Pollution of the Arctic Ocean by potentially toxic elements (PTEs) is a current environmental pro... more Pollution of the Arctic Ocean by potentially toxic elements (PTEs) is a current environmental problem. Humic acids (HAs) play an important role in the regulation of PTE mobility in soil and water. The permafrost thaw releases ancient organic matter (OM) with a specific molecular composition into the Arctic watersheds. This could affect the mobility of PTEs in the region. In our study, we isolated HAs from two types of permafrost deposits: the Yedoma ice complex, which contains pristine buried OM, and the alas formed in the course of multiple thaw–refreezing cycles with the most altered OM. We also used peat from the non-permafrost region as the recent environmental endmember for the evolution of Arctic OM. The HAs were characterized using 13C NMR and elemental analysis. Adsorption experiments were conducted to assess the affinity of HAs for binding Cu2+ and Ni2+. It was found that Yedoma HAs were enriched with aliphatic and N-containing structures as compared to the much more aromat...
Large scale isolation—in gram quantities—of dissolved organic matter (DOM) from natural waters is... more Large scale isolation—in gram quantities—of dissolved organic matter (DOM) from natural waters is necessary for detailed investigation of its role in chemical and microbial processes driving carbon cycling under conditions of global climate change. The best candidate for a use in these large-scale experiments is a bulk sorbent Bondesil PPL, which has the same modification as the widely used Bond Elut PPL sorbent. There have been no studies so far reported on interchangeability of these sorbents with regard to DOM isolation. This work was devoted to comparative studies on sorption efficiency and molecular selectivity of these two sorbents—Bond Elut PPL and Bondesil PPL with regard to DOM components. Fulvic acids (FA) from peat water leachate were used as a model DOM. Laboratory solid phase extraction (SPE) setup was used for monitoring sorption recovery and extraction yield. It included three parallel experiments on pre-packed Bond Elut PPL cartridges (500 mg/3 mL) and three self-pac...
Natural products (e.g., polyphenols) have been used as biologically active compounds for centurie... more Natural products (e.g., polyphenols) have been used as biologically active compounds for centuries. Still, the mechanisms of biological activity of these multicomponent systems are poorly understood due to a lack of appropriate experimental techniques. The method of tritium thermal bombardment allows for non-selective labeling and tracking of all components of complex natural systems. In this study, we applied it to label two well-characterized polyphenolic compounds, peat fulvic acid (FA-Vi18) and oxidized lignin derivative (BP-Cx-1), of predominantly hydrophilic and hydrophobic character, respectively. The identity of the labeled samples was confirmed using size exclusion chromatography. Using ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT ICR MS), key differences in the molecular composition of BP-Cx-1 and FA-Vi18 were revealed. The labeled samples ([3H]-FA-Vi18 (10 mg/kg) and [3H]-BP-Cx-1 (100 mg/kg)) were administered to female BALB/c mice...
Redox moieties, which are present in the molecular backbone of humic substances (HS), govern thei... more Redox moieties, which are present in the molecular backbone of humic substances (HS), govern their antioxidant properties. We hypothesized that a directed modification of the humic backbone via incorporation of redox moieties with known redox properties might provide an efficient tool for tuning up antioxidant properties of HS. In this work, hydroquinonoid and hydronaphthoquinonoid centres were used, which possess very different redox characteristics. They were incorporated into the structure of coal (leonardite) humic acids CHA) and peat fulvic acids (PFA). For this goal, an oxidative copolymerization of phenols was used. The latter was induced via oxidation of hydroquinones and hydroxynapjtaquinones with a use of Fenton’s reagent. The structure of the obtained products was characterized using NMR and FTIR spectroscopy. H/D labelling coupled to FT ICR mass spectrometry analysis was applied for identification of the reaction products as a tool for surmising on reaction mechanism. It...
Humic substances (HS) are natural supramolecular systems of high- and low-molecular-weight compou... more Humic substances (HS) are natural supramolecular systems of high- and low-molecular-weight compounds with distinct immunomodulatory and protective properties. The key beneficial biological activity of HS is their antioxidant activity. However, systematic studies of the antioxidant activity of HS against biologically relevant peroxyl radicals are still scarce. The main objective of this work was to estimate the antioxidant capacity (AOC) of a broad set of HS widely differing in structure using an oxygen radical absorption capacity (ORAC) assay. For this purpose, 25 samples of soil, peat, coal, and aquatic HS and humic-like substances were characterized using elemental analysis and quantitative 13C solution-state NMR. The Folin–Ciocalteu method was used to quantify total phenol (TP) content in HS. The determined AOC values varied in the range of 0.31–2.56 μmol Trolox eqv. mg−1, which is close to the values for ascorbic acid and vitamin E. Forward stepwise regression was used to reveal...
