The Catalytic Role of Superparamagnetic Iron Oxide Nanoparticles as a Support Material for TiO2 and ZnO on Chlorpyrifos Photodegradation in an Aqueous Solution.

Chlorpyrifos (CP) is a globally used pesticide with acute toxicity. This work studied the photocatalytic degradation of CP using TiO2, ZnO nanoparticles, and nanocomposites of TiO2 and ZnO supported on SPIONs (SPION@SiO2@TiO2 and SPION@SiO2@ZnO). The nanocomposites were synthesized by multi-step incipient wetness impregnation. The effects of the initial pH, catalyst type, and dose were evaluated. The nanocomposites of SPION@SiO2@TiO2 and SPION@SiO2@ZnO showed higher CP photodegradation levels than free nanoparticles, reaching 95.6% and 82.3%, respectively, at pH 7. The findings indicate that iron oxide, as a support material for TiO2 and ZnO, extended absorption edges and delayed the electron-hole recombination of the nanocomposites, improving their photocatalytic efficiency. At the same time, these nanocomposites, especially SPION@SiO2@TiO2, showed efficient degradation of 3,5,6-trichloropyridinol (TCP), one of the final metabolites of CP. The stability and reuse of this nanocomposite were also evaluated, with 74.6% efficiency found after six cycles. Therefore, this nanomaterial represents an eco-friendly, reusable, and effective alternative for the degradation of chlorpyrifos in wastewater treatment.

Meta-analysis of metal nanoparticles degrading pesticides: what parameters are relevant?

The rise in the global population demands an increasing food supply and methods to boost agricultural production. Pesticides are necessary for agricultural production models, avoiding losses of close to 40%. Nevertheless, the extensive use of pesticides can cause their accumulation in the environment, causing problems for human health, biota, and ecosystems. Thus, new technologies have emerged to remove these wastes efficiently. In recent years, metal and metal oxide nanoparticles (MNPs) have been reported as promising catalysts to degrade pesticides; however, a systematic understanding of their effect on pesticide degradation is still required. Therefore, this study focused on a meta-analysis of articles available in Elsevier's Scopus and Thomas Reuters Web of Science, found by searching for "nanoparticle pesticide" and "pesticide contamination." After passing different filters, the meta-analysis was performed with 408 observations from 94 reviews, which comprise insecticides, herbicides, and fungicides, including organophosphates, organochlorines, carbamates, triazines, and neonicotinoids. Herein, 14 different MNPs (Ag, Ni, Pd, Co3O4, BiOBr, Au, ZnO, Fe, TiO2, Cu, WO3, ZnS, SnO2, and Fe0), improved pesticide degradation, with the highest degradation rates achieved by Ag (85%) and Ni (82.5%). Additionally, the impact of the MNP functionalization, size, and concentration on pesticide degradation was quantified and compared. In general, the degradation rate increased when the MNPs were functionalized (~ 70%) compared to naked (~ 49%). Also, the particle size significantly affected the degradation of pesticides. To our knowledge, this study is the first meta-analysis performed about the impact of MNPs on pesticide degradation, providing an essential scientific basis for future studies.

Antioxidant Activity as an Indicator of the Efficiency of Plant Extract-Mediated Synthesis of Zinc Oxide Nanoparticles.

The green synthesis of zinc oxide nanoparticles (ZnO NPs) using a diverse range of plant species has been extensively reported. Despite the success achieved by biogenic synthesis, there are problems with the control and prediction of the properties of ZnO NPs, due to phytochemical diversity between plant species. In this sense, the main objective of our work was to investigate the effect of the antioxidant activity (AA) of plant extracts on the physicochemical characteristics of ZnO NPs (production yield, chemical composition, polydispersity index (PDI), surface charge (ζ-potential) and average particle size). In order to accomplish this objective, four plant extract with different antioxidant activities were used: Galega officinalis, Buddleja globosa, Eucalyptus globulus, and Aristotelia chilensis. Phytochemical screening, quantitative analysis of phenolic compounds and antioxidant activity determination of the different extracts were carried out. Chemical species such as catechin, malvidin, quercetin, caffeic acid, and ellagic acid were the dominant components, found in the extracts studied. The A. chilensis extract showed the highest value of total phenolic compounds (TPC) and AA, followed by E. globulus, B. globosa and G. officinalis. Zetasizer, Fourier-transform infrared (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) data show that plant extracts with lower AA leads to a decrease in the yield of ZnO NPs and an increase in the amount of residual organic extract that remains on the particles. The latter caused an increase in the average particle size, PDI and ζ-potential as a consequence of agglomeration and particle coarsening. Our result suggest that it is possible to use the AA as an indicator of the potential reducing capacity of plant extracts. In this way it is possible to guarantee the reproducibility of the synthesis process as well as ensure the formation of ZnO NPs with desired characteristics.

Optimization of enzymatic parameters for the production of formononetin from red clover (Trifolium pratense L.) through a response surface methodology.

Trifolium pratense, is a forage found worldwide, but it is negatively impacted by the clover root borer, Hylastinus obscurus. Methanolic extraction has been reported for isolating formononetin from vegetal tissues, with an antifeeding effect on H. obscurus. However, this methodology is time-consuming and also extracts other secondary metabolites, whereas enzymatic assays can provide higher specificity. Hence, the objective of this work was to determine the optimal conditions in pH, temperature, and incubation time for the activity of isoflavone synthase via a response surface model. Once these parameters were optimized, the concentration of formononetin in cultivars and experimental lines of T. pratense was evaluated enzymatically. The results showed that the best condition for developing the enzymatic assay was pH 9.1 with an incubation at 34.5 °C for 155 min. The formononetin content fluctuated between 0.74 and 1.96 mg/g of fresh weight, where Precoz-3, Precoz-1, and Superqueli-INIA presented the highest production.

Alteration of enzyme activities and functional diversity of a soil contaminated with copper and arsenic.

Copper (Cu) mining has to address a critical environmental issue related to the disposal of heavy metals and metalloids (HMs). Due to their deleterious effects on living organisms, Cu and arsenic (As) have gained global attention, and thus their monitoring in the environment is an important task. The aims of this study were: 1) to evaluate the alteration of soil enzyme activities (EAs) and soil microbial functional diversity with Cu/As contamination, and 2) to select the most reliable biochemical indicators of Cu/As contamination. A twelve-week soil experiment was performed with four increasing levels of Cu, As, and Cu/As from 150/15 to 1000/100 mg Cu/As kg-1. Soil enzyme activities and soil community-level physiological profile (CLPP) using MicroResp™ were measured during the experiment. Results showed reduced EAs over time with increasing Cu and Cu/As levels. The most Cu-sensitive EAs were dehydrogenase, acid phosphatase, and arylsulfatase, while arginine ammonification might be related to the resilience of soil microbial communities due to its increased activity in the last experimental times. There was no consistent response to As contamination with reduced individual EAs at specific sampling times, being urease the only EA negatively affected by As. MicroResp™ showed reduced carbon (C) substrate utilization with increasing Cu levels indicating a community shift in C acquisition. These results support the use of specific EAs to assess the environmental impact of specific HMs, being also the first assessment of EAs and the use of CLPP (MicroResp™) to study the environmental impact in Cu/As contaminated soils.