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Lars J. Tranvik
Limnology, Department of Ecology and Genetics,
Uppsala University, Sweden
The carbon fluxes along the land aquatic continuum
from land to sea
Lars J. Tranvik
Work presented here primarily by:
Katrin Attermeyer
Núria Catalán
Anne Kellerman
Birgit Koehler
Dolly Kothawala
Alina Mostovaya
Jeff Hawkes
Thorsten Dittmar
Limnology, Department of Ecology and Genetics,
Uppsala University, Sweden
The carbon fluxes along the land aquatic continuum
from land to sea
Earth has 117 million lakes > 0.002 km2 (a little less than half a soccer
field) , covering 4% of the continents
Verpoorter et al. 2014. Geophysical Research Letters
Swedish lakes
95700 lakes larger than 1 ha comprising
9% of the total land area
Swedish lakes : SMHI
Inland waters – perfusing the landscape
Recent
publications
Older
publications
The lake as a
microcosm
with a “closed”
C cycle
Forbes 1887
Recent
publications
Older
publications
The lake as a
microcosm
with a “closed”
C cycle
Thienemann 1925
Forbes 1887
Recent
publications
Older
publications
The lake as a
microcosm
with a “closed”
C cycle
The inland water
C cycle is heavily
influenced by
import
Thienemann 1925
Forbes 1887
Naumann 1932
Many lakes are small and strongly influenced by organic carbon
(mostly dissolved, DOC) imported from the watershed
Photo: Stefan Löfgren
Recent
publications
Older
publications
The lake as a
microcosm
with a “closed”
C cycle
The inland water
C cycle is heavily
influenced by
import
Thienemann 1925
Forbes 1887
Naumann 1932
Salonen et al. 1983
Tranvik 1988
del Giorgio and Peters 1993
Recent
publications
Older
publications
The lake as a
microcosm
with a “closed”
C cycle
The inland water
C cycle is heavily
influenced by
import
Thienemann 1925
Forbes 1887
Naumann 1932
Inland waters
are landscape
sinks and
sources of C
Salonen et al. 1983
Tranvik 1988
del Giorgio and Peters 1993
Cole et al. 1994
Kling et al. 1991
Recent
publications
Older
publications
The lake as a
microcosm
with a “closed”
C cycle
The inland water
C cycle is heavily
influenced by
import
Thienemann 1925
Forbes 1887
Naumann 1932
Inland waters
are landscape
sinks and
sources of C
Salonen et al. 1983
Tranvik 1988
del Giorgio and Peters 1993
Cole et al. 1994
Richey et al. 2002
Algesten et al. 2003
Dillon and Molot 1997
Duarte and Prairie 2005
Kling et al. 1991
Recent
publications
Older
publications
The lake as a
microcosm
with a “closed”
C cycle
The inland water
C cycle is heavily
influenced by
import
Thienemann 1925
Forbes 1887
Naumann 1932
Inland waters
are substantial
sinks and
sources of C at
global scale
Inland waters
are landscape
sinks and
sources of C
Salonen et al. 1983
Tranvik 1988
del Giorgio and Peters 1993
Cole et al. 1994
Richey et al. 2002
Algesten et al. 2003
Einsele et al. 2001
Dean and Gorham 1998Dillon and Molot 1997
Duarte and Prairie 2005
Kling et al. 1991
Recent
publications
Older
publications
Raymond et al. 2013
The lake as a
microcosm
with a “closed”
C cycle
The inland water
C cycle is heavily
influenced by
import
Thienemann 1925
Forbes 1887
Naumann 1932
Inland waters
are substantial
sinks and
sources of C at
global scale
Inland waters
are landscape
sinks and
sources of C
Salonen et al. 1983
Tranvik 1988
del Giorgio and Peters 1993
Cole et al. 1994
Richey et al. 2002
Algesten et al. 2003
Cole et al. 2007
Einsele et al. 2001
Dean and Gorham 1998Dillon and Molot 1997
Duarte and Prairie 2005
Kling et al. 1991
Tranvik, Cole, Prairie, LO Letters 2018
Atmosphere
OceanLand Freshwaters
“passive pipe”
Cole et al. 2007, Ecosystems
Atmosphere
OceanLand
Storage
Freshwaters
Cole et al. 2007, Ecosystems
“active pipe”
OceanLand Inland waters 0.92.9
1.4
0.6
Tranvik et al. Limnol. Oceanogr. 2009Gigatons per year
Gigatons per year Drake et al. Limnol. Oceanogr. Letters 2018
Fig 7.3 of IPCC 4th Assessment Report, 2007, WG I, “The Physical Science Basis”
The Global Carbon Cycle, IPCC 2007
Fig 7.3 of IPCC 4th Assessment Report, 2007, WG I, “The Physical Science Basis”
The Global Carbon Cycle, IPCC 2007
Fig 7.3 of IPCC 4th Assessment Report, 2007, WG I, “The Physical Science Basis”
The Global Carbon Cycle, IPCC 2007
?
