Evaluation of the sorption/desorption processes of pesticides in biodegradable mulch films used in agriculture.

Microplastics from mulch films can be a source of chemical contamination to agricultural soils. In this context, biodegradable films have been widely positioned as a greener choice. However, their sorption/desorption capabilities, in contrast to the conventional plastic types remain understudied. It is for this reason that objective evaluation of their interactions with residual agricultural contaminants becomes important. Our findings reveal that polyethylene (PE) mulch films retained lower amounts of pesticide residues and demonstrated a higher desorption/release [median desorption = 71.86 µg/L or about 50%], while polybutylene adipate terephthalate (PBAT) mulch films retained higher amounts of pesticide residues onto their surface and demonstrated a much lower desorption [median desorption = 24.27 µg/L or about 17%] after a spraying event. A higher ambient temperature had no significant effect on final desorption amounts in both PE [median = 65.27 µg/L at 20 °C and 74.23 µg/L at 40 °C] and PBAT [median = 24.26 µg/L at 20 °C and 24.78 µg/L at 40 °C] mulch films. However, it did favour a faster desorption pace in PE films. Desorption in PBAT and PE plastic types was correlated with the log Kow value [Spearman's correlation: 0.857 and 0.837 respectively, p < 0.05]. However, only a moderate correlation with pKa was observed in PBAT [Spearman's correlation: 0.478, p < 0.05], while none for PE plastic type. Sorption of pesticides onto biodegradable PBAT microplastics were best explained by Elovich [R2: 0.937-0.959] and pseudo-second order kinetics [R2: 0.942-0.987], suggesting the presence of chemisorption. Furthermore, Weber Morris plots suggested the presence of a multi-step process and Boyd plots indicated that film diffusion or chemical bond formation was the rate-limiting step governing this phenomenon.

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.