Patrycja Boguta

Interactions of Zn(II) Ions with Humic Acids Isolated from Various Type of Soils. Effect of pH, Zn Concentrations and Humic Acids Chemical Properties.

The main aim of this study was the analysis of the interaction between humic acids (HAs) from different soils and Zn(II) ions at wide concentration ranges and at two different pHs, 5 and 7, by using fluorescence and FTIR spectroscopy, as well as potentiometric measurements. The presence of a few areas of HAs structures responsible for Zn(II) complexing was revealed. Complexation at α-sites (low humified structures of low-molecular weight and aromatic polycondensation) and β-sites (weakly humified structures) was stronger at pH 7 than 5. This trend was not observed for γ-sites (structures with linearly-condensed aromatic rings, unsaturated bonds and large molecular weight). The amount of metal complexed at pH5 and 7 by α and γ-structures increased with a decrease in humification and aromaticity of HAs, contrary to β-areas where complexation increased with increasing content of carboxylic groups. The stability of complexes was higher at pH 7 and was the highest for γ-structures. At pH 5, stability decreased with C/N increase for α-areas and -COOH content increase for β-sites; stability increased with humification decrease for γ-structures. The stability of complexes at α and β-areas at pH 7 decreased with a drop in HAs humification. FTIR spectra at pH 5 revealed that the most-humified HAs tended to cause bidentate bridging coordination, while in the case of the least-humified HAs, Zn caused bidentate bridging coordination at low Zn additions and bidentate chelation at the highest Zn concentrations. Low Zn doses at pH 7 caused formation of unidentate complexes while higher Zn doses caused bidentate bridging. Such processes were noticed for HAs characterized by high oxidation degree and high oxygen functional group content; where these were low, HAs displayed bidentate bridging or even bidentate chelation. To summarize, the above studies have showed significant impact of Zn concentration, pH and some properties of HAs on complexation reactions of humic acids with zinc.

Statistical relationship between selected physicochemical properties of peaty-muck soils and their fraction of humic acids**

Abstract Influence of humic acids on soil environment is still subject of scientific discussions. The aim of above studies was to investigate the relationships between selected physicochemical properties of eleven peaty-muck soils and properties of humic acids isolated from these soils. The following parameters were determined for soils: total and organic carbon, density, ash, humification, and the water absorption index. Humic acids were described by: absorbance at 280 nm, absorbance ratios at 465 and 665 nm, at 260 and 665 nm, elemental composition and atomic ratios: H/C, O/H, O/C, C/N, the degree of internal oxidation, and the content of carboxylic and phenolic groups. Statistical analyses showed that an increase in density, humification, and water absorption indices of soils caused a significant increase in the humic acid parameters: absorbance at 280 nm, the oxygen content, O/H, O/C ratios, internal oxidation degree, and functional groups. Statistically significant negative correlations were found for the same parameters of soils and for the hydrogen and carbon content as well as the H/C ratio of humic acids. The relationships showed that there was a possibility to express the properties of humic acids on the basis of more simple parameters measured for soil and without time-consuming isolation of humic acids.

Photosensitizing properties of water-extractable organic matter from soils

Water-extractable organic matter (WEOM) was extracted using pure water from two black soils and from the Elliott reference soil of the International Humic Substances Society (IHSS). WEOMs were characterized by chemical and spectroscopic methods. The apparent quantum yields of singlet oxygen, triplet excited states and hydroxyl radicals formation upon irradiation within the wavelength range 290-450 nm were determined using chemical probes and compared to those of standard Elliott humic substances. In general, the aromatic content, as measured by the SUVA value, was close in WEOMs and humic substances, while the E2/E3 was higher and the humification index lower in the former. Quantum yield values measured for WEOMs fell within the range of those found for basic medium extracted humic substances or were even higher in one case. Thus, water soluble aromatic moiety of the soil organic matter, especially those with low humification degree, is important for the photosensitizing properties. We also found that WEOMs sensitized the bisphenol A phototransformation with rates of the same order of magnitude for all the samples.

Analysis of the sorption properties of different soils using water vapour adsorption and potentiometric titration methods

Abstract Parameters of specific surface area as well as surface charge were used to determine and compare sorption properties of soils with different physicochemical characteristics. The gravimetric method was used to obtain water vapour isotherms and then specific surface areas, whereas surface charge was estimated from potentiometric titration curves. The specific surface area varied from 12.55 to 132.69 m2 g−1 for Haplic Cambisol and Mollic Gleysol soil, respectively, and generally decreased with pH (R=0.835; α = 0.05) and when bulk density (R=−0.736; α = 0.05) as well as ash content (R=−0.751; α = 0.05) increased. In the case of surface charge, the values ranged from 63.00 to 844.67 μmol g−1 Haplic Fluvisol and Mollic Gleysol, respecively. Organic matter gave significant contributions to the specific surface area and cation exchange capacity due to the large surface area and numerous surface functional groups, containing adsorption sites for water vapour molecules and for ions. The values of cation exchange capacity and specific surface area correlated linearly at the level of R=0.985; α = 0.05.

