Bioavailability and bioaccessibility of polycyclic aromatic hydrocarbons from (post-pyrolytically treated) biochars

Bioaccessibility data of PAHs from biochar produced under real world conditions is scarce and the influence of feedstock and various post-pyrolysis treatments common in agriculture, such as co-composting or lacto-fermentation to produce silage fodder, on their bioavailability and bioaccessibility has hardly been studied. The total (C_total), and freely dissolved (i.e., bioavailable) concentrations (C_free) of the sum of 16 US EPA PAHs of 43 biochar samples produced and treated in such ways ranged from 0.4 to almost 2000 mg/kg, and from 12 to 81 ng/L, respectively, which resulted in very high biochar-water partition coefficients (4.2 ≤ log K_D ≤ 8.8 L/kg) for individual PAHs. Thirty three samples were incubated in contaminant traps that combined a diffusive carrier and a sorptive sink. Incubations yielded samples only containing desorption-resistant PAHs (C_res). The desorption resistant PAH fraction was dominant, since only eight out of 33 biochar samples showed statistically significant bioaccessible fractions (f_{bioaccessible} = 1 - C_res/C_total). Bioavailability correlated positively with C_total/surface area. Other relationships of bioavailability and -accessibility with the investigated post-pyrolysis processes or elemental composition could not be found. PAH exposure was very limited (low C_free, high C_res) for all samples with low to moderate C_total, whereas higher exposure was determined in some biochars with C_total > 10 mg/kg.