Maria Jerzykiewicz

Organic radicals and paramagnetic metal complexes in municipal solid waste composts. An EPR and chemical study

Abstract The physicochemical properties of composted municipal solid wastes (MSW) were investigated by chemical and spectroscopic methods (EPR, NMR, IR, UV-Vis, ICP). Transformations of the composted organic matter during 150 days were observed. The water content was controlled in the composts; in some cases the composted MSW were nitrogen enriched by urea addition. The maturation of the composts was observed using standard methods. Quantitative EPR measurements were made on isolated humic and fulvic acids; the concentration of semiquinone free radicals and g parameters were determined. The maximum radical concentration (1.2 · 10 17 spins/gram) in isolated humic acids was observed in about the 6th week of the composting process in good quality composts. Moreover, distinct linear changes in g parameters of isolated humic acids (HA) from 2.0031 to 2.0037 were observed during the composting process. These changes were correlated to increasing E 4 /E 6 ratio characterizing the intensity of the oxidation processes and formation of oxygen-rich functional groups. The heavy metal (Cu, Fe, Mn, Pb) concentrations were examined in the composts and humic (HA) and fulvic acid (FA) fractions. The increase of copper binding by HA extracted from composts enriched in nitrogen was observed;the coordination sites of the ligand were characterized on the basis of EPR spectra. The various Fe(III) and Mn(II) complexes in the HA and FA fractions detected by EPR were used as additional indicators of oxidation-reduction processes in the composts.

EPR investigations of structure of humic acids from compost, soil, peat and soft brown coal upon oxidation and metal uptake

Free radical concentration and theirg-values in humic acids (HA) isolated from various sources were studied by quantitative EPR technique. EPR data for HA formed during composting and natural humification processes occurring in soil, peat and brown coal are given. In more detail the EPR data were analyzed for brown coal HA under carbonization, air oxidation (150°C) as well as metal uptake (Ca(II), Zn(II), Cd(II), Hg(II), Co(II), Ni(II) and Cu(II)) and NO2 reaction. Two groups of metal complexes were distinguished on the basis of their interaction with free radicals in HA. Ca(II), Zn(II), Cd(II) and Hg(II) ions increase free radical concentration, while Co(II), Ni(II) and Cu(II) ions quench the radicals compared to the raw HA. This phenomenon can be explained either by the strong interaction of the metal ions with active centres responsible for the quinone-hydroquinone-semiquinone equilibria, and/or by the antiferromagnetic interaction between radical spins and metal d orbitals. Gaseous ammonia was found to be a very useful base easily penetrating the solid matrix of HA and strongly influencing the equilibria. β-Diketone groups present in HA react with NO2 yielding iminoxy radicals. In the HA-metal complexes these structural units are engaged in metal coordination which lowers effectiveness of the iminoxyl synthesis.

Influence of metal ions binding on free radical concentration in humic acids. A quantitative electron paramagnetic resonance study

Abstract The influence of metal ions, e.g. Co(II), Cu(II), Mn(II), Ni(II), Fe(II), on free radical concentration in humic acids isolated from soil, peat and compost was investigated by electron paramagnetic resonance (EPR). The results show that metal ions with unfilled d-shell exhibit antiferromagnetic interactions with semiquinone radicals. Moreover, coordinated metals shift the quinone–semiquinone–hydroquinone equilibrium in the macromolecular matrix of humic acids. A strong decrease of semiquinone radical concentration in humic acid–metal complexes is observed. This effect is caused by interactions of metal ions with oxygen-containing stable radicals occurring in the aromatic systems of humic acids. Furthermore, the effect of metal coordination on free radical concentration in humic acids–metal complexes depends on the humic acid origin. FTIR spectroscopy was also used as an additional tool for studies of the metal ions interactions with carboxylic groups.

Influence of Pb(II) ions on the EPR properties of the semiquinone radicals of humic acids and model compounds: high field EPR and relativistic DFT studies.

X-band (9.76 GHz) and high field (416.00 GHz) electron paramagnetic resonance spectroscopy (EPR) was used to study the interactions between Pb(II) ions and semiquinone radicals of natural humic acids and their simple models. The EPR experiments were performed on powder samples. The formation of Pb(II) complexes with the radicals was accompanied by a significant decrease of g parameters as compared to those observed for parent radicals. Two types of complexes were identified depending on the initial concentration of Pb(II) ions. For one of them the anisotropic hyperfine coupling with the (207)Pb nucleus was observed. Systematic DFT calculations were carried out for complexes with different forms of radical ligands (L(2)(-*), HL(-*), and H(2)L*) derived from 3,4-dihydroxybenzoic acid representing different ligation schemes. The g parameters calculated for the structure characterized by a significant accumulation of spin density on the Pb atom are strongly deviated from the values observed experimentally. Moreover, a decrease of the spin population on all oxygen atoms as a result of complexation of Pb(II) via carboxyl oxygens and protonation of hydroxyl oxygens is required to reproduce the experimental g parameters.

EPR in the environmental control: Copper complexes and free radicals in soil and municipal solid waste compost

Quantitative EPR technique was applied to examine Cu(II) complexes and free radicals in soil and municipal solid waste composts. Production and stabilization of free radicals in humic and humic-like substances depend on transition metal containing red-ox systems in soil. Termination of the reaction pathways yields relatively stable semiquinone free radicals in the polyphenol and melanoidin matrices. EPR investigations of municipal solid waste composts in different stages of their maturity show distinct correlation between free radical concentration and microbiological activity. Copper(II) sorption by living microorganisms and formation of the copper(II) complexes by humic substances in soils (Cambisols and Luvisols) result in decrease of the concentration of the semiquinone radicals. The Cu(II) complexes formed by various natural humic and humic-like substances produced in the composts were characterized on the basis of EPR measurements. The process of solubilization of inorganic copper compounds in soil and composts, and free radical activity in soil and composts can be characterized using EPR technique as the monitoring method.

