[tp metro ]chl1/sdahodtp e pp e tdp e dop e srp e %time srp e < 1µgp·l -1 [tp metro ] chl sd...

[TPMetro] Chl 1/SD AHOD TPe PPe TDPe DOPe SRPe%time SRPe

< 1µgP·L-1

[TPMetro]

Chl

SD

AHOD

TPe

PPe

TDPe

DOPe

SRPe

%time SRPe

< 1µgP·L-1

Correlation Matrix:TPMetro, Trophic State Metrics, and Forms of P

parameters correlated parameters not correlated

Bible StudyBible Study

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

As Considered Here …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.”

Martin T. Auer, Phillip A. DePetro, and Kevin A. BierleinDepartment of Civil & Environmental Engineering

Michigan Technological University

Steven C. ChapraDepartment of Civil & Environmental Engineering

Tufts University

1111thth Onondaga Lake Scientific Forum, Syracuse, New York, November 2009 Onondaga Lake Scientific Forum, Syracuse, New York, November 2009

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

UNTO HOW MANY GENERATIONS:UNTO HOW MANY GENERATIONS:LEGACY ORGANIC CARBON IN ONONDAGA LAKE SEDIMENTSLEGACY ORGANIC CARBON IN ONONDAGA LAKE SEDIMENTS

Let’s Get One Thing Straight …Let’s Get One Thing Straight …

Why? Why?

Time

Conc

entr

ation

whatextent

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)

, , 0

1water t

water t wat

k

erC C e

, , 0

sed t

sed t sed

kzC C e

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, StupidIt’s the Slow Eigenvalue, Stupid

sediment

water

burial

flushing

Eigenvalues and Lake RecoveryEigenvalues and Lake Recovery

0 20 40 60 80 100

fasteigenvalueeffect

sloweigenvalueeffect

Cw

ater

Cse

dim

ent

Time (yr)

Whatever Became of Shagawa Lake?Whatever Became of Shagawa Lake?

Ely, Minnesota

ShagawaLake

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

Whatever Became of Shagawa Lake?Whatever Became of Shagawa Lake?

Ely, Minnesota

ShagawaLake

Chapra, S.C. and R.P. Canale. 1991. Long-term phenomenological model of phosphorusand 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.”

So … What’s in the Bottom of Onondaga Lake?So … What’s in the Bottom of Onondaga Lake?

• win a UFI t-shirt text your answers to 22422

(1) Pere Lemoyne’s hat



(2) A Cornell coxswain




(3) Ben Schwartzwalder’s comb





(4) The veil of Onondaga





(4) The veil of Onondaga

(5) Le Soup d’Yesterjour

NH3

PO4

CH4

H2S

SODMeHg

SND

The Path to RecoveryThe Path to RecoveryRuns Through the SoupRuns Through the Soup

… when and to what extent?

Le Soupd’Yesterjour

… with organic carbon fueling the fire.

Diagenesis and the Slow Eigenvalue in Onondaga LakeDiagenesis and the Slow Eigenvalue in Onondaga Lake

P, NH3, Hg

, , 0

sed t

sed t sed

kzC C e

slow eigenvalue

burial; Hg

diagenesis; NH3, P

The Slow Eigenvalue in Onondaga LakeThe Slow Eigenvalue in Onondaga Lake

0.1 0.2 0.3 0.4 0.50

10

20

30

40

50

Dept

h in

Sedi

men

t (cm

)

Total Phosphorus (%DW)

0

5

10

15

1985 1990 1995 2000 2005 2010

P (m

gP∙m

-2∙d

-1)

PP

slow eigenvalue

They weren’t supposed to do this until I was dead.Chapra (2009)


0.0 0.2 0.4 0.6 0.8 1.00

10

20

30

40

50

Dep

th in

Sed

imen

t (cm

)

Total Nitrogen (%DW)

0

20

40

60

80

100

1990 1995 2000 2005 2010

NHNH33

NH

3-N (

mg∙

m-2∙d

-1)

slow eigenvalue


0

20

40

60

80

100

120

140

0 4 8 12 16

1997 Total Hg

Dep

th in

Sed

imen

t (cm

)

Total Mercury (µg∙gDW-1)

0

200

400

600

800

1000

2005 2006 2007 2008

MeH

g H

AR

(ng∙

m-2∙d

-1)

Hg, MeHgHg, MeHg

slow eigenvalue

Carbon Diagenesis and Water QualityCarbon Diagenesis and Water Quality

The EngineP NH3 H2S

MeHg CH4

The Fuel

The Gatekeepers

C

O2 NO3

external

loads

managementvariable

Carbon Diagenesis and Water QualityCarbon Diagenesis and Water Quality

The EngineP NH3 H2S

MeHg CH4

The Fuel

C

external

loadsinternal

loads

managementvariable

Organic Carbon Diagenesis in Sediments:Organic Carbon Diagenesis in Sediments:TheThe Slow Eigenvalue Slow Eigenvalue

