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This work aims to assess the surface coupling of molecularly imprinted polymers (MIP) on carbon adsorbents produced from spent brewery grain, namely biochar (BC) and activated carbon (AC), as a strategy to improve selectivity and the adsorptive removal of the antibiotic sulfamethoxazole (SMX) from water. BC and AC were produced by microwave-assisted pyrolysis, and MIP was obtained by fast bulk polymerization. Two different methodologies were used for the molecular imprinting of BC and AC, the resulting materials being tested for SMX adsorption. Then, after selecting the most favourable molecular imprinting methodology, different mass ratios of MIP:BC or MIP:AC were used to produce and evaluate eight different materials. Molecular imprinting was shown to significantly improve the performance of BC for the target application, and one of the produced composites (MIP1-BC-s(1:3)) was selected for further kinetic and equilibrium studies and comparison with individual MIP and BC. The kinetic behaviour was properly described by both the pseudo-first and pseudo-second order models. Regarding equilibrium isotherms, they fitted the Freundlich and Langmuir models, with MIP1-BC-s(1:3) reaching a maximum adsorption capacity (q m ) of 25 ± 1 μmol g - 1 , 19 % higher than BC. In comparison with other seven pharmaceuticals, the adsorption of SMX onto MIP1-BC-s(1:3) was remarkably higher, as for the specific recognition of this antibiotic by the coupled MIP. The pH study evidenced that SMX removal was higher under acidic conditions. Regeneration experiments showed that MIP1-BC-s(1:3) provided good adsorption performance, which was stable during five regeneration-reutilization cycles. Overall, this study has demonstrated that coupling with MIP may be a suitable strategy to improve the adsorption properties and performance of biochar for antibiotics removal from water, increasing its suitability for practical applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

A noticeable interest and steady rise in research studies reporting the design and assessment of smart adsorbents for sequestering aqueous metal ions and xenobiotics has occurred in the last decade. This motivates compiling and reviewing the characteristics, potentials, and performances of this new adsorbent generation's metal ion and xenobiotics sequestration. Herein, stimuli-responsive adsorbents that respond to its media (as internal triggers; e.g., pH and temperature) or external triggers (e.g., magnetic field and light) are highlighted. Readers are then introduced to selective adsorbents that selectively capture materials of interest. This is followed by a discussion of self-healing and self-cleaning adsorbents. Finally, the review ends with research gaps in material designs., (© 2021 Wiley-VCH GmbH.)

The main goal of this work was to produce an easily recoverable waste-based magnetic activated carbon (MAC) for an efficient removal of the antiepileptic pharmaceutical carbamazepine (CBZ) from wastewater. For this purpose, the synthesis procedure was optimized and a material (MAC4) providing immediate recuperation from solution, remarkable adsorptive performance and relevant properties (specific surface area of 551 m 2  g -1 and saturation magnetization of 39.84 emu g -1 ) was selected for further CBZ kinetic and equilibrium adsorption studies. MAC4 presented fast CBZ adsorption rates and short equilibrium times (< 30-45 min) in both ultrapure water and wastewater. Equilibrium studies showed that MAC4 attained maximum adsorption capacities (q m ) of 68 ± 4 mg g -1 in ultrapure water and 60 ± 3 mg g -1 in wastewater, suggesting no significant interference of the aqueous matrix in the adsorption process. Overall, this work provides evidence of potential application of a waste-based MAC in the tertiary treatment of wastewaters. Graphical abstract.

