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, 13 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.

The maximum temperature experienced by biomass during combustion has a strong effect on chemical properties of the resulting charcoal, such as sorption capacity (water and nonpolar materials) and microbial degradability. However, information about the formation temperature of natural charcoal can be difficult to obtain in ecosystems that are not instrumented prior to fires. Benzene polycarboxylic acids (BPCA) are molecular markers specific for pyrogenic carbon (PyC) which can provide information on the degree of aromatic condensation in charcoals. Here we apply the BPCA molecular marker method to a set of 10 charcoals produced during an experimental fire in a Pitch pine-scrub oak forest from litter and bark of pitch pine and inkberry plants in the Pinelands National Reserve in New Jersey, USA. We deployed temperature-sensitive crayons throughout the burn site, which recorded the maximum air temperature and made comparisons to the degree of thermal alteration recorded by BPCA molecular markers. Our results show an increase of the degree of aromatic condensation with monitored temperatures for bark biomass, while for needles no clear trend could be observed. For leaf-derived charcoals at increasing monitored fire temperatures, decreasing degree of aromatic condensation was obtained. This suggests that molecular markers can be used to roughly estimate the maximum fire temperatures experienced by bark and wood materials, but not based on leaf- and needle-derived materials. Possible applications include verifying declared pyrolysis temperatures of biochars and evaluating ecosystem fire temperature postburn.

Charcoal plays a significant role in the long-term carbon cycle, and its use as a soil amendment is promoted as a C sequestration strategy (biochar). One challenge in this research area is understanding the heterogeneity of charcoal properties. Although the maximum reaction temperature is often used as a gauge of pyrolysis conditions, pyrolysis duration also changes charcoal physicochemical qualities. Here, we introduce a formal definition of charring intensity (CI) to more accurately characterize pyrolysis, and we document variation in charcoal chemical properties with variation in CI. We find two types of responses to CI: either linear or threshold relationships. Mass yield decreases linearly with CI, while a threshold exists across which % C, % N, and δ(15)N exhibit large changes. This CI threshold co-occurs with an increase in charcoal aromaticity. C isotopes do not change from original biomass values, supporting the use of charcoal δ(13)C signatures to infer paleoecological conditions. Fractionation of N isotopes indicates that fire may be enriching soils in (15)N through pyrolytic N isotope fractionation. This influx of "black N" could have a significant impact on soil N isotopes, which we show theoretically using a simple mass-balance model.

Charcoal is a major component of the stable soil organic carbon reservoir, and the physical and chemical properties of charcoal can sometimes significantly alter bulk soil properties (e.g., by increasing soil water holding capacity). However, our understanding of the residence time of soil charcoal remains uncertain, with old measured soil charcoal ages in apparent conflict with relatively short modeled and measured residence times. These discrepancies may exist because the fate of charcoal on the landscape is a function not just of its resistance to biological decomposition but also its physical mobility. Mobility may be important in controlling charcoal landscape residence time and may artificially inflate estimates of its degradability, but few studies have examined charcoal vulnerability to physical redistribution. Charcoal landscape redistribution is likely higher than other organic carbon fractions owing to charcoal's low bulk density, typically less than 1.0 g/cm3. Here we examine both the physical and chemical properties of soil and charcoal over a period of two years following a 2011 wildfire in Texas. We find little change in properties with time; however, we find evidence of enhanced mobility of charcoal relative to other forms of soil organic matter. These data add to a growing body of evidence that charcoal is preferentially eroded, offering another explanation for variations observed in its environmental residence times.

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