1. [TP Metro ]Chl1/SDAHODTP e PP e TDP e DOP e SRP e %time SRP e < 1µgP·L -1 [TP Metro ] Chl SD AHOD TP e PP e TDP e DOP e SRP e %time SRP e < 1µgP·L -1 Correlation Matrix: TP Metro, Trophic State Metrics, and Forms of P parameters correlated parameters not correlated

2. Bible Study “And I looked, and behold a pale horse: and his name that sat on him was Death, and Hell followed with him.”

3. As Considered Here … “And I looked, and behold a pale horse: and his name that sat on him was AHOD, and Hell followed with him.”

4. Martin T. Auer, Phillip A. DePetro, and Kevin A. Bierlein Department of Civil & Environmental Engineering Michigan Technological University Steven C. Chapra Department of Civil & Environmental Engineering Tufts University 11 th Onondaga Lake Scientific Forum, Syracuse, New York, November 2009 SINS OF THE MOTHERS AND FATHERS: WHITHER REDEMPTION? UNTO HOW MANY GENERATIONS: LEGACY ORGANIC CARBON IN ONONDAGA LAKE SEDIMENTS

5. Let’s Get One Thing Straight …

6. Why? Time Concentration what extent when The question is not whether lakes will improve following external loading reductions, but when and to what extent. Restoration & Management of Lakes and Reservoirs; Cooke et al. (2005)

7. sediment water burial flushing with a rapid flushing rate, the fast eigenvalue for Onondaga Lake is fast indeed. the slow eigenvalue … not so much. It’s the Slow Eigenvalue, Stupid

8. sediment water burial flushing Eigenvalues and Lake Recovery fast eigenvalue effect slow eigenvalue effect C water C sediment Time (yr)

9. Whatever Became of Shagawa Lake? Ely, Minnesota Shagawa Lake Larsen, D.P. and Malueg, K.W. 1980. Whatever became of Shagawa Lake? pp. 67-72, In: Restoration of Lakes and Inland Waters, U.S. Environmental Protection Agency. water column TP of 50 ppb tertiary treatment reduced load by 80% not so much; they missed the slow eigenvalue a fast eigenvalue-based model predicted that water column TP would reach 12.5 ppb within 1.5 years

10. Whatever Became of Shagawa Lake? Ely, Minnesota Shagawa Lake Chapra, S.C. and R.P. Canale. 1991. Long-term phenomenological model of phosphorus and oxygen in stratified lakes. Water Research, 25(6): 707-715. “supply from the sediments had not diminished since treatment began … further recovery … will depend upon how long feedback from the sediments continues.”

11. So … What’s in the Bottom of Onondaga Lake? win a UFI t-shirt text your answers to 22422 (1)Pere Lemoyne’s hat

12. So … What’s in the Bottom of Onondaga Lake? (1)Pere Lemoyne’s hat (2)A Cornell coxswain

13. So … What’s in the Bottom of Onondaga Lake? (1)Pere Lemoyne’s hat (2)A Cornell coxswain (3) Ben Schwartzwalder’s comb

14. So … What’s in the Bottom of Onondaga Lake? (1)Pere Lemoyne’s hat (2)A Cornell coxswain (3) Ben Schwartzwalder’s comb (4) The veil of Onondaga

15. So … What’s in the Bottom of Onondaga Lake? (1)Pere Lemoyne’s hat (2) A Cornell coxswain (3) Ben Schwartzwalder’s comb (4)The veil of Onondaga (5) Le Soup d’Yesterjour NH 3 PO 4 CH 4 H2SH2S SOD MeHg SND

16. The Path to Recovery Runs Through the Soup … when and to what extent? Le Soup d’Yesterjour … with organic carbon fueling the fire.