The adsorption of pharmaceutical substances using carbonaceous materials, such as activated carbon (AC), biochar (BC) and hydrochar (HC), has received substantial attention by researchers working on water treatment, due to the simplicity, low-cost and high performance of this process. In order to widen the potentiality of these carbonaceous materials and to overcome some of their limitations, particularly the inefficient separation of powdered formulations from treated water, the incorporation of magnetic nanoparticles has been explored. The recovery of magnetic carbon materials (MCM) from the treated water can be attained by applying an external magnetic field, avoiding inefficient and costly filtration and centrifugation processes, typically applied in the case of non-magnetic carbonaceous adsorbents. In the last ten years, some work has been devoted to the preparation of MCM specifically from AC (MC AC M), biochar (MC BC M) and hydrochar (MC HC M). This review aims to present the different aspects of using MCM in water treatment, namely in the removal of pharmaceutical compounds. The synthesis routes used to produce MCM, their physical, morphologic and chemical features, and their application in the removal of these micro-organic contaminants from water will be assessed. The advantages and disadvantages of using MCM in water treatment, and their comparative performance with the carbonaceous non-magnetic precursors will be also discussed in this review., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Efforts to improve water quality have led to the development of green and sustainable water treatment approaches. Herein, nitrogen-doped magnetized hydrochar (mSBHC-N) was synthesized, characterized, and used for the removal of post-transition and transition heavy metals, viz. Pb 2+ and Cd 2+ from aqueous environment. mSBHC-N was found to be mesoporous (BET surface area - 62.5 m 2 /g) and paramagnetic (saturation magnetization - 44 emu/g). Both, FT-IR (with peaks at 577, 1065, 1609 and 3440 cm -1 corresponding to Fe - O stretching vibrations, C - N stretching, N - H in-plane deformation and stretching) and XPS analyses (with peaks at 284.4, 400, 530, 710 eV due to C 1s, N 1s, O 1s, and Fe 2p) confirmed the presence of oxygen and nitrogen containing functional groups on mSBHC-N. The adsorption of Pb 2+ and Cd 2+ was governed by oxygen and nitrogen functionalities through electrostatic and co-ordination forces. 75-80% of Pb 2+ and Cd 2+ adsorption at C o : 25 mg/L, either from deionized water or humic acid solution was accomplished within 15 min. The data was fitted to pseudo-second-order kinetic and Langmuir isotherm models, with maximum monolayer adsorption capacities being 323 and 357 mg/g for Cd 2+ and Pb 2+ at 318 K, respectively. Maximum Cd 2+ (82.6%) and Pb 2+ (78.7%) were eluted with 0.01 M HCl, simultaneously allowing minimum iron leaching (2.73%) from mSBHC-N. In conclusion, the study may provide a novel, economical, and clean route to utilize agro-waste, such as sugarcane bagasse (SB), for aquatic environment remediation., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

When adsorption is considered for water treatment, commercial activated carbon is usually the chosen adsorbent for the removal of pollutants from the aqueous phase, particularly pharmaceuticals. In order to decrease costs and save natural resources, attempts have been made to use wastes as raw materials for the production of alternative carbon adsorbents. This approach intends to increase efficiency, cost-effectiveness, and also to propose an alternative and sustainable way for the valorization/management of residues. This review aims to provide an overview on waste-based adsorbents used on pharmaceuticals' adsorption. Experimental facts related to the adsorption behaviour of each adsorbent/pharmaceutical pair and some key factors were addressed. Also, research gaps that subsist in this research area, as well as future needs, were identified. Simultaneously, this review aims to clarify the current status of the research on pharmaceuticals' adsorption by waste-based adsorbents in order to recognize if the right direction is being taken., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

This work describes the adsorptive removal of three widely consumed psychiatric pharmaceuticals (carbamazepine, paroxetine and oxazepam) from ultrapure water. Two different adsorbents were used: a commercial activated carbon and a non-activated waste-based carbon (PS800-150-HCl), produced by pyrolysis of primary paper mill sludge. These adsorbents were used in single, binary and ternary batch experiments in order to determine the adsorption kinetics and equilibrium isotherms of the considered pharmaceuticals. For the three drugs and both carbons, the equilibrium was quickly attained (with maximum equilibrium times of 15 and 120 min for the waste-based and the commercial carbons, respectively) even in binary and ternary systems. Single component equilibrium data were adequately described by the Langmuir model, with the commercial carbon registering higher maximum adsorption capacities (between 272 ± 10 and 493 ± 12 μmol g -1 ) than PS800-150-HCl (between 64 ± 2 and 74 ± 1 μmol g -1 ). Multi-component equilibrium data were also best fitted by the single component Langmuir isotherm, followed by the Langmuir competitive model. Overall, competitive effects did not largely affect the performance of both adsorbents. Binary and ternary systems maintained fast kinetics, the individual maximum adsorption capacities were not lower than half of the single component systems and both carbons presented improved total adsorption capacities for multi-component solutions., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Tricaine methanesulfonate (MS-222) has been widely used in intensive aquaculture systems to control stress during handling and confinement operations. This compound is dissolved in the water tanks and, once it is present in the Recirculating Aquaculture Systems (RASs), MS-222 can reach the environment by the discharge of contaminated effluents. The present work proposes the implementation of the adsorption process in the RASs, using pyrolysed biological paper mill sludge as adsorbent, to remove MS-222 from aquaculture wastewater. Adsorption experiments were performed under extreme operating conditions, simulating those corresponding to different farmed fish species: temperature (from 8 to 30 °C), salinity (from 0.8 to 35‰) and different contents of organic and inorganic matter in the aquaculture wastewater. Furthermore, the MS-222 adsorption from a real aquaculture effluent was compared with that from ultrapure water. Under the studied conditions, the performance of the produced adsorbent remained mostly the same, removing satisfactorily MS-222 from water. Therefore, it may be concluded that the produced adsorbent can be employed in intensive aquaculture wastewater treatment with the same performance independently of the farmed fish species., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

