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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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Aquatic humic substances (AHS) are defined as an important components of organic matter, being composed as small molecules in a supramolecular structure and can interact with metallic ions, thereby altering the bioavailability of these species. To better understand this behavior, AHS were extracted and characterized from Negro River, located near Manaus city and Carú River, that is situated in Itacoatiara city, an area experiencing increasing anthropogenic actions; both were characterized as blackwater rivers. The AHS were characterized by 13 C nuclear magnetic ressonance and thermochemolysis GC-MS to obtain structural characteristics. Interaction studies with Cu (II), Al (III), and Fe (III) were investigated using fluorescence spectroscopy applied to parallel factor analysis (PARAFAC) and two-dimensional correlation spectroscopy with Fourier transform infrared spectroscopy (2D-COS FTIR). The AHS from dry season had more aromatic fractions not derived from lignin and had higher content of alkyls moities from microbial sources and vegetal tissues of autochthonous origin, while AHS isolated in the rainy season showed more metals in its molecular architecture, lignin units, and polysacharide structures. The study showed that AHS composition from rainy season were able to interact with Al (III), Fe (III), and Cu (II). Two fluorescent components were identified as responsible for interaction: C1 (blue-shifted) and C2 (red-shifted). C1 showed higher complexation capacities but with lower complexation stability constants (K ML ranged from 0.3 to 7.9 × 10 5 ) than C2 (K ML ranged from 3.1 to 10.0 × 10 5 ). 2D-COS FTIR showed that the COO - and C-O in phenolic were the most important functional groups for interaction with studied metallic ions., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

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 HNO 3 . HLS extracted from oxidized and unoxidized HC were characterized by CHNS analysis and 13 C 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 HNO 3 allowed high yields of extracted HLS of above 80%. The oxidation carried out with 30% HNO 3 for 2 h showed the best result, since the HLS 30%(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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

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%., (© 2022. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Sugarcane bagasse, vinasse and a mixture of sugarcane bagasse and vinasse were hydrothermally carbonized (HTC), with and without the addition of phosphoric acid, in order to propose new applications of sucroenergetic industry by-products on soil. Detailed information on the composition and properties of hydrochars has been obtained through elemental composition, thermogravimetric analysis, nuclear magnetic resonance and, thermochemolysis GC-MS. The soluble acidic fraction from the hydrochar samples were applied to maize seeds to evaluate the agronomic potential as biostimulants and relate the molecular features with maize seed germination. The HTC treatment converted polysaccharide-based biomasses into hydrochars with hydrophobic characteristics (C-Aryl and C-Akyl). Furthermore, the addition of phosphoric acid further increased the overall hydrophobicity and shifted the thermal degradation of the hydrochars to higher temperatures. Biomass influenced the hydrochars that formed, in which the molecular features of sugarcane bagasse determined the formation of more polar hydrochar, due to the preservation of lignin and phenolic components. Meanwhile, the HTC of vinasse resulted in a more hydrophobic product with an enrichment of condensed and recalcitrant organic fractions. The germination assay showed that polar structures of bagasse may play a role in improving the maize seeds germination rate (increase of ~11%), while the hydrophobic domains showed negative effects. The responses obtained in germination seems to be related to the molecular characteristics that organic extracts can present in solution., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

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 13 C-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.

