Integrated occurrence of contaminants of emerging concern, including microplastics, in urban and agricultural watersheds in the State of São Paulo, Brazil.

Contaminants of emerging concern (CECs), including microplastics, have been the focus of many studies due to their environmental impact, affecting biota and human health. The diverse land uses and occupation of watersheds are important parameters driving the occurrence of these contaminants. CECs such as pesticides, drugs, hormones, and industrial-origin substances were analyzed in urban/industrial (Atibaia) and agricultural (Preto/Turvo) watersheds located in São Paulo state, Brazil. A total of 24 CECs were investigated, and, as a result, only 5 (caffeine, carbendazim, atrazine, ametrine and 2-hydroxytrazine) were responsible for 81.73 % of the statistical difference between watersheds contamination profile. The Atibaia watershed presented considerable concentrations of caffeine (ranging from 75 to 2025 ng L-1), while carbendazim (44 to 1144 ng L-1) and atrazine (3 to 266 ng L-1) presented highest levels in Preto/Turvo watershed. In all sampling points, the cumulative potential aquatic life risk assessed by the NORMAN database indicates some level of environmental concern associated to pesticides and caffeine (risk quotient >1). Microplastics had been analyzed in both watersheds, being the white/transparent fragments in size between 100 and 250 µm the most detected in this study. The estimated abundance in the Atibaia watershed ranged from 349 to 2898 items m-3 presenting some influence of pluviosity, while in Rio Preto/Turvo ranged from 169 to 6370 items m-3, being more abundant in the dam area without a clear influence of pluviosity. In both basins, polyethylene and polypropylene were the most detected polymers, probably due to the intense use of single-use plastics in urban areas. Possibly, due to the distinct physic-chemical properties of microplastics and organic CECs, no correlations were observed between their occurrence, which makes us conclude that they have different transport mechanism, behavior, and fate in the environment.

Oxidation of hydrochar produced from byproducts of the sugarcane industry for the production of humic-like substances: Characterization and interaction study with Cu(II).

Humic-like substances (HLS) are molecules extracted in an alkaline medium from different materials that have not been subjected to the natural process of humification that occurs in the soil. HLS have the potential to be used as organic fertilizers due to their ability to incorporate micronutrients such as Cu(II) and Co(II); in addition, they represent an alternative for the remediation of contaminated areas due to their high affinity for metals. HLS can be extracted from hydrochar (HC) but only with low yields of approximately 5%. Therefore, the present study aimed to increase the amount of HLS extracted from the HC produced from byproducts of the sugarcane industry through the oxidation of HC with HNO3. HLS extracted from oxidized and unoxidized HC were characterized by CHNS analysis and 13C CPMAS NMR. The interaction between HLS and Cu(II) was studied by molecular fluorescence quenching (EEM-PARAFAC) and applying the Ryan and Weber complexation model. The oxidation of HC with HNO3 allowed high yields of extracted HLS of above 80%. The oxidation carried out with 30% HNO3 for 2 h showed the best result, since the HLS30%(2h) were extracted with a very high yield (88.3%) in a short period of time. Oxidation promoted a decrease in HLS aromaticity and an increase in oxygen and nitrogen groups. HLS showed high affinity for Cu(II), as evidenced by the high logK values (between 5.5 and 5.9). HLS extracted from oxidized HCs showed higher complexation capacity due to the greater incorporation of the oxygenated groups promoted by oxidation, which are fundamental during the interaction with metallic cations. Therefore, the oxidation of HC substantially increased the production of HLS, representing a big advance for the production of carbonaceous materials with higher added value from byproducts of the sugarcane industry produced on a large scale in Brazil.

Increase of Fluorescence of Humic-Like Substances in Interaction with Cd(II): a Photoinduced Charge Transfer Approach.