This work describes the production of alternative adsorbents from industrial residues and their application for the removal of a highly consumed antidepressant (citalopram) from water. The adsorbents were produced by pyrolysis of both primary and biological paper mill sludge at different temperatures and residence times. The original sludge and the produced chars were fully characterized by elemental and proximate analyses, total organic carbon, specific surface area (BET), N₂ isotherms, FTIR, (13)C and (1)H solid state NMR and SEM. Batch kinetic and equilibrium experiments were carried out to describe the adsorption of citalopram onto the produced materials. The fastest kinetics and the highest adsorption capacity were obtained using primary sludge pyrolysed at 800 °C during 150 min. The use of pyrolysed paper mill sludge for the remediation of contaminated waters might constitute an interesting application for the valorization of those wastes., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Batch stirred tank experiments were carried out to study the effect of pH (range 2-10, at 294 K) and temperature (277, 294 and 313 K, at pH 5) on the uptake of Hg(2+) ions by ETS-4 microporous titanosilicate. Changes in the pH have a significant effect on the ETS-4 uptake efficiency, the optimal range being 4-6. Due to competition effects, the chemical used to adjust the pH of the Hg(2+) solution also influences the uptake efficiency. Thermodynamic parameters for the uptake of Hg(2+) ions were calculated. For the temperature range studied, the Hg(2+) sorption increased with decreasing temperature., ((c) 2009 Elsevier B.V. All rights reserved.)

Thermal parametric pumping is a cyclic adsorptive process based on periodic changes in the bed temperature simultaneously with flow reversal. This is an innovative technology which may allow removing phenolic compounds from waste solutions to be recovered and recycled. The recovery and/or purification of liquid streams containing phenol and 4-nitrophenol by adsorptive parametric pumping was studied in this work. An automated parametric pumping pilot unit was operated in semi-continuous recuperative mode. The adsorbent used was the polymeric resin Sephabeads SP206 (Mitsubishi Kasei Corporation, Japan) and temperatures of the hot and the cold half-cycles were 333 and 293 K, respectively. Basic data were obtained from batch equilibrium experiments and fixed-bed adsorption. Different experimental conditions were run and two simplified models were used to simulate the results: an equilibrium model and a linear driving force (LDF) model. Experimental and simulated results using the LDF model were in quite good agreement. Purification levels below three orders of magnitude lower than the concentration of the feed solution were obtained for phenol and 4-nitrophenol.

Selective serotonin reuptake inhibitors (SSRIs) are a class of antidepressants regularly detected in the environment. This indicates that the existing wastewater treatment techniques are not successfully removing them beforehand. This study investigated the potential of molecularly imprinted polymers (MIPs) to serve as sorbents for removal of SSRIs in water treatment. Sertraline was chosen as the template for imprinting. We optimized the composition of MIPs in order to obtain materials with highest capacity, affinity, and selectivity for sertraline. We report the maximum capacity of MIP for sertraline in water at 72.6 mg g−1, and the maximum imprinting factor at 3.7. The MIPs were cross-reactive towards other SSRIs and the metabolite norsertraline. They showed a stable performance in wastewater-relevant pH range between 6 and 8, and were reusable after a short washing cycle. Despite having a smaller surface area between 27.4 and 193.8 m2·g−1, as compared to that of the activated carbon at 1400 m2·g−1, their sorption capabilities in wastewaters were generally superior. The MIPs with higher surface area and pore volume that formed more non-specific interactions with the targets considerably contributed to the overall removal efficiency, which made them better suited for use in wastewater treatment. [ABSTRACT FROM AUTHOR]

