesticides were selected, namely dieldrin and chlorpyrifos, because they are commonly used in agriculture activities, and may remain in high concentrations in surface water used as drinking water sources. The results indicate that the adsorption of pesticides on activated carbons is influenced by physico‐chemical properties of the activated carbon and the pesticides such as the presence of an aromatic ring, and their molar mass. The activated carbon produced from bamboo can be employed as low‐cost and high performance adsorbent, alternative to commercial activated carbon for the removal of pesticides during drinking water production. The performance of activated carbon from bamboo was better due to its relatively large macroporosity and planar surface. The effect of adsorbent and pesticide characteristics on the performance was derived from batch experiments in which the adsorption behavior was studied on the basis of Freundlich isotherms.     

Adsorption of Cadmium Ions from Aqueous Solution Using Granular Activated Carbon and Activated Clay

The present study was aimed at removing cadmium ions from aqueous solution through batch studies using adsorbents, such as, granular activated carbon (GAC) and activated clay (A‐clay). GAC was of commercial grade where as the A‐clay was prepared by acid treatment of clay with 1 mol/L of H₂SO₄. Bulk densities of A‐clay and GAC were 1132 and 599 kg/m³, respectively. The surface areas were 358 m²/g for GAC and 90 m²/g for A‐clay. The adsorption studies were carried out to optimize the process parameters, such as, pH, adsorbent dosage, and contact time. The results obtained were analyzed for kinetics and adsorption isotherm studies. The pH value was optimized at pH 6 giving maximum Cd removal of 84 and 75.2% with GAC and A‐clay, respectively. The adsorbent dosage was optimized and was found to be 5 g/L for GAC and 10 g/L for A‐clay. Batch adsorption studies were carried out with initial adsorbate (Cd) concentration of 100 mg/L and adsorbent dosage of 10 g/L at pH 6. The optimum contact time was found to be 5 h for both the adsorbents. Kinetic studies showed Cd removal a pseudo second order process. The isotherm studies revealed Langmuir isotherm to better fit the data than Freundlich isotherm.     

Removal of Pyridine from Aqueous Solution by Adsorption on an Activated Carbon Cloth

Pyridine is a very toxic pollutant that has to be removed from wastewater. In this work, adsorption of pyridine on activated carbon cloth (ACC) is studied as a possible alternative for eliminating pyridine from aqueous solution. The ACC was produced from polyacrylonitrile. The adsorption equilibrium data of pyridine on ACC was obtained in a batch adsorber. The experimental data was interpreted with the isotherms of Langmuir, Freundlich, and Prausnitz‐Radke (PR), and the PR isotherm better represented the experimental data. The capacity of ACC for adsorbing pyridine was favored increasing the solution pH from 3 to 6, and this effect was due to the π–π dispersive and electrostatic interactions between the pyridine species in solution and the surface complexes of ACC. The modified Langmuir model fitted reasonably well the influence of pH on the adsorption capacity. In this model was assumed that both neutral pyridine and pyridinium were simultaneously adsorbed on ACC accordingly to the experimental results. The adsorption capacity was almost independent of temperature. The reversibility study revealed that 75% of the pyridine can be desorbed from ACC indicating that part of the pyridine was irreversibly adsorbed, and possibly chemisorbed.     

Removal of Selenium by Adsorption onto Granular Activated Carbon (GAC) and Powdered Activated Carbon (PAC)

The present work involves the study of Se(IV) adsorption onto granular activated carbon (GAC) and powdered activated carbon (PAC). The adsorbents are coated with ferric chloride solution for the effective removal of selenium. The physico-chemical characterization of the adsorbents is carried out using standard methods, e. g., proximate analysis, scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), thermo-gravimetric (TGA) and differential thermal analysis (DTA), etc. The FTIR spectra of the GAC and PAC indicate the presence of various types of functional groups, e. g., free and hydrogen bonded OH groups, silanol groups (Si-OH), alkenes, and CO group stretching from aldehydes and ketones on the surface of adsorbents. Batch experiments are carried out to determine the effect of various factors such as adsorbent dose (w), initial pH, contact time (t), and temperature (T) on the adsorption process. The optimum GAC and PAC dosage is found to be 10 g/L and 8 g/L, respectively, for Se(IV) removal with C₀ = 100 mg/L. The percent removal of Se(IV) increases with increasing adsorbent concentration, while removal per unit weight of adsorbent increases with decreasing adsorbent concentration. Se(IV) adsorption onto both the GAC and PAC adsorbents is high at low pH values, and decreases with increased initial pH. The results obtained are analyzed by various kinetic models. The parameters of pseudo-first order, pseudo-second order kinetics, and Weber-Morris intra particle kinetics are determined. It is seen that the sorption kinetics of Se(IV) onto GAC and PAC can be best represented by the pseudo-second order kinetic model.     

