LAUSR

Lake 227 of the Experimental Lakes Area (ELA) in Ontario, Canada, has been fertilized with phosphorus (P) since 1969, which resulted in a rapid transition from oligotrophic to eutrophic conditions. Sediment cores collected from the oxygenated epilimnion, and the mostly anoxic hypolimnion of this unique lake contain a historical record of the changes in sediment P speciation and burial rates across the trophic transition. To elucidate these changes, results of chemical extractions were combined with Pb sediment dating, and with P NMR, Mössbauer, and XANES spectroscopies. Prior to 1969, organic P (POrg) was the major sedimentary P sink in Lake 227. Eutrophication of the lake coincided with marked increases in the burial rate of total P (TP), as well as in the relative contribution of the NaHCO3‐extractable P pool (humic‐bound P, PHum). Together, PHum and POrg account for ≥70% of total P burial in the sediments deposited since artificial fertilization started. The PHum fraction likely comprises phosphate complexes with humic substances. The strong linear correlation between P and iron (Fe) extracted by NaHCO3 implies a close association of the two elements in the humic fraction. Mössbauer and XANES spectra further indicate that most Fe in the post‐1969 sediments remained in the Fe (III) oxidation state, which is attributed to the stabilization of reducible Fe by organic matter, in part via the formation of phosphate‐Fe (III)‐humic complexes. Importantly, our results show that the eutrophication experimentation of Lake 227 caused the accumulation of a large reservoir of reactive sediment P, whichmay continue to fuel internal P loading to the water column once artificial fertilization is terminated.