Four strains of bioflocculant-producing bacteria were isolated from a palm oil mill effluent (POME). The four bacterial strains were identified as Pseudomonas alcaliphila (B1), Pseudomonas oleovorans (B2), Pseudomonas chengduensis (B3), and Bacillus nitratireducens (B4) by molecular identification. Among the four bacterial strains, Bacillus nitratireducens (B4) achieved the highest flocculating activity (49.15%) towards kaolin clay suspension after eight hours of cultivation time and was selected for further studies. The optimum conditions for Eriochrome Black T (EBT) flocculation regarding initial pH, type of cation, and B4 dosage were determined to be pH 2, Ca2⁺ cations, and a dosage of 250 mL/L of nutrient broth containing B4. Under these conditions, above 90% of EBT dye removal was attained. Fourier transform infrared spectroscopic (FT-IR) analysis of the bioflocculant revealed the presence of hydroxyl, alkyl, carboxyl, and amino groups. This bioflocculant was demonstrated to possess a good flocculating activity, being a promissory, low-cost, harmless, and environmentally friendly alternative for the treatment of effluents contaminated with dyes. [ABSTRACT FROM AUTHOR]

In the present work, the adsorptive removal of diclofenac from water by biosorption onto non-living microalgae biomass was assessed. Kinetic and equilibrium experiments were carried out using biomass of two different microalgae strains, namely Synechocystis sp. and Scenedesmus sp. Also, for comparison purposes, a commercial activated carbon was used under identical experimental conditions. The kinetics of the diclofenac adsorption fitted the pseudo-second order equation, and the corresponding kinetic constants indicating that adsorption was faster onto microalgae biomass than onto the activated carbon. Regarding the equilibrium results, which mostly fitted the Langmuir isotherm model, these pointed to significant differences between the adsorbent materials. The Langmuir maximum capacity (Qmax) of the activated carbon (232 mg∙g−1) was higher than that of Scenedesmus sp. (28 mg∙g−1) and of Synechocystis sp. (20 mg∙g−1). In any case, the Qmax values determined here were within the values published in the recent scientific literature on the utilization of different adsorbents for the removal of diclofenac from water. Still, Synechocystis sp. showed the largest KL fitted values, which points to the affinity of this strain for diclofenac at relative low equilibrium concentrations in solution. Overall, the results obtained point to the possible utilization of microalgae biomass waste in the treatment of water, namely for the adsorption of pharmaceuticals. [ABSTRACT FROM AUTHOR]

The removal of Tricaine Methanesulfonate from water in a fixed-bed column packed with pyrolysed paper mill sludge was evaluated for application in Recirculating Aquaculture Systems. Breakthrough adsorption curves were determined for this pharmaceutical, under different operating conditions. In a laboratory-scale approach, with synthetic effluent, a bed adsorption capacity of 125 mg g −1 was obtained under a flux of 56 L min −1 m −2 , with 400 mg L −1 of MS-222 with 4.5 cm bed depth. The performance of the continuous adsorption in a column packed with biological paper mill sludge-based carbon, using real aquaculture wastewater as matrix, was not significantly affected. Then, scale-up was carried out and the bed depth service time model was applied and provided good predictions. Finally, the thermal regeneration of the exhausted adsorbent was assessed, which revealed satisfactory results for one cycle reusability after saturation; however, considering the nature of its precursor, the use of new adsorbent could be more profitable than its regeneration, functioning also as an additional option for the management of such wastes. [ABSTRACT FROM AUTHOR]

