Unveiling molecular DOM reactomics and transformation coupled with multifunctional nanocomposites under anaerobic...

Anaerobic digestion (AD) offers great potential for pollutant removal and bioenergy recovery. However, it faces challenges when using livestock manure (LSM) as a feedstock given its high content of refractory materials (e.g., lignocellulose, long-chain carbohydrates, lipids, and crude protein). This would significantly inhibit AD-microbial activities, reduce organic transformation efficiency and limit gas production. To overcome this, multifunctional metal-doped hydrochars (HCs) were introduced here as AD supplements/accelerators, given that LSM degradation under AD results in complex dissolved organic matter (DOM). To assess this, the current study investigates the molecular interactions/transformations within DOM during LSM-AD coupled with metal-doped HCs, via batch-mode experiments. Expansive data mining techniques were employed to analyze DOM using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Substantial increments in peptide-like along with decrements in highly unsaturated-like molecules were observed in HC@MnCl₂ containing-system. This indicates an increased capability for substrate hydrolysis and potential utilization of soluble microbial products (SMPs) (i.e., highly unsaturated-like molecules), leading to enhanced methane recovery (223.23 mL/g-VS_added, 1.77 times more than the control). However, accumulation of DOM-highly unsaturated molecules (i.e., a lack of SMPs' degradation) accompanied with low methane production (39.68 mL/g-VS_added) was noticed for HC@NiFe₂O₄. DOM reactivity during LSM-AD was validated via paired mass difference molecular network, indicating predominance of CHO and N-containing groups' transformations for HC@MnCl₂ and HC@NiFe₂O₄, respectively. Potential metabolites and abundant pathways were verified via KEGG database. This study improves our understanding of LSM-AD-DOM complex transformation matrix, the fate of bioavailable/recalcitrant compounds, and identification of potential DOM regulators from thousands of molecules.