Microplastics (MPs) are particles between 1 μm and 5 mm in size, originating mainly from poor solid waste and effluent management, that can reach water bodies from various sources. In freshwater environments, the occurrence, distribution, and characterization of this new class of pollutants are still little explored, especially in Brazil. The aim of this study was to assess the occurrence of MPs, as well as the presence and concentration of polychlorinated biphenyls (PCBs) sorbed to these particles in the surface waters of the Tietê River - SP. Surface water samples were collected in duplicate during the dry and wet seasons. The identification and characterization of the MPs was carried out through visual inspection and the chemical identity of the particles was verified using Fourier transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR). For the analysis of PCBs adsorbed to the MPs, the sample extracts were analyzed by gas chromatography coupled with mass spectrometry (GC-MS). The MPs were found in concentrations ranging from 6.67 to 1530 particles m⁻³, with a predominance of the polymers polyethylene (PE, with 58.17 %) and polypropylene (PP, with 23.53 %). The main morphological categories identified were fragments (56.63 %), fibers (28.42 %), and transparent films (13.06 %). Higher abundances of PCBs were observed in the lower size range, between 0.106 and 0.35 mm. The total concentrations of PCBs in MPs ranged from 20.53 to 133.12 ng g⁻¹. The results obtained here are relevant for understanding the dynamics and level of contamination of MPs and organic pollutants sorbed to these particles in the Tietê River, as well as helping with mitigation measures for the restoration and preservation of this ecosystem.

Polymer-based herbicide nanocarriers have shown potential for increasing the herbicide efficacy and environmental safety. This study aimed to develop, characterize, and evaluate toxicity to target and nontarget organisms of natural-based polymeric nanosystems for glyphosate. Polymers such as chitosan (CS), zein (ZN), and lignin (LG) were used in the synthesis. Nanosystem size, surface charge, polydispersity index, encapsulation efficiency, toxicity to weed species (Amaranthus hybridus, Ipomoea grandifolia, and Eleusine indica), and Roundup Ready (RR) crops, soil respiration, and enzyme activity were evaluated. The most stable system was the combination of ZN with the cross-linker poloxamer (PL), with higher weed control efficacy (90-96%) for A. hybridus, compared to commercial glyphosate (40%). No improvement was observed for I. grandifolia and E. indica. No glyphosate toxicity was observed in RR crops, soil respiration, or soil enzymes, indicating no toxic effects of the nanoformulation in these models. ZN-PL systems can be a promising alternative for glyphosate delivery, using environmentally friendly materials, with improved efficiency for weed control in agriculture.

Nanoformulations have been used to improve the delivery of fertilizers, pesticides, and growth regulators, with a focus on more sustainable agriculture. Nanoherbicide research has focused on efficiency gains through targeted delivery and environmental risk reduction. However, research on the behavior and safety of the application of these formulations in cropping systems is still limited. Organic matter contained in cropping systems can change the dynamics of herbicide–soil interactions in the presence of nanoformulations. The aim of this study was to use classical protocols from regulatory studies to understand the retention and mobility dynamics of a metribuzin nanoformulation, compared to a conventional formulation. We used different soil systems and soil with added fresh organic material. The batch method was used for sorption–desorption studies and soil thin layer chromatography for mobility studies, both by radiometric techniques. Sorption parameters for both formulations showed that retention is a reversible process in all soil systems (H~1.0). In deep soil with added fresh organic material, nanoformulation was more sorbed (14.61 ± 1.41%) than commercial formulation (9.72 ± 1.81%) (p < 0.05). However, even with the presence of straw as a physical barrier, metribuzin in nano and conventional formulations was mobile in the soil, indicating that the straw can act as a barrier to reduce herbicide mobility but is not impeditive to herbicide availability in the soil. Our results suggest that environmental safety depends on organic material maintenance in the soil system. The availability can be essential for weed control, associated with nanoformulation efficiency, in relation to the conventional formulation.

