Mildly acidic pH boosts up CO2 conversion to isobutyrate in H2 driven gas fermentation system

As a greenhouse gas, massive carbon dioxide (CO₂) has been generated due to organic matter degradation in wastewater treatment processes. Microbial gas fermentation offers a promising approach to capture CO₂ and generate various valuable chemicals. However, limited studies have achieved branched or medium-chain fatty acids production via gas fermentation. This study reported the production of isobutyrate and hexanoate by feeding H₂ and CO₂ into membrane biofilm reactors (MBfRs). The gas fermentation product in the reactor with neutral pH (pH of 7) was dominated by acetate (accounting for 90 % of the product spectrum), whereas a mildly acidic pH (pH of 6) resulted in isobutyrate and hexanoate as the dominant products, with a selectivity of 57 % and 42 %, respectively. Notably, a remarkably high concentration of isobutyrate (266 mmol C/L) was produced in the reactor with pH of 6. Subsequent batch test results suggest that the isobutyrate production in this study is coupled with acetogenesis and ethanol-driven chain elongation processes, rather than via methanol-driven chain elongation reported previously. High-throughput 16S rRNA gene amplicon sequencing revealed that the microbial community under neutral pH was dominated by acetate-producing homoacetogens Acetobacterium. By contrast, a mildly acidic pH promoted the community shifting towards chain elongation microorganisms, dominated by Clostridium sensu stricto 12, Oscillibacter and Caproiciproducens. Collectively, this study demonstrates the significant role of mildly acidic pH in boosting up bioisomerization and chain elongation in gas fermentation systems, thus triggering isobutyrate and hexanoate production. The findings highlight gas fermentation as a new green alternative route for generating highly valuable isobutyrate and hexanoate.