The pomegranate (Punica granatum) fruit peel exposed to mixture air pollutants were collected from two sites with different air quality around the industrial area of Gabes city, Tunisia. The first site presented the ‘Polluted site’, which is situated in the oasis close to the industrial area. While, the second site referred to the ‘Control site’ located at 37 km from the industrial area. Using HPLC ES-MS, 21 phenols were identified and quantified in methanol extract from pomegranate fruit peel. The results showed that various phytochemical substances, including phenols acids and flavonoids, were identified and quantified in the peel extract. The polyphenols content and the flavonoids contents in peel obtained from polluted site were higher than that collected from the control site. The concentrations of the identified polyphenols were ranged between 0.39 and 7803.68 mg/ kg DW. The stimulation of some free phenolic compounds such syringic acid, transfrulic acid, epicatechin, rutin and quercetin was enregistred only in peel collected from contaminated environment. The quali-qualitative changes between sites are probably related to the difference in the air quality. The increase of polyphenols could be implicated during adaptive mechanisms under air pollution. Phenolic composition changes in Punica granatum peel could be also suggested as useful approach air pollution monitoring.

Increasing rates of commercialization and industrialization have led to the comprehensive evaluation of toxic effects of microplastics on crop plants. However, research on the impact of functionalized polystyrene nanoplastics on the toxicity of heavy metals remains limited. This study investigated the effects of polystyrene, carboxy-modified polystyrene, and amino-modified polystyrene on lead (Pb) toxicity in dandelion seedlings. The results showed that carboxy -modified polystyrene with a negative charge absorbed more Pb²⁺ than polystyrene and amino-modified polystyrene, and their maximum adsorption amounts were 5.328, 0.247, and 0.153 μg g⁻¹, respectively. The hydroponic experiment demonstrated that single amino-modified polystyrene was more toxic to dandelion seedlings than polystyrene and carboxy-modified polystyrene. The presence of Pb²⁺ was found to increase antioxidant enzymes (superoxide dismutase and catalase) and non-antioxidant enzymes (glutathione and ascorbic acid) activities in response to excessive reactive oxygen species in dandelion leaves and roots treated with polystyrene and carboxy-modified polystyrene, while it did not change much when amino-modified polystyrene was added. Interestingly, compared with single Pb²⁺, the addition of amino-modified polystyrene with positive charges induced an obvious decrease in the above parameters; however, they declined slightly in the treatments with polystyrene and carboxy-modified polystyrene despite a stronger adsorption capacity for Pb²⁺. Similarly, the bioactive compounds, including flavonoids, polyphenols, and polysaccharides in dandelion, showed a scavenging effect on O₂⁻ and H₂O₂, thereby inhibiting the accumulation and reducing medicinal properties. This study found that the effects of microplastics on the uptake, distribution, and toxicity of heavy metals depended on the nanoparticle surface charge.

Quinone is the important redox functional group for electron transfer capacity (ETC) of humic acid (HA). Lignin, as major component in corn straw, can be decomposed into phenol monomers, then oxidation into quinones for synthesis of HA during composting process. However, it is still unclear that the effects of type and variation characteristics of phenol monomers on redox characteristics of HA during straw composting process. In this study, p-hydroxybenzoic acid (P1), vanillic acid (P2), syringic acid (P3), p-hydroxy benzaldehyde (P4), 4-coumaric acid (P5), 4-hydroxyacetophenone (P6), ferulic acid (P7) and 4-hydroxy-3-methylacetophenone (P8) were recognized and clustered into three groups. The concentration of polyphenol presented a significant downward trend during the straw composting process. Based on the relationships among phenol monomers to ETC, electron donating capacity (EDC), electron accepting capacity (EAC) and quinone, we found that P1, P2, P3, P5 and P7 were significantly related to ETC, EDC and EAC of HA (P < 0.05). Furthermore, NH₄⁺-N and NO₃⁻-N were the main micro-environmental factors linking to ETC-related phenol monomers and redox characteristics of HA in straw composts (P < 0.05). Finally, two groups of core microflora that promoting the ETC-related phenol monomers and NH₄⁺-N, and ETC-related phenol monomers and NO₃⁻-N were identified by Mantel test, respectively. This study contributes a new insight for polyphenol way for redox capacity of HA in traditional composting and utilization of straw compost in contaminated environments.

An emerging stress of pesticides in plant and soil is closely watched as it affects crop antioxidant systems, nutritional quality, and flavor. Although selenium (Se) can enhance the resistance of plants, the protective mechanism of nanoselenium is still not known under the long-term pesticide stress in tea trees. In this study, we investigated the potential effects of foliar application of nanoselenium for a two-year field experiment on tea plants under pesticide-induced oxidative stress. Compared to control, nano-Se (10 mg/L) markedly enhanced the protein, soluble sugar, carotenoid, tea polyphenols, and catechins contents. High levels of theanine, glutamic acid, proline, and arginine were found to be induced most likely by adjusting the GS-GOGAT cycle. Se-supplementation may promote tea leaves’ secondary metabolism, thus increasing the accumulation of total phenols and flavonoids (apigenin, kaempferol, quercetin, myricetin, and rutin). It also minimized the accumulation of malondialdehyde, hydrogen peroxide, and superoxide anion by activating the antioxidants enzymes including in the AsA-GSH cycle. Selenium-rich tea also showed better fragrance and flavor. In summary, nano-Se can ameliorate the nutrients quality and abiotic stresses resistance of crops.

