The objective of present study was to obtain the fixation of nano zero valent iron (nZVI) particles on a permeable matrix and evaluate the performance of this composite material for the removal of Cr(VI) from contaminated waters. The experiments were carried out using the cationic resin Dowex 50WX2 as porous support of the iron nanoparticles. The work was carried out in two phases. The first phase involved the fixation of nZVI on the resin matrix. The resin granules were initially mixed with a FeCl3 solution to obtain the adsorption of Fe(III). Then the Fe(III) loaded resin (RFe) was treated with polyphenol solutions to obtain the reduction of Fe(III) to the elemental state. Two polyphenol solutions were tested as reductants, i.e. green tea extract and gallic acid. Green tea was found to be inefficient, probably due to the relatively big size of the contained polyphenol molecules, but gallic acid molecules were able to reach adsorbed Fe(III) and reduce the cations to the elemental state. The second phase was focused on the investigation of Cr(VI) reduction kinetics using the nanoiron loaded resins (R-nFe). It was found that the reduction follows a kinetic law of first order with respect to Cr(VI) and to the embedded nanoiron. Compared to other similar products, this composite material was found to have comparable performance regarding reaction rates and higher degree of iron utilization. Namely the rate constant for the reduction of Cr(VI), in the presence of 1 mM nZVI, was equivalent to 1.4 h of half-life time at pH 3.2 and increased to 24 h at pH 8.5. The degree of iron utilization was as high as 0.8 mol of reduced Cr(VI) per mole of iron. It was also found that this composite material can be easily regenerated and reused for Cr(VI) reduction without significant loss of efficiency.

Gallic acid (GA), a natural plant polyphenol, was applied as amendment of Fe(III)/persulfate (PS) system for ibuprofen (IBP) degradation in this study. The impacts of all agentia (GA, Fe(III), PS) concentration and initial pH values on IBP removal efficiency were investigated, and their corresponding observed pseudo-first-order rate constants (kₒbₛ) were calculated. The addition of GA has significantly improved elimination efficiency of IBP due to the enhanced Fe(III)/Fe(II) cycle. Electron paramagnetic resonance (EPR) results confirmed that SO₄•⁻, HO• and O₂•⁻ were involved in GA/Fe(III)/PS system. However, quenching experiments further affirmed the impact of SO₄•⁻ and HO• towards IBP decomposition instead of O₂•⁻, with contribution ratio to IBP removal was 69.12% and 30.88%, respectively. SO₄•⁻ was the main radicals formed by directly activation of PS with Fe(II), while HO• was the transformation product of SO₄•⁻. Based on instrumental analysis (stopped-flow UV–vis spectrum and MS) and theoretical calculation, the potential reaction mechanism between GA and Fe(III) in the presence of PS was further proposed. GA complexed with Fe(III) firstly and the Fe(III)-GA complex was then converted into quinone substance, accompanied by the generation of Fe(II). Furthermore, the application of GA extended the optimal pH range to neutral as well, which made it a promising treatment in practical application.

Arsenic (As) is a highly toxic metalloid adversely affecting the environment, human health, and crop productivity. The present study assessed the synergistic effects of salinity and As on photosynthetic attributes, stomatal regulations, and metabolomics responses of the xero-halophyte Salvadora persica to decipher the As-salinity cross-tolerance mechanisms and to identify the potential metabolites/metabolic pathways involved in cross-tolerance of As with salinity. Salinity and As stress-induced significant stomatal closure in S. persica suggests an adaptive response to decrease water loss through transpiration. NaCl supplementation improved the net photosynthetic rate (by +39%), stomatal conductance (by +190%), water use efficiency (by +55%), photochemical quenching (by +37%), and electron transfer rate (54%) under As stress as compared to solitary As treatment. Our results imply that both stomatal and non-stomatal factors account for a reduction in photosynthesis under high salinity and As stress conditions. A total of 64 metabolites were identified in S. persica under salinity and/or As stress, and up-regulation of various metabolites support early As-salinity stress tolerance in S. persica by improving antioxidative defense and ROS detoxification. The primary metabolites such as polyphenols (caffeic acid, catechin, gallic acid, coumaric acid, rosmarinic acid, and cinnamic acid), amino acids (glutamic acid, cysteine, glycine, lysine, phenylalanine, and tyrosine), citrate cycle intermediates (malic acid, oxalic acid, and α-ketoglutaric acid), and most of the phytohormones accumulated at higher levels under combined treatment of As + NaCl compared to solitary treatment of As. Moreover, exogenous salinity increased glutamate, glycine, and cysteine, which may induce higher synthesis of GSH-PCs in S. persica. The metabolic pathways that were significantly affected in response to salinity and/or As include inositol phosphate metabolism, citrate cycle, glyoxylate and dicarboxylate metabolism, amino acid metabolism, and glutathione metabolism. Our findings indicate that inflections of various metabolites and metabolic pathways facilitate S. persica to withstand and grow optimally even under high salinity and As conditions. Moreover, the addition of salt enhanced the arsenic tolerance proficiency of this halophyte.