This work deals with a preliminary study aimed at evaluating the efficiency of three different microalgae strains, namely Chlorella sorokiniana , Chlorella vulgaris and Scenedesmus obliquus in the bioremediation of diclofenac contaminated water. For this purpose, microalgae were cultured in bubbling column photobioreactors (PBRs) under batch operation until the end of the exponential growth phase. For the three strains, the concentration of diclofenac in the PBRs aquatic medium decreased along microalgae growing, which pointed to biodegradation as the main removal mechanism. Among the three strains, S. obliquus was the most capable to reduce diclofenac concentration (99% removal from an initial concentration of 25,000 μg l −1 ). However, such a large removal does not guarantee an efficient treatment since transformation products (TPs) exceeding the concentration and/or toxicity of the parent compound may be generated during biodegradation of diclofenac. Thus, for a comprehensive evaluation of the microalgae treatments efficiency, the final effluents from the PBRs were tested for their effects on the embryonic development of zebrafish. Again, the S. obliquus treatment was the most efficient in the reduction of toxicity, with the corresponding effluents having no effects on the embryo's mortality or abnormalities incidence (at 80 h post fertilization). In any case, for the three strains, the toxicity effects of effluents were equal or lower than those determined for diclofenac solutions with the same concentration. Therefore, it may be stated that, at the end of the batch culture, the removal of diclofenac by the considered strains did not involve the generation of toxic TPs to zebrafish embryos. [ABSTRACT FROM AUTHOR]

Abstract: The magnetic removal of Hg2+ from water has been assessed using silica coated magnetite particles. The magnetite particles were first prepared by hydrolysis of FeSO4 and their surfaces were modified with amorphous silica shells that were then functionalized with organic moieties containing terminal dithiocarbamate groups. Under the experimental conditions used, the materials reported here displayed high efficiency for Hg2+ uptake (74%) even at contaminant levels as low as 50μgl−1. Therefore these eco-nanomagnets show great potential for the removal of heavy metal ions of polluted water, via magnetic separation. [Copyright &y& Elsevier]

Abstract: In this work, the removal of Cd2+ ions from aqueous solution using microporous titanosilicate ETS-10 was investigated in order to assess its potential as decontaminating agent in tertiary treatments. Accordingly, batch stirred tank experiments were carried out to study the ion exchange kinetics and equilibrium. Results show that pH affects considerably the ion exchange capability of ETS-10: at pH 4 it is 1.567×102 eqm−3, at pH 6 it is 3.629×103, and no further increment was observed at pH 8. This is an extremely important observation since pH of industrial effluents and other wastewaters rounds 6. Both Langmuir and Langmuir–Freundlich isotherms were fitted to the experimental data measured. The second model performs slightly better as the calculated absolute average deviations show: AADL =2.94% and AADLF =2.40%. Concerning the kinetic behavior, the ion exchange was successfully represented by a Nernst–Planck based model (AAD=11.9%). [Copyright &y& Elsevier]

The production of waste-based activated carbon (AC) for application in adsorptive water treatment is a hot research topic. The use of residues as AC precursors is generally presented as a promissory option because they are free of charge and allow for the minimization of non-renewable resources depletion. Despite waste-based AC being usually labelled as low-cost and environmental-friendly adsorbents, few studies involve cost estimations and even less assess the environmental impacts associated to their production and application. In the last few years, there has been a growing awareness about the search for greener processes, resulting in the increase of publications on the cost estimation and the life cycle assessment (LCA) of waste-based AC. Still, to the best of the authors' knowledge, a review focusing on the distinct approaches and conclusions carried out by different authors does not exist. Therefore, the aim of this work is to present an overview on relevant aspects of the economic and environmental costs of waste-based AC for application in water treatment. Overall, published studies show that the price of the precursors, the energy required for production (which can be optimized at industrial scale) and the properties of the produced material largely influence the AC final cost. As for LCA studies, they generally evidence that producing AC from wastes is an interesting management route that may present important energy and resource savings when compared to the production of AC from fossil resources. Moreover, literature points out that attention must be paid to regeneration of waste-based AC to sustainably post-pone their end-of-life. This review stresses the necessity of assessing the economic and environmental costs of waste-based AC in order to avoid vague and unsupported conclusions on their sustainability. • Waste-based activated carbons (WAC) for water treatment are a research hot topic. • This is the first literature review on WAC economic costs and environmental impacts. • Dependence of WAC cost on precursor, energy intake and final properties is discussed. • WAC main environmental impacts estimated by life cycle assessments are identified. • The need for cost and impact assessments to prove WAC sustainability is stressed. [ABSTRACT FROM AUTHOR]