Seasonal studies of aquatic humic substances from Amazon rivers: characterization and interaction with Cu (II), Fe (II), and Al (III) using EEM-PARAFAC and 2D FTIR correlation analyses.

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 13C 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 (KML ranged from 0.3 to 7.9 × 105) than C2 (KML ranged from 3.1 to 10.0 × 105). 2D-COS FTIR showed that the COO- and C-O in phenolic were the most important functional groups for interaction with studied metallic ions.

Uncovering the impact of agricultural activities and urbanization on rivers from the Piracicaba, Capivari, and Jundiaí basin in São Paulo, Brazil: A survey of pesticides, hormones, pharmaceuticals, industrial chemicals, and PFAS.

Rivers in Southeast Brazil are essential as sources of drinking water, energy production, irrigation, and industrial processes. The Piracicaba, Capivari, and Jundiaí rivers basin, known as the PCJ basin, comprises major cities, industrial hubs, and large agricultural areas, which have impacted the water quality in the region. Emerging contaminants such as pesticides, hormones, pharmaceuticals, industrial chemicals, and per- and polyfluoroalkyl substances (PFAS) are likely to be released into the rivers in the PCJ basin; however, the current Brazilian legislation does not require monitoring of most of these chemicals. Thus, the extent of emerging contaminants pollution and their risks to aquatic and human life in the basin are largely unknown. In this study, we investigated the occurrence of several pesticides, hormones, pharmaceuticals, and personal care products in 15 sampling points across the PCJ basin, while industrial chemicals and PFAS were assessed in 11 sampling points. The results show that agriculture and industrial activities are indeed causing the pollution of most rivers. Multivariate analysis indicates that some sampling points, such as Jundiaí, Capivari, and Piracicaba rivers, are largely impacted by pesticides used in agriculture. In addition, to the best of our knowledge, this is the first study reporting the presence of PFAS in rivers in São Paulo, the most populous state in Brazil. Four out of eight species of PFAS assessed in our study were detected in at least 5 sampling points at concentrations ranging from 2.0 to 50.0 ng L-1. The preliminary risk assessment indicates that various pesticides, caffeine, industrial chemicals, and PFAS were present at concentrations that could threaten aquatic life. Notably, risk quotients of 414, 340, and 178 were obtained for diuron, atrazine, and imidacloprid, respectively, in the Jundiaí River. Our study suggests that establishing a comprehensive monitoring program is needed to ensure the protection of aquatic life and human health.