First lacustrine application of the diatom‐bound nitrogen isotope paleo‐proxy reveals coupling of denitrification and N2 fixation in a hyper‐eutrophic lake

Abstract

AbstractPast changes in the input/output, and internal cycling, of bioavailable nitrogen (N) in marine and lacustrine environments can be reconstructed by analyzing the N isotopic composition (δ15N) of organic matter in the sedimentary record. To verify, and eliminate, potential biases of bulk sedimentary δ15N (δ15Nbulk) signatures by diagenetic alteration and external N inputs, we applied, for the first time, the diatom‐bound N isotope (δ15Ndb) paleo‐proxy to lake sediments. By comparing δ15Nbulk and δ15Ndb in a sedimentary record from eutrophic Lake Lugano (Switzerland), we demonstrate that changing redox conditions influence the degree of N‐isotopic alteration of the bulk sediment, emphasizing the need for caution when interpreting δ15Nbulk in paleolimnological studies. Furthermore, in combining δ15Ndb measurements with X‐ray fluorescence scanning and state‐of‐the‐art molecular biomarker analyses, we reconstruct nutrient cycling and paleoenvironmental conditions in the lake over the past ~ 125 yr. Coeval with the period of severe eutrophication in Lake Lugano in the 1960s, our proxy data indicate that export production, δ15Ndb, and the concentration of heterocyst glycolipids (a biomarker for N2‐fixing cyanobacteria) increased simultaneously. Together, these data suggest that the rise in δ15Ndb is likely the result of enhanced water‐column denitrification in response to increased phytoplankton productivity. We hypothesize that greater export production during eutrophication led to anoxic conditions in the hypolimnion as a result of enhanced organic matter remineralization, raising water‐column denitrification. Enhanced N loss and remobilization of phosphorous (P) from the sediments under anoxic conditions lowered the N : P ratio in the lake, fostering cyanobacterial N2 fixation in surface waters.