Interaction Of Humic Substances Research Articles

Size evolution of EuIII–fulvic acid complexes with pH, metal, and fulvic acid concentrations: implications for modelling of metal–humic substances interactions

Size evolution of EuIII–fulvic acid complexes with pH, metal, and fulvic acid concentrations: implications for modelling of metal–humic substances interactions

Porous polymer monolithic columns to investigate the interaction of humic substances with herbicides and emerging pollutants by affinity chromatography

BackgroundUnderstanding the interaction mechanisms and the relevant binding constants between humic acids and emerging or regulated pollutants is of utmost importance in predicting their geochemical mobility, bioavailability, and degradation. Fluorescence spectroscopy, UV–vis spectroscopy, equilibrium dialysis, and solid-phase extraction combined with liquid chromatography-mass spectrometry have been employed to elucidate interactions of humic acids with organic micropollutants, especially pharmaceutical drugs. These methods demand large sample volumes, long equilibration times, and laborious extraction steps which may imply analytical errors. Monolithic high-performance affinity chromatography is an alternative and simpler method to investigate these interactions and determine the binding constants. ResultsPolymer monoliths based on aminated glycidyl methacrylate and ethylene glycol dimethacrylate served to immobilize Cu(II) and then humic acid to produce monolithic affinity chromatography columns with humic acid as the active interaction phase. About 86.5 mg of humic acid was immobilized per gram of polymer. The columns enabled a comparison of the binding strength of humic acid with herbicides and emerging pollutants at 25 °C and pH 6.0 ± 0.1. Paracetamol, acetylsalicylic acid, and salicylic acid did not retain. Among the compounds that interacted with humic acid, the order of increasing affinity, estimated by the global affinity constant (nKa) or partition coefficient (KD) was: caffeine < simazine < atrazine ∼ propazine < benzophenone. The nKa (L mol−1) values ranged from (4.9 ± 0.3) × 102 for caffeine to (1.9 ± 0.3) × 103 for benzophenone, whereas KD (L kg−1) varied from 14 ± 1 to 56 ± 8 for the same compounds. Significance and noveltyTo our knowledge, this is the first paper demonstrating the use of a monolithic platform to immobilize supramolecular structures of humic acids exploiting immobilized metal affinity to comparatively evaluate their affinity towards emerging pollutants exploiting the concepts of high-performance affinity chromatography. The proposed approach needs only small amounts of humic acid, which is a relevant feature in preparing columns with humic substances isolated and purified from remote areas.

Interaction between roxarsone, an organic arsenic compound, with humic substances in the soil simulating environmental conditions

In environmental systems, the soil is a principal route of contamination by various potentially toxic species. Roxarsone (RX) is an arsenic (V) organic compound used to treat parasitic diseases and as an additive for animal fattening. When the animal excretes RX, the residues may lead to environmental contamination. Due to their physicochemical properties, the soil's humic substances (HS) are important in species distribution in the environment and are involved in various specific interaction/adsorption processes. Since RX, an arsenic (V) compound, is considered an emerging contaminant, its interaction with HS was evaluated in simulated environmental conditions. The HS-RX interaction was analyzed by monitoring intrinsic HS fluorescence intensity variations caused by complexation with RX, forming non-fluorescent supramolecular complexes that yielded a binding constant Kb (on the order of 103). The HS-RX interaction occurred through static quenching due to complex formation in the ground state, which was confirmed by spectrophotometry. The process was spontaneous (ΔG < 0), and the predominant interaction forces were van der Waals and hydrogen bonding (ΔH < 0 and ΔS < 0), with an electrostatic component evidenced by the influence of ionic strength in the interaction process. Structural changes in the HS were verified by synchronized and 3D fluorescence, with higher variation in the region referring to the protein-like fraction. In addition, metal ions (except ions Cu(II)) favored HS-RX interaction. When interacting with HS, the RX epitope was suggested by 1H NMR, which indicated that the entire molecule interacts with the superstructure. An enzyme inhibition assay verified the ability to reduce the alkaline phosphatase activity of free and complexed RX (RX-HS). Finally, this work revealed the main parameters associated with HS and RX interaction in simulated environmental conditions, thus, providing data that may help our understanding of the dynamics of organic arsenic-influenced soils.

