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Environmental Applications of Chemically Modified Clay Minerals

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A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Clays and Engineered Mineral Materials".

Deadline for manuscript submissions: closed (30 August 2020) | Viewed by 19562

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Dr. Martin P. Pentrak

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Illinois State Geological Survey, Prairie Research Institute, University of Illinois at Urbana-Champaign, Champaign, IL 61820, USA
Interests: smectite; illite; kaolinite; iron; reduction; XRD; XRF; Mössbauer spectroscopy; FT-IR spectroscopy; short-wave Infrared spectroscopy
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Special Issue Information

Dear Colleagues,

On behalf of the Minerals Journal, I would like to invite you to join me in the special issue related to the investigation of clay minerals with a focus on their environmental applications.

Clay minerals are natural materials with unique properties (large specific surface area, cation exchange capacity). Most known clay mineral groups, smectites, and kaolinites are investigated for decades, and their usage has now an extensive range from cosmetics through paper and paints additives to environmental applications. Smectites have a large specific surface area and cation exchange capacity due to the negative layer charge. They are excellent natural adsorbents, but their properties can be enhanced by chemical modification to study their: (1) structural stability under extreme pH conditions (the isolation layers of a toxic waste dumps and spent radioactive fuel storages - acid and alkali activation), (2) redox activity to remediate contaminated waters and soils by industrial or agricultural discharges (chemical and biological redox activation of structural Fe), and (3) reactivity with oversaturated saline solutions (geological clay barriers). These studies are highly recommended for this special issue of the Minerals Journal, but other environmental utilizations of chemically modified clay minerals are welcome, as well.

Finally, the overall goal of this issue is to bring a message about the actual environmental applications of chemically modified clay minerals.

Dr. Martin Pentrak
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Minerals is an international peer-reviewed open access monthly journal published by MDPI.

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Keywords

smectites
kaolinite
acid activation
redox activation
remediation
contamination
environmental application

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Related Special Issue

Environmental Applications of Chemically Modified Clay Minerals, Volume II in Minerals (2 articles)

Published Papers (6 papers)

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Research

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16 pages, 2657 KiB

Open AccessArticle

Sorption of Cu²⁺ Ions by Bentonite Modified with Al Keggin Cations and Humic Acid in Solutions with pH 4.5

by Yulia Izosimova, Inna Tolpeshta, Irina Gurova, Michail Karpukhin, Sergey Zakusin and Victoria Krupskaya

Minerals 2020, 10(12), 1121; https://doi.org/10.3390/min10121121 - 14 Dec 2020

Cited by 8 | Viewed by 2465

Abstract

The sorption of Cu²⁺ onto bentonite modified with Al Keggin cations and humic acid from CuCl₂ solutions at pH 4.5 was studied. Modification of Na-bentonite with Al Keggin cations was found to result in an increase in the basal spacing of montmorillonite from 1.29 nm for N-form to 1.85 and 1.78 nm for HAl₁₃ and Al₁₃ forms respectively, in a reduction of CEC (cation exchange capacity) and in the formation of additional sites with a variable charge with pH_PZC 4.2. Al₁₃-bentonite is not affected by heat. Under the conditions of the experiments at pH of 4.5 Na-bentonite adsorbs more Cu²⁺ from CuCl₂ solutions then Al₁₃ forms of bentonites. The main mechanism of copper sorption on Na-bentonite is the cation exchange Cu²⁺–Na⁺. The reduction of CEC of Na-bentonite after modification with Al Keggin cations leads to a decrease in the Cu²⁺ sorption. pH-dependent sorption sites on Al₁₃-bentonites have a pH_PZC of 4.2 and, therefore, under conditions of the experiment have positive charge which prevents Cu²⁺ sorption. Na-bentonite adsorbs more humic acid solution (HA) then Al₁₃-bentonite and the proportion of adsorbed HA remains constant over the entire concentration range. Treatment of the Al₁₃-bentonite with HA leads to the formation of the additional sorption sites. The amount of sorbed Cu²⁺ and the percentage of their extraction from solutions by HAAl₁₃-bentonite is similar to those values for Na-bentonite. Full article

(This article belongs to the Special Issue Environmental Applications of Chemically Modified Clay Minerals)

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14 pages, 7271 KiB

Open AccessArticle

Influence of Salinity on the Removal of Ni and Zn by Phosphate-Intercalated Nano Montmorillonite (PINM)

by Jiyeon Choi, Ardie Septian and Won Sik Shin

Minerals 2020, 10(11), 980; https://doi.org/10.3390/min10110980 - 2 Nov 2020

Cited by 5 | Viewed by 2403

Abstract

The salinity influence on the adsorptions of Ni and Zn onto phosphate-intercalated nano montmorillonite (PINM) were investigated. Single adsorption isotherm models fitted the single adsorption data well. The adsorption capacity of Ni was higher than that of Zn onto PINM at different salinities. [...] Read more.