The objective of this study was to synthesize iron (hydr)oxide nanoparticles (IONPs) stabilized b... more The objective of this study was to synthesize iron (hydr)oxide nanoparticles (IONPs) stabilized by humic substances, and to estimate the feasibility of their use for foliar application on iron deficient plants. The IONPs were synthesized by rapid hydrolysis of iron(III) nitrate in a solution of potassium humate. The iron speciation and nanoparticle morphologies were characterized using X-ray diffraction, transmission electron microscopy, and Mössbauer spectroscopy. The obtained sample of IONPs was applied at concentrations of 1- and 10-mM Fe, and 0.2% urea was used as an adjuvant. Wheat plants (Triticum aestivum L. cv. L15) were used for the iron uptake test. For both of the concentrations tested, spraying the nanoparticles resulted in a 70–75% higher iron content in wheat leaves compared to ferric ammonium salt of ethylenediaminetetraacetic acid (Fe-EDTA). The synergistic effect of humic substances acting as a surfactant seemed to promote an increase in the iron uptake of the ferri...
Parameters are proposed to describe the distribution of the effective electrophoretic mobilities ... more Parameters are proposed to describe the distribution of the effective electrophoretic mobilities of various anionic polyelectrolytes such as poly(styrene-4-sulfonates) and humic substances of different origins analyzed by capillary zone electrophoresis. The first step of the data treatment is a baseline correction and conversion of the electrophoretic raw time data to effective electrophoretic mobilities (μ-scale), taking into account the electroosmotic flow. With this new μ-scaling, the electropherograms are more representative of velocity-based separation phenomena than those using migration times, and a direct comparison of electropherograms is possible. Four different average electrophoretic mobilities were defined: the number-average effective mobility (μn), the weight-average effective mobility (μw), the z-average effective mobility (μz), and the peak-average electrophoretic mobility (μp). The polydispersity of the mobility of mixtures was described by the μw/μ⊓, μz/μw, and μp...
Eleven well characterized humic substances (HSs) were adsorbed from aqueous solution onto a Na‐ka... more Eleven well characterized humic substances (HSs) were adsorbed from aqueous solution onto a Na‐kaolin clay. The adsorption affinity (KL), maximum adsorption capacity (b), a coefficient of desorption hysteresis (H), and the concentration of irreversibly adsorbed HS (IHS) were derived from adsorption‐desorption isotherms. These parameters were correlated with structural features of the HS. The adsorption affinity was shown to correlate directly with the aromaticity of the HS and inversely with their polarity, expressed as the O/C atomic ratio. A dependency between polarity and maximum adsorption capacity was not confirmed. The parameters b, H, and IHS expose close correlation with the molecular weight (MW) and the partial negative charge of HS (Z) at the operating pH value. The following quantitative relationship was obtained: b = 715 − 0.06 × MW − 529 × Z (r = 0.92). It allows a selection of HS with respect to the largest content of organic matter in HS‐kaolin clay complexes. Among t...
Pollution of the Arctic Ocean by potentially toxic elements (PTEs) is a current environmental pro... more Pollution of the Arctic Ocean by potentially toxic elements (PTEs) is a current environmental problem. Humic acids (HAs) play an important role in the regulation of PTE mobility in soil and water. The permafrost thaw releases ancient organic matter (OM) with a specific molecular composition into the Arctic watersheds. This could affect the mobility of PTEs in the region. In our study, we isolated HAs from two types of permafrost deposits: the Yedoma ice complex, which contains pristine buried OM, and the alas formed in the course of multiple thaw–refreezing cycles with the most altered OM. We also used peat from the non-permafrost region as the recent environmental endmember for the evolution of Arctic OM. The HAs were characterized using 13C NMR and elemental analysis. Adsorption experiments were conducted to assess the affinity of HAs for binding Cu2+ and Ni2+. It was found that Yedoma HAs were enriched with aliphatic and N-containing structures as compared to the much more aromat...
Large scale isolation—in gram quantities—of dissolved organic matter (DOM) from natural waters is... more Large scale isolation—in gram quantities—of dissolved organic matter (DOM) from natural waters is necessary for detailed investigation of its role in chemical and microbial processes driving carbon cycling under conditions of global climate change. The best candidate for a use in these large-scale experiments is a bulk sorbent Bondesil PPL, which has the same modification as the widely used Bond Elut PPL sorbent. There have been no studies so far reported on interchangeability of these sorbents with regard to DOM isolation. This work was devoted to comparative studies on sorption efficiency and molecular selectivity of these two sorbents—Bond Elut PPL and Bondesil PPL with regard to DOM components. Fulvic acids (FA) from peat water leachate were used as a model DOM. Laboratory solid phase extraction (SPE) setup was used for monitoring sorption recovery and extraction yield. It included three parallel experiments on pre-packed Bond Elut PPL cartridges (500 mg/3 mL) and three self-pac...
Natural products (e.g., polyphenols) have been used as biologically active compounds for centurie... more Natural products (e.g., polyphenols) have been used as biologically active compounds for centuries. Still, the mechanisms of biological activity of these multicomponent systems are poorly understood due to a lack of appropriate experimental techniques. The method of tritium thermal bombardment allows for non-selective labeling and tracking of all components of complex natural systems. In this study, we applied it to label two well-characterized polyphenolic compounds, peat fulvic acid (FA-Vi18) and oxidized lignin derivative (BP-Cx-1), of predominantly hydrophilic and hydrophobic character, respectively. The identity of the labeled samples was confirmed using size exclusion chromatography. Using ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT ICR MS), key differences in the molecular composition of BP-Cx-1 and FA-Vi18 were revealed. The labeled samples ([3H]-FA-Vi18 (10 mg/kg) and [3H]-BP-Cx-1 (100 mg/kg)) were administered to female BALB/c mice...
