Assessment of hydropyrolysis as a method for the quantification of black carbon using standard reference materials

A wide selection of thermal, chemical and optical methods have been proposed for the quantification of black carbon (BC) in environmental matrices, and the results to date differ markedly depending upon the method used. A new approach is hydropyrolysis (hypy), where pyrolysis assisted by high hydrogen pressures (150 bar) facilitates the complete reductive removal of labile organic matter, so isolating a highly stable portion of the BC continuum (defined as BChypy). Here, the potential of hypy for the isolation and quantification of BC is evaluated using the 12 reference materials from the International BC Ring Trial, comprising BC-rich samples, BC-containing environmental matrices and BC-free potentially interfering materials. By varying the hypy operating conditions, it is demonstrated that lignocellulosic, humic and other labile organic carbon material (defined as non-BChypy) is fully removed by 550 °C, with hydrogasification of the remaining BChypy not commencing until over 575 °C. The resulting plateau in sample mass and carbon loss is apparent in all of the environmental samples, facilitating BC quantification in a wide range of materials. The BChypy contents for all 12 ring trial samples fall within the range reported in the BC inter-comparison study, and systematic differences with other methods are rationalised. All methods for BC isolation, including hypy are limited by the fact that BC cannot be distinguished from extremely thermally mature organic matter; for example in high rank coals. However, the data reported here indicates that BChypy has an atomic H/C ratio of less than 0.5 and therefore comprises a chemically well-defined polyaromatic structure in terms of the average size of peri-condensed aromatic clusters of >7 rings (24 carbon atoms), that is consistent across different sample matrices. This, together with the sound underlying rationale for the reductive removal of labile organic matter, makes hypy an ideal approach for matrix independent BC quantification. The hypy results are extremely reproducible, with BChypy determinations from triplicate analyses typically within ±2% across all samples, limited mainly by the precision of the elemental analyser

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