Smart Adsorbents for Aquatic Environmental Remediation.

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.

Development of Ultra-Performance Liquid Chromatography-Mass Spectrometry Method for Simultaneous Determination of Three Cationic Dyes in Environmental Samples.

Lower dye concentrations and the presence of several dyes along with other matrices in environmental samples restrict their determination. Herein, a highly sensitive and rapid ultra-performance tandem mass spectrometric method was developed for simultaneous determination of cationic dyes, namely methylene blue (MB), rhodamine B (RB) and crystal violet (CV), in environmental samples. To preconcentrate environmental samples, solid-phase extraction cartridges were developed by using hydrogen peroxide modified pistachio shell biomass (MPSB). The surface morphological and chemical functionalities of MPSB were well characterized. The developed method was validated considering different validation parameters. In terms of accuracy and precision, the %RSD for all three dyes at all four concentration points was found to be between 1.26 and 2.76, while the accuracy reported in terms of the recovery was found to be 98.02%-101.70%. The recovery was found to be in the range of 98.11% to 99.55%. The real sample analysis shows that MB, RB, and CV were found in the ranges of 0.39-5.56, 0.32-1.92 and 0.27-4.36 µg/mL, respectively.

Catalytic pyrolysis of harmful plastic waste to alleviate environmental impacts.

Wax is a detrimental byproduct of plastic waste pyrolysis causing challenges upon its release into the environment owing to persistence and potential toxicity. In this study, the valorization of wax materials through conversion into BTEX (i.e., benzene, toluene, ethylbenzene, and xylene) was achieved via catalytic pyrolysis using zeolite-based catalysts. The potential of two types of waxes, spent wax (SW), derived from the pyrolysis of plastic waste, and commercial paraffin wax (PW), for BTEX generation, was investigated. Using HZSM-5, higher yields of oil (54.9 wt%) and BTEX (18.2 wt%) were produced from the pyrolysis of SW compared to PW (32.3 and 14.1 wt%, respectively). This is due to the improved accessibility of lighter hydrocarbons in SW to Brønsted and Lewis acid sites in HZSM-5 micropores, promoting cracking, isomerization, cyclization, Diels-Alder, and dehydrogenation reactions. Further, the use of HZSM-5 resulted in significantly larger yields of oil and BTEX from SW pyrolysis compared to Hbeta and HY. This phenomenon is ascribed to the well-balanced distribution of Brønsted and Lewis acid sites and the identical geometric structure of HZSM-5 micropores and BTEX molecules. The addition of Ga to HZSM-5 further led to 2.24% and 28.30% enhancements in oil and BTEX yields, respectively, by adjusting the acidity of the catalyst through the introduction of new Lewis acid sites. The regeneration of the Ga/HZSM-5 catalyst by removing deposited coke on the spent catalyst under air partially recovered catalytic activity. This study not only offers an efficient transformation of undesirable wax into valuable fuels but also provides an environmentally promising solution, mitigating pollution, contributing to carbon capture, and promoting a healthier and more sustainable environment. It also suggests future research directions, including catalyst optimization and deactivation management, feedstock variability exploration, and techno-economic analyses for sustainable wax conversion into BTEX via catalytic pyrolysis.

Green Synthesis of Silver Nanoparticles Using Allium cepa var. Aggregatum Natural Extract: Antibacterial and Cytotoxic Properties.

The chemical content of plant excerpts can be efficiently employed to reduce the metal ions to nanoparticles in the one-pot green production method. Here, green production of silver nanoparticles (AC-AgNPs) is performed by means of Allium cepa var. Aggregatum (shallot) extract as a stabilizer and reducer. The shape, size, and morphology of resultant AC-AgNPs are examined by optical spectroscopy analysis such as UV for nucleation and coalescence processes of the AC-AgNPs. Through FTIR functional group is determined and through DLS size is defined, it was confirmed that metallic AgNPs were successfully synthesized through the green synthesis route, and these results agreed well with the results obtained in the XRD pattern along with TEM spectroscopy, where the TEM images confirm the formation of sphere-like nanostructures along with SAED analysis. The chemical characterization is performed with XPS; the obtained molecular species in the materials are determined from the energy profile. Antioxidant activity of AC-AgNPs versus DPPH substrate is carried out. Antibacterial activity is well established against Gram-negative and Gram-positive organisms. Cell viability is accomplished, followed by an MTT assay, and a cytotoxicity assay of AC-AgNPs on MCF-7 cell lines is also carried out. Highlights: (1). This study highlights the eco-friendly synthesis of silver nanoparticles from Allium cepa var. Aggregatum Natural Extract. (2). The synthesized AC-AgNPs were characterized by UV-VIS, FT-IR, XRD, TEM, and XPS. (3). The synthesized nanoparticles were well dispersed in nature and the size range of 35 ± 8 nm. (4). The anti-candidal activity of biosynthesized silver nanoparticles was evaluated against the following Gram-Negative organisms: Escherichia coli (E. coli), and the following Gram-positive organisms: Staphylococcus aureus strains. The biosynthesized AC-AgNPs showed enhanced antiseptic features anti both Gram-positive and negative organisms. (5). Besides, the in vitro cytotoxic outcomes of AC-AgNPs were assessed versus MCF-7 cancerous cells, and the reduction in the feasibility of cancer cells was established via MTT assay, which suggests potential biomedical applications.

