Exploring sorption of pesticides and PAHs in microplastics derived from plastic mulch films used in modern agriculture.

The sorption and vector effect of microplastics on the transfer of pesticides and polycyclic aromatic hydrocarbons (PAHs), as well as its impact on agriculture remain largely unexplored. This comparative study is first to investigate the sorption behavior of different pesticides and PAHs at environmentally realistic concentrations by model microplastics and microplastics derived from polyethylene mulch films. Sorption was found to be up to 90% higher in the case of microplastics derived from mulch films as opposed to pure polyethylene microspheres. For microplastics from mulch films, the sorption percentages for pesticides in media containing CaCl2 were reported to be: pyridate (75.68% and 52.44%), fenazaquin (48.54% and 32.02%), pyridaben (45.04% and 56.70%), bifenthrin (74.27% and 25.88%), etofenprox (82.16% and 54.16%) and pyridalyl (97.00% and 29.74%) at 5 µg/L and 200 µg/L pesticide concentration levels respectively. For PAHs, the sorption amounts were: naphthalene (22.03% and 48.00%), fluorene (38.99% and 39.00%), anthracene (64.62% and 68.02%) and pyrene (75.65% and 86.38%) at 5 µg/L and 200 µg/L PAH concentration levels respectively. Sorption was influenced by the octanol-water partition coefficient (log Kow) and ionic strength. Kinetics of the process in the case of sorption of pesticides were best explained by pseudo-first order kinetic model (R2 between 0.90 and 0.98) while the best fitting isotherm model was Dubinin-Radushkevich (R2 between 0.92 and 0.99). Results suggest the presence of surface level physi-sorption through a micropore volume filling mechanism and the role of hydrophobic and electrostatic forces. Pesticide desorption data in polyethylene mulch films indicate that pesticides with high log Kow were almost completely retained in mulch films, while those with lower log Kow were desorbed rapidly into the surrounding media. Our study highlights the role of microplastics from plastic mulch films as vectors for pesticide and PAH transport at environmentally realistic concentrations and the factors that influence it.

Supercritical fluid chromatography separation of chiral pesticides: Unique capabilities to study cyhalothrin and metalaxyl as examples.

Evaluation of chiral pesticides remains a frequently neglected matter in routine food control laboratories. This fact is due to the existence of many residue definitions but also due to the lack of robust instrumental methods for the evaluation of these isomeric compounds. However, supercritical fluid chromatography coupled to mass spectrometry (SFC-ESI-MS/MS) has been demonstrated to perform fast and highly efficient separations without the need to change the mobile phase employed in multiresidue pesticide analyses. Regarding chiral stationary phase columns, the polysaccharide-based ones clearly demonstrate the best separation technology. Two polysaccharide-based columns were tested in this study, and the robustness of their combination with SFC was verified. The enantiomers of lambda-cyhalothrin and metalaxyl were studied precisely due to their markedly distinct toxicity and enantioselectivity. Furthermore, the acute reference dose for gamma-cyhalothrin is half in comparison with its enantiomer (0.0025 and 0.005 mg/kg respectively), which is present in the lambda-cyhalothin residue definition. These enantiomers were analyzed in terms of linearity, reproducibility, and matrix effects in four representative matrices (tomato, orange, leek, and cayenne). Additionally, field tests under greenhouse conditions for these compounds were performed. The results obtained after different sample collections revealed a similar degradation in lambda-cyhalothrin enantiomers (R, S, S, and S, R, R) but not in the case of metalaxyl-M (mefenoxam) where the degradation in tomato was 2 to 6 times less in comparison with its S-enantiomer.

Distribution of chemical residues in the beehive compartments and their transfer to the honeybee brood.

Honeybee (Apis mellifera) is one of the most important crop and wild plant pollinators, playing an essential role in the agricultural production and the natural ecosystems. However, the number of honeybee colonies is decreasing alarmingly, which has motivated extensive research on the factors affecting their development and survival in some regions. Honeybees' exposure to pesticides and other chemicals has been identified as one of the causes of their decline. The present study evaluates the distribution of plant protection products, veterinary treatments and environmental contaminants inside the beehive, their persistence and their migration to the bee brood. During the five-month sampling period, only amitraz was applied to the colonies. Samples of beeswax, beebread (processed pollen) and bee brood were extracted and analyzed using GC-MS/MS and LC-MS/MS with a multiresidue method. The results showed the presence of 31 chemical residues in the samples. The highest concentrations of residues were detected in the beeswax and corresponded to amitraz (expressed as the sum of DMF and DMPF), coumaphos and tau-fluvalinate, with total concentrations of up to 16,858, 7102 and 1775 µg kg-1, respectively. These and other veterinary treatments were found to accumulate in the beeswax and migrate to other beehive matrices such as beebread and bee brood. Plant protection products used in agriculture were also found in the beehive matrices, especially in the beebread. Five different chemical residues (acrinathrin, amitraz, coumaphos, cypermethrin and tau-fluvalinate) were found in bee brood samples at concentration levels ranging from 1 to 167 µg kg-1. These findings reveal that bee brood reared in field conditions is in fact exposed to plant protection products and veterinary residues through direct contact with contaminated wax and via beebread although they had not been applied to the beehive.

NMR-Based Metabolomics Approach To Study the Influence of Different Conditions of Water Irrigation and Greenhouse Ventilation on Zucchini Crops.

This study describes the approach of 1H NMR metabolomic profiling for the differentiation of zucchini produced under different conditions of water irrigation (desalinated seawater -0.397 dS/m, 0.52 €/m3 vs groundwater -2.36 dS/m, 0.29 €/m3) and ventilation (surface area of the vent openings/greenhouse area was 15.0% for one sector and 9.8% for the other). Overall, 72 extracts of zucchini ( Cucubirta pepo L. cv Victoria) under four different conditions were regularly analyzed during the spring-summer cycle from April to July 2017. We have found that zucchini plants irrigated with desalinated seawater increased the zucchini production yield, presented fruits with higher concentration of glucose, fructose, and vitamin B3, and displayed an increased antioxidant activity. On the contrary, plant groundwater irrigation produced the increment of sucrose level that could rise the sweetness perception of the fruits. Finally, the ventilation variable produced a higher concentration of trigonelline, histidine, and phenylalanine but only on those zucchinis irrigated with groundwater.