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Cited by 35Adsorption and biosorption for pollutant removalZeolite Catalysis and SynthesisEnvironmental remediation with nanomaterials

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Natural Zeolite Clinoptilolite Application in Wastewater Treatment: Methylene Blue, Zinc and Cadmium Abatement Tests and Kinetic Studies

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Dosa, Melodj, Grifasi, Nadia, Galletti, Camilla, Fino, Debora, Piumetti, Marco·2022·Materials
DOI 10.3390/ma15228191PMC PMC9695311
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Abstract

In recent decades, several abatement techniques have been proposed for organic dyes and metal cations. In this scenario, adsorption is the most known and studied. Clinoptilolite was considered, since it is a zeolite with a relatively low cost (200–600 $ tons−1) compared to the most well-known adsorbent used in wastewater treatment. In this work, Clinoptilolite was used for the adsorption of Methylene Blue (MB) at three different concentrations, namely, 100, 200, and 250 ppm. Furthermore, the adsorption capacity of the natural zeolite was compared with that of Activated Charcoal (250 ppm of MB). The two adsorbents were characterized by complementary techniques, such as N2 physisorption at −196 °C, X-ray diffraction, and field emission scanning electron microscopy. During the adsorption tests, Clinoptilolite exhibited the best adsorption capacities at 100 ppm: the abatement reached 98% (t = 15 min). Both Clinoptilolite and Activated Charcoal, at 250 ppm, exhibited the same adsorption capacities, namely, 96%. Finally, at 250 ppm MB, the adsorption capacity of Clinoptilolite was analyzed with the copresence of Zn2+ and Cd2+ (10 ppm), and the adsorption capacities were compared with those of Activated Charcoal. The results showed that both adsorbents achieved 100% MB abatement (t = 40 min). However, cation adsorption reached a plateau after 120 min (Zn2+ = 86% and 57%; Cd2+ = 53% and 50%, for Activated Charcoal and Clinoptilolite, respectively) due to the preferential adsorption of MB molecules. Furthermore, kinetic studies were performed to fully investigate the adsorption mechanism. It was evidenced that the pseudo-second-order kinetic model is effective in describing the adsorption mechanism of both adsorbents, highlighting the chemical interaction between the adsorbent and adsorbate.

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  • TEM images indicate that clinoptilolite particles are relatively large, display a plate-like structural arrangement, and have an average dimension of approximately 200 × 74 nm.

    “The images indicate that Clinoptilolite particles are relatively large, displaying a “plate”-like structural arrangement, with an average dimension of approximately 200 × 74 nm.”

    From Fundamental properties and sustainable applications of the natural zeolite clinoptilolite (2024) · cites this paper as Dosa et al. 2022

    Section 3.1 reports that TEM images show a flake-like clinoptilolite structure, consistent with the cited plate-like description. It gives approximately 200 × 74 nm as the measured dimension of one particular particle, not an average across particles; it also does not characterize the particles as relatively large. (LLM, conf=0.87)

    Experimental — accuracy not yet measured

  • FESEM analysis shows the typical flake structure of clinoptilolite, with particles aggregated and grains having no well-defined crystal faces.

    “By performing a FESEM analysis, it is possible to see the typical “flake” structure of the clinoptilolite, as reported in Fig. 2. The particles appeared aggregated and characterized by grains with no well-defined crystal faces”

    From Fundamental properties and sustainable applications of the natural zeolite clinoptilolite (2024) · cites this paper as Dosa et al. 2022

    Section 3.1 (page unavailable) reports that FESEM analysis confirmed the typical flake-like structure of clinoptilolite. It does not describe aggregated particles or grains lacking well-defined crystal faces, so those details are not supported by our copy. (LLM, conf=0.89)

    Experimental — accuracy not yet measured

  • Greek clinoptilolite captured 100%, 99%, and 93% of Methylene Blue at initial concentrations of 100, 200, and 250 ppm after 210 min with an adsorbent load of 10 g/L.

    “it was able to capture 100%, 99%, and 93% respectively with an initial concentration of 100, 200, and 250 ppm of dye after 210 min and introducing an adsorbent load of 10 g/L.”

    From Fundamental properties and sustainable applications of the natural zeolite clinoptilolite (2024) · cites this paper as Dosa et al. 2022

    Methods §2.1 identifies the clinoptilolite as sourced from Greece, and §2.3.1 confirms tests at 100, 200, and 250 ppm. But §2.3.1 specifies 5 g/L for those tests, not 10 g/L; Results §3.2.1 reports 100% abatement at 100 ppm after about 30 minutes and approximately 94% at 250 ppm after 210 minutes, rather than the claimed set of percentages. The copy does not establish the claimed 99% result at 200 ppm. (LLM, conf=0.90)

    Experimental — accuracy not yet measured

  • In copresence of Methylene Blue and heavy metals at 10 ppm Zn2+ and Cd2+, both clinoptilolite and activated charcoal achieved 100% MB abatement at 40 min but less removal of heavy metals, indicating preferential adsorption of the dye on active sites.

    “both adsorbents achieved 100% MB abatement (t = 40 min), but less removal of heavy metals, highlighting the preferential adsorption of the dye on active sites.”

    From Fundamental properties and sustainable applications of the natural zeolite clinoptilolite (2024) · cites this paper as Dosa et al. 2022

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Authors
Dosa, M., Grifasi, N., Galletti, C., Fino, D., & Piumetti, M.
Affiliations
Politecnico di Torino (IT)
Corresponding author
Piumetti, Marco
ORCID
Venue
Materials
Publisher
MDPI AG
Published
2022-11-18
Volume
15
Issue
22
Pages
8191
ISSN
1996-1944 (ISSN-L)
DOI
10.3390/ma15228191
PMC
PMC9695311
OpenAlex
W4309287698
Cited by
35
References
0
Citations by year
2026: 12 · 2025: 6 · 2024: 9 · 2023: 8
FWCI
1.68
Type
journal article
Language
en
Open access
Licence
Locations
  • Materials (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • PORTO@Iris (submittedVersion, cc-by)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
Topics
  • Physical Sciences › Environmental Science › Water Science and Technology › Adsorption and biosorption for pollutant removal
  • Physical Sciences › Chemistry › Inorganic Chemistry › Zeolite Catalysis and Synthesis
  • Physical Sciences › Environmental Science › Environmental Engineering › Environmental remediation with nanomaterials
Keywords
clinoptilolite, natural zeolite, methylene blue, zinc adsorption, cadmium adsorption, dye removal, metal cation removal, adsorption kinetics, pseudo-second-order kinetics, activated carbon, wastewater treatment, adsorption capacity

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