The molecular conformation, but not disaggregation, of humic acid in water solution plays a crucial role in promoting plant development in the natural environment.

Many studies have shown the capacity of soil humic substances (HS) to improve plant growth in natural ecosystems. This effect involves the activation of different processes within the plant at different coordinated molecular, biochemical, and physiological levels. However, the first event triggered by plant root-HS interaction remains unclear. Some studies suggest the hypothesis that the interaction of HS with root exudates involves relevant modification of the molecular conformation of humic self-assembled aggregates, including disaggregation, which might be directly involved in the activation of root responses. To investigate this hypothesis, we have prepared two humic acids. A natural humic acid (HA) and a transformed humic acid obtained from the treatment of HA with fungal laccase (HA enz). We have tested the capacity of the two humic acids to affect plant growth (cucumber and Arabidopsis) and complex Cu. Laccase-treatment did not change the molecular size but increased hydrophobicity, molecular compactness and stability, and rigidity of HA enz. Laccase-treatment avoided the ability of HA to promote shoot- and root-growth in cucumber and Arabidopsis. However, it does not modify Cu complexation features. There is no molecular disaggregation upon the interaction of HA and HA enz with plant roots. The results indicate that the interaction with plant roots induced in both HA and laccase-treated HA (HA enz), changes in their structural features that showed higher compactness and rigidity. These events might result from the interaction of HA and HA enz with specific root exudates that can promote intermolecular crosslinking. In summary, the results indicate that the weakly bond stabilized aggregated conformation (supramolecular-like) of HA plays a crucial role in its ability to promote root and shoot growth. The results also indicate the presence of two main types of HS in the rhizosphere corresponding to those non-interacting with plant roots (forming aggregated molecular assemblies) and those produced after interacting with plant root exudates (forming stable macromolecules).

Recovery of phosphorus from wastewater containing humic substances through vivianite crystallization: Interaction and mechanism analysis

Vivianite crystallization has been regarded as a suitable option for recovering phosphorus (P) from P-containing wastewater. However, the presence of humic substances (HS) would inevitably affect the formation of vivianite crystals. Therefore, the influences of HS on vivianite crystallization and the changes in the harvested vivianite crystals were investigated in this study. The results suggested the inhibition effect of 70 mg/L HS on vivianite crystallization reached 12.24%, while it could be attenuated by increasing the pH and Fe/P ratio of the solution. Meanwhile, the addition of HS altered the size, purity, and morphology of recovered vivianite crystals due to the blockage of the growth sites on the crystal surface. Additionally, the formation of phosphate ester group, hydrogen bonding, and COOH–Fe2+ complexes are the potential mechanisms of HS interaction with vivianite crystals. The results obtained herein will help to elucidate the underlying mechanism of HS on vivianite crystallization from P-containing wastewater.

Interaction of Antibiotics and Humic Substances: Environmental Consequences and Remediation Prospects.

The occurrence and distribution of antibiotics in the environment has received increasing attention due to their potential adverse effects on human health and ecosystems. Humic substances (HS) influence the mobility, reactivity, and bioavailability of antibiotics in the environment significantly due to their interaction. As a result, HS can affect the dissemination of antibiotic-resistance genes, which is one of the main problems arising from contamination with antibiotics. The review provides quantitative data on the binding of HS with fluoroquinolones, macrolides, sulfonamides, and tetracyclines and reports the proposed mechanisms of their interaction. The main issues of the quantification of antibiotic-HS interaction are discussed, which are a development of standard approaches and the accumulation of a dataset using a standard methodology. This would allow the implementation of a meta-analysis of data to reveal the patterns of the binding of antibiotics to HS. Examples of successful development of humic-based sorbents for fluoroquinolone and tetracycline removal from environmental water systems or polluted wastewaters were given. Data on the various effects of HS on the dissemination of antibiotic-resistance genes (ARGs) were summarized. The detailed characterization of HS properties as a key point of assessing the environmental consequences of the formation of antibiotic-HS complexes, such as the dissemination of antibiotic resistance, was proposed.

