The main intent of the current research was to appraise if combined application of hydrogen sulfide (H₂S, 0.2 mM) and silicon (Si 2.0 mM) could improve tolerance of tomato plants to arsenic (As as sodium hydrogen arsenate heptahydrate, 0.2 mM) stress. Plant growth, chlorophylls (Chl), PSII maximum efficiency (Fv/Fm), H₂S concentration and L-cysteine desulfhydrase activity were found to be suppressed, but leaf and root As, leaf proline content, phytochelatins, malondialdehyde (MDA) and H₂O₂ as well as the activity of lipoxygenase (LOX) increased under As stress. H₂S and Si supplied together or alone enhanced the concentrations of key antioxidant biomolecules such as ascorbic acid, and reduced glutathione and the activities of key antioxidant system enzymes including catalase (CAT), superoxide dismutase (SOD), dehydroascorbate reductase (DHAR), glutathione reductase (GR), and glutathione S-transferase (GST). In comparison with individual application of H₂S or Si, the joint supplementation of both had better effect in improving growth and key biochemical processes, and reducing tissue As content, suggesting a putative collaborative role of both molecules in improving tolerance to As-toxicity in tomato plants.

Metal detoxification in plants is a complex process that involves different mechanisms, such as the retention of metals to the cell wall and their chelation and subsequent compartmentalization in plant vacuoles. In order to identify the mechanisms involved in metal accumulation and tolerance in Betula pubescens, as well as the role of mycorrhization in these processes, mycorrhizal and non-mycorrhizal plants were grown in two industrial soils with contrasting concentrations of heavy metals.Mycorrhization increased metal uptake at low metal concentrations in the soil and reduced it at high metal concentrations, which led to an enhanced growth and biomass production of the host when growing in the most polluted soil. Our results suggest that the sequestration on the cell wall is the main detoxification mechanism in white birch exposed to acute chronic metal-stress, while phytochelatins play a role mitigating metal toxicity inside the cells. Given its high Mn and Zn root-to-shoot translocation rate, Betula pubescens is a very promising species for the phytoremediation of soils polluted with these metals.

Antimony (Sb) is a contaminant of increased prevalence in the environment, but there is little knowledge about the mechanisms of its uptake and translocation within plants. Here, we applied for the synchrotron based X-ray absorption near-edge structure (XANES) spectroscopy to analyze the speciation of Sb in roots and shoots of rye grass (Lolium perenne L. Calibra). Seedlings were grown in nutrient solutions to which either antimonite (Sb(III)), antimonate (Sb(V)) or trimethyl-Sb(V) (TMSb) were added. While exposure to Sb(III) led to around 100 times higher Sb accumulation in the roots than the other two treatments, there was no difference in total Sb in the shoots. Antimony taken up in the Sb(III) treatment was mainly found as Sb-thiol complexes (roots: >76% and shoots: 60%), suggesting detoxification reactions with compounds such as glutathione and phytochelatins. No reduction of accumulated Sb(V) was found in the roots, but half of the translocated Sb was reduced to Sb(III) in the Sb(V) treatment. Antimony accumulated in the TMSb treatment remained in the methylated form in the roots. By synchrotron based XANES spectroscopy, we were able to distinguish the major Sb compounds in plant tissue under different Sb treatments. The results help to understand the translocation and transformation of different Sb species in plants after uptake and provide information for risk assessment of plant growth in Sb contaminated soils.

The rootless duckweed Wolffia globosa can accumulate and tolerate relatively large amounts of arsenic (As); however, the underlying mechanisms were unknown. W. globosa was exposed to different concentrations of arsenate with or without l-buthionine sulphoximine (BSO), a specific inhibitor of γ-glutamylcysteine synthetase. Free thiol compounds and As(III)–thiol complexes were identified and quantified using HPLC – high resolution ICP-MS – accurate mass ESI-MS. Without BSO, 74% of the As accumulated in the duckweed was complexed with phytochelatins (PCs), with As(III)–PC₄ and As(III)–PC₃ being the main species. BSO was taken up by the duckweed and partly deaminated. The BSO treatment completely suppressed the synthesis of PCs and the formation of As(III)–PC complexes, and also inhibited the reduction of arsenate to arsenite. BSO markedly decreased both As accumulation and As tolerance in W. globosa. The results demonstrate an important role of PCs in detoxifying As and enabling As accumulation in W. globosa.

Mineral sunscreen nanocomposites, based on a nano-TiO₂ core, coated with aluminium hydroxide and dimethicone films, were submitted to an artificial ageing process. The resulting Altered TiO₂ Nanocomposites (ATN) were then tested in the liquid phase on the plant model Vicia faba, which was exposed 48 h to three nominal concentrations: 5, 25 and 50 mg ATN/L. Plant growth, photosystem II maximum quantum yield, genotoxicity (micronucleus test) and phytochelatins levels showed no change compared to controls. Oxidative stress biomarkers remained unchanged in shoots while in roots, glutathione reductase activity decreased at 50 mg ATN/L and ascorbate peroxidase activity decreased for 5 and 25 mg ATN/L. Nevertheless, despite the weak response of biological endpoints, ICP-MS measurements revealed high Ti and Al concentrations in roots, and X-ray fluorescence micro-spectroscopy revealed titanium internalization in superficial root tissues. Eventual long-term effects on plants may occur.

