One-dimensional (1-D) and two-dimensional (2-D) nuclear magnetic resonance (NMR)-based metabolomics was used to investigate the toxic mode of action (MOA) of endosulfan, an organochlorine pesticide, and its degradation product, endosulfan sulfate, to Eisenia fetida earthworms in soil. Three soil concentrations (0.1, 1.0 and 10.0 mg/kg) were used for both endosulfan and endosulfan sulfate. Both earthworm coelomic fluid (CF) and tissues were extracted and then analyzed using 1H and 1H–13C NMR techniques. A similar separation trajectory was observed for endosulfan and endosulfan sulfate-exposed earthworms in the mean principal component analysis (PCA) scores plot for both the earthworm CF and tissue extracts.A neurotoxic and apoptotic MOA was postulated for both endosulfan and endosulfan sulfate exposed earthworms as significant fluctuations in glutamine/GABA–glutamate cycle metabolites and spermidine were detected respectively. This study highlights the application of NMR-based metabolomics to understand molecular-level toxicity of persistent organochlorine pesticides and their degradation products directly in soil.

Nickel is a ubiquitous heavy-metal pollutant in lakes and severely affects aquatic organisms. Aquatic plants are often initially linked to having heavy metal contents and further are proposed as phytoremediation agent to remove heavy metal from water. Although the toxic effects of nickel on aquatic plants are thoroughly explored, the effective investigation to increase Ni tolerance is still in its infancy. The role of rare-earth elements (REEs) in plant resisting heavy-metal pollution has recently received considerable interest. To explore the physiological effects of REEs on Potamogeton crispus under Ni stress, we explored whether or not the additive exposure to low-dose yttrium (Y; 2.5 μM) promotes the polyamine metabolism, antioxidation, and photosynthesis performance of P. crispus under Ni stress values of 0, 50, 100, 150, and 200 μM. Results showed that Y exposure did not influence Ni bioaccumulation in P. crispus. Furthermore, Y exposure alleviated the adverse effects of Ni stress to convergent degrees because Y positively converts putrescine into spermidine and spermine, inhibits oxidative stress, increases the total chlorophyll content, and maximum/potential quantum efficiency of photosystem II. We concluded that low-dose Y can positively regulate polyamine transformation, inhibit oxidative stress, stimulate photosynthesis, and finally promote the resist ability of P. crispus to nickel stress. Thus, REEs have potential to be applied in regulating submerged plant tolerance to aquatic heavy-metal pollution.

The open top chamber (OTC) method was used in a farmland to study the influence of different levels of O3 concentrations (40 ppb, 80 ppb and 120 ppb) on the enzymatic activity and metabolite contents of the antioxidation system of the winter wheat leaves during the jointing, heading and milk stage. The protective effect of exogenous spermidine (Spd) against the antioxidation of winter wheat under the O3 stress was investigated. With the increasing O3 concentrations and fumigation time, the injuries of the winter wheat leaves were observed to be more serious. For instance, when the O3 concentration reached 120 ppb, the activities of superoxide dismutase (SOD), catalase (CAT), ascorbate peroxidase (APX) and nitrate reductase (NR) in the jointing stage decreased by 50.3%, 64.9%, 75.5% and 92.9%, respectively; peroxidase (POD) and glutathione reductase (GR) increased by 45.1% and 80.5%, respectively; the contents of malondialdehyde (MDA), ascorbic acid (AsA) and reduced glutathione (GSH) increased by 314.3%, 8.4% and 31.7%, respectively; and the soluble protein (SP) content decreased by 47.5%. The O3 stress also had significant impact on the contents of proline (Pro), NO3––N and NH4+–N of the winter wheat leaves. During the heading stage, when the O3 concentration was 40 ppb and 80 ppb, the content of Pro was 163.9% and 173.2% higher than that in the control group, respectively. But under 120 ppb, it was decreased by 42.4%. Exogenous application of Spd increased the activities of SOD, POD, CAT, APX and GR, as well as the contents of GSH and SP, but decreased the contents of MDA and AsA. This indicates that Spd is an effective antioxidant to relieve the O3 stress on winter wheat leaves, thereby might be applicable to protect winter wheat from the harm of O3.

