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The analysis of pyrogenic carbon (PyC) in environmental samples is of great interest, e.g. for carbon cycle assessment, (bio-)char characterization and palaeo-environmental or archeological reconstruction. Here, an HPLC method (HPLC) is presented that reproducibly quantifies benzene polycarboxylic acids (BPCA) as molecular markers for PyC in various kinds of environmental samples. It operates at low pH without requiring an organic modifier and was thoroughly tested with PyC reference materials and a peatland core that served as a feasibility and plausibility check. Compared to the established gas chromatography (GC) method, the HPLC method results in higher BPCA quantification reproducibility by showing a significantly smaller coefficient of variation (HPLC: 5%, GC: 16-23%). It works well with small sample amounts, as for instance from sediment cores and aerosol collectors, and requires less sample preparation work than the GC method. Moreover, the here presented HPLC method facilitates 13C and 14C analyses on PyC from environmental samples.

Fire-derived, pyrogenic carbon (PyC), sometimes called black carbon (BC), is the carbonaceous solid residue of biomass and fossil fuel combustion, such as char and soot. PyC is ubiquitous in the environment due to its long persistence, and its abundance might even increase with the projected increase in global wildfire activity and the continued burning of fossil fuel. PyC is also increasingly produced from the industrial pyrolysis of organic wastes, which yields charred soil amendments (biochar). Moreover, the emergence of nanotechnology may also result in the release of PyC-like compounds to the environment. It is thus a high priority to reliably detect, characterize and quantify these charred materials in order to investigate their environmental properties and to understand their role in the carbon cycle.Here, we present the benzene polycarboxylic acid (BPCA) method, which allows the simultaneous assessment of PyC's characteristics, quantity and isotopic composition ( 13 C and 14 C) on a molecular level. The method is applicable to a very wide range of environmental sample materials and detects PyC over a broad range of the combustion continuum, i.e., it is sensitive to slightly charred biomass as well as high temperature chars and soot. The BPCA protocol presented here is simple to employ, highly reproducible, as well as easily extendable and modifiable to specific requirements. It thus provides a versatile tool for the investigation of PyC in various disciplines, ranging from archeology and environmental forensics to biochar and carbon cycling research.

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