Arsenate tolerance, As accumulation and As-induced phytochelatin accumulation were compared in populations of Silene paradoxa, one from a mine site enriched in As, Cu and Zn, the other from an uncontaminated site. The mine population was significantly more arsenate-tolerant. Arsenate uptake and root-to-shoot transport were slightly but significantly higher in the non-mine plants. The difference in uptake was quantitatively insufficient to explain the difference in tolerance between the populations. As accumulation in the roots was similar in both populations, but the mine plants accumulated much less phytochelatins than the non-mine plants. The mean phytochelatin chain length, however, was higher in the mine population, possibly due to a constitutively lower cellular glutathione level. It is argued that the mine plants must possess an arsenic detoxification mechanism other than arsenate reduction and subsequent phytochelatin-based sequestration. This alternative mechanism might explain at least some part of the superior tolerance in the mine plants. Neither decreased uptake nor phytochelatins seem to play a role in the As tolerance in Silene paradoxa.

Plants detoxify toxic metal(loid)s by accumulating diverse metabolites. Beside scavenging excess reactive oxygen species (ROS) induced by metal(loid)s, some metabolites chelate metal(loid) ions. Classically, thiol-containing compounds, especially glutathione (GSH) and phytochelatins (PCs) are thought to be the major chelators that conjugate with metal(loid)s in the cytoplasm followed by transport and sequestration in the vacuole. In addition to this classical detoxification pathway, a role for secondary metabolites in metal(loid) detoxification has recently emerged. In particular, anthocyanins, a kind of flavonoids with ROS scavenging potential, contribute to enhanced arsenic tolerance in several plant species. Evidence is accumulating that, in analogy to GSH and PCs, anthocyanins may conjugate with arsenic followed by vacuolar sequestration in the detoxification event. Exogenous application or endogenous accumulation of anthocyanins enhances arsenic tolerance, leading to improved plant growth and productivity. The application of some plant hormones and signaling molecules stimulates endogenous anthocyanin synthesis which confers tolerance to arsenic stress. Anthocyanin biosynthesis is transcriptionally regulated by several transcription factors, including myeloblastosis (MYBs). The light-regulated transcription factor elongated hypocotyl 5 (HY5) also affects anthocyanin biosynthesis, but its role in arsenic tolerance remains elusive. Here, we review the mechanism of arsenic detoxification in plants and the potential role of anthocyanins in arsenic tolerance beyond the classical points of view. Our analysis proposes that anthocyanin manipulation in crop plants may ensure sustainable crop yield and food safety in the marginal lands prone to arsenic pollution.

The main objective of the study was to assess if joint application of melatonin (MT, 0.1 mM) and salicylic acid (SA 0.5 mM) could improve tolerance of pepper plants to arsenic (As) as sodium hydrogen arsenate heptahydrate (0.05 mM). The imposition of arsenic stress led to accumulation of As in roots and leaves, and increased contents of leaf proline, phytochelatins, malondialdehyde (MDA) and H₂O₂, but it reduced plant biomass, chlorophylls (Chl), PSII maximum efficiency (Fv/Fm) and leaf water potential. Melatonin and SA applied jointly or alone enhanced nitrogen metabolism by triggering the activities of glutamate synthase, glutamine synthetase, and nitrite reductases and nitrate. In comparison with a single treatment of MT or SA, the joint treatment of MT and SA had better impact on enhancing growth and key biological events and decreasing tissue As content. This clearly shows a cooperative function of both agents in enhancing tolerance to As-toxicity in pepper plants.

The liverwort Lunularia cruciata was collected from the town of Acerra, in the heart of the so-called ‘Land of Fires’ a large area in the eastern part of Campania region of Italy affected by burning of waste and fraudulent dumping and one of the vertices of the “Italian Triangle of Death” so said for the high incidence and mortality from tumors. The data obtained from these samples were compared with samples collected in two other sites representing two different environmental conditions. The soil below the samples, and gametophytes, were collected and analyzed for the concentration of Al, As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, V. DNA damage, Reactive Oxygen Species production and localization, activity of antioxidant enzymes and presence of chelating molecules were investigated. All biomarkers provided an answer closely related to the pollution conditions at the 3 sites. We discuss the data considering the possibility of using these biological changes as environmental pollution biomarkers. Finally, it is underlined the importance of phytochelatins due to of their specificity for metal pollution.

Phytochelatins (PCs) play a vital role in the tolerance and enrichment of cadmium (Cd) in higher plants by chelating with Cd2+. The aim of this study was to perform a full-scale metabolomics analysis of metabolic responses highly correlated with PCs generation. These metabolites and metabolic pathways were expected to promote PCs generation and further optimize Cd absorption in plants. In the current study, Amaranthus hypochondriacus, a potential species for phytoremediation, was first adopted to investigate physiological responses to Cd stress via LCMS/MS-based metabolomics and the HPLC based determination of thiol compounds. The results showed that the leaves of A. hypochondriacus under high Cd stress accumulated 40 times the amount of Cd compared to the leaves of the plants not under Cd stress and had an increased content of three types of PCs. Metabolomics qualitatively identified 12084 substances in total, among which 41 were significantly different metabolites (SDMs) between the two groups and involved in 7 metabolic pathways. Among the SDMs, 12 metabolites were highly linearly correlated with PCs involved in three pathways (Val, Leu and Ile biosynthesis; Ala, Asp and Glu metabolism; and Arg and Pro metabolism). These results provide an innovative method to promote PCs synthesis for the restoration of Cd-contaminated-soil.