Feasibility assessment of bioethanol production from humic acid-assisted alkaline pretreated Kentucky bluegrass (Poa pratensis L.) followed by downstream enrichment using direct contact membrane distillation.

The effective fractionation of structural components of abundantly available lignocellulosic biomass is essential to unlock its full biorefinery potential. In this study, the feasibility of humic acid on the pretreatment of Kentucky bluegrass biomass in alkaline condition was assessed to separate 70.1% lignin and hydrolyzable biocomponents. The humic acid-assisted delignification followed by enzymatic saccharification yielded 0.55 g/g of reducing sugars from 7.5% (w/v) pretreated biomass loading and 16 FPU/g of cellulase. Yeast fermentation of the biomass hydrolysate produced 76.6% (w/w) ethanol, which was subsequently separated and concentrated using direct contact membrane distillation. The hydrophobic microporous flat-sheet membrane housed in a rectangular-shaped crossflow module and counter-current mode of flow of the feed (hot) and distillate (cold) streams yielded a flux of 11.6 kg EtOH/m2/24 h. A modular, compact, flexible, and eco-friendly membrane-integrated hybrid approach is used for the first time to effectively valorize Kentucky bluegrass biomass for sustainable production of biofuel.

MgO-modified activated biochar for biojet fuels from pyrolysis of sawdust on a simple tandem micro-pyrolyzer.

The aim of this work was to study on MgO-modified KOH activated biochar (AC) catalysts, in the pyrolysis of sawdust for the direct production of bio-jet fuels using a tandem micro-pyrolyzer. AC catalysts with various MgO contents (5 to 20 wt%) were synthesized using an impregnation method. The mesopores generated (4 to 18 nm) in the carbon has a great potential in the conversion of oxygenated to jet fuel. The importance of basic nature in the catalysts is demonstrated with the maximum bio-jet fuel yield of 29 % at 10 % MgO. Further, the temperature of 600 °C and a catalyst/sawdust ratio of 10 are identified as the optimal conditions. The nanosize of MgO and the synergism of acid and base sites seemed to enhance deoxygenation, via decarboxylation and decarbonylation, and oligomerization, which are required for jet fuel formation in high amounts from sawdust pyrolysis.

Technical benefits of using methane as a pyrolysis medium for catalytic pyrolysis of Kraft lignin.

Catalytic fast pyrolysis of low sulfonated Kraft lignin was performed under different atmospheric environments such as N2, CH4, and the gas derived from CH4 decomposition (CH4-D). The use of Zn- or Mo-loaded HZSM-5 as catalyst led to a higher pyrolytic oil yield compared to parent HZSM-5 in CH4 and CH4-D atmospheres. The yields of benzene, toluene, and xylenes were increased by the synergistic effects from metal loading, higher H/Ceff ratio, higher acidity, and CH4 activation. The enhanced CH4 activation via metal loading resulted in higher methylation of alkyl moieties and 33% increase in the total yield of benzene, toluene, and xylenes in comparison to parent HZSM-5. A higher H/Ceff ratio of 6 via CH4 decomposition led to the formation of a hydro-pyrolysis environment. Moreover, the CH4-D environment showed H2/CH4 ratio of 0.36 in the product gas which warranted the presence of more H2 under the CH4-D pyrolysis environment.

Simultaneous co-hydrothermal carbonization and chemical activation of food wastes to develop hydrochar for aquatic environmental remediation.