Redox moieties, which are present in the molecular backbone of humic substances (HS), govern thei... more Redox moieties, which are present in the molecular backbone of humic substances (HS), govern their antioxidant properties. We hypothesized that a directed modification of the humic backbone via incorporation of redox moieties with known redox properties might provide an efficient tool for tuning up antioxidant properties of HS. In this work, hydroquinonoid and hydronaphthoquinonoid centres were used, which possess very different redox characteristics. They were incorporated into the structure of coal (leonardite) humic acids CHA) and peat fulvic acids (PFA). For this goal, an oxidative copolymerization of phenols was used. The latter was induced via oxidation of hydroquinones and hydroxynapjtaquinones with a use of Fenton’s reagent. The structure of the obtained products was characterized using NMR and FTIR spectroscopy. H/D labelling coupled to FT ICR mass spectrometry analysis was applied for identification of the reaction products as a tool for surmising on reaction mechanism. It...
Humic substances (HS) are natural supramolecular systems of high- and low-molecular-weight compou... more Humic substances (HS) are natural supramolecular systems of high- and low-molecular-weight compounds with distinct immunomodulatory and protective properties. The key beneficial biological activity of HS is their antioxidant activity. However, systematic studies of the antioxidant activity of HS against biologically relevant peroxyl radicals are still scarce. The main objective of this work was to estimate the antioxidant capacity (AOC) of a broad set of HS widely differing in structure using an oxygen radical absorption capacity (ORAC) assay. For this purpose, 25 samples of soil, peat, coal, and aquatic HS and humic-like substances were characterized using elemental analysis and quantitative 13C solution-state NMR. The Folin–Ciocalteu method was used to quantify total phenol (TP) content in HS. The determined AOC values varied in the range of 0.31–2.56 μmol Trolox eqv. mg−1, which is close to the values for ascorbic acid and vitamin E. Forward stepwise regression was used to reveal...
The objective of this study was to synthesize iron (hydr)oxide nanoparticles (IONPs) stabilized b... more The objective of this study was to synthesize iron (hydr)oxide nanoparticles (IONPs) stabilized by humic substances, and to estimate the feasibility of their use for foliar application on iron deficient plants. The IONPs were synthesized by rapid hydrolysis of iron(III) nitrate in a solution of potassium humate. The iron speciation and nanoparticle morphologies were characterized using X-ray diffraction, transmission electron microscopy, and Mössbauer spectroscopy. The obtained sample of IONPs was applied at concentrations of 1- and 10-mM Fe, and 0.2% urea was used as an adjuvant. Wheat plants (Triticum aestivum L. cv. L15) were used for the iron uptake test. For both of the concentrations tested, spraying the nanoparticles resulted in a 70–75% higher iron content in wheat leaves compared to ferric ammonium salt of ethylenediaminetetraacetic acid (Fe-EDTA). The synergistic effect of humic substances acting as a surfactant seemed to promote an increase in the iron uptake of the ferri...
Parameters are proposed to describe the distribution of the effective electrophoretic mobilities ... more Parameters are proposed to describe the distribution of the effective electrophoretic mobilities of various anionic polyelectrolytes such as poly(styrene-4-sulfonates) and humic substances of different origins analyzed by capillary zone electrophoresis. The first step of the data treatment is a baseline correction and conversion of the electrophoretic raw time data to effective electrophoretic mobilities (μ-scale), taking into account the electroosmotic flow. With this new μ-scaling, the electropherograms are more representative of velocity-based separation phenomena than those using migration times, and a direct comparison of electropherograms is possible. Four different average electrophoretic mobilities were defined: the number-average effective mobility (μn), the weight-average effective mobility (μw), the z-average effective mobility (μz), and the peak-average electrophoretic mobility (μp). The polydispersity of the mobility of mixtures was described by the μw/μ⊓, μz/μw, and μp...
Eleven well characterized humic substances (HSs) were adsorbed from aqueous solution onto a Na‐ka... more Eleven well characterized humic substances (HSs) were adsorbed from aqueous solution onto a Na‐kaolin clay. The adsorption affinity (KL), maximum adsorption capacity (b), a coefficient of desorption hysteresis (H), and the concentration of irreversibly adsorbed HS (IHS) were derived from adsorption‐desorption isotherms. These parameters were correlated with structural features of the HS. The adsorption affinity was shown to correlate directly with the aromaticity of the HS and inversely with their polarity, expressed as the O/C atomic ratio. A dependency between polarity and maximum adsorption capacity was not confirmed. The parameters b, H, and IHS expose close correlation with the molecular weight (MW) and the partial negative charge of HS (Z) at the operating pH value. The following quantitative relationship was obtained: b = 715 − 0.06 × MW − 529 × Z (r = 0.92). It allows a selection of HS with respect to the largest content of organic matter in HS‐kaolin clay complexes. Among t...
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