Deltamethrin is an insecticide with high toxicity to non-target aquatic organisms. Environment-friendly alternatives to removing insecticides from water bodies, like phytoremediation, require species to uptake and/or dissipate pesticides from water. Our research investigated the ability of Egeria densa plants to absorb and dissipate ¹⁴C-deltamethrin from water, and bioaccumulation in Danio rerio. The variables were four densities of E. densa (0, 234, 337, and 468 g dry weight m^-3), in tanks with seven adults of D. rerio, with three replicates. Dissipation was evaluated at 0, 24, 48, 72, and 96 h after application (HAA). After 96 HAA, the uptake of ¹⁴C-deltamethrin by plants and accumulation in fish were assessed. The E. densa increased ¹⁴C-deltamethrin dissipation and reduced bioaccumulation in zebrafish. The DT₅₀ decreased 3-fold in treatments with 337 and 468 g m^-3 of E. densa. The plants absorbed 32% of the ¹⁴C-deltamethrin applied, regardless of plant density. The bioaccumulation in fish was 8.21% without E. densa and only 1% in treatments with 468 g m^-3 of plants. These results suggest phytoremediation using E. densa is a possible alternative to removing deltamethrin from water and reducing the accumulation in non-target organisms, reducing the environmental impact of insecticides in aquatic ecosystems.

Understanding the strategies of delivering active ingredients with nanoparticles to plant species is crucial to implement a safe-by-design approach for pesticides. Here, we used metribuzin (MTZ) as a study model to understand the plant uptake and distribution pathways of polymeric nanocarriers. We investigated the weed-control efficacy, uptake, internalization, and distribution of the (nano) herbicide MTZ in Amaranthus viridis (C4 species) and Bidens pilosa (C3 species) after soil and foliar application. A radiolabeled herbicide and a fluorescent probe were used as complementary tools to track both MTZ and nanoparticles in plants. The weed-control results indicated significant dose reductions with MTZ nanoencapsulation (from 1/2 to 10-fold doses). Root uptake was an efficient pathway for A. viridis and the B. pilosa entry of nanoMTZ occurred preferentially in the stomata and was internalized in leaf mesophyll cells. No differences in herbicide uptake were observed in the soil, and the nanoMTZ distribution was 1.3–1.5 lower than MTZ. After foliar application, nanoMTZ was absorbed 2.5 times more than MTZ in A. viridis and was similar in B. pilosa. NPs were concentrated in the vascular cells after soil application and in the stomata entrance after foliar application. For B. pilosa, the internalization in the leaf mesophyll was more evident than that in A. viridis. Our findings indicated that consideration of the target weed species and application mode will increase the efficacy of control using nanoformulations.

Pre-emergent herbicides are applied directly in the soil or over the straw in no-till systems and can be retained, reducing the product’s availability. The current study characterizes the retention of diclosulam and diuron in forage turnip (FT), buckwheat (BW), and black oat (BO) straws. Radiometric techniques evaluated the sorption–desorption and leaching processes. Spectroscopic and microscopic methods characterized chemical and morphological alterations in the straw. Sorption rates (Kf) of diclosulam and diuron followed the order BO > BW > FT. Irreversible sorption (hysteresis < 0.7) occurs to diclosulam applied to BO straw. The BO straw showed porous structures, indicating physical entrapment of the herbicides. Straw fragments (<1 mm) increased the sorption of herbicides. The increase in straw amount (2.5 to 5 t ha⁻¹) reduced herbicide leaching to 18.8%. Interactions between chemical groups (C-Cl, C-F, and C-N) from herbicides with straw characterize a chemical barrier. The present research suggests that entrapment and chemical interaction are involved in the sorption–desorption process of herbicides, such as diclosulam and diuron, in the straw matrix, directly interfering with their availability in the environment. This process can reduce the herbicide environmental risk but can decrease weed control efficiency.