Characteristics of rapeseed oil cake using nitrogen adsorption

Abstract Adsorption of nitrogen on the rapeseed oil cake and rapeseed oil cake with wheat meal extrudates was investigated. The results are presented as adsorption-desorption isotherms. The Brunauer-Emmet and Teller equation was used to analyse the experimental sorption data. To obtain estimates of the surface area and surface fractal dimension, the sorption isotherms were analyzed using the Brunauer-Emmet and Teller and Frenkel-Halsey-Hill equations. Mesopore analysis was carried out using the Dollimore and Heal method. The properties and surface characteristic of rapeseed oil cake extrudates are related to different basic properties of particular samples and duration of the extrusion process. Extrusion conditions lead to essential differences in particular products. For all kinds of rapeseed oil cakes the amount of adsorbed nitrogen was different, but for the rapeseed oil cake extrudates a large amount of adsorbed nitrogenwas observed. The average surface area of the rapeseed oil cake extrudates was about 6.5-7.0 m2 g-1, whereas it was equal to about 4.0-6.0 m2 g-1 for rapeseed oil cake with the wheat meal extrudates. In the case of non-extruded rapeseed oil cake and wheat meal, the dominant group included ca. 2 and 5 nmpores. The values of surface fractal dimension suggested that the surface of the extrudates was more homogenous than that of the raw material. Duration of the extrusion process to 80 s resulted in a decrease in the specific surface area, surface fractal dimension, and porosity of the extrudates.

A Comparative Study of the Application of Fluorescence Excitation-Emission Matrices Combined with Parallel Factor Analysis and Nonnegative Matrix Factorization in the Analysis of Zn Complexation by Humic Acids

The main aim of this study was the application of excitation-emission fluorescence matrices (EEMs) combined with two decomposition methods: parallel factor analysis (PARAFAC) and nonnegative matrix factorization (NMF) to study the interaction mechanisms between humic acids (HAs) and Zn(II) over a wide concentration range (0–50 mg·dm−3). The influence of HA properties on Zn(II) complexation was also investigated. Stability constants, quenching degree and complexation capacity were estimated for binding sites found in raw EEM, EEM-PARAFAC and EEM-NMF data using mathematical models. A combination of EEM fluorescence analysis with one of the proposed decomposition methods enabled separation of overlapping binding sites and yielded more accurate calculations of the binding parameters. PARAFAC and NMF processing allowed finding binding sites invisible in a few raw EEM datasets as well as finding totally new maxima attributed to structures of the lowest humification. Decomposed data showed an increase in Zn complexation with an increase in humification, aromaticity and molecular weight of HAs. EEM-PARAFAC analysis also revealed that the most stable compounds were formed by structures containing the highest amounts of nitrogen. The content of oxygen-functional groups did not influence the binding parameters, mainly due to fact of higher competition of metal cation with protons. EEM spectra coupled with NMF and especially PARAFAC processing gave more adequate assessments of interactions as compared to raw EEM data and should be especially recommended for modeling of complexation processes where the fluorescence intensities (FI) changes are weak or where the processes are interfered with by the presence of other fluorophores.

Use of thermal analysis coupled with differential scanning calorimetry, quadrupole mass spectrometry and infrared spectroscopy (TG-DSC-QMS-FTIR) to monitor chemical properties and thermal stability of fulvic and humic acids

Thermogravimetry–coupled with differential scanning calorimetry, quadrupole mass spectrometry, and Fourier-transform infrared spectroscopy (TG-DSC-QMS-FTIR)–was applied to monitor the thermal stability (in an N2 pyrolytic atmosphere) and chemical properties of natural polymers, fulvic (FA) and humic acids (HA), isolated from chemically different soils. Three temperature ranges, R1, 40–220°C; R2, 220–430°C; and R3, 430–650°C, were distinguished from the DSC data, related to the main thermal processes of different structures (including transformations without weight loss). Weight loss (ΔM) estimated from TG curves at the above temperature intervals revealed distinct differences within the samples in the content of physically adsorbed water (at R1), volatile and labile functional groups (at R2) as well as recalcitrant and refractory structures (at R3). QMS and FTIR modules enabled the chemical identification (by masses and by functional groups, respectively) of gaseous species evolved during thermal decomposition at R1, R2 and R3. Variability in shape, area and temperature of TG, DSC, QMS and FTIR peaks revealed differences in thermal stability and chemical structure of the samples between the FAs and HAs fractions of different origin. The statistical analysis showed that the parameters calculated from QMS (areas of m/z = 16, 17, 18, 44), DSC (MaxDSC) and TG (ΔM) at R1, R2 and R3 correlated with selected chemical properties of the samples, such as N, O and COOH content as well as E2/E6 and E2/E4 indexes. This indicated a high potential for the coupled method to monitor the chemical changes of humic substances. A new humification parameter, HTD, based on simple calculations of weight loss at specific temperature intervals proved to be a good alternative to indexes obtained from other methods. The above findings showed that the TG-DSC-QMS-FTIR coupled technique can represent a useful tool for the comprehensive assessment of FAs and HAs properties related to their various origin.