Controls of H(2)S, Fe(2 +), and Mn(2 +) on Microbial NO(3)(–)-Reducing Processes in Sediments of an Eutrophic Lake

Understanding the biogeochemical controls on the partitioning between nitrogen (N) removal through denitrification and anaerobic ammonium oxidation (anammox), and N recycling via dissimilatory nitrate (NO(3)(–)) reduction to ammonium (DNRA) is crucial for constraining lacustrine N budgets. Besides organic carbon, inorganic compounds may serve as electron donors for NO(3)(–) reduction, yet the significance of lithotrophic NO(3)(–) reduction in the environment is still poorly understood. Conducting incubation experiments with additions of (15)N-labeled compounds and reduced inorganic substrates (H(2)S, Fe(2+), Mn(2+)), we assessed the role of alternative electron donors in regulating the partitioning between the different NO(3)(–)-reducing processes in ferruginous surface sediments of Lake Lugano, Switzerland. In sediment slurry incubations without added inorganic substrates, denitrification and DNRA were the dominant NO(3)(–)-reducing pathways, with DNRA contributing between 31 and 46% to the total NO(3)(–) reduction. The contribution of anammox was less than 1%. Denitrification rates were stimulated by low to moderate additions of ferrous iron (Fe(2+) ≤ 258 μM) but almost completely suppressed at higher levels (≥1300 μM). Conversely, DNRA was stimulated only at higher Fe(2+) concentrations. Dissolved sulfide (H(2)S, i.e., sum of H(2)S, HS(–) and S(2−)) concentrations up to ∼80 μM, strongly stimulated denitrification, but did not affect DNRA significantly. At higher H(2)S levels (≥125 μM), both processes were inhibited. We were unable to find clear evidence for Mn(2+)-supported lithotrophic NO(3)(–) reduction. However, at high concentrations (∼500 μM), Mn(2+) additions inhibited NO(3)(–) reduction, while it did not affect the balance between the two NO(3)(–) reduction pathways. Our results provide experimental evidence for chemolithotrophic denitrification or DNRA with Fe(2+) and H(2)S in the Lake Lugano sediments, and demonstrate that all tested potential electron donors, despite the beneficial effect at low concentrations of some of them, can inhibit NO(3)(–) reduction at high concentration levels. Our findings thus imply that the concentration of inorganic electron donors in lake sediments can act as an important regulator of both benthic denitrification and DNRA rates, and suggest that they can exert an important control on the relative partitioning between microbial N removal and N retention in lakes.