Editorial

Wastewater Treatments Based on Adsorption, Catalysis,

Biodegradation, and Beyond
Dimitrios A. Giannakoudakis 1,2, * and Yongchang Sun 3, *

1 Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie-Sklodowska University, Maria Curie
Sklodowska Sq. 3, 20-031 Lublin, Poland
2 School of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
3 School of Water and Environment, Chang’an University, Xi’an 710054, China
* Correspondence: [email protected] (D.A.G.); [email protected] (Y.S.)

The ongoing technological advancements and industrial growth over the past few
decades have resulted in significant environmental challenges, with one of the most notable
being water pollution caused by the improper disposal of organic and inorganic pollutants.
Protecting the environment is an essential component of a sustainable future, leading
researchers and the public to focus on innovative remediation strategies. As a result, the
development of new “green”-oriented, low-cost, and efficient materials for environmental
remediation, especially those which facilitate the removal of pollutants from water bodies,
remains a vibrant area of research. This Special Issue encompasses 14 original research
articles and 2 review papers which aim to explore new methods outside of sorption,
biodegradation, and catalytic degradation, while also introducing new materials and
composites for effective (waste) water treatment and purification.
In their study, Gao et al. used a biomass, Medulla tetrapanacis (MT), as a sor-
bent. Known as “da-tong-cao” in China, where it is also famously used as a traditional
medicine [1], MT is a well-developed porous 3D structure with an ultra-thin cell wall,
predominantly consisting of holocellulose (~82 wt.%) and ash/minerals (~11 wt.%). MT
showed high remediation efficiency against methylene blue (MB) and crystal violet (CV),
achieving 411 and 553 mg/g adsorption, respectively. Interestingly, the depleted samples
were pyrolyzed to biochars, achieving adsorption performances of 320 mg/g for Cu2+ and
840 mg/g for Pb2. Crini et al. utilized individualized fibers of a pine wood by-product
Citation: Giannakoudakis, D.A.; Sun, (Pinus pinaster) were utilized as a sorbent for copper in poly-contaminated aqueous so-
Y. Wastewater Treatments Based on lutions [2]. Upon activation with sodium carbonate, the pine fibers successfully removed
Adsorption, Catalysis, Biodegradation, 2.5 mg/g copper regardless of the changing pH levels, which ranged from 3 to 5. The
and Beyond. Molecules 2024, 29, 5470. presence of the Na+ cation at concentrations of 0.1 M did not affect the performance of
https://doi.org/10.3390/ the material. The adsorption process was rapid, as most of the copper was absorbed
molecules29225470 within the first 10 min of exposure. The underlying mechanism is considerably more
Received: 25 October 2024 complex due to physisorption, chemisorption, and/or diffusion phenomena. Wang and
Accepted: 11 November 2024 coworkers followed a multistep protocol to synthesize chitosan modified with pyridine
Published: 20 November 2024 and crosslinked with glutaraldehyde (PYCS) material that achieved 66.2 mg/g of Fe(III)
adsorption at pH = 2.5 [3]. The surface pyridine groups were responsible for the formation
of stable chelate with Fe(III) ions. PYCS successfully maintained Fe sorption efficiency, since
the removal performance only decreased by 29% after six regeneration cycles. Another
Copyright: © 2024 by the authors.
lignocellulosic biomass composed of Luffa cylindrica fibers was used by Theocharis et al.
Licensee MDPI, Basel, Switzerland.
to synthesize biochar (LCC) after thermal treatment in a nitrogen atmosphere (at 650 ◦ C for
This article is an open access article
1 h), which was further oxidized (LCC_ox) using HNO3 [4]. The materials showed elevated
distributed under the terms and
adsorption of U-232 radionuclide at sub-picomolar initial concentrations. Oxidation of
conditions of the Creative Commons
the biochar had a positive effect on uranium removal, with the adsorption process being
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
affected by the dispersion pH. The interactions were found to be entropy-driven (∆H◦
4.0/).
and ∆S◦ > 0) based on the creation of inner-sphere complexes. Zhang et al. used recycled

