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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.)

In Brazil, studies evaluating the concentration of trace metals in fish farms are scarce. Therefore, studies investigating the presence and levels of these metals in aquatic biota, particularly in fish tissues, are crucial for developing appropriate strategies to mitigate the impact of possible toxic metals. Herein, we investigated the levels of trace metals (Cr, Mn, Co, Ni, Cu, Zn, Al, Ag, Cd, Pb, Fe, Na, Mg, Ca, K, and Ba) in water, feed, and sediment, as well as the bioconcentration and bioaccumulation factors in tambaqui muscles (Colossoma macropomum). For this purpose, eight commercial fish farms, which are also engaged in other agricultural activities, were selected. Fe, Zn, Mg, and Cr concentration in tambaqui muscles exceeded the limits set by the Brazilian regulations for daily consumption by adults. Mn, Zn, Al, Pb, Fe, Na, Cu, Co, Ag, Cd, and Ba levels were substantially higher in the liver tissue of tambaquis than those in the muscle tissue. The most prevalent metals found in the feed were Ca, K, Na, Mg, and Fe. However, the levels of Cr and Cd in the sediment, as well as Pb, Mn, Cu, and Fe in the water, exceeded the maximum limits allowed by the Brazilian legislation. The highest bioconcentration factors were observed for the metals, Na, Zn, and K, with concentrations up to 4.74, 12.61, and 72.08 times, respectively, higher in tambaqui muscle compared to those in water. The bioaccumulation factors for Ca, Zn, Mg, Na, and K were 2.90, 6.96, 21.21, 212.33, and 492.02 times, respectively, higher in the muscle tissue than those in the sediment values in fishponds across all fish farms. Therefore, our findings suggest that tambaquis have a remarkable ability to bioaccumulate trace metals, particularly the essential ones, and can be categorized as a bioindicator species for environmental quality. Furthermore, we observed that, although water exhibits the highest prevalence and diversity of elements above the values recommended by the Brazilian legislation, sediment is the primary source of trace metal contamination for tambaquis., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)