Sorption of Fulvic Acids and Their Compounds with Heavy Metal Ions on Clay Minerals

In real soils the interaction of humic substances with clay minerals often occurs with the participation of metal cations. The adsorption of fulvic acids (FA) solution and their solutions in the presence of heavy metal ions (Pb or Zn) on two clay minerals (kaolinite and bentonite) was investigated by measurement of the optical density changes in the of equilibrium solutions. The FA adsorption by bentonite at the concentrations 0.05–1 g/L proceeds according to the polymolecular mechanism and has a stepwise character. The adsorption of FA on kaolinite can be described by the mechanism of monomolecular adsorption. In three-component systems, including FA, trace element ions and a clay mineral, complex processes occur, including the formation of complexes and salts and their adsorption. The sorption of colored complexes of FA with Pb on the surface of kaolinite and bentonite increases with increasing metal concentrations (0.5–2 mmol/L). The interaction of the FA-Zn2+ compounds with bentonite is a more complicated process—adsorption takes place at the lowest concentration used only. Thus, binding of FA by clay minerals in the presence of metal cations is a complex phenomenon due to the chemical heterogeneity of FA, different properties of metals, characteristics of mineral surfaces and the variability of environmental conditions.

Application of humic substances and bottom ash compounds in improving soil quality in limestone post-mining land

Limestone mining leaves the ex-mine land with poor soil chemical quality. Humic substances can be used as fertilizer to increase macronutrient availability in the soil and improve pH. The application of coal ash can improve the soil’s chemical, physical, and biological properties because it has a pH value, high organic C content, available P, and basic cations such as K, Na, Ca, and Mg. This research aims to determine the effect and interaction of humic substances and bottom ash interaction with different doses to improve soil quality after a limestone quarry. This research uses a randomized block design in a factorial pattern. This experiment consisted of humic substances (H) with 4 levels H0, H1 (0.09%), H2 (0.12%), and H3 (0.15%), and bottom ash (B) with three levels: B0, B1 (400 grams), B2 (600 grams). Humic substances at H2 concentration (0.15%) significantly increased C-organic, K, P-available, Mg-dd, and increased plant height. In contrast, bottom ash treatment at a B2 (600 grams) dose significantly affected the increase in C-organic, P-available, and Mg-dd. The treatment of humic substances with concentrations of H3 (0.15%) and bottom ash at a dose of 600 grams is the best interaction characterized by an increase in soil pH, CEC, Ca-dd, K, and Na. The application of a concentration of H3 (0.15%) and the provision of a dose of B2 (600 grams) or 120 tons/ha significantly affect the chemical properties of post-mining soils limestone and increase plant height.

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.

Evaluation of Commercial Humic Substances and Other Organic Amendments for the Immobilization of Copper Through 13C CPMAS NMR, FT-IR, and DSC Analyses

