Assessing glyphosate and AMPA pesticides in the Ofanto River waters and sediments.

In the present study, we determined glyphosate (GPS) and aminomethylphosphonic acid (AMPA) in the water and sediments of the Ofanto River (Italy), evaluating their transport from the mouth to the sea. Sediments were collected twice in 2021 during low and high tide; waters were sampled on a seasonal basis. The results showed the prevalence of GPS and AMPA in the water with concentrations equal to 190 and 3053 ng/l, respectively. We also found GPS and AMPA in the sediments with values of 0.95 and 11.34 ng/g. In water, pesticides were detected in all seasons with peaks in concentrations during summer and spring. A significant positive correlation between the pesticides in the sediments and the water pH and a negative correlation with salinity was observed. An estimation of the average loads revealed a discharge of 64.11 kg/yr. of GPS and 958.37 kg/yr. of AMPA from the river to the marine environment.

Dithiocarbamates: Properties, Methodological Approaches and Challenges to Their Control.

Dithiocarbamates (DTCs) are a group of chemicals used primarily as fungicides, although they are exploited for various other applications. DTCs represent one of the oldest classes of broad-spectrum fungicides employed worldwide to control fungal diseases on many crops. Due to their ease of synthesis, low production costs (cheap and readily available starting materials) and a fungicidal activity with a multi-site mode of action, they are still among modern agriculture's most extensively used pesticides. Although the environmental degradation in air, water, and soil is relatively rapid due to photolysis and/or hydrolysis, they are among the most frequently detected pesticides in the European Union (EU), also with a high frequency of maximum residue level (MRL) exceedances. The current review aims to comprehensively survey all aspects of DTCs, including the environmental fate, toxicity and analytical methods for determining parental compounds and degradation products in environmental and food samples. Furthermore, the accumulation of carbamate and dithiocarbamate pesticides in vegetables, fruits, bioindicator organisms and human biological samples, as well as their health effects on humans, are also considered in this study.

Development of a UHPLC-MS/MS method to enhance the detection of Glyphosate, AMPA and Glufosinate at sub-microgram / L levels in water samples.

Glyphosate is the best-selling herbicide worldwide. The toxicity on ecosystems and the possible effects on human health have long been at the centre of a complex controversy concerning the authorisation for its use. The peculiar chemical-physical properties of glyphosate, AMPA and glufosinate make their determination at trace levels in the water a real analytical challenge. All three compounds can be derivatised to less polar ones and FMOC-Cl (9-fluorenylmethyl chloroformate) is the most common pre-column derivatisation reagent used for this analysis. It can be successfully combined with Ultra-High-Performance Liquid Chromatography with Mass Spectrometry (UHPLC-MS/MS) to determine all three analytes in one method as part of water monitoring programs. The developed method aims to determine glyphosate with AMPA and glufosinate at sub-micrograms/L levels in groundwater, surface and water by UHPLC-MS/MS after derivatisation with FMOC-Cl. The novelty of this method is its high simplicity, robustness and sensitivity allowing the identification and quantification of the compounds at the detection limits required by the European regulations (0.1 µg /L). No pre-concentration or purification steps (by using Solid Phase Extraction cartridges) are necessary for our method saving time and consumables costs. The method demonstrated an excellent linear relationship (R2 ≥ 0.999) in the concentration range from 0.025 to 10 µg /L for glyphosate and AMPA and 0.025 to 5 µg /L for glufosinate. The method Limit Of Quantification (LOQ) is 0.025 µg/L, the lowest among all previously published studies, and it was demonstrated according to the European SANTE guidelines.

Physiological response of two olive cultivars to secondary metabolites of Verticillium dahliae Kleb.

The effects of two purified fractions (formerly D-SXM and ND-SXM) produced in vitro by defoliating (Vd312D) and non-defoliating (Vd315ND) strains of Verticillium dahliae were studied on twigs of Olea europaea cvs Frantoio and Leccino. Symptoms, such as leaf curling, yellowing, vein clearing and defoliation, which are observed on the two cultivars naturally affected by Verticillium wilt, were produced by these fractions. Physiological changes were induced during the first seven days after the absorption of solutions containing ND-SXM or D-SXM. Both fractions increased the transpiration flow from abaxial leaf surfaces. Cell membrane and antioxidant activity were the most important action sites of ND-SXM and D-SXM. ND-SXM influenced malondialdehyde concentration in 'Leccino' leaves, while D-SXM increased the percentage of electrolyte leakage in 'Frantoio'. Both fractions reduced the total non-enzymatic antioxidant activity on the leaves of the treated twigs. The total phenol content increased in both cultivars, without differences to the control. Variations on electrolyte leakage and total antioxidant activity were effective in discriminating the two tested olive cultivars for V. dahliae tolerance or susceptibility. If V. dahliae strains Vd315ND and Vd312D produce ND-SXM and D-SXM in the infected plants, these metabolites may move via the xylem sap, accumulate in the leaves and induce changes that will lead symptoms on the leaf by compromising the cell membranes physiology.