Molecules 2024, 29, 5470. https://doi.org/10.3390/molecules29225470 https://www.mdpi.com/journal/molecules

Molecules 2024, 29, 5470 2 of 4

agricultural waste from corncobs and KOH/FeCl3 to prepare a biochar/alginate composite

bead (MCB/ALG) adsorbent via high-temperature pyrolysis (at 800 ◦ C for 2 h) [5]. Al-
though MCB/ALG did not exhibit high porosity (129 m2 /g), it achieved 1373 mg/g MB
removal, and the process was found to be endothermic and spontaneous. This performance
was linked to the filling of the pores, electrostatic interactions, and hydrogen bonding.
After five cycles of regeneration, the MB removal remained high (85% compared to the
first cycle). Tushar Kanti Sen delivered a comprehensive review based on an up-to-date
literature overview, focusing on studies that utilized a wide range of solid waste agricul-
tural biomass-based adsorbents (raw, modified, and treated) to purify water that had been
polluted with various metal ions [6]. Various important influential physicochemical process
parameters, like metal concentration, adsorbent dose, the initial pH of the solution, and the
temperature were considered as potential perspectives and conclusions for future work.
Deng and coworkers applied activated carbon in granular form (GAC) for water
purification upon the co-presence of three antibiotics, specifically thiamphenicol (THI),
sulfamethoxazole (SMZ), and tetracycline (TC) [7]. The carbon granules were obtained
from corn stover biomass that was dried, chopped into small pieces, and heated at 500 ◦ C
for 2 h and then at 700 ◦ C for 2 h under a N2 atmosphere, then underwent further activation
via a superheated steam (600 ◦ C, 2.0 MPa, 2 h). GAC had a surface area of 1059 m2 /g
and was predominately microporous (Vmic = 0.488 cm3 /g). The maximum capacities
were around 27, 17, and 30 mg/g for SMZ, TC, and THI, respectively; the sorption was
exothermic and spontaneous. The Weber–Morris intraparticle diffusion model and the
Boyd kinetic model demonstrated that diffusion across the boundary layer was the primary
determinant of the adsorption process. Activated porous carbons (PACs) were studied in
another work by Pavlovic et al. as adsorbents of three pharmaceuticals: sulfamethoxazole,
trimethoprim, and diclofenac. The removal efficiency was studied using ultra-pure water,
humic acid solution, or liquor from real samples collected from wastewater treatment
plants [8]. The best removal results were recorded for trimethoprim, followed by diclofenac
and sulfamethoxazole. The most notable differentiating factors were linked to the charge
and hydrophobicity of the pharmaceuticals at a specific pH. The maximum capacities varied
depending on the water matrix; the highest capacity was achieved for sulfamethoxazole
and diclofenac in humic acid solution. Multiwalled carbon nanotubes (MWCNTs) were
modified through oxidation and acidification [9] using concentrated HNO3 and H2 SO4 ,
respectively, and were studied as Mn(II) adsorbents by Dou et al. The chemical treatment
had a positive impact on the Mn remediation efficiency, which was almost four times
higher than that of the pristine nanotubes. The reliability of the experimental results was
thoroughly validated by the PSO-BP simulation, and the findings can serve as a basis for
subsequent simulations.
A molecularly imprinted polymer (MIP) was synthesized by Zekker and coworkers
through bulk polymerization and utilized in wastewater treatment to enhance the adsorp-
tion of specific template molecules [10]. This process utilized ethylene glycol dimethacrylate
(EGDMA) as the crosslinker, methacrylic acid (MAA) as the functional monomer, acid
black-234 (AB-234) as the template, 2,2′ -azobisisobutyronitrile (AIBN) as the initiator, and
methanol as the porogenic solvent. The adsorption capacity of the MIP for AB-234 was
significantly greater (94%) than that of the NIP (31%) at pH 5, with an estimated maxi-
mum capacity of 83 mg/g at 298 K based on the Langmuir model. The MIP exhibited an
imprinted factor (IF) of 5.13 and a Kd value of 0.53. Li and coworkers designed a new sul-
fonation process for an algal/polyethyleneimine (PEI) composite [11]. The functionalized
sorbent showed a triple sorption capacity for Sr(II) at pH 4 compared to its non-sulfonated
counterpart. The sulfonate groups played a key role in adsorption (as revealed by IR),
and sulfonation had a positive impact on thermal stability and porosity. The co-presence
of NaCl had a negligible influence on sorption, explaining the good Sr(II) remediation in
seawater samples, which was reproducible for at least five cycles. Wilfed and cowork-
ers tested solid-supported ionic liquid consisting of activated silica gel combined with
1-methyl-3-(3-trimethoxysilylpropyl) imidazolium thiosalicylate-based ionic liquid as an
Molecules 2024, 29, 5470 3 of 4

