Redox characterization of humins in sediments from the Yangtze Estuary to the East China Sea and their effects on microbial redox reactions

Purpose: Humins, as solid-phase redox mediators, are important for enhancing anaerobic biotransformation processes. Although humins are broadly distributed in estuarine and marine sediments, to date, their electron transfer capacity (ETC) from marine sediments has been poorly characterized. This study determined the potential of humins as redox mediators for microbial redox metabolic reactions in sediments along a transect from the Yangtze Estuary to the adjacent East China Sea and analyzed their electron-mediating characteristics. Materials and methods: Comparative analyses of humins in sediments along this transect were conducted to investigate their ETC as redox mediators for microbial redox metabolic reactions, namely dissimilatory iron reduction (DIR) and dissimilatory nitrate reduction to ammonium (DNRA), using Shewanella oneidensis MR-1. Elemental composition, electrochemical, and Fourier transform infrared analyses were performed to better understand the functional redox groups in humins. Results and discussion: All the humins functioned as solid-phase redox mediators and enhanced DIR and DNRA by Shewanella oneidensis, although with varying efficacy. The humins extracted from sampling site P1 (P1-HM), located close to the Yangtze Estuary, most effectively enhanced iron and nitrate reduction without nitrite accumulation. Electrochemical analysis confirmed the highest redox activity and ETC in P1-HM and a weakening trend of ETC with increasing distance from the estuary. Fourier transform infrared analysis suggested that quinone moieties might serve as key redox functional groups in humins. Conclusions: Considering their high yield and ETC, P1-HM could be important redox mediators that influence microbial redox metabolic reactions in sedimentary ecosystems of the Yangtze Estuary. Thus, this study provides insights into the distribution of humins, their ECT, and their potential role as redox mediators for microbial redox reactions, which could improve understanding of elemental biogeochemical cycling processes involving microorganisms in the Yangtze Estuary and East China Sea sedimentary ecosystems and provide important reference information for researches on other estuary areas.