Differentiating Inorganics in Biochars Produced at Commercial Scale Using Principal Component Analysis

[Image: see text] Characterizing the inorganic phase of biochar, beyond determining element concentration, is needed for appropriate application of these materials because mineral forms also influence element availability and behavior. Inorganics in 13 biochars (produced from Poultry litter, switchgrass, and different types of wood) were characterized by proximate analysis, chemical analysis, powder X-ray diffraction (XRD), and scanning electron microscopy with energy-dispersive X-ray (SEM-EDX) spectroscopy. Principal component analysis (PCA) was used to compare biochars and characterize associations between elements. The biochars were produced using commercial-scale reactors and represent materials with properties relevant to field application. Bulk inorganic concentration and composition were responsible for differentiating biochars after PCA of chemical data. In comparison, differentiation based on PCA of diffractogram fingerprints was more nuanced. Here, contributions from cellulose and turbostratic crystalline C influenced separation between samples. It was also sensitive to mineral forms of Ca (whewellite and calcite). Differences in crystalline C and Ca minerals separated two biochars generated from the same willow feedstock using the same pyrolysis conditions at different temperatures. PCA of 606 SEM-EDX point scans revealed that inorganics belong to four main clusters containing Ca, Fe, [Al, Si], and [Cl, K, Mg, Na, P, S] consistent with XRD identification of calcite, magnetic Fe-oxide, silicates, and sylvite. It further suggested that amorphous P-containing minerals associated with Ca (not identified through XRD) were constituents of willow and poultry litter-derived biochars. However, unlike PCA of XRD, it was not able to differentiate the two biochars derived from willow. The three analysis methods provided different perspectives on the properties of the biochar inorganic phase. Combining information from multiple methods is needed to better understand the inorganic composition of biochars.