Interactions fulvate-metal (Zn2+, Cu2+ and Fe2+): theoretical investigation of thermodynamic, structural and spectroscopic properties

Bertoli, Alexandre C.; Garcia, Jerusa Simone; Trevisan, Marcello G.; Ramalho, Teodorico C.; Freitas, Matheus P.

doi:10.1007/s10534-016-9914-8

Cited by 17 publications

(17 citation statements)

References 34 publications

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“…This may indicate that OH stretches of groups derived from alcohol or phenol and OH stretches of carboxylic groups participate together with the complexation with iron and copper ions. [13][14][15][16][17][18][19] X-ray diffraction (XRD)…”

Section: Vibrations Characteristic Of Chmentioning

confidence: 99%

New Organomineral Complex from Humic Substances Extracted from Poultry Wastes: Synthesis, Characterization and Controlled Release Study

Santos¹,

Bertoli²,

Borges³

et al. 2017

J. Braz. Chem. Soc.

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The present study reports the synthesis and characterization of complexes formed among humic (HA) and fulvic acids (FA) derived from poultry wastes and ions Cu 2+ , Fe 2+ and Zn 2+. The release of such metals in a buffer solution simulating the soil solution was also evaluated. After complexation, the Fourier transform infrared (FTIR) spectra presented alterations in the absorption bands related to changes in the humic structure, thus indicating the complexation with phenolic and carboxylic groups. Thermogravimetric analyses demonstrated that complexed metals decreased the thermal stability of humic substances. Analyses by atomic absorption spectroscopy (AAS) demonstrated that the release of metals is directly related to the origin of the sample, type of interaction of metal and humic structure and conditions of the medium in which the complex is inserted.

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Section: Vibrations Characteristic Of Chmentioning

confidence: 99%

New Organomineral Complex from Humic Substances Extracted from Poultry Wastes: Synthesis, Characterization and Controlled Release Study

Santos¹,

Bertoli²,

Borges³

et al. 2017

J. Braz. Chem. Soc.

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“…As a consequence, FAs exhibit a high sorption capacity to cationic substances, hence they can play a key role in controlling speciation, bioavailability, toxicity and mobility of metals [11][12][13]. According to Bertoli et al [14], the absence of chelates of metals, like Zn, Cu and Fe, makes these elements insufficient, thus causing deficiencies in the plant and inhibiting root growth. As suggested by Curie and Briat [15], this problem can stem from the predominantly hydrophilic character of cations and the hydrophobic nature of pores or openings in roots and leaves.…”

Section: Introductionmentioning

confidence: 99%

“…The complexity of interactions with Zn is also influenced by the properties of FAs originating from various sources. Soil, animal, vegetal or microbiological FAs can exhibit a different chemical composition and conformation revealing a varied molecular weight, humification degree, content of O, C, H and N, functional groups, aromatic and aliphatic structures [14,34,35]. In their studies on complexes between humic substances and ions Cu 2+ , Fe 2+ and Zn 2+ , Santos et al [4] noted that the interactions were influenced by the origin and structure of the organic samples used and should be evaluated separately.…”

Section: Introductionmentioning

confidence: 99%

“…In their studies on complexes between humic substances and ions Cu 2+ , Fe 2+ and Zn 2+ , Santos et al [4] noted that the interactions were influenced by the origin and structure of the organic samples used and should be evaluated separately. Moreover, high FAs heterogeneity and the variability of environmental factors may result in a high diversity of possible types of interactions, including ion-exchange, surface-adsorption, coagulation, peptization, chelation, metal bridging and hydrogen bonds participation [14,17,27,36].…”

Section: Introductionmentioning

confidence: 99%

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Zinc Binding to Fulvic acids: Assessing the Impact of pH, Metal Concentrations and Chemical Properties of Fulvic Acids on the Mechanism and Stability of Formed Soluble Complexes

Boguta

Sokołowska

2020

Molecules

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The aim of the study was defined as a complementary analysis of molecular interactions between zinc (Zn) and fulvic acids (FAs) at a broad pH range (3–7), different metal concentrations (0–50 mg dm−3) and chemical properties of FAs and their impact on the Zn binding mechanism, stability, and efficiency. The results showed that the complexation reaction prevailed at pH 6 and 7, whereas protons exchange dominated interactions at pH 3. Stability constant of the complexes increased along with pH (logK increased from ~3.8 to 4.2). Complexation was preferred by less-humidified structures of lower molecular mass containing more oxygen groups. The number of fluorophores available for Zn(II) increased from pH 3 to 7 by ~44%. Depending on the pH, complexation involved a bidentate chelate, monodentate and bidentate bridging mode. Zn(II) binding was insufficiently modeled by the classic Stern–Volmer equation and well described by the double logarithmic equation (R > 0.94) as well as by a modified Stern–Volmer formula assuming the existence of available and unavailable fluorophore populations (R > 0.98). The fluorescence ratio of different fluorophores was proposed as an indicator of the binding affinity of various structures. A positive relationship was found between the fraction of accessible fluorophores and Zn(II) binding at pH 7 determined based on proton release (R = 0.91–0.97). The obtained results can find application in controlling the mobility and bioavailability of Zn in different conditions.

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“…The chelating properties of FA can either reduce toxicity when there is an excess of copper, or prevent it from precipitating as insoluble hydroxide, which renders it inaccessible to the plant (Boguta and Sokołowska, 2020;Bertoli et al, 2016;Stevenson, 1994). Tadini et al (2020) studied the interaction of copper with FA from Amazonian Spodosols.…”

Section: Introductionmentioning

confidence: 99%

Fulvic acids from Amazonian anthropogenic soils: Insight into the molecular composition and copper binding properties using fluorescence techniques

Santos

Fregolente

Mounier

et al. 2020

Ecotoxicology and Environmental Safety

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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 oxygenfunctional 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.

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Interactions fulvate-metal (Zn2+, Cu2+ and Fe2+): theoretical investigation of thermodynamic, structural and spectroscopic properties

Cited by 17 publications

References 34 publications

New Organomineral Complex from Humic Substances Extracted from Poultry Wastes: Synthesis, Characterization and Controlled Release Study

New Organomineral Complex from Humic Substances Extracted from Poultry Wastes: Synthesis, Characterization and Controlled Release Study

Zinc Binding to Fulvic acids: Assessing the Impact of pH, Metal Concentrations and Chemical Properties of Fulvic Acids on the Mechanism and Stability of Formed Soluble Complexes

Fulvic acids from Amazonian anthropogenic soils: Insight into the molecular composition and copper binding properties using fluorescence techniques

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