RESUMEN

In contaminated soils, excessive concentrations of metals and their high mobility pose a serious environmental risk. A suitable soil amendment can minimize the negative effect of metals in soil. This study investigated the effect of different biochars on metal (Cu, Pb, Zn) immobilization in industrial soil. Biochars produced at 300 and 600 °C from conventional (MS, maize silage; WP, wooden pellets) and alternative (SC, sewage sludge compost; DR, digestate residue) feedstocks were used as soil amendments at a dosage of 10 % (w/w). The type of feedstock and pyrolysis temperature affected the properties of the biochars and their ability to immobilize metal in soil. Compared to production at 300 °C, all biochars produced at 600 °C had higher pH (6.2-10.7), content of ash (7.2-69.0 %) and fixed carbon (21.1-56.7 %), but lower content of volatile matter (9.7-37.2 %). All biochars except DR biochar had lower dissolved organic carbon (DOC) content (1.4-2.3 g C/L) when made at 600 °C. Only MS and SC biochars had higher cation exchange capacity (25.2 and 44.7 cmol/kg, respectively) after charring at 600 °C. All biochars contained low concentrations of Cd, Cu, Ni, Pb and Zn; Cd was volatilized to the greatest extent during pyrolysis. Based on FTIR analysis and molar ratios of H/C and O/C, biochars had a greater degree of carbonization and aromaticity after charring at 600 °C. The efficiency of the biochars in metal immobilization depended mainly on their pH, ash content, and concentration of DOC. SC and DR biochars were more effective for Cu and Zn immobilization than MS and WP biochars, which makes them attractive options for large-scale soil amendment.

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RESUMEN

(1)H nuclear magnetic resonance relaxometry is applied to reveal information on the translational and rotational dynamics of the ionic liquid: 1-butyl-3-methyl imidazoliumoctyl sulfate (BMIM-OcSO4) in bulk and in a confinement formed by a nanoporous SiO2 matrix. The experimental studies were performed in a very broad frequency range, from 8 kHz to 40 MHz (referring to the (1)H resonance frequency), in order to probe motional processes at very different time scales using a single experiment, and in the temperature range of 243-303 K. The relaxation results for BMIM-OcSO4 in bulk are interpreted in terms of three relaxation contributions: a term associated with the translational dynamics of the ions (it has been assumed that the translational dynamics of cations and anions can be described by one diffusion coefficient) and two terms associated with the rotational motion of the anion and the cation, respectively. The relationships between the obtained dynamic parameters (rotational correlation times and translational diffusion coefficients) are thoroughly discussed and used as a "reference" for the dynamics of BMIM-OcSO4 confined in an SiO2 matrix. Analysis of the corresponding relaxation data for the confined liquid shows that the confinement does not significantly affect the rotational dynamics, but it has a considerable impact on the translational motion. It is demonstrated that the relaxation term associated with the translational dynamics stems from two contributions: a contribution from a core (bulk-like) fraction of the liquid and from a fraction moving near the pore surface and therefore being for some time adsorbed on the pore walls. The translational diffusion coefficient for the last fraction is determined and several conclusions regarding the residence lifetime of the ions on the surface are drawn. Moreover, an additional motional process on the timescale of ns or shorter is revealed in the confinement.

RESUMEN

(1) H NMR relaxometry was used to reveal information on the dynamical properties of the molecular crystal (PyH)5 Bi2 Br11 (PyH=C5 H6 N, pyridinium cation), chosen as an example of a solid that exhibits a complex structure and rotational-like dynamics. Experimental studies were performed over a very broad frequency range, from 4 kHz to 40 MHz (referring to the (1) H resonance frequency) versus temperature. The extensive set of data was thoroughly analyzed in terms of two motional models differing with respect to the assumed mechanism (heterogeneous versus homogenous) of the motion of the PyH cations. A Cole-Davidson distribution of the correlation times describing the assumed motional heterogeneity was tested against a concept of two correlation times characterizing the rotation-like dynamics of the PyH cation around the perpendicular axes differing by about one order of magnitude. The parameters describing the dynamics of the cation, obtained by means of both models, were compared and discussed.