Plants used for phytoextraction of metals need to tolerate toxicity conditions. Potassium (K) participates in physiological and biochemical processes that can alleviate toxicity by heavy metals, including cadmium (Cd). This study aimed to evaluate the effect of K on photosynthesis and on the changes in the antioxidant system of tanzania guinea grass [Panicum maximum Jacq. cv. Tanzania (syn. Megathyrsus maximus (Jacq,) B.K. Simon & S.W.L. Jacobs)] under Cd toxicity. Plants were grown in a greenhouse, in nutrient solution, in a randomized complete block design, arranged in a 3 × 4 factorial, with three replications. Plants were supplied with three K levels (0.4 [K deficiency], 6.0, and 11.6 mmol L⁻¹) and exposed to four Cd levels (0.0, 0.5, 1.0, and 1.5 mmol L⁻¹). Two plant growth periods were evaluated. High Cd level (1.5 mmol L⁻¹) led to a reduction in net photosynthesis (76%) by causing low stomatal conductance and losses in quantum efficiency of photosystem II. However, high K supply (11.6 mmol L⁻¹) increased the net photosynthesis by 15% in plants exposed to 1.0 mmol L⁻¹ Cd, due to upregulation of proline synthesis. Cd toxicity resulted in increases in lipid peroxidation and hydrogen peroxide concentration (35 and 50%; 25 and 30%, at first and second harvest, respectively) and reduction by 80–100% in activity of the antioxidant enzymes: superoxide dismutase, catalase, ascorbate peroxidase, guaiacol peroxidase, and glutathione reductase in the shoots of the grass. However, the high K supply (11.6 mmol L⁻¹) increased the activity of these enzymes (about 50–75%) and reduced lipid peroxidation (36%), restoring cellular homeostasis. Moreover, high K supply promoted a 25% increase in spermidine and spermine concentrations in the shoots. Therefore, K reduced the Cd-induced oxidative stress and increased the net photosynthesis in tanzania guinea grass by increasing the activity of antioxidant enzymes and proline and polyamines synthesis, which enhances the tolerance of this grass to Cd.

Biogenic amines (BAs) are natural toxicants produced during the metabolism of their precursor amino acids or due to the proteolytic activities of some microorganisms. The objective of this study was to estimate the formed BAs in five types of the most commonly consumed and retailed cheese in Egypt. The examined cheese types included Feta, Karish, Mozzarella, Rumy, and Mish. Besides, the total mesophilic (TMC) and total psychrophilic (TPsC) bacterial counts were investigated. Furthermore, the estimated daily intakes (EDI) of BAs via the ingestion of various types of cheese were calculated, and their potential health risks were discussed. The achieved results indicated the formation of histamine (HIS), tyramine (TYR), cadaverine (CAD), putrescine, spermine, and spermidine at different concentrations. Except for Feta cheese, all samples (100%) of other cheese types had HIS concentrations higher than the established maximum permissible limits. Mish cheese contained the highest concentrations of total BAs, particularly, HIS, TYR, and CAD. TBA content showed significant positive correlations with TMC in the examined cheese types. The recorded EDI values of the different BAs in the current study would not have adverse effects. However, excessive consumption of cheese contaminated with BA might have serious health implications such as symptoms of histamine poisoning. Therefore, the adoption of strict hygienic measures during the production, storage, and distribution of cheese is highly recommended to reduce the formation of BAs in cheese.

In order to study potential antioxidant defense mechanisms, the effects of increasing concentrations of lead (Pb) on polyamines (PAs), various thiols, vitamins C and E, and proline contents in sterilized seedlings of Nymphoides peltata (S.G. mel.) Kuntze were investigated after 5 days of exposure. The levels of total putrescine (Put), spermidine (Spd), and spermine (Spm) decreased significantly, while the ratio of (Spd + Spm)/Put first increased but then declined as the concentration of Pb increased. The trends for free, perchloric acid soluble-conjugated (PS-conjugated), and perchloric acid insoluble-bound (PIS-bound) PAs were similar to the trend seen for total PAs. Moreover, reduced glutathione (GSH), nonprotein thiols (NP-SH), phytochelatins (PCs), and vitamin C were induced at high Pb concentrations. No significant change was observed in vitamin E. An initial decline in proline content was followed by an increase as the Pb concentration rose. The reduced level of Put and elevated contents of GSH, NP-SH, PCs, vitamin C, and proline were found to be associated with antioxidant efficiency, which supports the hypothesis that they could play a significant role in the adaptation mechanisms of N. peltatum under Pb stress.