IPCC 5th Assessment Report, 2013, WG I, “The Physical Science Basis”
The Global Carbon Cycle, IPCC 2013
Literature review:
Inland waters are hot spots of OC decay,
half life ≈ 2.5 years
Catalán et al. Nature Geoscience 2016
OceanLand Inland waters
Things that transform the organic matter
Flocculation/Sedimentation
Microbial mineralization
Photochemical mineralization
bacterial enzymes
photons and photochemically
produced reactive
oxygen species
OH
OH
OH
OH
HOOC
HOOC
OHO
OH
O
COOH
N
OH
NH
O O
-
O O
OH
O
OHOH
OH
C H3
O
OH
OH
OH
OH
NH
NH2
NH
NH
O
O
NH
COOH
COOH
NH C H2
O
C H2 NH2
CH3
H
Fe
2+
O
O
O
C H3O
O
O
-
OO
-
NH2
O
CH 2OH
O
NH2
O
NH2
CH 2OH
O O
NH2
OH
OO
C H3
O
N
C H2
H
NH C H2 NH
C H2
OH
NO 2
O
NH
C H2
NH
O
C H2
COOH
O
NH
OH
OH
O
O
O
-
O
OH
OCH 3OH
OH
C H2C H2OC
O
NHC
C H2O
-
O
O
H
O H
O N
O
H
O
O
NH C H C H2
COOH
O
C H2 C H2
NNH
O
H3CO
O O
O
H3CO
H
O
H CH 2OH
O C H3
COOH
H
K
+
Si
OH
OH
O H
O H
Fe
2+
Fe
2+
Fe
O
O
H
H
O
-
O
NH2
H O
H
Al
+
OH
OH
O
O
Al
Si
O
H
O
O
O
O
Si
O
O OH
Fe
2+O
H
H
.
.
.
OH
OH
O
O
O
O
NHCH3
OH
O
-
OH
O OH
OH
OH
NO2
OH
OH
O
NH2
O
OH
O
O
N
OH
O
C H2C H2
O
NH
OH
NH2
O
O
-
H
H
H
OH
OH
O O
H3CO
OH
O
CH 2OH
CH 2OH
O O
O
O
C H2
O
OO
CH 2OH
OO
C H2
O
CH 2OH
O
O
H
HOH
C H3
OH
H
H
H
OH
OH
O
-
O
LMW labile
organic C
CO2
”Photo-oxidative production of DIC from DOC is a significant
process in the carbon budget of temperate lakes”
“UV has the potential to account for most of the DOC losses …
and thus may play a significant role in regulating DOC
concentrations in lakes”
Photochemical mineralization of organic matter
It is an easy an safe experiment to put some water in a thin quartz
vessel under the sun or under some lamp
Many nice experiments,
especially in surface water on
sunny days – but does it
matter at larger scales?
