Removal of micropollutants from aerobically treated grey water via ozone and activated carbon

Ozonation and adsorption onto activated carbon were tested for the removal micropollutants of personal care products from aerobically treated grey water. MilliQ water spiked with micropollutants (100-1600 μgL⁻¹) was ozonated at a dosing rate of 1.22. In 45 min, this effectively removed (>99%): Four parabens, bisphenol-A, hexylcinnamic aldehyde, 4-methylbenzylidene-camphor (4MBC), benzophenone-3 (BP3), triclosan, galaxolide and ethylhexyl methoxycinnamate. After 60 min, the removal efficiency of benzalkonium chloride was 98%, tonalide and nonylphenol 95%, octocrylene 92% and 2-phenyl-5-benzimidazolesulfonic acid (PBSA) 84%. Ozonation of aerobically treated grey water at an applied ozone dose of 15 mgL⁻¹, reduced the concentrations of octocrylene, nonylphenol, triclosan, galaxolide, tonalide and 4-methylbenzylidene-camphor to below limits of quantification, with removal efficiencies of at least 79%. Complete adsorption of all studied micropollutants onto powdered activated carbon (PAC) was observed in batch tests with milliQ water spiked with 100-1600 μgL⁻¹ at a PAC dose of 1.25 gL⁻¹ and a contact time of 5 min. Three granular activated carbon (GAC) column experiments were operated to treat aerobically treated grey water. The operation of a GAC column with aerobically treated grey water spiked with micropollutants in the range of 0.1-10 μgL⁻¹ at a flow of 0.5 bed volumes (BV)h⁻¹ showed micropollutant removal efficiencies higher than 72%. During the operation time of 1728 BV, no breakthrough of TOC or micropollutants was observed. Removal of micropollutants from aerobically treated grey water was tested in a GAC column at a flow of 2 BVh⁻¹. Bisphenol-A, triclosan, tonalide, BP3, galaxolide, nonylphenol and PBSA were effectively removed even after a stable TOC breakthrough of 65% had been reached. After spiking the aerobically treated effluent with micropollutants to concentrations of 10-100 μgL⁻¹, efficient removal to below limits of quantification continued for at least 1440 BV. Both ozonation and adsorption are suitable techniques for the removal of micropollutants from aerobically treated grey water.     

Regeneration of ortho-chlorophenol-exhausted activated carbons with liquid water at high pressure and temperature

A study was undertaken of the regeneration of three activated carbons exhausted with ortho-chlorophenol. The regeneration process was carried out using liquid water at 623 K and 150 atm in the absence of oxygen. The efficiency of this procedure was analyzed by determining the rate and amount of ortho-chlorophenol adsorbed in successive adsorption-regeneration cycles. The present procedure showed a much greater efficiency than that reported for chemical and/or thermal regeneration. Effects of this regeneration on the adsorption kinetics, adsorption capacity and textural characteristics of the carbon were investigated. The increase in adsorption capacity of the regenerated carbon compared with that of the original carbon seems mainly due to the opening of porosity during the regeneration treatment.     

Heterogeneous reactions of ozone and D-limonene on activated carbon

If released in significant amounts, products formed by reactions between ozone (O3) and volatile organic compounds (VOCs) sorbed on activated carbon (AC) filters could degrade indoor air quality (IAQ). Heterogeneous reactions were investigated in laboratory experiments aimed at characterizing reaction products. Effluent air of AC loaded with limonene and exposed to O3 (5.8 ppm) yielded unreacted limonene (501+/-197 microg/m3), low levels of 4-acetyl-1-methylcyclohexene (AMCH) (20+/-2 microg/m3), and limonene oxides (25+/-7 microg/m3). Most of the O3-limonene products remained on the AC, and most (58%) of the limonene remained unreacted on the AC after exposure to a stoichiometric excess of O3 for 48 h. Thus, in addition to known homogenous reactions, O3-limonene reactions occur heterogeneously on AC but to a much lesser extent. However, the fate of 95% of the depleted limonene was not determined; much of the missing portion was attributed to desorption from the AC, but the formation of other secondary indoor air pollutants is possible. VOC-loaded AC air filters exposed to O3 seem unlikely, however, to constitute a significant emission source of reaction products. More studies are necessary to investigate other pollutants, effects of environmental conditions, and VOC releases from AC that may be enhanced by O3 exposure. PRACTICAL IMPLICATIONS: Reactions between ozone and certain volatile organic compounds such as limonene (a common ingredient of many consumer products) occurring on the surface of ventilation filters could impact indoor air quality if products are released in significant amounts. This study suggests that although very small amounts of limonene adsorbed on a filter will react with O3, ventilation filters are not likely to be significant sources of ozone oxidation products. More studies are needed to investigate whether ozone exposure enhances desorption of pollutants from ventilation filters and to measure the formation of formaldehyde and other products that are not easily retained by charcoal filters.     

