Generalized Two-Dimensional Perturbation Correlation Infrared Spectroscopy Reveals Mechanisms for the Development of Surface Charge and Recalcitrance in Plant-Derived Biochars

Fundamental knowledge of how biochars develop surface-charge and resistance to environmental degradation is crucial to their production for customized applications or understanding their functions in the environment. Two-dimensional perturbation-based correlation infrared spectroscopy (2D-PCIS) was used to study the biochar formation process in three taxonomically different plant biomass, under oxygenlimited conditions along a heat-treatment-temperature gradient (HTT; 200-650 degrees C). Results from 2D-PCIS pointed to the systematic, HTT-induced defragmenting of lignocellulose H-bonding network and demethylenation/demethylation, oxidation, or dehydroxylation/dehydrogenation of lignocellulose fragments as the primary reactions controlling biochar properties along the HTT gradient. The cleavage of OH-O-type H-bonds, oxidation of free primary hydroxyls to carboxyls (carboxylation; HTT <= 500 degrees C), and their subsequent dehydrogenation/dehydroxylation (HTT > 500 degrees C) controlled surface charge on the biochars; while the dehydrogenation of methylene groups, which yielded increasingly condensed structures (R-CH2-R -> R=CH-R -> R=C=R), controlled biochar recalcitrance. Variations in biochar properties across plant biomass type were attributable to taxa-specific transformations. For example, apparent inefficiencies in the cleavage of wood-specific H-bonds, and their subsequent oxidation to carboxyls, lead to lower surface charge in wood biochars (compared to grass biochars). Both nontaxa and taxa-specific transformations highlighted by 2D-PCIS could have significant implications for biochar functioning in fire-impacted or biochar-amended systems.