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Distinct Non-conservative Behavior of Dissolved Organic Matter after Mixing Solimoes/Negro and Amazon/Tapajos River Waters.

ABSTRACT: Positive and negative electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry and ¹H NMR revealed major compositional and structural changes of dissolved organic matter (DOM) after mixing two sets of river waters in Amazon confluences: the Solimões and Negro Rivers (S + N) and the Amazon and Tapajós Rivers (A + T). We also studied the effects of water mixing ratios and incubation time on the composition and structure of DOM molecules. NMR spectra demonstrated large-scale structural transformations in the case of S + N mixing, with gain of pure and functionalized aliphatic units and loss of all other structures after 1d incubation. A + T mixing resulted in comparatively minor structural alterations, with a major gain of small aliphatic biomolecular binding motifs. Remarkably, structural alterations from mixing to 1d incubation were in essence reversed from 1d to 5d incubation for both S + N and A + T mixing experiments. Heterotrophic bacterial production (HBP) in endmembers S, N, and S + N mixtures remained near 0.03 μgC L^-1 h^-1, whereas HBP in A, T, and A + T were about five times higher. High rates of dark carbon fixation took place at S + N mixing in particular. In-depth biogeochemical characterization revealed major distinctions between DOM biogeochemical changes and temporal evolution at these key confluence sites within the Amazon basin.

SUBMITTER: Li S

PROVIDER: S-EPMC10425957 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature

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Distinct Non-conservative Behavior of Dissolved Organic Matter after Mixing Solimões/Negro and Amazon/Tapajós River Waters.

Li Siyu S Harir Mourad M Schmitt-Kopplin Philippe P Machado-Silva Fausto F Gonsior Michael M Bastviken David D Enrich-Prast Alex A Valle Juliana J Hertkorn Norbert N

ACS ES&T water 20230612 8

Positive and negative electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry and <sup>1</sup>H NMR revealed major compositional and structural changes of dissolved organic matter (DOM) after mixing two sets of river waters in Amazon confluences: the Solimões and Negro Rivers (S + N) and the Amazon and Tapajós Rivers (A + T). We also studied the effects of water mixing ratios and incubation time on the composition and structure of DOM molecules. NMR spectra demonstrat ...[more]

PMID: 37588807

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Project description:The purpose of this work was to evaluate the somatosensory system of methylmercury-exposed inhabitants living in the communities of the Tapajós river basin by using psychophysical tests and to compare with measurements performed in inhabitants of the Tocantins river basin. We studied 108 subjects from Barreiras and São Luiz do Tapajós, two communities of the Tapajós river basin, State of Pará, Amazon, Brazil, aged 13-53 years old. Mercury analysis was performed in head hair samples weighting 0.1-0.2 g by using atomic absorption spectrometry. Three somatosensory psychophysical tests were performed: tactile sensation threshold, vibration sensation duration, and two-point discrimination. Semmes-Weinstein 20 monofilaments with different diameters were used to test the tactile sensation in the lower lip, right and left breasts, right and left index fingers, and right and left hallux. The threshold was the thinner monofilament perceived by the subject. Vibration sensation was investigated using a 128 Hz diapason applied to the sternum, right and left radial sides of the wrist, and right and left outer malleoli. Two trials were performed at each place. A stopwatch recorded the vibration sensation duration. The two-point discrimination test was performed using a two-point discriminator. Head hair mercury concentration was significantly higher in mercury-exposed inhabitants of Tapajós than in non-exposed inhabitants of Tocantins (p < 0.01). When all subjects were divided in two groups independently of age-mercury-exposed and non-exposed-the following results were found: tactile sensation thresholds in mercury-exposed subjects were higher than in non-exposed subjects at all body parts, except at the left chest; vibration sensation durations were shorter in mercury-exposed than in non-exposed subjects, at all locations except in the upper sternum; two-point discrimination thresholds were higher in mercury-exposed than in non-exposed subjects at all body parts. There was a weak linear correlation between tactile sensation threshold and mercury concentration in the head hair samples. No correlation was found for the other two measurements. Mercury-exposed subjects had impaired somatosensory function compared with non-exposed control subjects. Long-term mercury exposure of riverside communities in the Tapajós river basin is a possible but not a definitely proven cause for psychophysical somatosensory losses observed in their population. Additionally, the relatively simple psychophysical measures used in this work should be followed by more rigorous measures of the same population.

Project description:The determination of copper (Cu) speciation and its bioavailability in natural waters is an important issue due to its specific role as an essential micronutrient but also a toxic element at elevated concentrations. Here, we report an improved anodic stripping voltammetry (ASV) method for organic Cu speciation, intended to eliminate the important problem of surface-active substances (SAS) interference on the voltammetric signal, hindering measurements in samples with high organic matter concentration. The method relies on the addition of nonionic surfactant Triton-X-100 (T-X-100) at a concentration of 1 mg L-1. T-X-100 competitively inhibits the adsorption of SAS on the Hg electrode, consequently 1) diminishing SAS influence during the deposition step and 2) strongly improving the shape of the stripping Cu peak by eliminating the high background current due to the adsorbed SAS, making the extraction of Cu peak intensities much more convenient. Performed tests revealed that the addition of T-X-100, in the concentration used here, does not have any influence on the determination of Cu complexation parameters and thus is considered "interference-free." The method was tested using fulvic acid as a model of natural organic matter and applied for the determination of Cu speciation in samples collected in the Arno River estuary (Italy) (in spring and summer), characterized by a high dissolved organic carbon (DOC) concentration (up to 5.2 mgC L-1) and anthropogenic Cu input during the tourist season (up to 48 nM of total dissolved Cu). In all the samples, two classes of ligands (denoted as L1 and L2) were determined in concentrations ranging from 3.5 ± 2.9 to 63 ± 4 nM eq Cu for L1 and 17 ± 4 to 104 ± 7 nM eq Cu for L2, with stability constants logK Cu,1 = 9.6 ± 0.2-10.8 ± 0.6 and logK Cu,2 = 8.2 ± 0.3-9.0 ± 0.3. Different linear relationships between DOC and total ligand concentrations between the two seasons suggest a higher abundance of organic ligands in the DOM pool in spring, which is linked to a higher input of terrestrial humic substances into the estuary. This implies that terrestrial humic substances represent a significant pool of Cu-binding ligands in the Arno River estuary.

Dataset Information

Distinct Non-conservative Behavior of Dissolved Organic Matter after Mixing Solimoes/Negro and Amazon/Tapajos River Waters.

Publications

Distinct Non-conservative Behavior of Dissolved Organic Matter after Mixing Solimões/Negro and Amazon/Tapajós River Waters.

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