Nitrogen loss in coastal sediments driven by anaerobic ammonium oxidation coupled to microbial reduction of Mn(IV)-oxide.

Coastal sediments play a central role in regulating the amount of land-derived reactive nitrogen (Nr) entering the ocean, and their importance becomes crucial in vulnerable ecosystems threatened by anthropogenic activities. Sedimentary denitrification has been identified as the main sink of Nr in marine environments, while anaerobic ammonium oxidation with nitrite (anammox) has also been pointed out as a key player in controlling the nitrogen pool in these locations. Collected evidence in the present work indicates that the microbial biota in coastal sediments from Baja California (northwestern Mexico) has the potential to drive anaerobic ammonium oxidation linked to Mn(IV) reduction (manganammox). Unamended sediment showed ammonification, but addition of vernadite (δMnO2 with nano-crystal size ∼15 Å) as terminal electron acceptor fueled simultaneous ammonium oxidation (up to ∼400 µM of ammonium removed) and production of Mn(II) with a ratio ∆[Mn(II)]/∆[NH4+] of 1.8, which is very close to the stoichiometric value of manganammox (1.5). Additional incubations spiked with external ammonium also showed concomitant ammonium oxidation and Mn(II) production, accounting for ∼30 % of the oxidized ammonium. Tracer analysis revealed that the nitrogen loss associated with manganammox was 4.2 ± 0.4 µg 30N2/g-day, which is 17-fold higher than that related to the feammox process (anaerobic ammonium oxidation linked to Fe(III) reduction, 0.24 ± 0.02 µg 30N2/g-day). Taxonomic characterization based on 16S rRNA gene sequencing revealed the existence of several clades belonging to Desulfobacterota as potential microorganisms catalyzing the manganammox process. These findings suggest that manganammox has the potential to be an additional Nr sink in coastal environments, whose contribution to total Nr losses remains to be evaluated.

Electron shuttling mediated by humic substances fuels anaerobic methane oxidation and carbon burial in wetland sediments.

Key pathways for the anaerobic oxidation of methane (AOM) have remained elusive, particularly in organic rich ecosystems. In this work, the occurrence of AOM driven by humus-catalyzed dissimilatory iron reduction was investigated in sediments from a coastal mangrove swamp. Anoxic sediment incubations supplied with both goethite (α-FeOOH) and leonardite (humic substances (HS)) displayed an average AOM rate of 10.7 ±â€¯0.8 µmol CH4 cm-3 day-1, which was 7 and 3 times faster than that measured in incubations containing only goethite or HS, respectively. Additional incubations performed with 13C-methane displayed Pahokee Peat HS-mediated carbonate precipitation linked to 13CH4 oxidation and ferrihydrite reduction (~1.3 µmol carbonate cm-3 day-1). These results highlight the role of HS on mitigating greenhouse gases released from wetlands, not only by mediating the AOM process, but also by enhancing carbon sequestration as inert minerals (calcite, aragonite and siderite).