Fulvic acids (FA) are one of the components of humic substances and play an important role in the interaction with metallic species and, consequently, the bioavailability, distribution and toxicity of metals. However, only a few studies have investigated these FA properties in specific environment, such as anthropogenic soils. Therefore, knowledge about FA molecular composition as well as the FA-metal interaction is essential to predict their behavior in the soil. For this reason, the aim of this study was to investigate the molecular composition of FA extracted from two sites in an anthropogenic soil (Terra Mulata), from the Amazon region, as well as their interactions with Cu(II) ions as a model. Results from 13 C NMR, infrared and elemental analysis showed that these FA are composed mostly by alkyl structures and oxygen-functional groups, e.g., hydroxyl, carbonyl and carboxyl. The interaction with Cu(II) ions was evaluated by fluorescence quenching, in which the FA showed both high quantity of complexing sites per gram of carbon and good affinity to interact with the metal when compared with other soil FA. The results showed that the complexation capacity was highly correlated by the content of functional groups, while the binding affinity was largely influenced by structural factors. In addition, through the lifetime decay given by time-resolved fluorescence, it was concluded that static quenching took place in FA and Cu(II) interaction with the formation of a non-fluorescent ground-state complex. Therefore, this fraction of soil organic matter will fully participate in complexation reactions, thereby influencing the mobility and bioavailability of metal in soils. Hence, the importance of the study, and the role of FA in the environment, can be seen especially in the Amazon, which is one of the most important biomes in the world., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Organic matter plays many roles in the soil ecosystem. One property of the substance concerns the metal complexation and interaction with organic contaminants. In this sense, the humic substances (HS), a heterogeneous mixture of compounds, naturally derived from degradation of biomass, have been widely studied in environmental sciences. Recent advances showed a new way to produce humic-like substances (HLS) through hydrothermal carbonization of biomass. Thus, this study aimed to evaluate the HLS of hydrochars, produced by using a mixture of sugarcane bagasse and vinasse with sulfuric acid added (1 and 4% v/v), and to assess their interactions with metal ions, (Fe(III), Al(III), Cu(II) and Co(II)) using EEM-PARAFAC and a two-dimensional FTIR correlation analysis. The results were compared to the humic substances extracted from the Amazonian Anthrosol, as a model of anthropogenic organic matter. NMR analysis showed that humic-like extracts from hydrochar are mainly hydrophobic, while the soil has a greater contribution of polar moieties. The HLS and HS showed similar complexation capacities for Fe(III), Al(III) and Cu(II) assays. For Co(II) HLS exhibited larger affinities than HS. Two-dimensional correlation analysis FTIR showed that chemical groups may undergo conformational alteration with metal additions to achieve more stable arrangements (higher stability constant). Therefore, these results contribute more knowledge about the mechanism of HS and metal ion interaction, as well as showing that HTC can be an interesting option for HLS production, to be used as humic based materials., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Humic acids (HA) play an important role in the distribution, toxicity, and bioavailability of metals in the environment. Humic-like acids (HLA) that simulate geochemical processes can be prepared by NaOH aqueous extraction from hydrochars produced by hydrothermal carbonization (HTC). HLA can exhibit properties such as those found in HA from soils, which are known for their ability to interact with inorganic and organic compounds. The molecular characteristics of HLA and HA help to explain the relationship between their molecular features and their interaction