The Enigmatic Great Lakes Nitrogen Cycle: Review and Insights from Isotopic Records Nathaniel E. Ostrom, Peggy H. Ostrom and Kateri R. Salk Department of Zoology, Michigan State University visibleearth.nasa.gov Outline and Objectives: 1. Review temporal concentration and isotopic records 2. Review our understanding of the Great Lakes N cycle 3. Future research directions visibleearth.nasa.gov Long-term trend of increasing nitrate: Lake Superior P levels have remained low, lower than central N. Pacific gyre NO3-/PO43- ~ 10,000; 600 times requirement for primary production Half the watershed is the lake itself Proposed that atm. deposition the primary cause (Ostrom et al., 1998) Based on low d15N-NO3 ( ~ -2 ‰) Sterner, 2011 Inland Waters 1: 29-46 Long-term trend of increasing nitrate: Lake Superior (Finlay et al., 2007) Stable isotope data indicate atm. deposition not the source of NO3NO3- generated in the lake via nitrification low potential for denitrification (Carlton et al., 1989) Superior is a net NO3- producer Lake Superior Data (Finlay et al., 2007) d18O-NO3 Precipitation River Water Lake Water d15N-NO3 From Kendall et al. 2007 Long-term trend of increasing nitrate: other Great Lakes Rising NO3- evident in all of the Great Lakes But not likely to be for the same reasons 0.04 PO43- mg/L 0.03 Lake Ontario 1970-2008 Eutrophic 0.02 Mesotrophic 0.01 Oligotrophic 0 http://www.on.ec.gc.ca/solec/nearshore-water/paper/part5.html Lake Erie (central basin) NO3- mg/L NO3- mg/L Lake Ontario 1970-2008 0.3 Dove, 2009 0.2 http://www.on.ec.gc.ca/solec/nearshore-water/paper/part5.html Lake Ontario Sediment C and N Isotope Record Eutrophication and recovery evident in C isotopes definitive evidence of the success of the Clean Air and Water Act Driver of N isotope record unclear interpreted as an increase in denitrification toward present lack of denitrification rate data Hodell and Schelske (1998) Grand Traverse Bay, Lake Michigan 85° 30’ 85° 15’ 45° 15’ GT3 45° 00’ GT1 44° 85’ Macrellis, 1999; McCusker et al., 1999 Grand Traverse Bay: Seasonal Progression in Temperature 1997 a cool year, 1998 El Niño 0 GT1 1997 -20 -40 -60 Depth (m) -80 22 C 0 GT3 1997 -20 -40 -60 -80 18 14 10 -100 6 0 GT3 1998 -20 -40 -60 -80 -100 April May June July August 2 Grand Traverse Bay: Station GT3 1997 Stratification well established at end of June Chl focused at or above thermocline SRP diminishes, NH4+ accumulates Temperature ( °C) Chlorophyll Fluorescence (RFU) SRP (mM) Ammonium (mM) 0 Depth (m) -20 -40 -60 -80 -100 0 Depth (m) -20 -40 -60 -80 -100 April May June July Aug. April May June July Aug. Grand Traverse Bay: Station GT3 1998, El Niño Stratification well established at end of May, one month earlier Chl focused at or above thermocline SRP diminishes, NH4+ accumulates Temperature ( °C) Chlorophyl Fluorescence (RFU) Depth (m) 0 -20 -40 -60 -80 -100 SRP (mM) Ammonium (mM) 0 Depth (m) -20 -40 -60 -80 -100 April May June July Aug. April May June July Aug. Grand Traverse Bay: Station GT3 1997 NO3- declines at surface, phytoplankton uptake d15N: NO3- constant at ~ 2.5 ‰; NH4+ averaged 12.1 ‰ d15N-PON largely controlled by uptake of 15N depleted NO3- and enriched NH4+ Nitrate (mM) Depth (m) 0 -20 -40 -60 -80 -100 Weighted d15N – PON (o/oo) 10 9 8 7 6 5 4 Mean = 5.6 ‰ 3 d15N - NO3 (o/oo) 0 Depth (m) -20 -40 -60 -80 -100 April May June July Aug. 7 6 5 4 3 2 1 0 Weighted d15N - NO3 (o/oo) Mean = 2.5 ‰ April May June July Aug. Grand Traverse Bay: Station GT3 1998, El Niño Decline in d15N-NO3- in July-Aug.; fractionation during nitrification average d15N-NO3- similar to 1997 d15N-PON higher by > 6 ‰ relative to 1997 Weighted d15N – PON (o/oo) Nitrate (mM) Depth (m) 0 15 14 13 12 11 10 9 8 -20 -40 -60 -80 -100 0 d15N - NO3 (o/oo) Depth (m) -20 -40 -60 -80 -100 April May June July Aug. 7 6 5 4 3 2 1 0 Mean = 12.2 ‰ Weighted d15N - NO3 (o/oo) Mean = 3.3 ‰ April May June July Aug. Implications to Great Lakes N Cycling d15N of NO3- and seston very dynamic indicates rapid turnover of PON and NO3Strong influence of the timing of spring stratification on d15N of PON earlier stratification leads to preferential uptake of 15N enriched NH4+ Lake Ontario d15N record might be driven by climate warming Need to know rates of NO3- and NH4+ uptake and denitrification Hodell and Schelske (1998) The “New” Nitrogen Cycle: Classical view that nitrification and denitrification dominate the N cycle is changing Anammox and DNRA increasingly being recognized as important Anammox (ANaerobic AMMonium OXidation) NO3- +NH4+ N2 DNRA (Dissimilatory Nitrate Reduction to Ammonium) NO3- NH4+ N retained in ecosystem; often provides source of NH4+ to Anammox Francis et al 2007 ISME Journal 1, 19-27. The “New” Nitrogen Cycle: Anammox dominant N-loss pathway in OMZ’s off Peru, Chile and Namibia can occur at higher O2 levels; greatly expanding area of NO3 loss Denitrification dominates in Arabian Sea OMZ Anammox is autotrophic and may outcompete denitrification where organic C is less bioavailable Francis et al 2007 ISME Journal 1, 19-27. Nitrogen Rate Measurements in Great Lakes very limited: While not exhaustive, “hits” found by Web of Science: Ecosystem and Denitrification Chesapeake Bay 124 Baltic Sea 141 Narragansett Bay 25 Great Lakes* 20 Nitrification 73 48 25 9 Anammox 7 20 0 0 DNRA 3 7 2 1 N2O 12 29 6 2 * Only 2 papers reporting rates of denitrification, one of DNRA, no nitrification rates Lake Huron and Ontario, no rate data More is known about N cycling in Lake Cadagno, Switzerland, than we do in the entire Great Lakes (i.e. Halm et al., 2009) Regime Change: Narragansett Bay Shift in primary production to blue-greens (N2 fixers) Decrease in deposition of labile organics Decrease in rates of denitrification increase in DNRA and retention of N in the ecosystem Increase in nitrate export Great Lakes? N fixers are increasing Is this changing the N cycle? Finlay et al 2007 Ecological Applications, 17(8), 2007, pp. 2323–2332 Lane N. NATURE Vol 449 18 October 2007 778-780 and Fulweiler et al (2007) vol 448 pg. 180-182. Summary: NO3- is rising but likely for different reasons in different lakes Sediment d15N is rising: cause uncertain Important Aspects of N cycling in the Great Lakes: Large and predictable hypoxic zone (Lake Erie) Hydraulic residence times from 3 to 173 y Range of trophic states from ultra-oligotrophic (Superior) to hyper-eutrophic (Sandusky Bay, Lake Erie) Eutrophic to Oligotrophic conditions in the same lake (Erie) Marked response to climate change Superior warming at twice the rate of the atm. increased sediment resuspension by storms Great Lakes could very well be a harbinger of what is to come in the oceans Austin and Colman 2008 Limnol. Oceanogr. 53: 2724-2730 Additional References: Carlton et al. (1989) J. Great Lakes Res. 15: 133-140. Dove A. (2009) Aquatic Ecosystem Health and Management 12: 281-295. Finlay et al. (2007) Ecol. Appl. 17: 2323-2332. Halm et al. (2009) Environmental Microbiology 11: 1945-1958. Hodell D.A. and C.L. Schelske (1998) Limnology and Oceanography 43: 200-214. Kendall et al. (2007) In: Stable Isotopes in Ecology and Environmental Science, R. Michener and K. Lajtha (Eds.) Blackwell Publishing, pp. 375-449. Macrellis A.N. (1999) Geochemical and isotope dynamics of dissolved inorganic nitrogen in Grand Traverse Bay, Lake Michigan. Unpublished masters thesis, Geological Sciences, Michigan State University. McCusker et al. (1999) Organic Geochemistry 30: 1543-1557. Ostrom et al. (1998) Chemical Geology 152: 13-28. Quinn F.H. (1992) Hydraulic residence times for the Laurentian Great Lakes. J. Great Lakes Research 18: 22-28.
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