Phycoremediation technologies significantly contribute to solving serious problems induced by heavy metals accumulation in the aquatic systems. Here we studied the mechanisms underlying Al stress tolerance in two diazotrophic cyanobacterial species, to identify suitable species for Al phycoremediation. Al uptake as well as the physiological and biochemical responses of Anabaena laxa and Nostoc muscorum to 7 days Al exposure at two different concentrations i.e., mild (100 μM) and high dose (200 μM), were investigated. Our results revealed that A. laxa accumulated more Al, and it could acclimatize to long-term exposure of Al stress. Al induced a dose-dependent decrease in photosynthesis and its related parameters e.g., chlorophyll content (Chl a), phosphoenolpyruvate carboxylase (PEPC) and Ribulose‒1,5‒bisphosphate carboxylase/oxygenase (RuBisCo) activities. The affect was less pronounced in A. laxa than N. muscorum. Moreover, Al stress significantly increased cellular membrane damage as indicated by induced H₂O₂, lipid peroxidation, protein oxidation, and NADPH oxidase activity. However, these increases were lower in A. laxa compared to N. muscorum. To mitigate the impact of Al stress, A. laxa induced its antioxidant defense system by increasing polyphenols, flavonoids, tocopherols and glutathione levels as well as peroxidase (POX), catalase (CAT), glutathione reductase (GR) and glutathione peroxidase (GPX) enzymes activities. On the other hand, the antioxidant increases in N. muscorum were only limited to ascorbate (ASC) cycle. Overall, high biosorption/uptake capacity and efficient antioxidant defense system of A. laxa recommend its feasibility in the treatment of Al contaminated waters/soils.

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.

Heavy metal accumulation in agricultural land causes crop production losses worldwide. Metal homeostasis within cells is tightly regulated. However, homeostasis breakdown leads to accumulation of reactive oxygen species (ROS). Overall plant fitness under stressful environment is determined by coordination between roots and shoots. But little is known about organ specific responses to heavy metals, whether it depends on the metal category (redox or non-redox reactive) and if these responses are associated with heavy metal accumulation in each organ or there are driven by other signals. Maize seedlings were subjected to sub-lethal concentrations of four metals (Zn, Ni, Cd and Cu) individually, and were quantified for growth, ABA level, and redox alterations in roots, mature leaves (L1,2) and young leaves (L3,4) at 14 and 21 days after sowing (DAS). The treatments caused significant increase in endogenous metal levels in all organs but to different degrees, where roots showed the highest levels. Biomass was significantly reduced under heavy metal stress. Although old leaves accumulated less heavy metal content than root, the reduction in their biomass (FW) was more pronounced. Metal exposure triggered ABA accumulation and stomatal closure mainly in older leaves, which consequently reduced photosynthesis. Heavy metals induced oxidative stress in the maize organs, but to different degrees. Tocopherols, polyphenols and flavonoids increased specifically in the shoot under Zn, Ni and Cu, while under Cd treatment they played a minor role. Under Cu and Cd stress, superoxide dismutase (SOD) and dehydroascorbate reductase (DHAR) activities were induced in the roots, however ascorbate peroxidase (APX) activity was only increased in the older leaves. Overall, it can be concluded that root and shoot organs specific responses to heavy metal toxicity are not only associated with heavy metal accumulation and they are specialized at the level of antioxidants to cope with.

Metalaxyl is a broad-spectrum chiral fungicide that used for the protection of plants, however extensive use of metalaxyl resulted in serious environmental problems. Thus, a study on the detoxification mechanism in algae/cyanobacteria and their ability for phycoremediation is highly recommended. Here, we investigated the physiological and biochemical responses of two cyanobacterial species; Anabaena laxa and Nostoc muscorum to R-metalaxyl toxicity as well as their ability as phycoremediators. Two different levels of R-metalaxyl, at mild (10 mg/L) and high dose (25 mg/L), were applied for one-week. We found that A. laxa absorbed and accumulated more intracellular R-metalaxyl compared to N. muscorum. R-metalaxyl, which triggered a dose-based reduction in cell growth, photosynthetic pigment content, and photosynthetic key enzymes’ activities i.e., phosphoenolpyruvate carboxylase (PEPC) and ribulose‒1,5‒bisphosphate carboxylase/oxygenase (RuBisCo). These decreases were significantly less pronounced in A. laxa. On the other hand, R-metalaxyl significantly induced oxidative damage markers, e.g., H₂O₂ levels, lipid peroxidation (MDA), protein oxidation and NADPH oxidase activity. However, these increases were also lower in A. laxa compared to N. muscorum. To alleviate R-metalaxyl toxicity, A. laxa induced the polyphenols, flavonoids, tocopherols and glutathione (GSH) levels as well as peroxidase (POX), glutathione peroxidase (GPX), glutathione reductase (GR) and glutathione-s-transferase (GST) enzyme activities. On the contrary, the significant induction of antioxidants in N. muscorum was restricted to ascorbate, catalase (CAT) and ascorbate peroxidase (APX), dehydroascorbate reductase (DHAR) enzyme activities. Although A. laxa accumulated more R-metalaxyl, it experienced less stress due to subsequent induction of antioxidants. Therefore, A. laxa may be a promising R-metalaxyl phycoremediator. Our results provided basic data for understanding the ecotoxicology of R-metalaxyl contamination in aquatic habitats and the toxicity indices among cyanobacteria.

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.