Artificial formation of benzene polycarboxylic acids during sample processing of black carbon analysis : the role of organic carbon amount

Abstract

Black carbon is also known as pyrogenic carbon formed by partial combustion of organic material under limited oxygen supply. It occurs along a continuum from original organic slightly charred material to highly aromatic combustion residues such as charcoal, graphite, and soot. Black carbon is extensively studied in various environments due to its ubiquity. It is also important for the biochar community because it can specifically trace the stable polycondensed part of biochar. Different methods have been adopted for black carbon determination; among them using benzene polycarboxylic acids (BPCA) as molecular markers for the polycondensed aromatic moieties of charred materials. However, different researchers have shown interferences from organic matter during BPCA analysis. Therefore, the aim of this work was to assess if artificial formation of BPCA occurs in soil samples when the organic carbon load exceeds 5–10 mg. For this purpose, we conducted black carbon analysis of different soil samples with varying TOC contents of up to 20 mg. In addition, organic matter-rich plant materials were used as a black carbon-free control (leaves of Ivy and Beech, leaves/needles of Spruce and needles of Thuja). To exclude the high-pressure digestion as source of artificial black carbon formation, a comparison between the conventional and a microwave-assisted extraction (MAE) oxidation process was included. Our results show that for soil samples, no artificial BPCA formation occurred at least up to 20 mg of total organic carbon. Higher sample weights are unrealistic for BPCA analysis of soils using current methodology. Therefore, our results clearly demonstrate that there is no artificial BPCA formation during properly performed black carbon analysis of soil samples. On the contrary, for some samples, BPCA contents tended to decrease with increasing sample weight, and thus increasing amount of TOC. In contrast, for plant samples, artificial BPCA formation of up to 3 g kg−1 occurred when more plant material equivalent to 10 mg total organic carbon was used. However, there was no amount dependence of artificial BPCA formation. The reason for artificial BPCA formation was not the high-pressure digestion, as microwave-assisted digestion showed comparable results. However, for real-world analysis, this artificial BPCA formation is not relevant because such high soil sample weights cannot be used. Nevertheless, when using organic-rich material such as peat and charred materials, the samples should contain less than 10 mg of total organic carbon.