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Activated carbon is employed for the adsorption of organic micropollutants (OMPs) from water, typically present in concentrations ranging from ng L-1 to µg L-1. However, the efficacy of OMP removal is considerably deteriorated due to competitive adsorption from background dissolved organic matter (DOM), present at substantially higher concentrations in mg L-1. Interpreting the characteristics of competitive DOM is crucial in predicting OMP adsorption efficiencies across diverse natural waters. Molecular weight (MW), aromaticity, and polarity influence DOM competitiveness. Although the aromaticity-related metrics, such as UV254, of low MW DOM were proposed to correlate with DOM competitiveness, the method suffers from limitations in understanding the interplay of polarity and aromaticity in determining DOM competitiveness. Here, we elucidate the intricate influence of aromaticity and polarity in low MW DOM competition, spanning from a fraction level to a compound level, by employing direct sample injection liquid chromatography coupled with ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry. Anion exchange resin pre-treatment eliminated 93% of UV254-active DOM, predominantly aromatic and polar DOM, and only minimally alleviated DOM competition. Molecular characterization revealed that nonpolar molecular formulas (constituting 26% PAC-adsorbable DOM) with medium aromaticity contributed more to the DOM competitiveness. Isomer-level analysis indicated that the competitiveness of highly aromatic LMW DOM compounds was strongly counterbalanced by increased polarity. Strong aromaticity-derived π-π interaction cannot facilitate the competitive adsorption of hydrophilic DOM compounds. Our results underscore the constraints of depending solely on aromaticity-based approaches as the exclusive interpretive measure for DOM competitiveness. In a broader context, this study demonstrates an effect-oriented DOM analysis, elucidating counterbalancing interactions of DOM molecular properties from fraction to compound level.

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Multicomponent adsorption processes are affected by both mixture and process variables viz. feed composition, pH, adsorbent dosage, and adsorbent type. Optimization of multicomponent adsorption processes with multiple objectives is challenging. It is important to accurately identify possible solutions and select the compromise solution that best satisfies the different objectives. Conventional algorithms, when applied to multicomponent adsorption, were found to identify the Pareto front less accurately, thereby necessitating the need for a reliable method. The steep portion of the Pareto front was especially not captured satisfactorily by the different conventional algorithms such as pattern search (PS), Non-dominated Sorting Genetic Algorithm (NSGA-II), and Epsilon-Constraint (EC). This portion assumes importance, if the compromise solution occurs in its vicinity. To address these challenges, a novel bi-objective optimization technique termed as elliptical method (EM) was developed and described in this work. It involves an exhaustive search, provides a well distributed Pareto front, and clearly delineates the steep region. After validating with benchmark problems, EM was applied to batch multi-component adsorption. The two objectives optimized simultaneously were adsorbent loading and percentage removal of the different solutes. The Pareto front and the compromise solution involving the best combination of the two objectives were significantly superior in the elliptical method when compared to those obtained from typical algorithms including epsilon-constraint (EC) method. The Pareto front was also well defined by the elliptical method without discontinuities near the extreme and steep regions. The number of points found by EM in the steeper region for the grade II adsorbent was 10 times greater than those found by the EC method while the PS and NSGA could not delineate this portion. The average time taken (considering both adsorbents) for EM per solution was 0.17 s which was at least 30.6% faster than the other methods. The compromise solution with the elliptical method was superior to the other methods. For instance, with grade II adsorbent, the compromise solution from the elliptical method suggested operating conditions that led to a total adsorbent loading and percentage removal of 333.4 mg/g and 56.0%. On the other hand, pattern search gave 324.1 mg/g and 56.5%, whereas the NSGA-II method gave 321.9 mg/g and 53.3%. For this adsorbent, elliptical method's compromise solution was 50% and 20% closer in terms of the Euclidean distance to the utopia point than NSGA and PS methods, respectively. The elliptical method will facilitate reliable wastewater tertiary treatment taking into cognizance the utilization of the adsorbent as well as the percentage purity requirement.

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Chromatography is a widely used separation process for purification of biopharmaceuticals that is able to obtain high purities and concentrations. The phenomena that occur during separation, mass transfer and adsorption are quite complex. To better understand these phenomena and their mechanisms, multi-component adsorption isotherms must be investigated. High-throughput methodologies are a very powerful tool to determine adsorption isotherms and they waste very small amounts of sample and chemicals, but the quantification of component concentrations is a real bottleneck in multi-component isotherm determination. The behavior of bovine serum albumin, Corynebacterium diphtheriae CRM197 protein and lysozyme, selected as model proteins in binary mixtures with hydrophobic resin, is investigated here. In this work we propose a new method for determining multi-component adsorption isotherms using high-throughput experiments with filter plates, by exploiting microfluidic capillary electrophoresis. The precision and accuracy of the microfluidic capillary electrophoresis platform were evaluated in order to assess the procedure; they were both found to be high and the procedure is thus reliable in determining adsorption isotherms for binary mixtures. Multi-component adsorption isotherms were determined with a totally high-throughput procedure that turned out to be a very fast and powerful tool. The same procedure can be applied to every kind of high-throughput screening.

