The status of organochlorine pesticide contamination in Greek agricultural soils: the ghost of traditional agricultural history.

Inadequate information regarding pesticide contamination in Greek agricultural soils is currently available, while national soil monitoring programs have not been initiated yet. The aim of the present study was to assess the levels, compositions, and distribution of thirty three organochlorine pesticides (OCPs) in Greek agricultural soils, due to the environmental threat posed by these compounds, even after decades from their abrogation from the market. Determination of the organochlorine pesticides was achieved using gas-chromatography-mass spectrometry, following a QuEChERS sample preparation method. A total of 60 soil samples, from two soil horizons (up to 60 cm), were obtained from agricultural lands in Greece throughout 2019-2020. The major findings presented DDTs, γ-HCH, alachlor, and 4,4- DCBP in the examined soil samples, with DDTs being the major compounds with their maximum cumulative concentration (ΣDDTs) reaching 1273.4 µg kg-1 d.w. Compositional profile and diagnostic ratios suggested that the occurrence of DDT residues was due to historical inputs. Most of the samples did not exceed the target values set by the Netherlands and Canadian guidelines for DDTs in soil; however, there was one exception in the case of Aegina Island. Finally, based on the environmental exposure assessment conducted, the vast majority of the analytes presented lower concentrations compared to the predicted environmental concentrations, with an exemption for DDE metabolite where the measured and predicted concentrations were almost equal.

Validation and Simultaneous Monitoring of 311 Pesticide Residues in Loamy Sand Agricultural Soils by LC-MS/MS and GC-MS/MS, Combined with QuEChERS-Based Extraction.

Soil can be contaminated by pesticide residues through agricultural practices, by direct application or through spray-drift in cultivations. The dissipation of those chemicals in the soil may pose risks to the environment and human health. A simple and sensitive multi-residue analytical method was optimized and validated for the simultaneous determination of 311 active substances of pesticides in agricultural soils. The method involves sample preparation with QuEChERS-based extraction, and determination of the analytes with a combination of GC-MS/MS and LC-MS/MS techniques. Calibration plots were linear for both detectors over the range of five concentration levels, using matrix-matched calibration standards. The obtained recoveries from fortified-soil samples ranged from 70 to 119% and from 72.6 to 119% for GC-MS/MS and LC-MS/MS, respectively, while precision values were <20% in all cases. As regards the matrix effect (ME), signal suppression was observed in the liquid chromatography (LC)-amenable compounds, which was further estimated to be negligible. The gas chromatography (GC)-amenable compounds showed enhancement in the chromatographic response estimated as medium or strong ME. The calibrated limit of quantification (LOQ) value was 0.01 µg g-1 dry weight for most of the analytes, while the corresponding calculated limit of determination (LOD) value was 0.003 µg g-1 d.w. The proposed method was subsequently applied to agricultural soils from Greece, and positive determinations were obtained, among which were non-authorized compounds. The results indicate that the developed multi-residue method is fit for the purpose of analyzing low levels of pesticides in soil, according to EU requirements.

Changes in sugar metabolism associated to stem bark thickening partially assist young tissues of Eriobotrya japonica seedlings under boron stress.

Boron (B) toxicity frequently affects plant performances and productivity, especially in arid and semi-arid environments. In this experiment, loquat seedlings were subjected to 25 µM (control) or 400 µM B (B excess) to test the hypothesis that (i) B alters sugar/polyol metabolism in polyol-producing tree species as loquat and (ii) changes of leaf and stem anatomy assist young tissues against toxic effect of B. Gas exchange was monitored from the beginning of the experiment (FBE) till one week after the first visible symptoms of B toxicity appeared in the upper part of the stems (147 d FBE). At 147 FBE, plant biometric parameters and pattern of B accumulation, leaf and stem anatomy, chlorophyll a fluorescence kinetics as well as biochemical measurements were assessed in top (asymptomatic) leaves and upper stem bark. Boron accumulated principally (in the row) in top leaves > top bark > top wood in B-stressed plants, but no changes in allocation pattern were found between controls and B-stressed plants. Excess B promoted the increase in the spongy layer of top leaves and caused the development of cork and numerous collenchyma cells with increased cell wall thickness. This mechanism, which has never been described before, can be considered an attempt to store excessive B in tissues where B ions are less harmful. The accumulation of sorbitol (B-complexing polyol) in top leaves and stem bark can be considered as a further attempt to detoxify B excess. However, B toxicity drastically affects the photosynthetic rate of top leaves, mainly due to non-stomatal limitations, i.e., reduction of ambient CO2 use efficiency and of photosystem II (PSII) efficiency, modification of the partitioning excess energy dissipation in PSII, thus leading to an increased level of lipid peroxidation. Our results suggest that changes in sugar metabolism associated with leaf and stem bark thickening partially assist (but not totally preserve) young tissues of loquat plants under B stress.