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Water Res. 2014 Oct 1;62:229-40. doi: 10.1016/j.watres.2014.06.005. Epub 2014 Jun 11.

Phosphorus speciation in a eutrophic lake by ³¹P NMR spectroscopy.

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Cary Institute of Ecosystem Studies, Millbrook, NY, USA; Center for Limnology, University of Wisconsin-Madison, Madison, WI, USA. Electronic address:
Department of Chemistry, University of Vermont, Burlington, VT, USA.
Center for Limnology, University of Wisconsin-Madison, Madison, WI, USA.
Agriculture and Agri-Food Canada, Swift Current, Saskatchewan, Canada.
Civil and Environmental Engineering Department, University of Wisconsin-Madison, Madison, WI, USA; Department of Bacteriology, University of Wisconsin-Madison, Madison, WI, USA.


For eutrophic lakes, patterns of phosphorus (P) measured by standard methods are well documented but provide little information about the components comprising standard operational definitions. Dissolved P (DP) and particulate P (PP) represents important but rarely characterized nutrient pools. Samples from Lake Mendota, Wisconsin, USA were characterized using 31-phosphorus nuclear magnetic resonance spectroscopy ((31)P NMR) during the open water season of 2011 in this unmatched temporal study of aquatic P dynamics. A suite of organic and inorganic P forms was detected in both dissolved and particulate fractions: orthophosphate, orthophosphate monoesters, orthophosphate diesters, pyrophosphate, polyphosphate, and phosphonates. Through time, phytoplankton biomass, temperature, dissolved oxygen, and water clarity were correlated with changes in the relative proportion of P fractions. Particulate P can be used as a proxy for phytoplankton-bound P, and in this study, a high proportion of polyphosphate within particulate samples suggested P should not be a limiting factor for the dominant primary producers, cyanobacteria. Hypolimnetic particulate P samples were more variable in composition than surface samples, potentially due to varying production and transport of sinking particles. Surface dissolved samples contained less P than particulate samples, and were typically dominated by orthophosphate, but also contained monoester, diester, polyphosphate, pyrophosphate, and phosphonate. Hydrologic inflows to the lake contained more orthophosphate and orthophosphate monoesters than in-lake samples, indicating transformation of P from inflowing waters. This time series explores trends of a highly regulated nutrient in the context of other water quality metrics (chlorophyll, mixing regime, and clarity), and gives insight on the variability of the structure and occurrence of P-containing compounds in light of the phosphorus-limited paradigm.


(31)P NMR; Cyanobacteria; Eutrophication; Lake Mendota; Phosphorus

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