Photochemical rate model, DOC > DIC
Photon absorption rate (λ, z) = Spectral scalar irradiation (λ) *
DOC absorption coefficient (λ) *
Diffuse attenuation (λ, 0-z)
Photoproduction rate (λ, z) = Photon absorption rate (λ, z) *
Apparent quantum yield (λ, z)
𝑒−𝐾 𝑑(λ)𝑧
λ = Wavelength
DOM= Dissolved organic matter
z = Depth
Kd = Diffuse attenuation coefficient
Koehler et al. 2014
Apparent quantum yield of DIC photoproduction,
measured in the lab
Absorbance and attenuation spectra
Ø DOC absorbance spectra of 1086 lakes across Sweden,
Riksinventering 2009
Ø Assuming that attenuation only due to
absorption from dissolved organic
matter and water
Irradiance spectra, at each time point, at each lake
Atmospheric radiative transfer model libRadTran
Ø Absorption and scattering by atmospheric constituents
Ø Using actual ozone and cloud profiles from 2009 for each
spatial point
Ø Hourly time scale
Fichot and Miller 2010; Mayer et al. 2011
Irradiance spectra, at each time point, at each lake
Atmospheric radiative transfer model libRadTran
Ø Absorption and scattering by atmospheric constituents
Ø Using actual ozone and cloud profiles from 2009 for each
spatial point
Ø Hourly time scale
Fichot and Miller 2010; Mayer et al. 2011
Upscaling of photomineralization to the scale of
Sweden
• integration of photochemically
active radiation over time
Koehler et al. 2014
Upscaling of photomineralization to the scale of
Sweden
• integration of photochemically
active radiation over time
• wavelength dependent
depth attenuation of the
photochemically active
radiation
Koehler et al. 2014
Upscaling of photomineralization to the scale of
Sweden
• integration of photochemically
active radiation over time
• wavelength dependent
depth attenuation of the
photochemically active
radiation
• wavelength dependent
photochemical
reactivity of DOC
Koehler et al. 2014
Comparing model with photomineralization observed by
Granéli et al. (1996)
Depth profiles of DIC photoproduction
example from two lakes, one day
Brownwater vs. Clearwater lake
~10-fold difference in a350:
6.7 vs. 60.5 m-1
Similar DIC photoproduction:
26.9 vs. 25.5 mg C m-2 day-1
Photomineralization is photon-limited
Annual course of DIC photoproduction,
example from one lake, one year
Clear-sky irradiances
Annual course of DIC photoproduction,
example from one lake, one year
Clear-sky irradiances
Cloud-corrected
irradiances
Annual total Swedish CO2-C emissions
Photomineralization (this study):
0.1-0.3 Mtons C yr-1, i. e. 6-18% of total emissions*
Hence, photochemistry is significant, but not the
main driver of lake CO2 emissions
*Algesten et al. 2003
Koehler et al. 2014
OceanLand Inland waters
Things that transform the organic matter
Flocculation/Sedimentation
Microbial mineralization
Photochemical mineralization
Sediment sequestration
“Dystrophic“ lake sediment, fluffy and hopeless…
The OC collected in sediment traps is to a large extent of
terrestrial origin
von Wachenfeldt and Tranvik Ecosystems 2008
Allochthony calculated
from 13C
CO2
DOC
Plankton
CO2
CO2
Light
100%
C
C
~ 50 %
DOCPOC
The OC settling onto the sediment can only to a
minor extent be explained by particles imported
from land
Flocculation of DOC accounts for most of the OC
found in sediments of boreal lakes
von Wachenfeldt and Tranvik Ecosystems 2008, L&O 2008, 2009
CO2
DOC
Plankton
CO2
CO2
Light
100%
C
C
~ 50 %
DOCPOC
Flocculation:
• Microbial “triggering” of flocculation
• Photochemical Fe redox effect
von Wachenfeldt and Tranvik Ecosystems 2008, L&O 2008, 2009
OceanLand Inland waters
Whatever the things are that make the organic carbon
dissappear – how fast do they act?