C

, , 0

sed t

sed t sed

kzC C e

slow eigenvalueoperative processes

burial

diagenesis

P NH3 H2SMeHg CH4

C

DIAGENESIS with constant deposition

0

10

20

30

40

50

0 1 2 3 4 5Total Organic Carbon (%DW)

Dep

th in

Sed

imen

t (cm

)

Quantifying Legacy CarbonQuantifying Legacy Carbon

DIAGENESIS with variable deposition

Total Organic Carbon (%DW)

Dep

th in

Sed

imen

t (cm

)0

10

20

30

40

50

60

2 4 6 8 10 12


LABILITY ASSAYS under oxic conditionsO

xyge

n C

onsu

med

(mgO

2∙gD

W-1)

byoxidativemetabolism

Z = 2.0-2.5 cm

Z = 58-60 cm

Incubation Time (d)

0

5

10

15

20

25

0 5 10 15 20


0

2

4

6

8

10

12

14

0 2 4 6 8

Oxy

gen

Con

sum

ed (m

gO2∙g

DW

-1)

byfermentativemetabolism

Z = 21 cm

Z = 49 cm

Incubation Time (d)


LABILITY ASSAYS under anoxic conditions

LABILITY AT DEPOSITION

byfermentative metabolism56%

byoxidativemetabolism

90%


EXPECTATIONS for downcore changes in lability

0

10

20

30

40

50


Dep

th in

Sed

imen

t (cm

)


LABILITY PROFILE under oxic conditions

Labile Organic Carbon (%TOC)

Dep

th in

Sed

imen

t (cm

)

0

10

20

30

40

50

60

70

80

0 25 50 75 100

oxidativemetabolism



Dep

th in

Sed

imen

t (cm

)

0

10

20

30

40

50

60

2 4 6 8 10 12

NoRedemption

0

10

20

30

40

50

60

70

80

0 25 50 75 100Labile Organic Carbon (%TOC

Dep

th in

Sed

imen

t (cm

)

fermentative metabolism



Dep

th in

Sed

imen

t (cm

)

0

10

20

30

40

50

60

2 4 6 8 10 12

NoRedemption

LABILITY PROFILE under anoxic conditions

22 2 2( )C OH O CO H O

3 232 2 2( )C H O N CO HCO H ONO

2 24 2

2( )C H O Mn COMn H O

2 23 2

2( )C H O Fe COFe H O

22 2 2 24( )C H O H S CO H OSO

42 2( ) C OC HH O C

electrondonor

electronacceptor CO2+ reduced species

end product+

various various


MAPPING DIAGENESIS

MAPPING DIAGENESIS• ETSA and the localization of oxidative processes

20010000

10

20

30

40

50

60

Electron Transport System Activity(mgO2∙gDW-1∙hr-1)

Dept

h in

Sed

imen

t (cm

)

Redrawn from Stromquist1996

region of oxidative metabolism

~0-10 cm

22 2 2( )C OH O CO H O

3 232 2 2( )C H O N CO HCO H ONO

2 24 2

2( )C H O Mn COMn H O

2 23 2

2( )C H O Fe COFe H O

22 2 2 24( )C H O H S CO H OSO


Methane (mg L∙ -1)

0

10

20

30

40

50

60

0.0 0.5 1.51.0

MAPPING DIAGENESIS• localization of methanogenesis

region of fermentative metabolism

~10-20 cm

42 2( ) C OC HH O C

Dept

h in

Sed

imen

t (cm

)



0

5

10

15

20

25

2 4 6 8 10 12

om

rmDe

pth

in S

edim

ent (

cm)

Total Organic Carbon (%DW)LITANY OF LEGACY• 14 years in the mud

Preservation (think iceman)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

Does this mean … ?Does this mean … ?

0

5

10

15

20

25

2 4 6 8 10 12

om

rm

Dept

h in

Sed

imen

t (cm

)


preservation

0

10

20

30

40

50

60


Dep

th in

Sed

imen

t (cm

)

Ah … yes … redemption!Ah … yes … redemption!

1 2, , ,0 , ,0

k t k OETPOC t poc labile poc conditionally labile refractoryc c e c e c

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

Carbon Diagenesis and Water QualityCarbon Diagenesis and Water QualityThe ModelThe Model

The EngineP NH3 H2S

MeHg CH4

The Fuel

The Gatekeepers

C

O2 NO3

external

loads

managementvariable

THETHE• load driven• water column linked • coupled • flux predicting

MODELMODEL

[tp metro ]chl1/sdahodtp e pp e tdp e dop e srp e %time srp e < 1µgp·l -1 [tp metro ] chl sd...

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