The application of organic amendments to contaminated agricultural lands can immobilize metals and improve soil conditions. The chemical structures and long-term stability of commercial humic substances and other composted organic amendments (sheep and horse manure, vermicompost, pine bark, and pruning waste) were analyzed using 13C CPMAS NMR, FT-IR, and DSC to evaluate their use in soil remediation. The interactions of humic substances and manure with Cu (0 and 5000 mg kg−1) at different pH (2.5 and 5.0) were studied through a batch adsorption experiment observing the changes in their molecular structure using spectroscopic techniques. Humic substances exhibited high aromaticity and phenolic and carboxylic group content, with great affinity for Cu complexation. Humic substances and pruning waste were the most stable due to their high recalcitrant organic matter contents, whereas manure was the least stable, given the labile nature of its organic matter content. There were considerable changes in the carboxylic and phenolic groups of humic substances with pH, and also with Cu, albeit in a lesser extent, especially at pH 5.0, suggesting the great sorption capacity of humic substances and the key role of pH and these functional groups in metal complexation. Manure did not exhibit such changes. Commercial humic substances could be useful amendments for the remediation of contaminated agricultural soils due to their high sorption capacities and long-term stability.

Adsorption of Cu(II) on soil humin: batch and spectroscopy studies

Understanding the interactions of humic substances with metal ions is of great importance in forecasting the behaviors and fates of trace metals in the environment. Humin is the least understood humic substance fraction due to its close association with the mineral matrix in soil. In this study, humin was prepared from three zonal soils (i.e., dark brown soil, yellow brown soil, and latosol) in eastern China by demineralization using HF–HCl solution after removing alkaline-soluble humic substance fractions. The adsorption properties of Cu(II) onto both humin and humic acid were examined using batch and spectroscopy (SEM, EDS, FTIR, XPS, and XAS) techniques. With respect to humic acid, humin was more aliphatic and less polar. The adsorption kinetics of humin and humic acid were best fit with pseudo-second-order kinetics equation, and the adsorption isotherms were well depicted by the Langmuir model. However, the quantity of adsorbed Cu(II) on humin was inferior to that of Cu(II) adsorbed onto humic acid. After adsorption, the surface morphology of humin and humic acid changed. Carboxyl, hydroxyl, aromatic N, and primary amine N on the surfaces of the two humic substance fractions took part in Cu(II) adsorption, and Cu(II) was bound with O/N and C atoms via inner-sphere complexation. Our results suggested that humin and humic acid had different adsorption capacity but similar adsorption mechanisms toward Cu(II).

Effect of Soil Fulvic and Humic Acids on Pb Binding to the Goethite/Solution Interface: Ligand Charge Distribution Modeling and Speciation Distribution of Pb.

The effect of adsorbed soil fulvic (JGFA) and humic acid (JGHA) on Pb binding to goethite was studied with the ligand charge distribution (LCD) model and X-ray absorption fine structure (XAFS) spectroscopy analysis. In the LCD model, the adsorbed small JGFA particles were evenly located in the Stern layer, but the large JGHA particles were distributed over the Stern layer and the diffuse layer, which mainly depended on the JGHA diameter and concentrations. Specific interactions of humic substances (HS) with goethite were modeled by inner-sphere complexes between the -FeOH20.5+ of goethite and the -COO- of HS and by Pb bridges between surface sites and COO- groups of HS. At low Pb levels, nearly 100% of Pb was bound as Pb bridges for both JGFA and JGHA. At high Pb levels and low HS loading, Pb-goethite almost dominated over the entire studied pH range, but at high HS loading, the primary species was goethite-HS-Pb at acidic pH and goethite-Pb at alkaline pH. Compared with JGFA, there was a constant contribution of Pb bridges of about 10% for JGHA. The linear combination fit of EXAFS, using Pb-HS and Pb-goethite as references, indicated that with increased HS loading more Pb was bound to adsorbed HS and less to goethite, which supported the LCD calculations.

The research of the influence of heavy metal ions on the aggregation of humic substances on the mica by atomic force microscopy

The conformation of molecules of humic substances of peats sorbed on hydrophilic mica in the absence and presence of heavy metal ions was studied by atomic-force microscopy in semi-contact mode in an aqueous medium. A model of the lignin-carbon complex is proposed, which ensures the conformation of the three-dimensional ring structure of humic substances depending on pH and allows accurate description of the surface structure of humic substances. The sizes of single globular molecules of humic substances were determined: 140-320 nm in diameter and 5-25 nm in height. Possible ways of the interaction of humic substances of peats with metal cations (Pb 2 + and Zn 2 +) with account of conformational changes of humic substances have been established. It has been proven that lead cations are sorbed mainly on the surface of humic molecules, and sorption of zinc cations proceeds with reorientation of humic substances around zinc ions.