Understanding natural semiquinone radicals – Multifrequency EPR and relativistic DFT studies of the structure of Hg(II) complexes

Multifrequency EPR spectroscopy and DFT calculations were used to investigate Hg(II) complexes with semiquinone radical ligands formed in a direct reaction between the metal ions and tannic acid (a polyphenol closely related to tannins). Because of the intricate structure of tannic acid a vast array of substituted phenolic compounds were tested to find a structural model mimicking its ability to react with Hg(II) ions. The components of the g matrix (the g tensor) determined from the high field (208 GHz) EPR spectra of the Hg(II) complexes with the radical ligands derived from tannic acid and from the model compounds were analogous, indicating a similar coordination mode in all the studied Hg(II) complexes. Since catechol (1,2-dihydroxybenzene) was the simplest compound undergoing the reaction with Hg(II) it was selected for DFT studies which were aimed at providing an insight into the structural properties of the investigated complexes. Various coordination numbers and different conformations and protonation states of the ligands were included in the theoretical analyses. g Matrices were computed for all the DFT optimized geometries. A good agreement between the theoretical and experimental values was observed only for the model with the Hg(II) ion tetracoordinated by two ligands, one of the ligands being monoprotonated with the unpaired electron mainly localized on it.

pH-dependent formation of Hg(II)-semiquinone complexes from natural phenols.

The ability of various natural phenols to form Hg(II)-semiquinone complexes was tested in the pH range of 2.8-12. EPR experiments performed at 9.6 and 34 GHz (the X- and Q-band, respectively) revealed that the complexes formed at low and high pH values exhibit a significant dissimilarity between their g-matrices (g-tensors), strongly suggesting that the complexes differ structurally. Our previous investigation on the low pH complex (Chemosphere 2015, 119, 479-484) had shown the Hg(II) ion to be tetracoordinated by two ligands, one of the ligands being monoprotonated with the unpaired electron mainly located on it. In order to reveal the molecular structure of the high pH form a DFT-based theoretical analysis was carried out in this work. For all the optimized model structures the g-matrices were computed and compared with their experimental counterparts. Good agreement was observed only if the geometry of the model Hg(II) complex was planar and the coordination sphere was composed of one fully deprotonated radical ligand and hydroxyl anions.

Humic and hymatomelanic acids interaction with lanthanide ions.

The interactions of lanthanide ions, REE(III), with semiquinone radicals naturally occurring in humic (HA) and hymatomelanic (HY) acids of different origin were studied mainly by EPR spectroscopy. Quantitative EPR analysis proved that only the semiquinone free radical concentration in both, HA and HY, was affected by interaction with some of the lanthanide ions, whereas the EPR g parameters of the formed radical-REE(III) complexes remained unchanged. The radical concentration was practically unaffected by the REE(III) ions with 4f(1)-4f(6) electron configurations and in some degree increased by REE(III) ions with 4f(8)-4f(14) configuration. The lanthanide playing an exceptional role was Gd(III) (4f(7)), which diminished strongly the free radicals concentration. The quenching ability of Gd(III) was stronger towards the radicals provided by HA than by HY, what was assigned to higher content in HA of both, oxygen-containing functional groups and conjugated aromatic rings, leading to more efficient Gd(III)-radical interaction. The semiquinone free radicals of HA and HY originated from the compost were more reactive than those from peat, as the humic acids from mature compost with less bulk density have more accessible functional groups.

Can Carbamates Undergo Radical Oxidation in the Soil Environment? A Case Study on Carbaryl and Carbofuran

Radical oxidation of carbamate insecticides, namely carbaryl and carbofuran, was investigated with spectroscopic (electron paramagnetic resonance [EPR] and UV-vis) and theoretical (density functional theory [DFT] and ab initio orbital-optimized spin-component scaled MP2 [OO-SCS-MP2]) methods. The two carbamates were subjected to reaction with •OH, persistent DPPH• and galvinoxyl radical, as well as indigenous radicals of humic acids. The influence of fulvic acids on carbamate oxidation was also tested. The results obtained with EPR and UV-vis spectroscopy indicate that carbamates can undergo direct reactions with various radical species, oxidizing themselves into radicals in the process. Hence, they are prone to participate in the prolongation step of the radical chain reactions occurring in the soil environment. Theoretical calculations revealed that from the thermodynamic point of view hydrogen atom transfer is the preferred mechanism in the reactions of the two carbamates with the radicals. The activity of carbofuran was determined experimentally (using pseudo-first-order kinetics) and theoretically to be noticeably higher in comparison with carbaryl and comparable with gallic acid. The findings of this study suggest that the radicals present in soil can play an important role in natural remediation mechanisms of carbamates.

Iron(III) bis(pyrazol-1-yl)acetate based decanuclear metallacycles: synthesis, structure, magnetic properties and DFT calculations

The synthesis, structural aspects, magnetic interpretation and theoretical rationalizations for a new member of the ferric wheel family, a decanuclear iron(iii) complex with the formula [Fe10(bdtbpza)10(μ2-OCH3)20] (1), featuring the N,N,O tridentate bis(3,5-di-tert-butylpyrazol-1-yl)acetate ligand, are reported. The influence of the steric effect on both the core geometry and coordination mode is observed. Temperature dependent (2.0-300 K range) magnetic susceptibility studies carried out on complexes 1 established unequivocally antiferromagnetic (AF) interactions between high-spin iron(iii) centers (S = 5/2), leading to a ground state S = 0. The mechanism of AF intramolecular coupling was proved using a broken-symmetry approach within the density functional method at the B3LYP/def2-TZVP(-f)/def2-SVP level of theory.