INTRODUCTION: The goal of the present study was to investigate the effects of Cu contamination on the above-mentioned biochemical and physiological parameters in order to explore possible prevention strategies against heavy metal stress. MATERIALS AND METHODS: Effects of copper (Cu) on the roots of Sagittaria sagittifolia L. were studied after 10 days of treatment at five concentration levels. The accumulation of Cu, the generation rate of O₂ ·–, the contents of thiobarbituric acid reactive substances (TBARS) and polyamines, as well as the activities of arginine decarboxylase (ADC) and polyamine oxidase (PAO) in the roots were measured and analyzed. RESULTS AND DISCUSSION: It was observed that endogenous Cu content increased in roots of S. sagittifolia L. in a concentration-dependent manner, along with an increased production of O₂ ·–. TBARS content increased progressively up to 5 μmol l⁻¹ Cu. A constant increase in ADC activity was also observed. The results indicated that lower Cu concentrations (2.5 and 5 μmol l⁻¹, respectively) had greater enhancing effect on the contents of free Put and perchloric acid-soluble conjugated (PS-conjugated) putrescine (Put), while Cu treatments at different concentration levels had similar enhancing effect on the content of perchloric acid-insoluble bound Put. In total, Put content in each Cu-treated group was higher than that in the control group. PAO activity was inhibited up to 10 μmol l⁻¹ Cu but enhanced at higher Cu concentrations (20 and 40 μmol l⁻¹). This explained the initial rise and subsequent decline of the contents of all forms of spermine (Spm), free and PS-conjugated spermidine (Spd). However, with the increase of Cu concentration, total Spm content increased gradually while total Spd content decreased. Our results suggest that Cu is phytotoxic to the roots of S. sagittifolia L. at high concentrations, and that the increased Spm level is not sufficient to resist Cu-induced oxidative damages.

The objective of the present investigation was to consider the effectiveness of exogenous silicate supplementation in reviving the arsenate imposed alterations on pigment content, Hill activity, photosynthetic parameters, sugar metabolism, polyamine, and ion contents in wheat (Triticum aestivum L. cv. PBW-343) seedlings. Experiments were conducted under different levels of arsenate (0, 25 μM, 50 μM, and 100 μM) in combination with silicate (0, 5 mM) in a hydroponic environment with modified Hoagland’s solution for 21 days to determine the ameliorative role of silicon (Si). Arsenate exposure led to a decline in chlorophyll content by 28% and Hill activity by 30% on an average along with photosynthetic parameters. Activity of starch phosphorylase increased causing a subsequent decrease in starch contents by 26%. Degradation of starch enhanced sugar contents by 61% in the test cultivar. Dose-dependant increments in the activities of carbohydrate metabolizing enzymes viz., sucrose synthase, sucrose phosphate synthase, and acid invertase were also noted. Putrescine content was significantly enhanced along with a consequent decline in spermidine and spermine contents. The macro- and micronutrient contents declined proportionally with arsenate imposition. Conversely, silicate amendments irrespective of all arsenate concentrations brought about considerable alterations in all parameters tested with respect to arsenate treatment alone. Marked improvement in pigment content and Hill activity also improved the gas exchange parameters. Soluble sugar contents decreased and starch contents were enhanced. Increase in polyamine contents improved the ionic balance in the test cultivar as well. This study highlights the potentiality of silicon in ameliorating the ecotoxicological risks associated with arsenic pollution and the probable ability of silicon to offer an approach in mitigating arsenate-induced stress leading to restoration of growth and metabolism in wheat seedlings.

The manuscript illustrates the ameliorative effects of exogenously applied higher polyamine (PA), spermidine (Spd) in the susceptible indica rice cultivar IR-64 subjected to prolonged fluoride stress. The Spd treatment drastically reduced fluoride bioaccumulation by restricting entry of the anions through chloride channels and enabled better maintenance of the proton gradient via accumulation of P-H⁺/ATPase, thereby improving the root and shoot lengths, fresh and dry weights, RWC, chlorophyll content and activities of pyruvate dehydrogenase (PyrDH), α-amylase, and nitrate reductase (NR) in the Spd-treated, stressed plants. Expression of RuBisCo, PyrDH, α-amylase, and NR was stimulated. Spd supplementation reduced the molecular damage indices like malondialdehyde, lipoxygenase, protease activity, electrolyte leakage, protein carbonylation, H₂O₂, and methylglyoxal (detoxified by glyoxalase II). Mitigation of oxidative damage was facilitated by the accumulation and utilization of proline, glycine-betaine, total amino acids, higher PAs, anthocyanin, flavonoids, β-carotene, xanthophyll, and phenolics as verified from the expression of genes like P5CS, BADH1, SAMDC, SPDS, SPMS, DAO, PAO, and PAL. Spd treatment activated the ascorbate-glutathione cycle in the stressed seedlings. Expression and activities of enzymatic antioxidants showed that GPOX, APX, GPX, and GST were the chief ROS scavengers. Exogenous Spd promoted ABA accumulation by upregulating NCED3 and suppressing ABA8ox1 expression. ABA-dependent osmotic stress-responsive genes like Osem, WRKY71, and TRAB1 as well as ABA-independent transcription factor encoding gene DREB2A were induced by Spd. Thus, Spd treatment ameliorated fluoride-mediated injuries in IR-64 by restricting fluoride uptake, refining the defense machinery and activating the ABA-dependent as well as ABA-independent stress-responsive genes.