Organic Pollutant Removal from Water and Wastewater Using Clay Minerals

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Environmental Mineralogy and Biogeochemistry".

Deadline for manuscript submissions: closed (15 January 2022) | Viewed by 7303

Special Issue Editors


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Guest Editor
Departamento de Química Fundamental, Universidade de Sao Paulo, Sao Paulo 05508-060, Brazil
Interests: environmental analytical chemistry; development of sorbents for water treatment and solid phase extraction; flow-based analytical methods; monolithic materials; liquid chromatography

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Guest Editor
Departamento de Química, Universidade Federal do Paraná, Centro Politécnico, Curitiba 81531-980, Brazil
Interests: environmental analytical chemistry; modification of clay minerals and the application as sorbent phases; miniaturized solid-phase extraction; interaction between clay minerals and pollutants

Special Issue Information

Dear Colleagues,

Contamination of waters by persistent and emerging organic pollutants (herbicides, pharmaceuticals, hormones, food additives) imposes serious risks to environmental and human health. There is a continuous quest for materials that can efficiently remove these pollutants from wastewaters before reaching rivers, lakes, and groundwaters. In their natural or modified forms, clay minerals are promising materials because of their physicochemical properties, abundance, low cost, and environmental compatibility. Their high surface area, permanent negative charge, and hydroxyl group content make them potentially useful sorbents interacting via hydrogen-bonding and cation-exchange mechanisms. On the other hand, natural clay minerals are not very efficient for removing anions and hydrophobic compounds. However, more and more studies have demonstrated that clay minerals work as an efficient platform for chemical modification and fine-tuning of surface chemistries to enhance their affinity to a wide variety of organic pollutants. Organoclays, composite materials, bioreactive organoclays, and clay minerals containing magnetic nanomaterials work as efficient sorbents with potential applicability for the remediation of wastewaters. They also exhibit a high degree of reusability. This Special Issue aims at presenting the state of the art on the preparation, characterization, and application of clay-mineral-based materials proposed for the remediation of waters and wastewaters, emphasizing the removal of organic pollutants.

Prof. Dr. Jorge César Masini
Prof. Dr. Gilberto Abate
Guest Editors

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Keywords

  • bentonites
  • organoclays
  • intercalation
  • pillarization
  • clay-based composites
  • characterization
  • adsorption isotherms
  • remediation
  • emerging organic pollutants
  • persistent organic pollutants

Published Papers (3 papers)

