Ecotoxicological strategies employing biochemical markers and organisms to monitor the efficacy of malathion photolysis treatment.

The objective of this study was to assess the photolysis-mediated degradation of malathion in standard and commercial formulations, and to determine the toxicity of these degraded formulations. Degradation tests were carried out with 500 µg L-1 of malathion and repeated three times. The initial and residual toxicity was assessed by using Lactuca sativa seeds for phytotoxicity, Stegomyia aegypti larvae for acute toxicity, and Stegomyia aegypti mosquitoes (cultivated from the larval stage until emergence as mosquitoes) to evaluate the biochemical markers of sublethal concentrations. For the standard formulations the photolytic process efficiently reduced the initial concentration of malathion to levels below the regulatory limits however, the formation of byproducts was revealed by chromatography, which allowed for a more complete proposal of photolytic-mediated malathion degradation route. The degraded formulations inhibited the growth of L. sativa seeds, while only the untreated formulations showed larvicidal activity and mortality. Both formulations slightly inhibited acetylcholinesterase activity in S. aegypti mosquitoes, while the standard formulation decreased and the commercial formulation increased glutathione S-transferase activity. However, there were no significant differences for superoxide dismutase, esterase-α, esterase-ß and lipid peroxidation. These findings indicate that in the absence of the target compound, the presence of byproducts can alter the enzymatic activity. In general, photolysis effectively degrade malathion lower than the legislation values; however, longer treatment times must be evaluated for the commercial formulation.

Stability of Leaf Yerba Mate (Ilex paraguariensis) Metabolite Concentrations over the Time from the Prism of Secondary Sexual Dimorphism.

The yerba mate leaf metabolic composition depends mainly on genetics, sex, plant and leaf age, light intensity, harvest time, climate, and fertilization. In yerba mate, the secondary sexual dimorphism (SSD), the leaf metabolic SSD association with the frequency of leaf harvests, and the stability of the metabolites in the two genders over the years is not known. It was hypothesized that (1) the SSD in the metabolite segregation would differ among the winter and summer growth pauses, (2) females would show lower metabolite concentrations, and (3) the metabolic concentrations would show stability over the years on the same plants, not obligatorily associated with the SSD stability expression. Variations in theobromine, caffeine, chlorogenic and caffeic acids were correlated to the increasing time since the previous harvest, especially in females. However, the frequency of the metabolic SSD were associated with the studied growth pauses, rejecting the first hypothesis. No regular gender superiority was expressed in the yerba mate leaf secondary metabolites, rejecting our second hypothesis, even though more cases of superior female metabolite accumulation were identified. The stability of the leaf protein was preserved over the four years, with no SSD cases observed. The leaf methylxanthines were time stable, while the decrease in the phenolic content occurred with tree aging, which was not associated with the SSD expression, partially proving our third hypothesis. The novelty was related to the time stability of the leaf metabolic SSD observed over the winter and summer growth pauses, and over the four consecutive years without a regular expression of the male- or female-biased concentrations in the studied metabolites. To demystify the random metabolic gender responses in yerba mate, gender-orientated experiments with a high number of tree repetitions must be conducted, including clonal plants grown in various environments, such as monoculture and agroforestry, or on plantations in different climates and altitudes.

Removal of micropollutants by UASB reactor and post-treatment by Fenton and photo-Fenton: Matrix effect and toxicity responses.

Literature is scarce on the performance of Fenton-based processes as post-treatment of municipal wastewater treated by upflow anaerobic sludge blanket (UASB) reactor. This study aims to perform Fenton and photo-Fenton from UASB influent and effluent matrices to remove micropollutants (MPs) models: atrazine (ATZ), rifampicin (RIF), and 17α-ethynylestradiol (EE2). A UASB reactor at bench-scale (14 L) was operated with these MPs, and the AOPs experiments at bench-scale were performed on a conventional photochemical reactor (1 L). A high-pressure vapor mercury lamp was used for photo-Fenton process (UVA-Vis) as a radiation source. Microcrustacean Daphnia magna (acute toxicity) and seeds of Lactuca sativa (phytotoxicity) were indicator organisms for toxicity monitoring. The UASB reactor showed stability removing 90% of the mean chemical oxygen demand, and removal efficiencies for ATZ, RIF, and EE2 were 16.5%, 45.9%, and 15.7%, respectively. A matrix effect was noted regarding the application of both Fenton and photo-Fenton in UASB influent and effluent to remove MPs and toxicity responses. The pesticide ATZ was the most recalcitrant compound, yet the processes carried out from UASB effluent achieved removal >99.99%. The post-treatment of the UASB reactor by photo-Fenton removed acute toxicity in D. magna for all treatment times. However, only the photo-Fenton conducted for 90 min did not result in a phytotoxic effect in L. sativa.