The H/C and O/C ratios decrease with increasing temperature, and it is assumed that the lower the ratio the greater the degree of aromaticity and stability. This is confirmed by NMR data suggesting that increasing temperature enhances degree of aromaticity (Baldock and Smernik, 2002 and Smernik et al., 2006). However, the changes are also a function of heating time. Almendros et al. (1990) heated a peat sample between 60 and 180 s while keeping the temperature constant at 35 °C and found that H/C and O/C ratios significantly decreased. The data also show that there is a comparably larger variability in biochars generated at temperatures below 400 °C, whereas H/C and O/C values converge above 450 °C. Recent developments in this area show that NMR is relatively insensitive to changes above 400 °C. McBeath and Smernik (2009) analyzed 17 heat-treated materials and confirmed that aromatic condensation increases with increasing heat-treatment temperature and that activated chars contained the most highly condensed aromatic structures. This study also highlighted the importance of starting material and heat-treatment time on aromatic condensation.
2.3. Specific surface area and microporosity of biochars
One of the unique properties of the biochars is their high specific surface area (SSA). While this key property governs most soil–biochar interactions, SSA itself is affected by the nature of the starting organic material (biomass) and the conditions under which the biochar is produced (see review by Downie et al., 2009). Both SSA and microporosity of biochars have been shown to increase with temperature, as these properties are interlinked. Nevertheless, different biochars produced from the same feedstock or biomass have very different SSA and microporosities, depending on the production technology employed (Downie et al., 2009). Chun et al. (2004) studied a series of biochar samples produced by pyrolyzing a wheat residue (Triticum aestivum L.) for 6 h at temperatures between 300 and 700 °C. They observed the biochar SSA increased with increasing charring temperatures (300–600 °C); however, the SSA value of char produced at 700 °C was lower than that of char produced at 600 °C ( Fig. 3). The authors speculated this to be due to microporous structures which were destroyed at 700 °C. Similarly, Brown et al. (2006) found that regardless of differences in the ramp rate, maximum SSA was realized at a final temperature of 750 °C ( Fig. 3). The chars produced at the lowest final temperature (i.e., 450 °C) had a SSA of < 10 m2/g, while those produced at intermediate temperatures of 600–750 °C had SSA of ~ 400 m2/g. They suggested that this is most likely due to the effect of ramp rate on pore structure ( Brown et al., 2006).