with metallic species. The aim of this study is to assess the molecular features of HA extracted from Terra Mulata (TM) and HLA from hydrochars as well as their interaction with metals by using Cu(II) ions as a model. The results from 13 C NMR, elemental analysis, FTIR, and UV-Vis showed that HA are composed mostly of aromatic structures and oxygenated functional groups, whereas HLA showed a mutual contribution of aromatic and aliphatic structures as main constituents. The interactions of HA and HLA with Cu(II) ions were evaluated through fluorescence quenching, in which the density of complexing sites per gram of carbon for interaction was higher for HLA than for HA. Furthermore, the HLA showed similar values for stability constants, and higher than those found for other types of HA in the literature. In addition, the average lifetime in both humic extracts appeared to be independent of the copper addition, indicating that the main mechanism of interaction was static quenching with a non-fluorescent ground-state complex formation. Therefore, the HLA showed the ability to interact with Cu(II) ions, which suggests that their application can provide a new approach for remediation of contaminated areas., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Inspired by the presence of anthropogenic organic matter in highly fertile Amazonian Dark Earth (ADE), which is attributed to the transformation of organic matter over thousands of years, we explored hydrothermal carbonization as an alternative for humic-like substances (HLS) production. Hydrothermal carbonization of sugarcane industry byproducts (bagasse and vinasse) in the presence and absence of H 3 PO 4 afforded HLS, which were isolated and compared with humic substances (HS) isolated from ADE in terms of molecular composition and maize seed germination activity. HLS isolated from sugarcane bagasse hydrochar produced in the presence or absence of H 3 PO 4 comprised both hydrophobic and hydrophilic moieties, differing from other HLS mainly in terms of phenolic content, while HLS isolated from vinasse hydrochar featured hydrophobic structures mainly comprising aliphatic moieties. Compared to that of HLS, the structure of soil-derived HS reflected an increased contribution of fresh organic matter input and, hence, featured a higher content of O-alkyl moieties. HLS derived from lignocellulosic biomass were rich in phenolics and promoted maize seed germination more effectively than HLS comprising alkyl moieties. Thus, HLS isolated from bagasse hydrochar had the highest bioactivity, as the presence of amphiphilic moieties therein seemed to facilitate the release of bioactive molecules from supramolecular structures and stimulate seed germination. Based on the above results, the hydrothermal carbonization of lignocellulosic biomass was concluded to be a viable method of producing amphiphilic HLS for use as plant growth promoters., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Hydrothermal carbonization (HTC) is a thermochemical process carried out in an aqueous medium. It is capable of converting biomass into a solid, carbon-rich material (hydrochar), and producing a liquid phase (process water) which contains the unreactive feedstock and/or chemical intermediates from the carbonization reaction. The aim of this study was to evaluate the characteristics of process water generated by HTC from vinasse and sugarcane bagasse produced by sugarcane industry and to evaluate its toxicity to both marine (using Artemia salina as a model organism) and the terrestrial environment (through seed germination studies of maize, lettuce, and tomato). The experiments showed that concentrated process water completely inhibited germination of maize, lettuce, and tomato seeds. On the other hand, diluted process water was able to stimulate seedlings of maize and tomato and enhance root and shoot growth. For Artemia, the LC 50 indicated that the process water is practically non-toxic; however, morphological changes, especially damages to the digestive tube and antennas of Artemia, were observed for the concentration of 1000 mg C L -1 .