Adsorption of Cr(III) on ozonised activated carbon. Importance of Cpi-cation interactions

The adsorption of Cr(III) in aqueous solution was investigated on a series of ozonised activated carbons, analysing the effect of oxygenated surface groups on the adsorption process. A study was carried out to determine the adsorption isotherms and the influence of the pH on the adsorption of this metal. The adsorption capacity and affinity of the adsorbent for Cr(III) increased with the increase in oxygenated acid groups on the surface of the activated carbon. These findings imply that electrostatic-type interactions predominate in the adsorption process, although the adsorption of Cr(III) on the original (basic) carbon indicates that other forces also participate in the adsorption process. Thus, the ionic exchange of protons in the -Cpi-H3O(+) interaction for Cr(III) accounts for the adsorption of cationic species in basic carbons with positive charge density. Study of the influence of pH on the adsorption of Cr(III) showed that, in each system, the maximum adsorption occurred when the charge of the carbon surface was opposite that of the species of Cr(III) present at the pH of the experiment. These results confirmed that electrostatic interactions predominate in the adsorption process.     

Adsorption-desorption characteristics of phenol and reactive dyes from aqueous solution on mesoporous activated carbon prepared from waste tires

Liquid-phase adsorption-desorption characteristics and ethanol regeneration efficiency of an activated carbon prepared from waste tires and a commercial activated carbon were investigated. Water vapor adsorption experiments reveal that both activated carbons showed hydrophobic surface characteristics. Adsorption experiments reveal that the prepared activated carbon possessed comparable phenol adsorption capacity as the commercial one but clearly larger adsorption capacity of two reactive dyes, Black 5 and Red 31. It was ascertained that the prepared activated carbon exhibited less irreversible adsorption of phenol and the two dyes than its commercial counterpart. Moreover, ethanol regeneration efficiency of the prepared AC saturated with either dye was higher than that of the commercial AC. Because of its superior liquid-phase adsorption-desorption characteristics as well as higher ethanol regeneration efficiency, the prepared activated carbon is more suitable for wastewater treatment, especially for adsorbing similarly bulky adsorbates.     

Regeneration of acid orange 7-exhausted granular activated carbons with microwave irradiation

An investigation was performed for the regeneration of three granular activated carbons (GACs) exhausted with acid orange 7 (AO7). The three GACs were made from different materials, i.e. coconut shells, almond nucleus and coal. The AO7 adsorption process was carried out in a continuous-flow adsorption column. After adsorption, the AO7-saturated GAC was dried at 120 °C, then regenerated in a quartz reactor by 2450 MHz microwave (MW) irradiation at 850 W for 5 min. The efficacy of this procedure was analyzed by determining the rates and amounts of AO7 adsorbed in successive adsorption–MW regeneration cycles. Effects of this regeneration on the structural properties, surface chemistry and the AO7 adsorption capacities of GAC samples were examined. It was found that after several adsorption–MW regeneration cycles, the adsorption rates and capacities of GACs could maintain relatively high levels, even higher than those of virgin GACs, as indicated by AO7 breakthrough curves and adsorption isotherms. The improvement of GAC adsorption properties resulted from the modification of pore size distribution and surface chemistry by MW irradiation.     

Performance of activated carbon and bentonite for adsorption of amoxicillin from wastewater: Mechanisms, isotherms and kinetics

Amoxicillin's traces within pharmaceutical effluents have toxic impact toward the algae and other lower organisms within food web. Adsorption, as an efficient process to remove contaminants from water was chosen; in particular with bentonite and activated carbon as adsorbents. The study was carried out at several pH values. Langmuir and Freundlich models were then employed to correlate the equilibria data on which both models equally well-fit the data. For kinetic data, pseudo-first and second order models are selected. While chemisorption is the dominant adsorption mechanism on the bentonite case, both physisorption and chemisorption play important roles for adsorption onto activated carbon. Also, several possible mechanisms for these adsorption systems were elaborated further.     