Removal of COD from Industrial Effluent Containing Indigo Dye Using Adsorption Method by Activated Carbon Cloth: Optimization,Kinetic, and Isotherm Studies

The pollution of underground and surface water streams is a tremendous environmental problem. Adsorption, in which activated carbon (AC) is used as an adsorbent, is one of efficient procedures to remove organic and inorganic pollutants from industrial wastewaters. Activated carbon fiber (ACF), a newly developed form of AC, has high adsorption rate and surface area and can be used for the treatment of industrial wastewaters. In this work, ACF was prepared by physicochemical activation method from kenaf and we studied its ability in the treatment of indigo‐containing wastewater produced from a dying factory. The filtered wastewater was treated via adsorption by ACF, and response surface experimental design method was used to study the effect of ACF dosage, contact time, temperature, and pH of the wastewater on the removal process. ACF dosage of 0.256 g, temperature of 12.5°C, pH 8.5, and contact time of 125 min were optimum treatment conditions. The adsorption process obeys pseudo‐second‐order kinetic and Freundlich isotherm models.     

Adsorption Kinetics of Chloroform from Aqueous Solutions onto Activated Lignite

The lignite coal researched by this study was subjected to a two‐stage activation process performed in the scope of obtaining active carbon from domestic resources. “Activation” and “carbonization” stages were used in the experiments. The modified lignite was produced by impregnating lignite with KOH and washing the activation product with 15% HCl solution after thermal treatment. Increasing KOH dosage also increased the removal efficiency. The variables investigated in adsorption experiments were contact time, initial concentration, pH, and sorbent dosage. Adsorption kinetics was fitted by using the pseudo‐first‐order equation, pseudo‐second‐order equation, and intra‐particle diffusion. Isotherm modeling was carried out using Langmuir, Freundlich, and Dubinin–Radushkevich equations. Selected target compound in this work is common environmental pollutant in waters. A commonly known effect of chloroform is its carcinogenic effect. Therefore, removal of these compounds from water is considerably important. Chloroform removal of 97% for was achieved by the use of Konya region activated lignite.     

Adsorption Kinetic Modeling of Safranin onto Rice Husk Biomatrix Using Pseudo‐first‐ and Pseudo‐second‐order Kinetic Models: Comparison of Linear and Non‐linear Methods

Batch kinetic studies were carried out for the removal of safranin from aqueous solution using a biomatrix prepared from rice husk. The adsorption kinetic data were modeled using the pseudo‐first‐order and pseudo‐second‐order kinetic equations. The linear and non‐linear forms of these two widely used kinetic models were compared in this study. In order to determine the best‐fitting equation, the coefficient of determination (r²), 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‐squared test (χ²) were used as error analysis methods. Results showed that the non‐linear forms of pseudo‐first‐order and pseudo‐second‐order models were more suitable than the linear forms for fitting the experimental data. Non‐linear method is thus more appropriate for estimating the kinetic parameters and should primarily be used to describe adsorption kinetics.     

Influence of the pore structure and surface chemical properties of activated carbon on the adsorption of mercury from aqueous solutions

Reactivation and chemical modification were used to obtain modified activated carbons with different pore structure and surface chemical properties. The samples were characterized by nitrogen absorption–desorption, Fourier transform infrared spectroscopy and the Bothem method. Using mercury chloride as the target pollutant, the Hg²⁺ adsorption ability of samples was investigated. The results show that the Hg²⁺ adsorption capacity of samples increased significantly with increases in micropores and acidic functional groups and that the adsorption process was exothermic. Different models and thermodynamic parameters were evaluated to establish the mechanisms. It was concluded that the adsorption occurred through a monolayer mechanism by a two-speed process involving both rapid adsorption and slow adsorption. The adsorption rate was determined by chemical reaction.     

Adsorption of Chromium(III), Nickel(II), and Copper(II) from Aqueous Solution by Activated Alumina

The possible use of activated alumina powder (AAP) as adsorbent for Cr(III), Ni(II), and Cu(II) from synthetic solutions was investigated. The effect of various parameters on batch adsorption process such as pH, contact time, adsorbent dosage, particle size, temperature, and initial metal ions concentration were studied to optimize the conditions for maximum metal ion removal. Both higher (molar) and lower (ppm) initial metal ion concentration sets were subjected to adsorption on AAP. Adsorption process revealed that equilibrium was established in 50 min for Cr(III) at pH 4.70, 80 min for Ni(II) at pH 7.00, and 40 min for Cu(II) at pH 3.02. Percentage removal was found to be highest at 55°C for Cr(III) and Ni(II) with 420 µm and 45°C for Cu(II) with 250‐µm particle size AAP. A dosage of 2 g for Cr(III), 8 g for Ni(II), and 10 g Cu(II) gave promising data in the metal ion removal. The adsorption process followed Langmuir as well as Freundlich models. The thermodynamics of adsorption of these metal ions on activated aluminum indicated that the adsorption was spontaneous and endothermic in nature. Present study indicates that AAP can act as a promising adsorbent for industrial wastewater treatment.     

