Aromaticity and degree of aromatic condensation of char

The aromatic carbon structure is a defining property of chars and is often expressed with the help of two concepts: (i) aromaticity and (ii) degree of aromatic condensation. The varying extent of these two features is assumed to largely determine the relatively high persistence of charred material in the environment and is thus of interest for, e.g., biochar characterization or carbon cycle studies. Consequently, a variety of methods has been used to assess the aromatic structure of chars, which has led to interesting insights but has complicated the comparison of data acquired with different methods. We therefore used a suite of seven methods (elemental analysis, MIR spectroscopy, NEXAFS spectroscopy, C NMR spectroscopy, BPCA analysis, lipid analysis and helium pycnometry) and compared 13 measurements from them using a diverse sample set of 38 laboratory chars. Our results demonstrate that most of the measurements could be categorized either into those which assess aromaticity or those which assess the degree of aromatic condensation. A variety of measurements, including relatively inexpensive and simple ones, reproducibly captured the two aromatic features in question, and data from different methods could therefore be compared. Moreover, general patterns between the two aromatic features and the pyrolysis conditions were revealed, supporting reconstruction of the highest heat treatment temperature (HTT) of char. 1

Reduced complexity of multidimensional and diffusion NMR spectra of soil humic fractions as simplified by Humeomics

Background: Humeomics is a sequential step-wise chemical fractionation that simplifies the complex matrix of a humic acid (HA) and weakens its supramolecular interactions, thereby allowing a detailed characterization of the involved molecules. A recalcitrant residual end product of Humeomics, namely RES4, was successfully solubilized here in alkaline conditions and subjected to a semi-preparative high-performance size exclusion chromatography (HPSEC). Results: The resulting six size fractions separated by HPSEC were analyzed by different NMR techniques. 1D 1H-NMR spectra did not reveal significant molecular differences among size fractions, although all of them differed from the spectrum of the bulk RES4 especially in signal intensity for aliphatic materials, which were assigned by 2D NMR to lipidic structures. Diffusion-ordered spectroscopy (DOSY)-NMR spectra showed that the homogeneity of RES4 was significantly changed by the HPSEC separation. In fact, nominally large size fractions, rich in lipidic signals, had significantly lower and almost constant diffusivity, due to stable supramolecular associations promoted by hydrophobic interactions among alkyl chains. Conversely, diffusivity is gradually increased with the content of aromatic and hydroxyaliphatic signals, which accompanied the reduction of fractions sizes and was related to smaller superstructures. Conclusions: This study not only confirmed the occurrence of supramolecular structures in the recalcitrant humic residue of Humeomics, but also highlighted that more homogeneous size fractions were more easily characterized by NMR spectroscopy