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Research

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17 pages, 2865 KiB  
Article
Effect of Oxycations in Clay Mineral on Adsorption—Vanadyl Exchange Bentonites and Their Ability for Amiloride Removal
by Leandro Oliveira, Josy Osajima, Ramon Raudel Peña-Garcia, Edson Cavalcanti Silva-Filho and Maria Gardennia Fonseca
Minerals 2021, 11(12), 1327; https://doi.org/10.3390/min11121327 - 27 Nov 2021
Cited by 2 | Viewed by 2030
Abstract
The presence of drugs in aquatic bodies is a prevailing issue, and their removal by adsorption is an effective treatment. Among the adsorbents, those based clay minerals have been proposed. Bentonite is a clay mineral that is widely studied as an adsorbent due [...] Read more.
The presence of drugs in aquatic bodies is a prevailing issue, and their removal by adsorption is an effective treatment. Among the adsorbents, those based clay minerals have been proposed. Bentonite is a clay mineral that is widely studied as an adsorbent due to its unique physicochemical properties, such as cation exchange capacity (CEC), intercalation, and adsorption. The properties of bentonites can be improved through chemical modifications, such as the incorporation of organic and/or inorganic compounds. These modifications allow for the efficient removal of different contaminants, including pharmaceutical compounds. In this work, raw sodium bentonite (Na+-Bent) and vanadyl bentonites were prepared using 100 (BentV1), 300 (BentV3), and 500% (BentV5) of the cationic exchange capacity of the Na+-Bent and further used for amiloride removal from aqueous solution. Analysis of X-ray fluorescence and Na+ in solution after interaction indicated that the principal mechanism of interaction between bentonite and ions was the ion exchange between sodium of the matrix and vanadyl in solution. Infrared spectroscopy suggested the contribution of coordination of the interlayer water with the vanadyl ions and hydrogen bonding between vanadyl and structural OH. X-ray diffraction analysis indicated that vanadyl ions were incorporated onto Na+-Bent. Amiloride adsorption was better at pH 5.8, using a solid dosage of 75 mg of Na+-Bent, 25 mg of BentV1 and BentV5, and 50 mg of BentV3. The adsorption occurred briefly until 20 min, and maximum removal values were 457.08, 374.64, 102.56, and 25.63 mg·g−1 for Na+-Bent, BentV1, BentV3, and BentV5, respectively. At lower drug concentrations (48.78 and 91.24 mg·g−1 for Na+-Bent and BentV3), the best performance was obtained for the BentV3 sample. Full article
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13 pages, 2816 KiB  
Article
Clay–Magnetite Co-Aggregates for Efficient Magnetic Removal of Organic and Inorganic Pollutants
by Eliana Pecini and Marcelo Avena
Minerals 2021, 11(9), 927; https://doi.org/10.3390/min11090927 - 27 Aug 2021
Cited by 4 | Viewed by 1867
Abstract
This work reports the behavior of montmorillonite–magnetite mixtures of varying composition in aqueous dispersions and evaluates their adsorbing properties using a cationic organic pollutant, methylene blue (MB+), and an anionic inorganic pollutant, arsenate (As(V)), as the adsorbing species. The effects of [...] Read more.
This work reports the behavior of montmorillonite–magnetite mixtures of varying composition in aqueous dispersions and evaluates their adsorbing properties using a cationic organic pollutant, methylene blue (MB+), and an anionic inorganic pollutant, arsenate (As(V)), as the adsorbing species. The effects of the presence of montmorillonite on the As(V) adsorption by magnetite and the effects of magnetite on the MB+ adsorption by the clay were specially addressed. The simple mixture of a montmorillonite dispersion with a magnetite dispersion led to the spontaneous formation of montmorillonite–magnetite co-aggregates. These co-aggregates showed a unimodal electrophoretic mobility distribution, with no evidence of the presence of separate populations of montmorillonite or magnetite. The application of a magnetic field confirmed the formation of co-aggregates and showed that their separation rate increased as the magnetite content increased. Adsorption studies as a function of the aggregate composition demonstrated that MB+ uptake was mainly controlled by the content of montmorillonite, while As(V) adsorption was mainly controlled by the content of Fe3O4. This permits an easy tuning of the adsorbing properties of cations and anions by controlling the composition of the system. Full article
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Review

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29 pages, 10215 KiB  
Review
Guidelines to Study the Adsorption of Pesticides onto Clay Minerals Aiming at a Straightforward Evaluation of Their Removal Performance
by Jorge Cesar Masini and Gilberto Abate
Minerals 2021, 11(11), 1282; https://doi.org/10.3390/min11111282 - 18 Nov 2021
Cited by 16 | Viewed by 2615
Abstract
Natural and modified clay minerals have been extensively used for the adsorption/desorption of organic substances, especially pesticides, from waters and wastewater, aiming at pollution control and more efficient use of the herbicides through controlled release. While natural clay minerals efficiently remove organic cations [...] Read more.
Natural and modified clay minerals have been extensively used for the adsorption/desorption of organic substances, especially pesticides, from waters and wastewater, aiming at pollution control and more efficient use of the herbicides through controlled release. While natural clay minerals efficiently remove organic cations such as paraquat and diquat, the adsorption of anionic or neutral species demands surface chemical modification with, for instance, quaternary ammonium salts containing long alkyl chains. Basic pesticides, on the other hand, are better absorbed in clay minerals modified with polycations. Kinetic studies and adsorption/desorption isotherms provide the parameters needed to evaluate the clay mineral’s adsorptive performance towards the pollutant target. However, the direct comparison of these parameters is complicated because the experimental conditions, the analytical techniques, the kinetic and isotherm models, and the numerical fitting method differ among the various studies. The free-energy-related Langmuir constant depends on the degree of site occupation; that is, it depends on the concentration window used to construct the adsorption isotherm and, consequently, on the analytical technique used to quantify the free concentrations. This paper reviews pesticides’ adsorption on natural and modified clay minerals and proposes guidelines for designing batch adsorption/desorption studies to obtain easily comparable and meaningful adsorption parameters. Articles should clearly describe the experimental conditions such as temperature, contact time, total concentration window, the solution to adsorbent ratio, the analytical technique, and its detection and quantification limits, besides the fitting models. Research should also evaluate the competitive effects of humic substances, colloidal inorganic particles, and ionic strength to emulate real-world adsorption experiments. Full article
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