Flocculation/Sedimentation
Microbial mineralization
Photochemical mineralization
Time
DOC0/DOCt
IncubationTime
DOCConcentration
The simplest model of degradation:
Exponential decay
154.2
192.9
226.9
254.9
292.9
326.8
369.2
429.2
505.1
561.1
655.1
0.0
0.2
0.4
0.6
0.8
1.0
9
x10
200 400 600 800 1000 1200 1400 1600 1800 m/z
…but there are hundred thousands (or more!)
components in the organic matter with different
properties, some degrade slowly, some fast
Degradability of organic carbon decreases over time, due to gradual
loss of the more labile compounds, and
Reactivity continuum
Boudreau and Rudick, 1991; Koehler et al. 2012
Apparent initial age of DOC (a)
Distribution of the intrinsic reactive types (ν)
Decayconstant,k
Time, t
Data from 208 bioassays
and 107 field studies
Longer retention time -> slower decay
Data in previous slide vs marine sediments
The same general pattern of slower decay extends
over 10 orders of magnitude
Open symbols: Marine
sediment OC decay
(Middelburg 1989)
Catalán et al. 2016
DOC input/output budgets of 82 water bodies,
mostly from Europe and North America
DOC input/output budgets of 82 water bodies,
mostly from Europe and North America
Evans et al. 2017, Nature Geoscience
Loss of DOC overestimated at long WRT, and
underestimated at short WRT*
PredictedremainingDOC
*if an average decay rate is used
Evans et al. 2017, Nature Geoscience
Loss of DOC overestimated at long WRT, and
underestimated at short WRT*
PredictedremainingDOC
*if an average decay rate is used
Loss is faster in the
beginning, before labile
compounds are exhausted
Evans et al. 2017, Nature Geoscience
Loss of DOC overestimated at long WRT, and
underestimated at short WRT*
PredictedremainingDOC
*if an average decay rate is used
Loss is faster in the
beginning, before labile
compounds are exhausted
Loss is slower in the
end, when
predominantly
recalcitrant
compounds remain
Evans et al. 2017, Nature Geoscience
Loss of DOC overestimated at long WRT, and
underestimated at short WRT*
PredictedremainingDOC
*if an average decay rate is used
Loss is faster in the
beginning, before labile
compounds are exhausted
Loss is slower in the
end, when
predominantly
recalcitrant
compounds remain
…and when loss is
increasingly
counteracted by
new primary
production
Evans et al. 2017, Nature Geoscience
OceanLand Inland waters
Different molecular properties are lost at different rates
Will this result in emergent patterns across aquatic
environments?
Flocculation/Sedimentation
Microbial mineralization
Photochemical mineralization
Köhler et al. PloSONE 2013
Increasing water retention time
Basin A: 0.07 years; Basin F: 2.8 years
DOC half-life: 6.1 years
Color (abs420) half life: 1.7 years
Fe half-life: 0.6 years
The DOC becomes “fresher”
Köhler et al. PloSONE 2013
Increasing water retention time
Basin A: 0.07 years; Basin F: 2.8 years
Loss rate: DOC < Color < Fe
Colored DOC lost by co-precipitation with Fe, and with photodecay
311.113615
367.139846
ESI_neg_Annsjon1x_Anne_20111110_000001.d: -isCID MS
0.0
0.5
1.0
1.5
2.0
8x10
Intens.