Understanding how engineered nanoparticles (ENPs) interact with natural organic acids is important to ecological risk assessment of ENPs, but this interaction remains poorly studied. Here, we investigate the dispersion stability, ion release, and toxicity of yttrium oxide nanoparticles (nY2O3) suspensions after exposure to two low molecular weight natural organic acids (LOAs), namely benzoic acid and gallic acid. We find that in the presence of LOAs the nY2O3 suspensions become more stable with surface zeta potential more positive or negative, accompanied by small agglomerated size. LOA interaction with nY2O3 is shown to promote the release of dissolved yttrium from the nanoparticles, depending on the concentrations of LOAs. Toxic effects of the nY2O3 suspensions incubated with LOAs on Scenedesmus obliquus as a function of their mixture levels show three types of signs: stimulation, inhibition, and alleviation. The mechanism of the effects of LOAs on the nY2O3 toxicity may be mainly associated with the degree of agglomeration, particle-induced oxidative stress, and dissolved yttrium. Our results stressed the importance of LOA impacts on the fate and toxicity of ENPs in the aquatic environment.

Various experiments on the isolation of phenolic components from olive mill wastewaters (OMW) have been conducted and several methods have been used separately or in combination. Adsorption is characterized by its low cost and high efficiency. Nonetheless, the high initial cost of common commercial sorbents renders their substitution and the demand for a regeneration procedure essential. The purpose of this study was the investigation of the effectiveness of a coffee industry waste, spent coffee ground (SCG), for the adsorption of OMW bioactive components, after the extraction of its phenolics using emerging methods. The novelty of the present research is based on the holistic exploitation of SCG for the waste management of another food industry by-product, both of which are being produced in high quantities, consisting a potential hazard for the environment. The effects of different factors, such as the solution’s pH (2.0–10.0), temperature (20–60 °C), initial sorbate concentration (50–500 mg/L), and sorbent mass concentration (0.01–0.05 g/mL), on adsorption efficiency, were investigated performing batch experiments. The results were correlated to the effects of the investigated factors on the adsorption of gallic acid, which is one of the most abundant phenolic species in OMW. Adsorption yield reached a maximum of 45.44% after 20 min, at 30 °C and pH of 8.0, with an initial concentration of 162.5 mg/L and sorbent ratio of 0.02 g/mL. Different effects were found during gallic acid adsorption, where the efficiency was higher (70.69%).