Q_{m L}^{*}

and

b_{L}^{*}

). The

Q_{m L}^{*}

of Zn was lower than that of Ni. The simultaneous presence of Ni and Zn decreased the adsorption capacities. The single and binary adsorptions onto PINM were affected by the salinity. The competitive Langmuir model (CLM), P-factor, Murali and Aylmore (M−A) models, and ideal adsorbed solution theory (IAST) were satisfactory in predicting the binary adsorption data; the CLM showed the best fitting results. Our results showed that the PINM can be used as an active Ni and Zn adsorbent for a permeable reactive barrier (PRB) in the remediation of saline groundwater. Full article

(This article belongs to the Special Issue Environmental Applications of Chemically Modified Clay Minerals)

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16 pages, 1988 KiB

Open AccessArticle

Removal of Salicylic and Ibuprofen by Hexadecyltrimethylammonium-Modified Montmorillonite and Zeolite

by Jiyeon Choi and Won Sik Shin

Minerals 2020, 10(10), 898; https://doi.org/10.3390/min10100898 - 10 Oct 2020

Cited by 18 | Viewed by 3169

Abstract

The removal of salicylic acid (SA) and ibuprofen (IB) by sorption onto HDTMA-modified montmorillonite (HM) and zeolite (HZ) was investigated at pH 7. The single sorption data were fitted well by the Freundlich, Langmuir, Dubinin−Radushkevich (DR), and Polanyi−Dubinin−Manes (PDM) models (R² > 0.94). The sorption affinity of Freundlich and the maximum sorption capacity of Langmuir and PDM models of pharmaceuticals onto HM were consistently higher than that of HZ mainly owing to the higher organic carbon content. In addition, the K_F, q_mL, and q_m values were in the order of IB > SA owing to higher hydrophobicity and molar volume. Since the predominant speciation of SA and IB is anionic at pH 7 (>pKa), sorption onto HM occurs mainly by the two-dimensional surface adsorption onto the pseudo-organic medium in the HM, whereas the interaction of anionic pharmaceuticals with the positively charged “head” of HDTMA is responsible for HZ. Sorption isotherms were fitted well by the PDM model, which indicated that pore-filling was one of the dominating sorption mechanisms. The extended Langmuir model, modified Langmuir competitive model, and ideal adsorbed solution theory employed with Freundlich and Langmuir sorption models were applied to predict binary sorption. The effect of competition between the solutes was clearly evident in the characteristic curves; the maximum sorbed volume (q_v.m) was reduced, and the sorbed volume (q_v) had a wider distribution toward the sorption potential density. Full article

(This article belongs to the Special Issue Environmental Applications of Chemically Modified Clay Minerals)

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13 pages, 1561 KiB

Open AccessArticle

Modified Vermiculite as Adsorbent of Hexavalent Chromium in Aqueous Solution

by Celia Marcos, Valeria Medoro and Alaa Adawy

Minerals 2020, 10(9), 749; https://doi.org/10.3390/min10090749 - 24 Aug 2020

Cited by 5 | Viewed by 3118

Abstract

The aim of this study was to investigate the efficiency of removing Cr⁶⁺ from aqueous solutions using two exfoliated vermiculite: (1) heated abruptly at 1000 °C and (2) irradiated with microwave radiation. The effects investigated were contact time, adsorbate concentration and initial Cr⁶⁺ concentration. The adsorption with both exfoliated vermiculites was well described by the DKR isotherm, indicative of a cooperative process and with the pseudo second order kinetic model. The K_d value for the two exfoliated vermiculites was similar, 0.2 ·10¹⁰ μg/Kg. The maximum adsorption capacity of Cr⁶⁺ with thermo-exfoliated vermiculite, 2.81 mol/g, was much higher than with microwave irradiated vermiculite, 0.001 mol/g; both values were obtained with 0.5 g of vermiculite in contact with distilled water enriched with 1 ppm of Cr⁶⁺ for 24 h. Factors such as ion chemistry, the solution pH and ionic strength, influence the values of capacity, adsorption energy and initial adsorption rate values of the exfoliated vermiculite. In addition, these values depended on the exfoliation process, being the adsorption capacity highest with abrupt heating of vermiculite, while the adsorption energy and rate values showed just a slight increase with microwave irradiation. This aspect is important to select the most suitable vermiculite modification treatment to use it as an adsorbent. Full article