Locally generated food wastes, such as Arabic coffee ground (ACG) and olive oil cake (OOC) were converted to N-ACG: OOC - 3 hydrochar (HC) through simultaneous co-hydrothermal carbonization (Co-HTC) and chemical activation. The optimized ACG: OOC mass ratio (g: g) and chemical activation agent used were 1.2: 0.8 and 0.1 M HNO3, respectively. Spectroscopic analyses confirmed the dominance of oxygen-containing functionalities, whereas the X-ray diffraction pattern displayed peaks for both sucrose and cellulose on N-ACG: OOC - 3. The developed HC was tested for methylene blue (MB) and crystal violet (CV) adsorption in aqueous systems. Batch scale adsorption studies showed pH, initial concentration (Co), time (t), and temperature (T) dependent dye uptake. Maximum dye uptake was observed at pH 7, with 50 - 70% and 76 - 90 % CV and MB removal achieved within 15 min at varied Co: 50 - 200 mg/L. Adsorption was governed by multiple mechanisms, including hydrogen bonding, electrostatic interactions, π-π interactions, and n-π interactions. Dye elution was higher in ethanol (EtOH: C2H5OH), and CV elution (50.8%) was more significant than MB elution (14.8%).

Integrated hydrothermal and deep eutectic solvent-mediated fractionation of lignocellulosic biocomponents for enhanced accessibility and efficient conversion in anaerobic digestion.

Effective fractionation of lignocellulosic biocomponents of lignocellulosic biomass can increase its utilization in anaerobic digestion for high yield biomethane production. A hydrothermal process was optimized and integrated with a deep eutectic solvent (DES) pretreatment to preferentially fractionate hemicellulose, cellulose, and lignin in rice straw. The optimized hydrothermal process resulted in 96% hemicellulose solubilization at moderately low combined pretreatment severity (log S = 2.26), allowing increased hemicellulosic sugar recovery with minimal formation of inhibitory byproducts. Subsequent DES pretreatment resulted in highly bioaccessible cellulosic pulp, removing 81.3% of lignin that can be recovered and converted into value-added products. Anaerobic digestion of hemicellulosic fraction and cellulosic pulp using a microbial methanogenic consortium seed acclimatized to the lignocellulosic inhibitors resulted in a 33.4% higher yield of methane (467.84 mL g-1 VSinitial) than with anaerobic digester sludge seed. This integrated approach can facilitate and maximize the targeted utilization of different biocomponents through sustainable biorefining.

Syntrophic bacteria- and Methanosarcina-rich acclimatized microbiota with better carbohydrate metabolism enhances biomethanation of fractionated lignocellulosic biocomponents.

An inadequate lignocellulolytic capacity of a conventional anaerobic digester sludge (ADS) microbiota is the bottleneck for the maximal utilization of lignocellulose in anaerobic digestion. A well-constructed microbial consortium acclimatized to lignocellulose outperformed the ADS in terms of biogas productivity when fractionated biocomponents of rice straw were used to achieve a high methane bioconversion rate. A 33.3 % higher methane yield was obtained with the acclimatized consortium (AC) compared to that of ADS control. The dominant pair-wise link between Firmicutes (18.99-40.03 %), Bacteroidota (10.94-28.75 %), and archaeal Halobacteriota (3.59-20.57 %) phyla in the AC seed digesters indicated that the keystone members of these phyla were responsible for higher methane yield. A high abundance of syntrophic bacteria such as Proteiniphilum (1.22-5.19 %), Fermentimonas (0.71-5.31 %), Syntrophomonas (0.87-3.59 %), and their syntrophic partner Methanosarcina (4.26-18.80 %) maintained the digester stability and facilitated higher substrate-to-methane conversion in the AC seed digesters. The present combined strategy will help in boosting the 'biomass-to-methane" conversion.

Systematic Assessment of Visible-Light-Driven Microspherical V2O5 Photocatalyst for the Removal of Hazardous Organosulfur Compounds from Diesel.