Emphysema is associated with an abnormal airspace enlargement distal to the terminal bronchioles accompanied by destructive changes in the alveolar walls and chronic inflammation. Air pollution can cause respiratory diseases such as chronic obstructive pulmonary disease (COPD) and emphysema in urban areas. As a natural antioxidant compound, gallic acid may be effective in controlling inflammation and preventing disease progression. In this research, we investigated the protective role of gallic acid in the inflammatory process and the possible signaling pathway in the elastase-induced emphysema. Forty-eight rats were divided into six different groups including the following: control, gallic acid (7.5, 15, and 30 mg/kg), porcine pancreatic elastase (PPE), and PPE+gallic acid 30 mg/kg. Oxidative stress indexes such as malondialdehyde and antioxidant enzyme activity were measured in all groups. The gene expression levels of heme oxygenase-1 (HO-1), nuclear factor (erythroid-derived 2)-like 2 (Nrf2), and nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) were determined as key regulators of antioxidant and inflammation system. The PPE group showed pulmonary edema and a significant change in arterial blood gas values, which was associated with decreased antioxidant activity of enzymes and changes in NF-κB, HO-1, and Nrf2 gene expression in comparison to the control group. Co-treatment with gallic acid preserved all these changes approximately to the normal levels. The results confirmed that elastase-induced emphysema leads to lung injuries, which are associated with oxidative stress and inflammation. Also, the results suggested that gallic acid as a natural antioxidant agent can modulate the Nrf2 signaling pathway to protect the lung against elastase-induced emphysema. Therefore, we documented the evidence for the importance of NF-κB inhibitors and Nrf2 activators as a target for new treatments in respiratory dysfunction caused by oxidative agents.

Due to the public and environmental health impact of cyanotoxins, investigations have been focused on finding environmental friendly algaecides from aquatic plants. The present study had the objective to evaluate the population control and physiological response of Microcystis aeruginosa (Kützing) Kützing (strain BCCUSP232) exposed to Pistia stratiotes L. extracts. Aqueous and ethanolic extracts of P. stratiotes at different concentrations (10, 25, and 50 mg L⁻¹) were submitted to M. aeruginosa and reduced significantly (p<0.05) the cyanobacterium cell density. The ethanolic extract presented the greatest growth inhibition of the strain at the highest concentration. During exposure to P. stratiotes extracts, intracellular hydrogen peroxide levels, malondialdehyde content, and antioxidant enzymes (peroxidase, catalase, and glutathione S-transferase) activities increased in M. aeruginosa, while total protein concentration decreased when compared to the control group. Superoxide dismutase (SOD) activities presented a sharp decline, suggesting superoxide radical and peroxide accumulation. This implied that SOD was a target for bioactive substance(s) from aqueous and ethanolic extracts of P. stratiotes. Phytochemical screening of the extracts revealed that the ethanolic extract presented 93.36 mg gallic acid equivalent (GAE) per gram dry weight (g⁻¹ DW) total polyphenols and 217.33 mg rutin equivalent (RE) per gram dry weight total flavonoids, and for the aqueous extract, 5.19 mg GAE g⁻¹ DW total polyphenols and 11.02 mg RE g⁻¹ DW total flavonoids were detected. Gas chromatography (GC)/mass spectrometry (MS) analyses of the ethanolic and aqueous extracts presented palmitic acid ethyl ester as major allelochemical. In view of these results, it can be concluded that P. stratiotes showed potential in controlling M. aeruginosa populations.

The present study focused on the full valorization of the tomato by-product, also known as tomato pomace consisting mainly of tomato peels and tomato seeds, by recovering natural antioxidants and edible oil, and subsequently reutilizing the leftover solid residues for the production of low-cost biosorbent. The tomato peel extract recovered using ethanol as food-grade solvent contained high phenol and flavonoid contents (199.35 ± 0.35-mg gallic acid equivalents (GAE)/g and 102.10 ± 0.03-mg quercetin equivalent (QE)/g, respectively). Even its lower content of lycopene (3.67 ± 0.04 mg/100 g), tomato peel extract showed potent antioxidant activity and can be therefore used as natural antioxidants either for food or cosmetic applications. High nutritional quality edible oil (17.15%) was extracted from tomato seeds and showed richness in unsaturated fatty acids (74.62%), with linoleic acid being the most abundant polyunsaturated fatty acid (49.70%). After recovery of these valuable compounds, the extraction solid leftovers were used to produce low-cost biosorbent tested for dye removal. Results showed that the highest biosorption yields were increasingly attributed to the acidic, direct, anthraquinone, then reactive dyes. Overall, the obtained results strongly support the complete utilization of tomato pomace for the recovery of valuable compounds and the sequential production of low-cost biosorbent.

