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.

Linking above and belowground carbon sequestration, soil organic matter properties, and soil health in Brazilian Atlantic Forest restoration.

Forest restoration mitigates climate change by removing CO2 and storing C in terrestrial ecosystems. However, incomplete information on C storage in restored tropical forests often fails to capture the ecosystem's holistic C dynamics. This study provides an integrated assessment of C storage in above to belowground subsystems, its consequences for greenhouse gas (GHG) fluxes, and the quantity, quality, and origin of soil organic matter (SOM) in restored Atlantic forests in Brazil. Relations between SOM properties and soil health indicators were also explored. We examined two restorations using tree planting ('active restoration'): an 8-year-old forest with green manure and native trees planted in two rounds, and a 15-year-old forest with native-planted trees in one round without green manure. Restorations were compared to reformed pasture and primary forest sites. We measured C storage in soil layers (0-10, 10-20, and 20-30 cm), litter, and plants. GHG emissions were assessed using CH4 and CO2 fluxes. SOM quantity was evaluated using C and N, quality using humification index (HLIFS), and origin using δ13C and δ15N. Nine soil health indicators were interrelated with SOM attributes. The primary forest presented the highest C stocks (107.7 Mg C ha-1), followed by 15- and 8-year-old restorations and pasture with 69.8, 55.5, and 41.8 Mg C ha-1, respectively. Soil C stocks from restorations and pasture were 20% lower than primary forest. However, 8- and 15-year-old restorations stored 12.3 and 28.3 Mg ha-1 more aboveground C than pasture. The younger forest had δ13C and δ15N values of 2.1 and 1.7‰, respectively, lower than the 15-year-old forest, indicating more C derived from C3 plants and biological N fixation. Both restorations and pasture had at least 34% higher HLIFS in deeper soil layers (10-30 cm) than primary forest, indicating a lack of labile SOM. Native and 15-year-old forests exhibited higher soil methane influx (141.1 and 61.9 µg m-2 h-1). Forests outperformed pasture in most soil health indicators, with 69% of their variance explained by SOM properties. However, SOM quantity and quality regeneration in both restorations approached the pristine forest state only in the top 10 cm layer, while deeper soil retained agricultural degradation legacies. In conclusion, active restoration of the Atlantic Forest is a superior approach compared to pasture reform for GHG mitigation. Nonetheless, the development of restoration techniques to facilitate labile C input into deeper soil layers (>10 cm) is needed to further improve soil multifunctionality and long-term C storage.

Dissolved organic matter in bovine slaughterhouse wastewater using fluorescence spectroscopy associated with CP/PARAFAC and PCA methods.

In this work, we evaluated the potential application of fluorescence spectroscopy, associated with the canonical polyadic/parallel factor analysis and principal component analysis, to monitor the dissolved organic matter (DOM) generated from a slaughterhouse industry. During the monitoring process, we analyzed the residual water at the entrance and exit sites of the slaughterhouse effluent treatment as well as downstream and upstream the effluent receiving water body of a local river. The results revealed that the fluorescence analysis was able to identify proteins, chlorophylls, and humic substances at the entrance and exit sites of the slaughterhouse treatment plant and humic substances at the river water bodies. Our data also demonstrated that the industrial effluent discharged into the river did not impact the receiving water body quality as determined by the biological and humification indices obtained by fluorescence analysis, which was confirmed by conventional physicochemical analysis. In summary, the present findings indicate that fluorescence spectroscopy, in association with multivariate analysis, can be successfully applied as an analytical tool for evaluating the quality of DOM in slaughterhouse wastewater.

Humic extracts from hydrochar and Amazonian Anthrosol: Molecular features and metal binding properties using EEM-PARAFAC and 2D FTIR correlation analyses.

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.

Modeling the quenching of fluorescence from organic matter in Amazonian soils.

Knowledge of the interactions of soil organic matter (SOM) with metal species is important in order to obtain information concerning the fates of the metals in environment, whose reactive functional groups present in SOM can provide high complexation capacity. The aim of this study was to evaluate the interactions involving humic acids (HA) and fulvic acids (FA), extracted from Amazonian soils, with Cu(II) and Al(III) ions, using fluorescence quenching spectroscopy. The obtained results showed that the data for the humic fractions of the Amazonian Spodosols could be fitted with one to one complexation model, which provided the best representation of the changes in fluorescence quenching after addition of Cu(II) or Al(III) ions. It was found that the HA presented fewer complexation sites and lower stability constants, compared to the FA samples. Furthermore, the FA showed selective interaction with the metals, while the HA fraction was less selective and could be associated its homogeneous structure. The results showed that the humic acids required 10 times more carbon in their structures than fulvic acids for complexing a metal atom. This behavior can be associated to the fact that the Fulvic Acid fraction has higher mobility and greater interaction during the profile when compare humic acids. Hence, given the diversity of metals to which the HA has affinity, this soil fraction appears to be mainly responsible for soil fertility, while the FA fraction has higher mobility and greater interaction with water.

Fluorescence lifetime evaluation of whole soils from the Amazon rainforest.

Time-resolved fluorescence spectroscopy (TRFS) is a new tool that can be used to investigate processes of interaction between metal ions and organic matter (OM) in soils, providing a specific analysis of the structure and dynamics of macromolecules. To the best of our knowledge, there are no studies in the literature reporting the use of this technique applied to whole/non-fractionated soil samples, making it a potential method for use in future studies. This work describes the use of TRFS to evaluate the fluorescence lifetimes of OM of whole soils from the Amazon region. Analysis was made of pellets of soils from an oxisol-spodosol system, collected in São Gabriel da Cachoeira (Amazonas, Brazil). The fluorescence lifetimes in the oxisol-spodosol system were attributed to two different fluorophores. One was related to complexation of an OM fraction with metals, resulting in a shorter fluorophore lifetime. A short fluorescence lifetime (2-12 ns) could be associated with simpler structures of the OM, while a long lifetime (19-66 ns) was associated with more complex OM structures. This new TRFS technique for analysis of the fluorescence lifetime in whole soil samples complies with the principles of green chemistry.

The importance of humin in soil characterisation: A study on Amazonian soils using different fluorescence techniques.

Soil organic matter (SOM) is a complex mixture of molecules with different physicochemical properties, with humic substances (HS) being the main component as it represents around 20-50% of SOM structure. Soil of the Amazon region is considered one of the larger carbon pools of the world; thus, studies of the humic fractions are important for understanding the dynamics of organic matter (OM) in these soils. The aim of this study was to use laser-induced fluorescence spectroscopy (LIFS) and a combination of excitation-emission matrix (EEM) fluorescence with Parallel Factor Analysis (CP/PARAFAC) to assess the characteristics of humin (HU) extracted from Amazonian soils. The results obtained using LIFS showed that there was an increasing gradient of humification degree with depth, the deeper horizon presenting a higher amount of aromatic groups in the structure of HU. From the EEM, the contribution of two fluorophores with similar behaviour in the structures of HU and whole soil was assessed. Additionally, the results showed that the HU fraction might represent a larger fraction of SOM than previously thought: about 80-93% of some Amazon soils. Therefore, HU is an important humic fraction, thus indicating its role in environmental analysis, mainly in soil analysis.

Off-line TMAH-GC/MS and NMR characterization of humic substances extracted from river sediments of northwestern São Paulo under different soil uses.

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.