Absorbability of estrone and 17beta-estradiol in water onto activated carbon

With a view to reducing pollution in the aquatic environment, estrone (E1) and 17beta-estradiol (E2) were tested for their absorbability in water onto activated carbons (ACs) with various pore-size distributions. In batch-type adsorption measurements, all adsorption isotherms obtained were found to fit a Freundlich equation. In case of eight different kinds of commercial AC in pure water, the amount adsorbed at equilibrium concentration of 1 microg/L was in the range of 25.6-73.5mg/g for E1 and 21.3-67.6 mg/g for E2. In case of pre-used ACs in water sand-filtered for use as drinking water, the amount adsorbed at 1 microg/L was in the range of 3.5-8.2mg/g for E2. In the case of two commercial ACs in river water and in effluent from secondary clarifier at municipal sewage treatment plant (MSTP), both originally containing E2, was in the range of 0.1-0.2 and 0.3-1 microg/g, respectively, at 1 ng/L. The difference of amount adsorbed onto AC was discussed in view of hydrophobicity of target chemicals, specific surface area and mean pore diameter of AC, and the difference in the absorbability and the ratios of co-present substances for the target compound.     

Mineralisation of coloured aqueous solutions by ozonation in the presence of activated carbon

The degradation of organic matter in coloured solutions of different classes of dyes by ozonation in the presence of activated carbon is investigated. The kinetics of the decolourisation and mineralisation of three different dyes solutions (CI Acid Blue 113, CI Reactive Red 241 and CI Basic Red 14) were studied in a laboratory scale reactor by three different processes: adsorption on activated carbon, oxidation with ozone and ozonation in the presence of activated carbon. The mineralisation of the solutions was followed by measuring the total organic carbon (TOC). Under the experimental conditions used in this work, activated carbon was not capable of completely removing the colour of the solutions in reasonable time. On the other hand, ozonation quickly decolourised all the solutions, but satisfactory removal of TOC was never achieved by this process. The combination of activated carbon with ozone enhanced the decolourisation of the solutions and especially the mineralisation of the organic matter. Activated carbon acts both as an adsorbent and as a catalyst in the reaction of ozonation. The surface chemistry of the activated carbon is an important parameter; it was observed that basic samples improve TOC removal. The main conclusions of this work were validated by treating a real textile effluent collected after the conventional biological treatment.     

User-oriented batch reactor solutions to the homogeneous surface diffusion model for different activated carbon dosages

This paper presents a simplified approach and user-oriented solutions to the homogeneous surface diffusion model (HSDM) equations for determining the surface diffusivity using a batch reactor system. Once the surface diffusivity is known, this model could also be used to estimate the performance of activated carbon (AC) applications as a function of contact time. In addition, fixed-bed performance can be predicted using the user-oriented solutions to the HSDM for fixed beds. The step-by-step procedure for determining surface diffusion coefficients of an activated carbon adsorber, which was initially developed by Hand, Crittenden and Thacker in 1983 for a carbon dose where C_equilibrium/C₀ = 0.5, is modified to allow calculations for different carbon dosages. This modification provides solutions to the HSDM equations for different activated carbon dosages. The solutions to the HSDM framework are provided as simplified algebraic equations suitable for quick and easy estimations of D_S. The excel spread sheet is provided in the supplemental information and a detailed example is discussed.     

Improvement of thermal reactivation of activated carbon for the removal of 2-methylisoborneol

Rapid small-scale column tests (RSSCTs) were employed to evaluate the impact of the dissolved oxygen (DO) concentration in the water used to create steam on the reactivation of spent granular activated carbon (GAC) using three novel thermal reactivation procedures: steam-curing, steam-curing with ramped temperature, and steam pyrolysis reactivation. Evaluation of the physical properties of the reactivated carbon showed a change in mass and volume loss with a change in DO. Performance testing of the carbons for removal of the taste- and odor-causing compound 2-methylisoborneol (MIB) showed that MIB uptake generally increased as the DO concentration decreased. Decrease in MIB removal with an increase in surface acidity, a phenomenon found in the literature, may be responsible for the changes in adsorption performance, as the higher DO concentrations yielded carbons with higher total surface acidity. In addition, the steam-curing process, which was implemented at 375 degrees C (i.e. about 400 degrees C lower than typical reactivation temperatures) with a low DO concentration (i.e. 3-4mg/L) had comparable performance to the virgin carbon counterpart, which could manifest cost-savings due to the low temperature associated with this protocol compared to conventional reactivation. Furthermore, since the mass loss associated with this steam-curing protocol was low, less virgin carbon make-up would be required also improving the economic viability of this reactivation protocol.     