extractant of Pb(II) ions from aqueous solutions [12]. The formation of covalent bonds was
confirmed by solid-state NMR. The maximum Pb(II) removal capacity was recorded as
~9 mg/g, with the kinetics to be better described by a pseudo-second order model.
Linh Do et al. developed a system that utilizes sulfate-reducing and sulfide-oxidizing
processes to treat organic wastewater with high sulfate and sulfide levels [13]. The effects
of the COD/SO4 2− ratio and hydraulic retention time (HRT) on the removal efficiencies
of sulfate, COD, sulfide, and electricity generation were examined. The results indicated
that the removal efficiencies for COD and sulfate were stable, reaching ~95 and 93%,
respectively, throughout the operation. A power density of 18.0 ± 1.6 mW/m2 was recorded
alongside a sulfide removal efficiency of 93%. However, both sulfide removal efficiency and
power density gradually declined after 45 days. Scanning electron microscopy combined
with energy-dispersive X-ray analysis revealed that sulfur accumulated on the anode,
leading to decreases in sulfide oxidation and electrical generation. This study presents a
promising treatment system that could be scaled up for practical applications related to the
management of this type of wastewater.
Alhogbi and Balawi presented composite adsorbents consisting of kaolin-derived
zeolite and different mass ratios of palm tree fibers (Zeo-FPT) [14]. Mixing the two counter-
parts resulted in a composite that achieved faster and more efficient removal of methylene
blue. The remediation efficiency of the material, which consisted of a one-to-one mass ratio
of fibers and zeolite was strong; it achieved >99% removal of a low initial MB concentration
in bottled, tap, and well water. He and co-authors prepared a photo-active composite
using aminated lignin (AL) and titanate nanotubes [15]. AL was prepared according to
the Mannich reaction by modifying technical lignin (TL), while the composite (AL-TiNTs)
was formed via a hydrothermal synthesis approach. AL-TiNTs had a specific surface
area of 189 m2 /g, indicating the formation of titanate nanotubes. AL-TiNTs showed an
ability to reduce Cr(VI) to Cr(III) and Cr under exposure to visible light, with maximum
chromium removal of 90 mg/g. AL-TiNTs also achieved high adsorption performances
against Zn2+ (64 mg/g), Cd2+ (59 mg/g), and Cu2+ (66 mg/g), with high efficiency in
simulated wastewater for up to four cycles.
Nair and co-authors reviewed the application of biochar-based materials as adsorbents
and support for microorganisms to achieve efficient bioremediation of various heavy
metal ions and/or pesticides, emphasizing and summarizing the predominant interaction
mechanisms and how the immobilized bacteria on biochar contribute to the improvement
of bioremediation strategies [16]. In conclusion, this paper outlines the future scopes of this
field based on the reviewed and discussed research.

Author Contributions: D.A.G. and Y.S.: Writing-original draft preparation and review and editing.
All authors have read and agreed to the published version of the manuscript.
Acknowledgments: The Guest Editors would like to express their gratitude to all the authors for
their contributions to this Special Issue, to the reviewers for their efforts in assessing the submitted
articles, and to the editorial team of Molecules for their valuable support.
Conflicts of Interest: The authors declare no conflicts of interest.

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