Missisquoi Bay Sediment Phosphorus Cycling: the Role of Organic Phosphorus and Seasonal Redox Fluctuations

Missisquoi Bay, Lake Champlain is a eutrophic, northern shallow freshwater bay that experiences toxic cyanobacteria blooms during the summer months, largely as result of high nutrient (P and N) loading from the agricultural watershed. The sediments, which contain minerals that readily sorb P, can act as a sink or source of water column nutrients. Phosphorus, both inorganic and some organic forms, sorbs to metal oxides at neutral pH in the sediment, thus P release into overlying and pore water can be significantly affected by the reduction and subsequent solubilization of these oxides. This study addresses novel aspects of nutrient cycling in lake sediments as part of a larger study to better understand the link between phosphorus forms, mobility, and cyanobacteria blooms. These aspects include: 1) diel and seasonal sediment redox fluctuations and 2) the role of organic P (Porg) in overall P mobility within sediments as a function of depth and time. Missisquoi Bay sediment porewater redox chemistry was monitored across diel and seasonal cycles over the course of two summers (May-October, 2007 and 2008) by using in-situ voltammetry. Redox chemistry was monitored at the sediment-water interface (SWI) continuously over diel cycles, and the vertical concentration profiles of several key redox species (O2, Mn2+, Fe2+, and FeS(aq)) were obtained from cores collected at different times. The sediments were then analyzed for Total P (TP), Reactive P (RP), Porg, Mn, Fe, Ca, Al, Total Organic C and N. A bloom did not occur in Missisquoi Bay during the summer of 2007, but did in summer of 2008, providing an opportunity to compare the sediment chemistry between non-bloom and bloom conditions. Increasingly anoxic SWI conditions across summer 2008 were observed but the SWI remained oxic for the duration of summer 2007. Significant changes in diel cycle redox chemistry at the SWI were also detected in both summers. Reactive P in the surface sediments decreased across the 2008 season but not in 2007. A strong correlation found between RP and RFe (operationally defined as Fe(III)OOH) suggests that a significant portion of sediment P (30-40%) is closely associated with Fe(III)OOHs, which are susceptible to reduction in anoxic conditions. Phosphorus mobility from the sediment into the water column can be limited by the amount of Fe(III)OOH at the surface, thus P flux from the sediments would be greatest when reducing conditions promote solubilization of these minerals. Completely anoxic surface sediments were only observed during the presence of a bloom, explaining the loss of RP in the surface sediments in 2008 in the late summer. Organic P species represent 18-26% of the P in sediments and the lack of a definite, consistent trend of Porg fractionation across the season suggests that there is variable mobility and degradation of these complex organic compounds on small timescales. The loss of RP from the sediment in 2008 could have contributed to an estimated water column P increase on the order of thousands of μg/L, which in addition to measured increases in NH4+ gradients and subsequent N flux estimates in the upper sediment, could have sustained the bloom for an extended period of time. The relationship between the bloom and reducing sediment conditions suggest that bloom dynamics enhance nutrient release from the sediments, allowing for proliferation and sustainability of the bloom