The organosulfur compounds present in liquid fuels are hazardous for health, asset, and the environment. The photocatalytic desulfurization technique works at ordinary conditions and removes the requirement of hydrogen, as it is an expensive gas, highly explosive, with a broader flammability range and is declared the most hazardous gas within a petroleum refinery, with respect to flammability. The projected work is based on the synthesis of V2O5 microspheres for photocatalytic oxidation for the straight-run diesel (SRD) and diesel oil blend (DOB). The physicochemical properties of V2O5 microspheres were examined by FT-IR, Raman, UV-vis DRS, SEM, and Photoluminescence evaluations. The as-synthesized photocatalyst presented a trivial unit size, a narrow bandgap, appropriate light-capturing capability, and sufficient active sites. The desulfurization study discovered that the anticipated technique is substantial in desulfurizing DOB up to 37% in 180 min using methanol as an interfacing agent. Furthermore, the outcome of employing a range of polar interfacing solvents was examined, and the 2-ethoxyethanol elevated the desulfurization degree up to 51.3%. However, the anticipated technology is constrained for its application in sulfur removal from SRD. Additionally, the mechanism for a photocatalytic reaction was seen in strong agreement with pseudo-first-order kinetics. The investigated photocatalyst exhibited a compromised recyclability and regeneration tendency.

Carbon Based Polymeric Nanocomposites for Dye Adsorption: Synthesis, Characterization, and Application.

Agglomeration and restacking can reduce graphene oxide (GO) activity in a wide range of applications. Herein, GO was synthesized by a modified Hummer's method. To minimize restacking and agglomeration, in situ chemical oxidation polymerization was carried out to embed polyaniline (PANI) chains at the edges of GO sheets, to obtain GO-PANI nanocomposite. The GO-PANI was tested for the adsorptive removal of brilliant green (BG) from an aqueous solution through batch mode studies. Infrared (FT-IR) analysis revealed the dominance of hydroxyl and carboxylic functionalities over the GO-PANI surface. Solution pH-dependent BG uptake was observed, with maximum adsorption at pH 7, and attaining equilibrium in 30 min. The adsorption of BG onto GO-PANI was fit to the Langmuir isotherm, and pseudo-second-order kinetic models, with a maximum monolayer adsorption capacity (qm) of 142.8 mg/g. An endothermic adsorption process was observed. Mechanistically, π-π stacking interaction and electrostatic interaction played a critical role during BG adsorption on GO-PANI.

Kinetic Studies on the Catalytic Degradation of Rhodamine B by Hydrogen Peroxide: Effect of Surfactant Coated and Non-Coated Iron (III) Oxide Nanoparticles.

Iron (III) oxide (Fe3O4) and sodium dodecyl sulfate (SDS) coated iron (III) oxide (SDS@Fe3O4) nanoparticles (NPs) were synthesized by the co-precipitation method for application in the catalytic degradation of Rhodamine B (RB) dye. The synthesized NPs were characterized using X-ray diffractometer (XRD), vibrating sample magnetometer (VSM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infra-red (FT-IR) spectroscopy techniques and tested in the removal of RB. A kinetic study on RB degradation by hydrogen peroxide (H2O2) was carried out and the influence of Fe3O4 and SDS@Fe3O4 magnetic NPs on the degradation rate was assessed. The activity of magnetic NPs, viz. Fe3O4 and SDS@Fe3O4, in the degradation of RB was spectrophotometrically studied and found effective in the removal of RB dye from water. The rate of RB degradation was found linearly dependent upon H2O2 concentration and within 5.0 × 10-2 to 4.0 × 10-1 M H2O2, the observed pseudo-first-order kinetic rates (kobs, s-1) for the degradation of RB (10 mg L-1) at pH 3 and temperature 25 ± 2 °C were between 0.4 and 1.7 × 104 s-1, while in presence of 0.1% w/v Fe3O4 or SDS@Fe3O4 NPs, kobs were between 1.3 and 2.8 × 104 s-1 and between 2.6 and 4.8 × 104 s-1, respectively. Furthermore, in presence of Fe3O4 or SDS@Fe3O4, kobs increased with NPs dosage and showed a peaked pH behavior with a maximum at pH 3. The magnitude of thermodynamic parameters Ea and ΔH for RB degradation in presence of SDS@Fe3O4 were 15.63 kJ mol-1 and 13.01 kJ mol-1, respectively, lowest among the used catalysts, confirming its effectiveness during degradation. Furthermore, SDS in the presence of Fe3O4 NPs and H2O2 remarkably enhanced the rate of RB degradation.

Bioflocculants Produced by Bacterial Strains Isolated from Palm Oil Mill Effluent for Application in the Removal of Eriochrome Black T Dye from Water.

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.