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We developed biochar by pyrolysis of pinewood wastes at different temperatures and investigated its potential to nitrate and phosphate from single and binary solutions. An in-depth characterization of biochar was carried out to study its physical, surface morphological and chemical characteristics using X-ray diffraction, Fourier transform infrared and scanning electron microscopy analyses. The impact of pyrolysis temperatures (300-600 °C) on the biochar yield, the biochar's elemental composition, and its adsorption characteristics was examined. Biochar produced at 600 °C showed a maximum uptake for both nitrate and phosphate due to its high C content (63.8%), pore volume (0.201 cm3/g), surface area (204.2 m2/g) and reduced acidic binding groups. The influence of pH, initial solute concentrations, contact time on the removal of a single solute at a time by biochar was examined. Results revealed that pinewood-derived biochar had its maximum performance at pH 2, with predicted equilibrium uptakes of 20.5 and 4.20 mg/g for phosphate and nitrate, respectively at initial solute concentrations of 60 mg/L within 360 min. The single solute isotherm was studied using the Freundlich, Langmuir and Toth models, and kinetics was described using the pseudo-first and -second order models. While using dual-solutes, biochar showed preference towards phosphate as confirmed by high affinity factor. The dual-solute kinetic experiments showed that around 95% of phosphate was removed within 45 min, whereas it took 240 min to achieve 95% total nitrate removal from the mixture. Thus, the biochar removes phosphate preferentially with high selectivity as compared to nitrate.

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The adsorptive removal of a pollutant from water is significantly affected by the presence of coexisting ions with various concentrations. Here, we have studied adsorption of arsenate [As(V)] by calcined Mg-Fe-(CO3)-LDH in the presence of different cations (Mg2+, Na+, K+, Ca2+, and Fe3+) and anions (CO32‒, Cl‒, PO43‒, SO42‒, and NO3‒) with their different concentrations to simulate the field condition. The experimental results indicated that Ca2+, Mg2+, and Fe3+ have a synergistic effect on removal efficiency of As(V), whereas PO43‒ and CO32‒ ions have a significant antagonistic impact. Overall, the order of inhibiting effect of coexisting anions on adsorption of As(V) was arrived as NO3-˂Cl-

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Lead (Pb) is one of the most toxic, hazardous pollutants available in landfill leachate. Loess-amended soil buffers are found suitable and effective in attenuating migration of Pb and the other trace metals. High concentration of ammonium (NH4+ > 1000 mg/l) is also reported in landfill leachate, and therefore, it is essential to investigate the transport of lead under such condition. In this study, the mechanisms and the capacity of loess to adsorb Pb under high NH4+ concentration were investigated. Adsorption isotherm test data were obtained for 25 °C, 35 °C and 45 °C. The maximum adsorption capacity is estimated to be 2101.97 mg/g at 25 °C and 4292.8 mg/g at 45 °C under 1000 mg/l NH4+. The binding sites of Pb on loess are positively related to each other at low temperatures (25-35 °C). The thermodynamic analysis indicates that adsorption process is endothermic and non-spontaneous and the system randomness increases with reaction time. The kinetic test data, fitted with a pseudo-second-order kinetic model and an intraparticle diffusion model, suggests that removal of Pb is driven by both membrane and intraparticle diffusions. The SEM, XRD and FTIR analyses indicate flocculation, precipitations as well as some ion exchange processes, which perhaps combinedly increases adsorption of both NH4+ and Pb in loess. The two kinds of precipitations are involved for the removal of Pb. The precipitations of PbCO3, Pb(OH)2 and PbCO3·2H2O are formed by the reactions between calcite and lead. The other precipitation of white basic salt (Pb2O(NO3)2) is formed by the reactions among Pb2+, NO3- and aqueous ammonia under alkaline environment of loess slurry.

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This work aims to propose an optimum resin that can be used in industrial adsorption process for tuning flavor-active components or removal of ethanol for producing an alcohol-free beer. A procedure is reported for selective adsorption of volatile aroma components from water/ethanol mixtures on synthetic hydrophobic resins. High throughput 96-well microtiter-plates batch uptake experimentation is applied for screening resins for adsorption of esters (i.e. isoamyl acetate, and ethyl acetate), higher alcohols (i.e. isoamyl alcohol and isobutyl alcohol), a diketone (diacetyl) and ethanol. The miniaturized batch uptake method is adapted for adsorption of volatile components, and validated with column breakthrough analysis. The results of single-component adsorption tests on Sepabeads SP20-SS are expressed in single-component Langmuir, Freundlich, and Sips isotherm models and multi-component versions of Langmuir and Sips models are applied for expressing multi-component adsorption results obtained on several tested resins. The adsorption parameters are regressed and the selectivity over ethanol is calculated for each tested component and tested resin. Resin scores for four different scenarios of selective adsorption of esters, higher alcohols, diacetyl, and ethanol are obtained. The optimal resin for adsorption of esters is Sepabeads SP20-SS with resin score of 87% and for selective removal of higher alcohols, XAD16N, and XAD4 from Amberlite resin series are proposed with scores of 80 and 74% respectively. For adsorption of diacetyl, XAD16N and XAD4 resins with score of 86% are the optimum choice and Sepabeads SP2MGS and XAD761 resins showed the highest affinity towards ethanol.

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In the present work, the simultaneous adsorption of Remazol Red 3BS (reactive dye) and Cr(VI) onto chitosan powder grafted with poly(ethylene imine) and cross-linked with epichlorohydrin is experimentally studied. Such a combination of a dye molecule and a heavy metal can be found in real/practical conditions of environmental pollutants' removal, so their mutual interaction on the adsorption efficiencies is very important. The experimental data revealed a competitive type of interaction between the dye molecule and heavy metal ion. An attempt is made to quantitatively describe the data through appropriate isotherms and kinetic equations. The data demonstrated that the common thermodynamic equilibrium is not obtained for the present problem and the final composition of the adsorbed phase depends also on the kinetics. A new scenario of irreversible kinetic-based equilibrium was introduced and examined in detail. None of the scenarios considered here is fully able to cover the whole data, so semi-empirical equations are introduced for their description. It is shown that further development of phenomenological models requires more complicated experimental protocols than simple simultaneous adsorption of the species.