Described is the enhancement of fluorescence intensity due to the interaction of a humic-like substance (HLS 1%) extracted from process water (PW) and Cd(II) ions in aqueous solution. Using Canonical Polyadic/Parallel Factor Analysis (CP/PARAFAC), two main components were seen that contributed to fluorescence, the first one increased it and the second one kept it constant in both static and dynamic fluorescence studies. Two-dimensional FTIR analysis indicated that the interaction of HLS 1% and Cd(II) ions occurred in the following order of affinity with the groups: C-O bonds in polysaccharides > C-O bonds in carboxylic acid. The results obtained suggest that the increase in fluorescence intensity and lifetime suggest a photoinduced charge transfer (PCT) between Cd(II) ions and carboxylic acid groups present in HLS 1%.

Insights on Molecular Characteristics of Hydrochars by 13C-NMR and Off-Line TMAH-GC/MS and Assessment of Their Potential Use as Plant Growth Promoters.

Hydrochar is a carbon-based material that can be used as soil amendment. Since the physical-chemical properties of hydrochar are mainly assigned to process parameters, we aimed at evaluating the organic fraction of different hydrochars through 13C-NMR and off-line TMAH-GC/MS. Four hydrochars produced with sugarcane bagasse, vinasse and sulfuric or phosphoric acids were analyzed to elucidate the main molecular features. Germination and initial growth of maize seedlings were assessed using hydrochar water-soluble fraction to evaluate their potential use as growth promoters. The hydrochars prepared with phosphoric acid showed larger amounts of bioavailable lignin-derived structures. Although no differences were shown about the percentage of maize seeds germination, the hydrochar produced with phosphoric acid promoted a better seedling growth. For this sample, the greatest relative percentage of benzene derivatives and phenolic compounds were associated to hormone-like effects, responsible for stimulating shoot and root elongation. The reactions parameters proved to be determinant for the organic composition of hydrochar, exerting a strict influence on molecular features and plant growth response.

Biochemical effects of fipronil and its metabolites on lipid peroxidation and enzymatic antioxidant defense in tadpoles (Eupemphix nattereri: Leiuperidae).

Amphibians are very sensitive to environmental change and pollution because they have both aquatic and terrestrial life cycle stages and high skin permeability. Particularly during the larval stages, when these animals are restricted to small, transient ponds, exposure to high concentrations of pesticides is inevitable in agricultural areas. Given that pesticide application increases during the summer, which coincides with the reproductive season and the occurrence of most neotropical tadpoles in their natural environment, strong indications exist that tadpoles are developing in contaminated ponds. Fipronil is one of the primary insecticides used in sugarcane cultivation in Brazil, and little is known about its toxic effects on non-target organisms such as tadpoles. The purpose of this study was to evaluate the effects of fipronil and its metabolites on oxidative stress in Eupemphix nattereri tadpoles after exposure in water and sediment at concentrations of 35, 120 and 180µgkg-1. We assessed the activities of the antioxidant enzymes glutathione S-transferase (GST), glucose 6-phosphate dehydrogenase (G6PDH) and catalase (CAT) and lipid peroxidation (malondialdehyde, MDA). The results showed that fipronil has an inherent capacity to cause oxidative stress in tadpoles, as evidenced by a decrease in CAT activity and an increase in lipid peroxidation levels at all concentrations tested. Fipronil sulfone also produced elevated MDA levels at two of the tested concentrations and increased G6PDH activity in tadpoles exposed to the highest concentration of this metabolite but did not affect MDA levels. Our data showed that fipronil and its degradation products promoted oxidative stress in Eupemphix nattereri tadpoles exposed to environmentally relevant concentrations and could lead to a decrease in the long-term physiological performance of these animals, leading to detrimental effects at the population level.

Development, validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water, soil, and sediment.

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L(-1), and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L(-1)), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L(-1) and 20.4, 9.0, 21.6, and 13.0 ng L(-1), respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L(-1) and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg(-1)), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg(-1)), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg(-1)). The relative standard deviation for the recovery of pesticides was under 15%.