17. Diagenesis and the Slow Eigenvalue in Onondaga Lake P, NH 3, Hg slow eigenvalue burial; Hg diagenesis; NH 3, P

18. The Slow Eigenvalue in Onondaga Lake P (mgP∙m -2 ∙d -1 )P slow eigenvalue They weren’t supposed to do this until I was dead. Chapra (2009)

19. The Slow Eigenvalue in Onondaga Lake 0.0 0.2 0.4 0.6 0.8 1.0 0 10 20 30 40 50 Depth in Sediment (cm) Total Nitrogen (%DW) NH 3 NH 3 -N (mg∙m -2 ∙d -1 ) slow eigenvalue

20. The Slow Eigenvalue in Onondaga Lake 1997 Total Hg Depth in Sediment (cm) Total Mercury (µg∙gDW -1 ) MeHg HAR (ng∙m -2 ∙d -1 ) Hg, MeHg slow eigenvalue

21. Carbon Diagenesis and Water Quality The Engine P NH 3 H 2 S MeHg CH 4 The Fuel The Gatekeepers O2O2 NO 3 external loads management variable

22. Carbon Diagenesis and Water Quality The Engine P NH 3 H 2 S MeHg CH 4 The Fuel external loads internal loads management variable

23. Organic Carbon Diagenesis in Sediments: The Slow Eigenvalue C slow eigenvalue operative processes burial diagenesis P NH 3 H 2 S MeHg CH 4

24. DIAGENESIS with constant deposition Total Organic Carbon (%DW) Depth in Sediment (cm) Quantifying Legacy Carbon

25. DIAGENESIS with variable deposition Total Organic Carbon (%DW) Depth in Sediment (cm) Quantifying Legacy Carbon

26. LABILITY ASSAYS under oxic conditions Oxygen Consumed (mgO 2 ∙gDW -1 ) by oxidative metabolism Z = 2.0-2.5 cm Z = 58-60 cm Incubation Time (d) Quantifying Legacy Carbon

27. Oxygen Consumed (mgO 2 ∙gDW -1 ) by fermentative metabolism Z = 21 cm Z = 49 cm Incubation Time (d) Quantifying Legacy Carbon LABILITY ASSAYS under anoxic conditions

28. LABILITY AT DEPOSITION by fermentative metabolism 56% by oxidative metabolism 90% Quantifying Legacy Carbon

29. EXPECTATIONS for downcore changes in lability Total Organic Carbon (%DW) Depth in Sediment (cm) Quantifying Legacy Carbon

30. LABILITY PROFILE under oxic conditions Labile Organic Carbon (%TOC) Depth in Sediment (cm) oxidative metabolism Quantifying Legacy Carbon Total Organic Carbon (%DW) Depth in Sediment (cm) No Redemption

31. Labile Organic Carbon (%TOC Depth in Sediment (cm) fermentative metabolism Quantifying Legacy Carbon Total Organic Carbon (%DW) Depth in Sediment (cm) No Redemption LABILITY PROFILE under anoxic conditions

32. electron donor electron acceptor  CO 2 + reduced species end product + various Quantifying Legacy Carbon MAPPING DIAGENESIS

33. ETSA and the localization of oxidative processes region of oxidative metabolism ~0-10 cm Quantifying Legacy Carbon

34. MAPPING DIAGENESIS localization of methanogenesis region of fermentative metabolism ~10-20 cm Depth in Sediment (cm) Quantifying Legacy Carbon

35. om rm Depth in Sediment (cm) Total Organic Carbon (%DW) LITANY OF LEGACY 14 years in the mud

36. Preservation (think iceman) Mayer et al. 1994a,b, 2004; Zimmerman et al. 2004; Curry et al. 2007 MECHANISMS surface adsorption on mineral particles encapsulation in the mineral microfabric biological protection (necromass) humification (enzyme resistance) Thompsen et al. 2002; Arnarson and Keil 2007; Curry et al. 2007 Ladd and Paul 1973; Mayer 2004 Hedges 1988; Hedges et al. 1999; Hedges and Keil 1995 b. 3300 BCE Ötzi the Iceman

37. Does this mean … ? om rm Depth in Sediment (cm) Total Organic Carbon (%DW)  preservation 

38. Total Organic Carbon (%DW) Depth in Sediment (cm) Ah … yes … redemption!

39. SINS OF THE MOTHERS AND FATHERS: WHITHER REDEMPTION?

40. Carbon Diagenesis and Water Quality The Model The Engine P NH 3 H 2 S MeHg CH 4 The Fuel The Gatekeepers O2O2 NO 3 external loads management variable THE load driven water column linked coupled flux predictingMODEL