(This article belongs to the Special Issue Environmental Applications of Chemically Modified Clay Minerals)

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12 pages, 8035 KiB

Open AccessArticle

Relationship between Textural Parameters of Lamellar Products Obtained by Acid Activation of Pure and Commercial Vermiculites and Their Iron and Water Content

by Celia Marcos, Alaa Adawy and Irene Rodríguez

Minerals 2020, 10(8), 661; https://doi.org/10.3390/min10080661 - 26 Jul 2020

Cited by 1 | Viewed by 2458

Abstract

The relationship between textural parameters (specific superficial area (S_BET) and porosity (V_p)) of lamellar products obtained from HNO₃-activated vermiculites and their iron and water content has been established. Two commercial vermiculites, one thermoexfoliated commercial vermiculite, and one pure vermiculite were nitric-acid-treated at 4 and 8 M concentrations for 1, 3, and 7 days. Untreated and treated samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and N₂ physisorption analysis. The untreated vermiculites showed a direct relationship between their iron content and the values of S_BET, V_p, and pore size; an inverse relationship was observed in the case of the treated samples. The iron content may prevent further leaching of cations but not water loss, therefore forming lamellar products with lower S_BET and V_p values. The S_BET and V_p values of the studied thermoexfoliated sample were higher than those of the starting sample. The S_BET and V_p values of the activated thermoexfoliated sample were lower than those of the activated non-thermoexfoliated sample. Full article

(This article belongs to the Special Issue Environmental Applications of Chemically Modified Clay Minerals)

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Review

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41 pages, 2547 KiB

Open AccessFeature PaperReview

Applications of Chemically Modified Clay Minerals and Clays to Water Purification and Slow Release Formulations of Herbicides

by Tomas Undabeytia, Uri Shuali, Shlomo Nir and Baruch Rubin

Minerals 2021, 11(1), 9; https://doi.org/10.3390/min11010009 - 24 Dec 2020

Cited by 23 | Viewed by 4925

Abstract

This review deals with modification of montmorillonite and other clay-minerals and clays by interacting them with organic cations, for producing slow release formulations of herbicides, and efficient removal of pollutants from water by filtration. Elaboration is on incorporating initially the organic cations in micelles and liposomes, then producing complexes denoted micelle- or liposome-clay nano-particles. The material characteristics (XRD, Freeze-fracture electron microscopy, adsorption) of the micelle– or liposome–clay complexes are different from those of a complex of the same composition (organo-clay), which is formed by interaction of monomers of the surfactant with the clay-mineral, or clay. The resulting complexes have a large surface area per weight; they include large hydrophobic parts and (in many cases) have excess of a positive charge. The organo-clays formed by preadsorbing organic cations with long alkyl chains were also addressed for adsorption and slow release of herbicides. Another examined approach includes “adsorptive” clays modified by small quaternary cations, in which the adsorbed organic cation may open the clay layers, and consequently yield a high exposure of the siloxane surface for adsorption of organic compounds. Small scale and field experiments demonstrated that slow release formulations of herbicides prepared by the new complexes enabled reduced contamination of ground water due to leaching, and exhibited enhanced herbicidal activity. Pollutants removed efficiently from water by the new complexes include (i) hydrophobic and anionic organic molecules, such as herbicides, dissolved organic matter; pharmaceuticals, such as antibiotics and non-steroidal drugs; (ii) inorganic anions, e.g., perchlorate and (iii) microorganisms, such as bacteria, including cyanobacteria (and their toxins). Model calculations of adsorption and kinetics of filtration, and estimation of capacities accompany the survey of results and their discussion. Full article

(This article belongs to the Special Issue Environmental Applications of Chemically Modified Clay Minerals)

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