Adsorption of Cationic Dyes from Aqueous Solution by Termite Feces,a Non‐Conventional Adsorbent

The adsorption of three cationic dyes (rhodamine B, RB; crystal violet, CV; and malachite green, MG) onto termite feces, a low‐cost adsorbent, was investigated. The adsorbent was characterized by IR spectroscopy, point of zero charge measurement, and the Boehm titration method. The adsorption follows the pseudo‐second‐order kinetic model and the Langmuir–Freundlich isotherm with maximum adsorption capacities of 95.53 mg g^?1 (RB), 75.71 mg g^?1 (CV), and 44.78 mg g^?1 (MG). The study of thermodynamics showed that the adsorption is a spontaneous and endothermic process. This works suggest that termite feces can be used as a new low‐cost adsorbent for cationic dye removal.     

Characterization of Chlorinated Tire‐Derived Mesoporous Activated Carbon for Adsorptive Removal of Toluene

A series of chlorinated mesoporous activated carbons were derived from waste tires by pyrolysis, activation, and chlorination at different temperatures. The physical and chemical properties of the samples were studied by Brunauer–Emmett–Teller (BET) analysis, Fourier Transform IR Spectroscopy (FT‐IR), point of zero charge measurement, thermogravimetric analysis, and by testing their behavior as adsorbents for toluene removal. Our results showed that the tire‐derived activated carbon samples have highly mesoporous volumes and surface areas, and chlorination treatment has a slight effect on the pore structure. Lewis acidity of the sample increases after chlorination and the chlorine content increases from 0.24 to 2.32% with chlorination temperature increasing from 50 to 400°C. The higher the chlorine content, the more is the toluene adsorption. In comparison with the commercial carbon (F‐400), all the samples have significantly higher adsorption capacity for toluene due to the presence of mesopores, inductive effect of the partial positive chemisorbed chlorine and resonance effects of C? Cl structures. The mesopores probably render easier diffusion of toluene molecule to inner carbon matrix and the strong π–π interaction between toluene and C? Cl resonance structure in the carbon significantly affects the interplay bonding process thus enhances the toluene removal.     

Adsorption of Metal Ions onto the Chemically Modified Agricultural Waste

This paper discusses about the adsorption of metal ions such as Cu(II), Cd(II), Zn(II), and Ni(II) from aqueous solution by sulfuric acid treated cashew nut shell (STCNS). The adsorption process depends on the solution pH, adsorbent dose, contact time, initial metal ions concentration, and temperature. The adsorption kinetics was relatively fast and equilibrium was reached at 30 min. The adsorption equilibrium follows Langmuir adsorption isotherm model. The maximum adsorption capacity values of the modified cashew nut shell (CNS) for metal ions were 406.6 mg/g for Cu(II), 436.7 mg/g for Cd(II), 455.7 mg/g for Zn(II), and 456.3 mg/g for Ni(II). The thermodynamic study shows the adsorption of metal ions onto the STCNS was spontaneous and exothermic in nature. The kinetics of metal ions adsorption onto the STCNS followed a pseudo‐second‐order kinetic model. The external mass transfer controlled metal ions removal at the earlier stages and intraparticle diffusion at the later stages of adsorption. A Boyd kinetic plot confirms that the external mass transfer was the slowest step involved in the adsorption of metal ions onto the STCNS. A single‐stage batch adsorber was designed using the Langmuir adsorption isotherm equation.     

Adsorption studies of aqueous Pb(II) onto a sugarcane bagasse/multi-walled carbon nanotube composite

Adsorption of Pb²⁺ from aqueous solution onto a sugarcane bagasse/multi-walled carbon nanotube (MWCNT) composite was investigated by using a series of batch adsorption experiments and compared with the metal uptake ability of sugarcane bagasse. The efficiency of the adsorption processes was studied experimentally at various pH values, contact times, adsorbent masses, temperatures and initial Pb²⁺ concentrations. A pH of 4.5 was found to be the optimum pH to obtain a maximum adsorption percentage in 120 min of equilibration time. The composite showed a much enhanced adsorption capacity for Pb²⁺ of 56.6 mg g⁻¹ compared with 23.8 mg g⁻¹ for bagasse at 28 °C. The Langmuir adsorption isotherm provided the best fit to the equilibrium adsorption data. The pseudo first-order, pseudo second-order, intraparticle diffusion and Elovich kinetics models were used to analyse the rate of lead adsorption and the results show that the Elovich model is more suitable. The thermodynamic parameters of adsorption, namely ΔG°, ΔH° and ΔS°, were determined over the temperature range of 20–45 °C. The adsorption of Pb²⁺ onto both bagasse and the sugarcane bagasse/MWCNT composite was found to be spontaneous but for the former adsorbent it was enthalpy-driven whereas for the latter it was entropy-driven. Desorption of the lead-loaded adsorbents was fairly efficient with 0.1 mol dm⁻³ HCl. Overall this composite has the potential to be a good adsorbent for the removal of Pb²⁺ from wastewaters.     