Organic Matter Stocks and the Interactions of Humic Substances with Metals in Araucaria Moist Forest Soil with Humic and Histic Horizons

ABSTRACT Soils with humic and histic horizons in tropical and subtropical ecosystems play an important role in determining the atmospheric C stock and its stabilization, climate regulation, water holding capacity, and environmental filtering, due to the different functions of soil organic matter (SOM). However, the processes and mechanisms that regulate SOM dynamics in these soils are not clear. The objectives of this study were: i) determine the C and N stocks and ii) investigate the SOM chemical fractions and their [...]

The roles of humic substances in the interactions of phenanthrene and heavy metals on the bentonite surface

The fate of complex contaminants in soils has aroused increasing attention of environmental scientists. Although heavy metals and polycyclic aromatic hydrocarbons (PAHs) are often encountered together in contaminated sites, the interactions between the co-existing contaminants with clay minerals and humic substances require further investigation. Phenanthrene, lead (Pb), and cadmium (Cd) were selected as the representatives to investigate their interactions on the surface of bentonite (primarily montmorillonite) and humic acid/fulvic acid-coated bentonite in batch sorption experiments. Their bonding strengths were assessed in terms of extractability by various chemical extraction methods. The humic acid coating on bentonite enhanced the Pb and Cd sorption capacity, especially at the high Pb loading where the linear sorption coefficient was dramatically increased. The fulvic acid coating had less significant effects because of its higher solubility. The co-existing phenanthrene promoted the Pb sorption to a greater extent on humic acid-coated bentonite due to greater phenanthrene sorption, while the phenanthrene sorption was also promoted by the co-existing Pb. However, the enhancement was less obvious for Cd sorption, possibly due to greater hydration and weaker complexation with oxygen-containing groups despite higher electron polarizability of Cd. On the other hand, the presence of humic acid coating increased both (weakly bound) exchangeable fraction and (strongly bound) residual fraction of sorbed Pb. In contrast, co-existing phenanthrene and Pb resulted in redistribution of each other from weakly bound to strongly bound fractions. Such strengthened bonding of both Pb and phenanthrene indicated the significance of strong cation-π bonding on the bentonite. Yet, such enhancement might be alleviated by the humic acid coating. Understanding the intercorrelated interactions of humic substances, phenanthrene, and heavy metals on clay minerals would help us to maneuver an effective in situ remediation of complex soil contamination.

Interaction of humic substances on fouling in membrane distillation for seawater desalination

The interaction of humic substances on organic and biofouling during the treatment of seawater using direct contact membrane distillation (DCMD) was studied. Organic fouling was investigated at different feed temperatures in terms of distillate flux pattern and detailed organic characterization using liquid chromatography-organic carbon detection. The penetration of organics through the membrane pores was observed with SEM cross-section analysis. Also, chemical cleaning analysis showed seawater organic fouling was irreversible in DCMD. Humic substances and low molecular weight (LMW) organics are dominant organic contents in seawater. In the tested DCMD system, humic substances were thermally disaggregated to LMW–humic organics. This phenomenon was more significant in the presence of salt (NaCl), while inorganic scalant (CaSO4) reduced the disaggregation of humic substances due to the binding effect. In this study, the assimilable organic carbon (AOC) test was used to estimate the biological fouling potential during the MD process. AOC concentration is closely associated with biofilm growth in water and on the membrane (biofouling). The AOC concentration increased as the concentration of LMW–humic organics increased. This indicated the possibility of biofouling increasing in the feed and on the membrane in the MD process.

