Valentina Marsala

Nature of water-biochar interface interactions

A poplar biochar obtained by an industrial gasification process was saturated with water and analyzed using fast field cycling (FFC) NMR relaxometry in a temperature range between 299 and 353 K. Results revealed that the longitudinal relaxation rate increased with the increment of the temperature. This behavior was consistent with that already observed for paramagnetic inorganic porous media for which two different relaxation mechanisms can be accounted for: outer‐ and inner‐sphere mechanisms. The former is due to water diffusing from the closest approach distance to infinity, whereas the second is due to water interacting by nonconventional H‐bonds to the porous surface of the solid material. In particular, the inner‐sphere relaxation appeared to be predominant in the water‐saturated biochar used in the present study. This study represents a fundamental first step for the full comprehension of the role played by biochar in the draining properties of biochar‐amended soils.

Fast field cycling NMR relaxometry characterization of biochars obtained from an industrial thermochemical process

PurposeBiochar has unique properties which make it a powerful tool to increase soil fertility and to contribute to the decrease of the amount of atmospheric carbon dioxide through the mechanisms of C sequestration in soils. Chemical and physical biochar characteristics depend upon the technique used for its production and the biomass nature. For this reason, biochar characterization is very important in order to address its use either for agricultural or environmental purposes.Materials and methodsThree different biochars obtained from an industrial gasification process were selected in order to establish their chemical and physical peculiarities for a possible use in agronomical practices. They were obtained by charring residues from the wine-making industry (marc) and from poplar and conifer forests. Routine analyses such as pH measurements, elemental composition, and ash and metal contents were performed together with the evaluation of the cross-polarization magic angle spinning (CPMAS) 13C NMR spectra of all the biochar samples. Finally, relaxometry properties of water-saturated biochars were retrieved in order to obtain information on pore size distribution.Results and discussionAll the biochars revealed basic pH values due to their large content of alkaline metals. The quality of CPMAS 13C NMR spectra, which showed the typical signal pattern for charred systems, was not affected by the presence of paramagnetic centers. Although paramagnetism was negligible for the acquisition of solid state spectra, it was effective in some of the relaxometry experiments. For this reason, no useful information could be retrieved about water dynamics in marc char. Conversely, both relaxograms and nuclear magnetic resonance dispersion profiles of poplar and conifer chars indicated that poplar char is richer in small-sized pores, while larger pores appear to be characteristic for the conifer char.ConclusionsThis study showed the potential of relaxometry in revealing chemical–physical information on industrially produced biochar. This knowledge is of paramount importance to properly direct biochar agronomical uses.

Structure alteration of a sandy-clay soil by biochar amendments

PurposeThe aim of the present study was to investigate structure alterations of a sandy-clay soil upon addition of different amounts of biochar (fbc).Materials and methodsAll the fbc samples were analyzed by high energy moisture characteristic (HEMC) technique and 1H nuclear magnetic resonance (NMR) relaxometry. HEMC was applied in order to evaluate aggregate stability of biochar-amended soil samples. 1H NMR relaxometry experiments were conducted for the evaluation of the pore distributions through the investigation of water dynamics of the same samples.Results and discussionThe HEMC technique revealed improvement in aggregate stability through measurements of the amount of drainable pores and the stability ratio. The latter increased as the amount of biochar was raised up. The 1H NMR relaxometry revealed a unimodal T1 distribution for both the sole sandy-clay soil and the biochar. Conversely, a bimodal T1 distribution was acquired for all the different fbc samples.ConclusionsImprovement in aggregate stability was obtained as biochar was progressively added to the sandy-clay soil. A dual mechanism of water retention has been hypothesized. In particular, intra-aggregate porosity was indicated as the main responsible for molecular water diffusion when fbc comprised between 0 and 0.33. Conversely, inter-aggregate porosity resulted predominant, through swelling processes, when fbc overcame 0.33.

Mechanisms of Water Interaction with Pore Systems of Hydrochar and Pyrochar from Poplar Forestry Waste

The aim of this study was to understand the water-surface interactions of two chars obtained by gasification (pyrochar) and hydrothermal carbonization (hydrochar) of a poplar biomass. The two samples revealed different chemical compositions as evidenced by solid state (13)C NMR spectroscopy. In fact, hydrochar resulted in a lignin-like material still containing oxygenated functionalities. Pyrochar was a polyaromatic system in which no heteronuclei were detected. After saturation with water, hydrochar and pyrochar were analyzed by fast field cycling (FFC) NMR relaxometry. Results showed that water movement in hydrochar was mainly confined in very small pores. Conversely, water movement in pyrochar led to the conclusion that a larger number of transitional and very large pores were present. These results were confirmed by porosity evaluation derived from gas adsorption. Variable-temperature FFC NMR experiments confirmed a slow-motion regime due to a preferential diffusion of water on the solid surface. Conversely, the higher number of large pores in pyrochar allowed slow movement only up to 50 °C. As the temperature was raised to 80 °C, water interactions with the pore surface became weaker, thereby allowing a three-dimensional water exchange with the bulk liquid. This paper has shown that pore size distribution was more important than chemical composition in affecting water movement in two chemically different charred systems.