Toxic Effects of Copper‐Based and Synthetic Organic Pesticides on Activated Sludge

Toxic effects of five commonly used pesticides on the biomass of a municipal activated sludge system were determined on the basis of the reduction in the oxygen uptake rate (OUR) and specific oxygen uptake rate (SOUR). Toxicity levels of the selected pesticides were determined by employing a modified OECD 209 (Organisation for Economic Cooperation and Development) method which was performed as batch experiments using a respirometer. Copper sulphate (CuSO₄ · 5 H₂O), copper oxychloride (Cu₂Cl(OH)₃), copper calcium oxychloride (CaCu₃Cl₂(OH)₆) as copper‐based pesticides and chlorsulphuron (C₁₂H₁₂ClN₅O₄S), 2,4‐dichlorophenoxyacetic acid (2,4‐D) (C₈H₆Cl₂O₃) as synthetic organic pesticides were selected for the experiments. The EC₅₀ values were determined to be 78, 249 and 281 mg/L for CuSO₄ · 5 H₂O, Cu₂Cl(OH)₃ and CaCu₃Cl₂(OH)₆, respectively. Corresponding values for C₁₂H₁₂ClN₅O₄S and 2,4‐D were 860 and 3664 mg/L, respectively. Results indicated that toxicity effects of copper‐based pesticides were higher than that of synthetic organic pesticides. CuSO₄ · 5 H₂O was found to exert the highest toxicity among the copper‐based pesticides, whereas, C₁₂H₁₂ClN₅O₄S was determined to be the most toxic among the organic pesticides on activated sludge biomass.     

Removal of Cadmium from Aqueous Solution Using Castor Seed Hull: A Kinetic and Equilibrium Study

The effects of various parameters such as initial concentration, adsorbent loading, pH, and contact time on kinetics and equilibrium of adsorption of Cd²⁺ metal ion from its aqueous solution by castor seed hull (CSH) and also by activated carbon have been investigated by batch adsorption experiments. The amount of adsorption increases with initial metal ion concentration, contact time, solution pH, and the loading of adsorbent for both the systems. Kinetic experiments indicate that adsorption of cadmium metal ion on both CSH and on activated carbon consists of three steps – a rapid adsorption of cadmium metal ion, a transition phase, and an almost flat plateau region. This has also been confirmed by the intraparticle diffusion model. The lumped kinetic results show that the cadmium adsorption process follows a pseudo‐second order rate law. The kinetic parameters including the rate constant are determined at different initial metal ion concentrations, pH, amount, and type of adsorbent, respectively. The Langmuir and Freundlich adsorption isotherm models are used to describe the experimental data. The Langmuir model yields a better correlation coefficient than the other model. A comparison of the monolayer adsorption capacity (q_m) of CSH, activated carbon, and several other reported adsorbents has been provided. The value of separation factor (R_L) calculated from the Langmuir equation also gives an indication of favorable adsorption of the metal ion. From comparative studies, it has been found that CSH is a potentially attractive adsorbent than commercial activated carbon for cadmium metal ion (Cd²⁺) removal.     

Scum in Activated Sludge Plants: Impact of Non‐filamentous and Filamentous Bacteria

Excessive scum production is a widespread phenomenon in present activated sludge wastewater treatment. The question how foaming is initiated and stabilized is still unanswered. Hydrophobic wastewater ingredients and surface active material such as synthetic surfactants are discussed among others as major causative agents for scum production. Focusing on biological impacts non‐filamentous bacteria isolated from scum turned out to contribute to flotation by both cell surface hydrophobicity and emulsification activity, depending on the prevailing substrate and milieu conditions. The biological characterization of scum based on microscopic sludge investigation of conspicuous microorganisms resulted in a significant shift of filamentous and non‐filamentous organism populations with Gram‐positive bacteria prevailing in present nutrient removal plants as compared to the situation ten years ago. Their hydrophobic cell surface is supposed to support adherence and stabilization of interfaces and thus promote sludge flotation. In scum six types of filamentous bacteria turned out to be numerous: Microthrix parvicella and nocardioform actinomycetes, both of them being enriched in the scum fraction, moreover Nostocoida limicola and Eikelboom types 0041/0675, 1851, and 0092. Possible interactive mechanisms between non‐filamentous and filamentous scum bacteria and their selection factors are discussed in order to contribute to a better understanding of scum formation and to provide efficient troubleshooting measures.