Hydrothermal carbonization transforms biomass into value-added material called hydrochar. The release of nutrients (P, N, Ca, Mg, and K) and organic carbon (TOC) from hydrochar in different extractive solutions was investigated in this study. Two sets of hydrochar were produced: (i) hydrochar prepared from sugarcane bagasse and vinasse mixture (BV-HC) and (ii) hydrochar prepared by the addition of H 3 PO 4 to this mixture (BVA-HC). Both hydrochar types released significative amounts of nutrient and organic carbon, mainly Ca (5.0 mg g -1 ) in the mixture (KCl, K 2 SO 4 , NaOH, 1:1:1) extractive solution and TOC (72.6 mg g -1 ) in the NaOH extractive solution, for BV-HC. Nutrient release was influenced by pH and ionic strength. The release of P, Ca, and Mg was affected by the presence of insoluble phosphate phases in BVA-HC. The release of nutrients P, N, Ca, Mg, and K and organic carbon demonstrated that hydrochar has potential for soil application purposes.

In this study, nutrients were immobilized on the hydrochars obtained by hydrothermal carbonization (HTC) of a vinasse and sugarcane bagasse mixture, in the presence of acid, base and salt additives at temperatures of 150, 190 and 230°C. The increase in temperature caused higher immobilization of Ca, Mg, K, N, Cu, Mn, Zn, B, P and Fe in all hydrochars produced. H 3 PO 4 and NaOH immobilized higher amounts of P, Mg and Mn, while Ca was immobilized in higher quantities in the presence of H 3 PO 4 and (NH 4 ) 2 SO 4 . The addition of H 2 SO 4 , H 3 PO 4 and (NH 4 ) 2 SO 4 was responsible for an increased immobilization of P, N, Ca, Mg and K. The immobilization of B, not present in the starting raw material, was possible with the addition of H 3 BO 3 . The results showed that it is possible to alter the reaction medium to immobilize nutrients on hydrochars produced from vinasse and sugarcane bagasse, for agricultural applications., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Aquatic humic substances (AHSs) differ from one environment to another depending on land use and occupation. In addition, the effects of planting sugarcane on AHSs are not well known. Thus, the aim of this study was to characterize AHSs extracted from a river in a typical region of sugarcane cultivation during dry and rainy seasons. The main characteristics of the AHSs were obtained using Fourier transformation infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and off-line pyrolysis coupled with gas chromatography and mass spectrometry (off-line tetramethylammonium hydroxide (TMAH)-GC-MS-thermochemolysis). The FTIR and NMR results were used to infer that no distinctions occurred between the sampling periods. The samples were composed of aromatic groups that were potentially associated with the presence of residual vegetable materials (lignin). The results of the off-line TMAH-GC-MS-thermochemolysis indicated that the structures of the AHSs had uniform compositions that were rich in fatty acid methyl esters (FAMEs), polysaccharide derivatives, aliphatic biopolymers derived from plants, long hydrocarbon chains, branched alkyl groups and methylene carbons. Thus, the results showed that the AHSs obtained from the sugarcane cultivation area during the crop period mainly consisted of resistant aliphatic hydrocarbons, which are derivatives of lignin and FAMEs in compounds rich in humic acid. Therefore, we concluded that sugarcane cultivation produces changes in AHSs because greater amounts of lignin derivatives were observed during the dry season, corresponding to sugarcane cultivation., (Copyright © 2015. Published by Elsevier B.V.)

Humic substances (HS) vary according to the physical and chemical factors present in the environment. Thus, the characterization of HS is very important because it improves the understanding of the groups that comprise the chemical structure. Sediment HS were extracted from four locations representative of sugar cane cultivation, pasture, urban area and the impoundment of the Água Vermelha Hydroelectric Power Plant. Characterization using nuclear magnetic resonance (NMR) allowed us to infer that the HS from an area predominantly characterized by sugar cane cultivation (41.9%) and a typical rural area (35.0%) showed the highest aromaticity percentage. Using the off-line TMAH-thermochemolysis-GC-MS, we inferred that the HS of a typical rural area had a structure rich in plant waxes, plant biopolyester and a large amount of fatty acid methyl ester, which are related to the large amount of humic acid in the structure. The HS samples from the sugar cane cultivation area and the impoundment receiving all of the pollution load from the Turvo/Grande Hydrographic Basin (Bacia Hidrográfica do Turvo/Grande-BHTG) contained contributions from compounds rich in lipids and fatty acid methyl esters, highlighting the presence of the breakdown of petroleum-derived hydrocarbons in the area receiving the entire pollution load. We conclude that the HS extracted from the sediments of the Preto, Turvo and Grande rivers showed well-defined characteristics that varied depending on soil use and occupation, especially the HS extracted from sediments sampled in areas typically planted with sugar cane and rural areas, whose structures contained more aromatic groups., (Copyright © 2014 Elsevier B.V. All rights reserved.)

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%.

The sorption of Hg (II) onto four different types of Amazon soils from the A-horizon was investigated by means of column experiments under saturation conditions and controlled metal load. Higher organic matter contents in the soil resulted in higher Hg (II) adsorptions, reaching values as high as 3.8 mg Hg g(-1) soil. The amount of mercury adsorbed on a soil column (Q) shows a very poor correlation with soil clay content (r2 = 0.2527), indicating that Hg sorption in these topsoil samples is chiefly governed by the organic matter content. Desorption experiments using Negro River (Amazon) waters were conducted using soil saturated with Hg (II) in order to better understand the metal leaching mechanism. The amount of Hg (II) released from soils was around 30% of the total sorbed mercury upon saturation, suggesting that mercury sorption in the soils present in the catchment area of the Negro River basin is not a reversible process.