Sorption of humic acids by quartz sands

The sorption of humic acids on different types of silicon-containing materials was studied. It was shown that the interaction of humic acid fragments with a mineral surface depends on acid-base and surfaceactive properties and on the composition of the mineral sorbent surface. An increase in the aluminum content of the sorbent strengthens the interaction of humic substances with the mineral surface. It was established that the humic acids of peat were better sorbed on the silicon-containing surface due to the predominance of oxygen-containing groups in the composition of fragments.

Influence of humic acid on neptunium(V) sorption and diffusion in Opalinus Clay

SummaryThe influence of14C-labeled M42 humic acid (HA) on the interaction between neptunium(V) and natural clay rock (Opalinus Clay (OPA), Switzerland) has been investigated in batch sorption and diffusion experiments under ambient air conditions. The effect of 10 mg/L HA on the diffusion of 8 μM Np(V) in OPA has been investigated in synthetic OPA pore water (pH 7.6, I = 0.4M) for the first time. Batch sorption experiments as a function of solid-to-liquid ratio (4-20 g/L) were performed under same experimental conditions to compare distribution coefficients obtained from both diffusion and sorption experiments. These experiments showed only a slight influence of HA on Np(V) uptake by OPA in both cases and provided comparable distribution coefficients (presence of HA: Kd= 22-32 L/kg, absence of HA: Kd= 30-46 L/kg). As it is known that the interactions of humic substances with actinides depend on various experimental parameters, the effect of HA on Np(V) sorption on 15 g/L OPA was also investigated as a function of pH (6-10) and initial Np concentration (8 μM and 7 pM). A saturated calcite solution was used as a background electrolyte in this case to prevent any dissolution of calcite contained in OPA at low pH. The results showed that the presence of M42 HA increases Np(V) sorption at pH &lt; 7 while lower sorption was obtained above pH 8. Higher sorption at acidic pH can be attributed to strong sorption of HA which increases the number of sorption sites, while sorption decreases at higher pH probably due to formation of soluble ternary neptunium humate carbonate species.

Investigating humic substances interactions with Th4+, [formula omitted], and [formula omitted] at high pH: Relevance to cementitious disposal of radioactive wastes

A number of geodisposal concepts for intermediate level radioactive waste involve geological emplacement within cementitious repositories. Such facilities, once rehydrated with groundwater, will create high pH environments due to aqueous phase reaction of the cements. This work focuses on the interactions of several important long-lived radionuclide cations with dissolved organic matter (DOM) constituents (humic and fulvic acids) under high pH conditions. We also sought to test the comprehensive speciation model WHAM/Humic Ion Binding Model VII for these specific conditions. Results for Th demonstrate high fractions present as organic complexes at all pH values. Binding of neptunyl to DOM shows a maximum over the pH range expected within an evolving repository. Uranyl exhibits decreasing binding with pH, however, the majority of metal in solution is present as organic complexes under the lower pH conditions investigated (10–10.5). We have updated the WHAM/Model VII binding values for UO22+, and have for the first time added NpO2+ values to the database. These updates now allow application of the model for more complex mixtures across the entire repository pH range. Calculations for three simulated cement interstitial waters (representing different degradation phases) suggest U(VI) and Np(V) are not likely to be significantly bound to DOM under these conditions.

Humic substances from sediments of Lobos Pond (Argentina). Isolation, characterization and limnological implications

Humic substances (HS) were isolated from the sediments of Lobos Pond (Argentina) using mild conditions to preserve their native structure. The HS (humic and fulvic acids) were characterized by means of elemental analysis and FTIR spectroscopy. Also a by-product obtained during fulvic acids (FA) fractionation (an amorphous white solid residue) was analyzed. Results revealed possible interactions between FA and inorganic-organic substances that may have implications referring to bioavailability. Other limnological implications, such as autochtonous origin of HS linked with the hydrology, and change of pH during stormy weather that affects HS interactions, are discussed.