Variations of respiratory activity and glutathione in activated sludges exposed to low ozone doses

Ozonation is one of the most effective treatments for reducing the production of activated sludges in wastewater treatment plants. However, because microorganisms are present in the form of microcolonies, some bacteria may be exposed to sub-lethal ozone doses that could lead to adaptation and resistance to further exposition to oxidative treatment. This represents a major question as it may limit the effect of the treatment, especially when low ozone doses are applied. The critical ozone dosage, defined as the lowest specific transferred ozone concentration leading to a decrease in the maximum oxygen uptake rate was estimated to range between 0.9 and 13.6mg O(3)g(-1) COD(sludges), according to the sludges tested. The lowest ozone dosage leading to the decrease of GSH and GSHt concentrations could be estimated to be lower than 10mg O(3)g(-1) COD(sludges) for GSH, and close to 10mg O(3)g(-1) COD(sludges) for GSHt. After sludge exposure to low ozone doses, no higher amounts of glutathione were synthesized, suggesting that no development of resistance to ozonation occurred after sludge treatment with low ozone doses.     

Adsorption kinetics of polyethylene glycol from aqueous solution onto activated carbon

The adsorption equilibrium and kinetics of polyethylene glycol (PEG) in three aqueous systems were examined in this study. Langmuir isotherm was used to satisfactorily predict the adsorption capacity of PEG on activated carbon F-400 and applied to the investigation of adsorption kinetics. The surface diffusion, pore diffusion, and branched pore kinetics models successfully described the adsorption behavior of PEG on F-400 in the completely stirred tank reactor. The pore diffusion coefficients obtained from the pore diffusion model were compared with those computed by the experimental data of the short fixed-bed reactor combined with the assumption of non-hindered pore diffusion. In addition, the effects of initial concentrations of PEG and the relative importance of external and internal mass transfers for the adsorption were also taken into account and discussed in this study.     

An overall isotherm for activated carbon adsorption of dissolved natural organic matter in water

Design and analysis of activated carbon processes in water treatment often requires the adsorption isotherm for dissolved natural organic matter (NOM). Of the isotherm models available, the Summers and Roberts (SR) equation, capable of describing the adsorbent dose effect with the fewest parameters, has been successfully used to normalize NOM isotherm data. In this study, we show that the adsorbent dose in the SR equation can be eliminated as an intermediate variable and the initial concentration effect on NOM adsorption is then described explicitly. Comparing with the original SR equation, the derived isotherm equation is in a form more amenable to analysis. To ensure that the prediction is physically attainable, we introduced the limiting adsorption capacity by taking the adsorbent pore volume and size exclusion into consideration. Subsequently, we develop a simple relationship that can be used to determine the minimum adsorbent usage required for any desirable level of treatment. By comparing with extensive isotherm data previously published by Li et al. [2003a. Polydisperse adsorbability composition of several natural and synthetic organic matrices. J. Colloid Interface Sci. 265(2), 265-275], we demonstrated that the isotherm equation derived herein yields predictions that agree with the much more complicated fictive component-ideal adsorbed solution theory (IAST)-based model for NOM from different sources and over a range of initial concentrations.     

Adsorption of p-nitrophenol on activated carbon fixed-bed

Carbon fixed-beds are usually used to remove organic contaminants. Adsorption in a carbon filter is a dynamic, non-steady process which is not yet completely understood. The objective of this paper is to establish a methodology to simplify the study of this process based on the wave theory, rapid small-scale column test and experimental design/surface response analysis. The constant pattern wave hypothesis was confirmed by the experimental data. The influence of the inlet concentration of p-nitrophenol and the flow rate on dynamic adsorption was studied at 20 degrees C following a central composite design using a second-order model. Both parameters have an important influence on the response variables studied. The methodology used is a useful tool for studying the dynamic process and shows interactions that are difficult to verify by the classical step-by-step method.     

Adsorption behavior of pesticide methomyl on activated carbon in a high gravity rotating packed bed reactor

High gravity rotating packed bed (HGRPB) reactor possesses the property of high mass transfer rate, which is expected to promote the adsorption rate for the process. In this study, HGRPB has been applied on adsorption removal of methomyl from solution, adopting the adsorbent of activated carbon F400. The influence of operating parameters of HGRPB on mass transfer such as the rotating speed (N_R), the flow rate of solution (F_L) and initial concentration of methomyl (C_b0) were examined. The traditionally internal mass transfer models combined with Freundlich isotherm were used to predict the surface and effective diffusion coefficients. In addition, the results have also been compared with those obtained from the traditional basket stirred batch reactor (BBR). The results showed that the larger values of N_R and F_L enhanced the effective intraparticle diffusion and provided more accessible adsorption sites so as to result in lower equilibrium concentration in HGRPB system when compared to SBR system. The results of adsorption kinetics demonstrated that surface and effective diffusions were both significantly greater in HGRPB system instead of BBR system. Furthermore, the values of Bi_S also manifested less internal mass transfer resistance in HGRPB system. The contribution ratio (R_F) of the surface to pore diffusion mass transport showed that the larger contribution resulted from the surface diffusion in HGRPB system. Therefore, the results reasonably led to the conclusion that when the HGRPB system applied on the adsorption of methomyl on F400, the lower equilibrium concentration and faster internal mass transfer can be obtained so as to highly possess great potential to match the gradually stricter environmental standard.     

