Photodegradation of pyrogenic dissolved organic matter increases bioavailability: Novel insight into bioalteration, microbial community succession, and C and N dynamics

Photodegradation and biodegradation of pyrogenic dissolved organic matter (pyDOM) play crucial roles in regulating greenhouse gas emissions and stabilizing organic matter. In this study, we conducted a 56-day microbial laboratory incubation to investigate the biodegradation patterns of pristine and photobleached pyDOM leached from a thermal series of chars (300, 450, and 600 °C) based on FT-ICR-MS, gas analysis, N speciation, and 16S rDNA sequencing. As the pyrolysis temperature increased, the among of biomineralized carbon of pyDOM decreased, while the molecular diversity and aromaticity increased. Photobleaching increased the among of biomineralized carbon of pyDOM from 40%–70% to 60%–80%, but decreased the molecular diversity, molecular weight, and aromaticity, with a major removal of lignin-like compounds. Microbial incubation lowered the molecular diversity but increased the molecular weight and aromaticity of both pristine and photobleached samples. Tannin-like structures, carbohydrates, and aliphatic/protein were preferentially biodegraded, while lipid, lignin-like structures, unsaturated hydrocarbons, and condensed aromatics were more likely to be preserved or newly produced. The photobio-resistant components were mainly comprised of lignin-like and tannin-like structures. Photobleached pyDOM samples released more CO2 but less N2O, as they may possess high denitrification rate due to their high carbon reactivity. The bacterial richness and diversity in pyDOM were lower than the original inoculum. In addition, distinct differences were noted between the bacterial community structure of the original inoculum and that of pristine and photobleached pyDOM samples following various incubation times. Specifically, proteobacteria was increased and remained the predominant phylum in all pyDOM solutions compared to the original inoculum, while Actinobacteriota, Bdellovibrionota, Firmicutes, or Nitrospirota phyla were increased in several samples either after 7 or 56 days of incubation. In particular, photobleached pyDOM pyrolyzed at 600 °C exhibited the strongest filtration effects on the bacterial microflora. These results help to elucidate the biogeochemical cycling and turnover of pyDOM in sunlit and dark aquatic environments such as fluvial and groundwater networks, lakes, and the ocean.