Diverse aromatic mediators have often been used to increase the degradation of organic pollutants by Fenton reaction (Fe²⁺ + H₂O₂ → Fe³⁺ + HO● + HO⁻). The presence of reducing mediators can minimize the accumulation of Fe³⁺ in solution, which leads to accelerated Fe²⁺ regeneration and enhances the generation of reactive oxygen species, such as the HO● radical, i.e., the strongest oxidant in Fenton-based processes. On the other hand, a few non-reducing compounds can be converted into reducing intermediates during reactions, in addition to assisting degradation processes. Therefore, the influence of aromatic mediators, reducers and non-reducers, on decolorization kinetics of Bismarck Brown Y (BBY) dye oxidized by Fenton processes (Fe²⁺/H₂O₂, Fe³⁺/H₂O₂) has been investigated herein by using data from a previous study that had been developed by the present research group. In general, the second-order reaction kinetic model was better fit to the experimental data. Improvements in apparent second-order rate constants (k₂) were observed due to the presence of mediators. Reducers were more effective than non-reducers in increasing k₂ values. In another kinetic model, BMG, maximum oxidation capacity was increased due to the presence of mediators. In a new set of experiments, a decrease in apparent activation energy was verified due to introducing mediators into reactions initially containing either Fe²⁺ or Fe³⁺ as catalysts to oxidize BBY at different temperatures. This indicates that the tested mediators, two reducers (hydroquinone, gallic acid) and a non-reducer (salicylic acid), can decrease the energy barrier to allow Fenton reaction to oxidize dyes more effectively.

A multi-herbal combination (MHC) of five herbs, namely Punica granatum L., Putranjiva roxburghii Wall., Swertia chirata Buch.-Ham., Tinospora cordifolia (Willd.) Miers and Trigonella corniculata L. was assessed against the paracetamol-induced acute hepatotoxicity in female Wistar rats. The animals were randomly assorted into seven groups with six animals in each group. The rats were pre-treated with MHC (50, 100, and 200 mg/kg bw) and silymarin (50 mg/kg bw) once daily for seven consecutive days via oral route followed by administration of paracetamol (3 g/kg bw) on day 7, an hour after the last administration of MHC and silymarin. It was observed that MHC administration significantly (p ≤ 0.05) overturned the paracetamol-induced increase in serum liver function biomarkers (serum glutamic oxaloacetic transaminase, serum glutamic pyruvic transaminase, alkaline phosphatase, and total bilirubin), phase I reaction enzymes (NADPH-cytochrome P450 reductase and NADH-cytochrome b5 reductase), and oxidant biomarkers (lactate dehydrogenase, lipid peroxidation, lipid hydroperoxides, and protein content). MHC administration also reinstated the paracetamol-induced significant decrease (p ≤ 0.05) in haematological indices (haematocrit, haemoglobin, red and white blood cells, and platelets), phase II reaction enzymes (glutathione-S-transferase and DT-diaphorase), membrane-bound enzymes (Na⁺/K⁺-ATPase, Ca²⁺-ATPase, and Mg²⁺-ATPase), and antioxidant biomarkers (reduced glutathione, superoxide dismutase, catalase, glutathione peroxidase, and glutathione reductase). Overall, MHC at 200 mg/kg bw dose significantly (p ≤ 0.05) sheltered the red blood cells from the assault of free radicals, stabilized the structural and functional integrity of hepatocytes, hindered acetaminophen (APAP) biotransformation to its toxic metabolites, and endorsed conjugating abilities to detoxify toxic entities. Furthermore, MHC significantly (p ≤ 0.05) activated enzymatic machinery to scavenge/inhibit the formation of reactive oxygen species, regulated nucleic acid metabolism, surface potential, and membrane fluidity, attenuated tissue breakdown, quenched peroxyl radicals, and provided protection against tissue injury. The necroinflammatory scores revealed strong evidence of MHC (200 mg/kg bw) effectiveness against the paracetamol-induced hepatotoxicity in rats at p ≤ 0.05. The synergistic effect of major inherent phytoconstituents (kaempferol, ellagic acid, and gallic acid), detected by HPLC-PDA, in MHC might have overturned the paracetamol-induced biochemical toxic alterations in rat liver.