Adsorption of phenol and reactive dye from aqueous solution on activated carbons derived from solid wastes

Activated carbons were produced from several solid wastes, namely, waste PET, waste tires, refuse derived fuel and wastes generated during lactic acid fermentation from garbage. Activated carbons having various pore size distributions were obtained by the conventional steam-activation method and via the pre-treatment method (i.e., mixture of raw materials with a metal salt, carbonization and acid treatment prior to steam-activation) that was proposed by the authors. The liquid-phase adsorption characteristics of organic compounds from aqueous solution on the activated carbons were determined to confirm the applicability of these carbons, where phenol and a reactive dye, Black5, were employed as representative adsorbates. The hydrophobic surface of the carbons prepared was also confirmed by water vapor adsorption. The characteristics of a typical commercial activated carbon were also measured and compared. It was found that the activated carbons with plentiful mesopores prepared from PET and waste tires had quite high adsorption capacity for large molecules. Therefore they are useful for wastewater treatment, especially, for removal of bulky adsorbates.     

Enhanced mitigation of para-chlorophenol using stratified activated carbon adsorption columns

The adsorptive removal of toxic para-chlorophenol using activated carbon adsorption columns is a proven effective engineering process. This paper examined the possibility to stratify an adsorbent bed into layers, in order to enhance the adsorption process performance in terms of increased column service time and adsorbent bed saturation. Four different types of fixed-bed adsorption columns are used and compared under the same operating conditions, but with the variation of column geometry and activated carbon particle size stratification. The Type 3 column - a cylindrical column with particle stratification packing, is found to be the most efficient choice, as the extent of column service time and adsorbent bed saturation are the largest. This could eventually decrease the frequency of adsorbent replacement/regeneration and hence reduce the operating cost of the fixed-bed adsorption process. The Homogeneous Surface Diffusion Model (HSDM) was applied successfully to describe the dynamic adsorption of para-chlorophenol onto Filtrasorb 400 (F400) activated carbon in different types of columns. The Redlich-Peterson isotherm model equation, an experimentally derived external mass transfer correlation and a constant surface diffusivity are used in the HSDM. The optimised surface diffusivity of para-chlorophenol is found to be 1.20E-8 cm²/s, which is in good agreement with other phenolics/F400 carbon diffusing systems in literature.     

Vapor adsorption characteristics of toluene in an activated carbon adsorbent-loaded nonwoven fabric media for chemical filters applied to cleanrooms

Chemical filters are used extensively in the cleanrooms of the semiconductor factories to remove airborne molecular contamination (AMC). Adsorption by activated carbons (AC) as media within the chemical filter is one of the practical methods for removal of gaseous contamination in a cleanroom. The objective of this study is to evaluate coconut shell activated carbon adsorbent-loaded nonwoven fabric media performance by determining the breakthrough curves, the linear driving force (LDF), the intra-particle diffusion characteristics, the empty bed contact time (EBCT) and the bed depth service time (BDST), the mass-transfer zone (MTZ), and pressure drop. The testing conditions were maintained at 28 ± 1 °C, and relative humidity at 40 ± 2% with face velocities of 0.076, 0.114 and 0.152 m/s for removal efficiency and capacity determination. The challenge gas concentrations of toluene were fixed at 10, 31, 42 and 70 ppm to accelerate the breakthrough of media adsorption. The concentrations were measured by a real-time photoionization detector. Results showed that breakthrough curves correlate to the challenge vapor concentration and the face velocity. Saturated adsorption ratio was increased with raised challenge gas concentration and increased face velocity significantly.     

Assessment of organic chlorinated compound removal from aqueous matrices by adsorption on activated carbon

Adsorption on activated carbon is currently the most frequently used technology to remove organic chlorinated pollutants from wastewaters. The present study examines the ability of five commercially available types of activated carbon to remove organic chlorinated compounds from the effluent of a chemical plant. The various types were tested on the basis of Freundlich adsorption isotherms for 14 pure organic chlorinated compounds, of molecular weight ranging from that of dichloromethane (MW=84.93 gmol(-1)) to hexachlorobenzene (MW=284.78 gmol(-1)). The best was selected and used in a laboratory fixed-bed column to assess its removal efficiency with respect to the tested organic chlorinated compounds. Removal efficiency was always higher than 90%. These results provide information necessary to optimize scale-up from the pilot plant to the real one.