Dissolved black nitrogen: an overlooked active nano-catalyst in the abiotic transformation of chlorophenols by sulfides in the subsurface water

The incomplete combustion of biomass and fossil fuels results in the formation of not only black carbon (BC) but also black nitrogen (BN), the dissolved fractions of which (i.e., DBC and DBN) are important components of dissolved organic matter pool. Relative to DBC, the activity and reactivity of DBN are much less understood. Here, we investigated the catalytic effect of DBN derived from N-enriched biomass in the abiotic transformation of chlorophenols by sulfides. The medium-temperature DBN (450 °C) exhibited 13–144% higher catalytic efficiency than other DBN samples and 9.3 times higher than its DBC counterpart. Both electron paramagnetic resonance spectra and fluorescent probe technique indicated that the attached sulfides contributed to the formation of reactive oxygen species (ROS) as the “primary” radicals by favoring electron transfer from DBN to chemisorbed oxygen, and then the generated ROS reacted with N-oxides in DBN to form reactive nitrogen species (RNS) as the “secondary” radicals. The contribution of RNS to the decay of 2-chlorophenol by DBN450 was up to 72%, much higher than that of ROS and non-radical mechanism. These findings suggest that the catalytic effect of DBN is distinct but no less significant than that of DBC to the abiotic transformation of micropollutants in water/soil systems.