150 200 250 300 350 400 450 500 550 600 650 m/z
Detailed analysis of DOC chemistry
by ultra-high resolution ESI FT ICR MS
Ultra high resolution mass spectrometry
Kellerman et al. Nature Communications 2014
1000s of formula plotted in space of elemental ratios,
H/C and O/C
Spearmancorrelation
-0.75
0.75
ESI-FT-ICR-MS, specific molecular formula
Condensed “humic-type” DOC correlates negatively
Aliphatic “algal-type” DOC correlates positively
Water Residence Time
Kellerman et al. Nature Communications 2014
Spearmancorrelation
-0.75
0.75
ESI-FT-ICR-MS, specific molecular formula
Condensed “humic-type” DOC correlates positively
Aliphatic “algal-type” DOC correlates negatively
Mean Annual Precipitation
Kellerman et al. Nature Communications 2014
OceanLand Inland waters
Yes, there is some apparent selective loss of compounds resulting in
emergent patterns across the inland water continuum
Flocculation/Sedimentation
Microbial mineralization
Photochemical mineralization
Take home message
• DOC in inland waters is a major agent in
continental carbon budgets
Take home message
• DOC in inland waters is a major agent in
continental carbon budgets
Take home message
• Transformations of DOC results in
substantial emissions to the
atmosphere and a significant sediment
C sink
• DOC in inland waters is a major agent in
continental carbon budgets
Take home message
• The composition of organic
matter is shaped by selective
biogeochemical processes
• Transformations of DOC results in
substantial emissions to the
atmosphere and a significant sediment
C sink
• Thank you for listening!

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Tranvik, Lars: The carbon fluxes at the land-ocean-atmosphere continuum

  • 1. Lars J. Tranvik Limnology, Department of Ecology and Genetics, Uppsala University, Sweden The carbon fluxes along the land aquatic continuum from land to sea
  • 2. Lars J. Tranvik Work presented here primarily by: Katrin Attermeyer Núria Catalán Anne Kellerman Birgit Koehler Dolly Kothawala Alina Mostovaya Jeff Hawkes Thorsten Dittmar Limnology, Department of Ecology and Genetics, Uppsala University, Sweden The carbon fluxes along the land aquatic continuum from land to sea
  • 3. Earth has 117 million lakes > 0.002 km2 (a little less than half a soccer field) , covering 4% of the continents Verpoorter et al. 2014. Geophysical Research Letters
  • 4. Swedish lakes 95700 lakes larger than 1 ha comprising 9% of the total land area Swedish lakes : SMHI Inland waters – perfusing the landscape
  • 5. Recent publications Older publications The lake as a microcosm with a “closed” C cycle Forbes 1887
  • 6. Recent publications Older publications The lake as a microcosm with a “closed” C cycle Thienemann 1925 Forbes 1887
  • 7. Recent publications Older publications The lake as a microcosm with a “closed” C cycle The inland water C cycle is heavily influenced by import Thienemann 1925 Forbes 1887 Naumann 1932
  • 8. Many lakes are small and strongly influenced by organic carbon (mostly dissolved, DOC) imported from the watershed
  • 10. Recent publications Older publications The lake as a microcosm with a “closed” C cycle The inland water C cycle is heavily influenced by import Thienemann 1925 Forbes 1887 Naumann 1932 Salonen et al. 1983 Tranvik 1988 del Giorgio and Peters 1993
  • 11. Recent publications Older publications The lake as a microcosm with a “closed” C cycle The inland water C cycle is heavily influenced by import Thienemann 1925 Forbes 1887 Naumann 1932 Inland waters are landscape sinks and sources of C Salonen et al. 1983 Tranvik 1988 del Giorgio and Peters 1993 Cole et al. 1994 Kling et al. 1991
  • 12. Recent publications Older publications The lake as a microcosm with a “closed” C cycle The inland water C cycle is heavily influenced by import Thienemann 1925 Forbes 1887 Naumann 1932 Inland waters are landscape sinks and sources of C Salonen et al. 1983 Tranvik 1988 del Giorgio and Peters 1993 Cole et al. 1994 Richey et al. 2002 Algesten et al. 2003 Dillon and Molot 1997 Duarte and Prairie 2005 Kling et al. 1991
  • 13. Recent publications Older publications The lake as a microcosm with a “closed” C cycle The inland water C cycle is heavily influenced by import Thienemann 1925 Forbes 1887 Naumann 1932 Inland waters are substantial sinks and sources of C at global scale Inland waters are landscape sinks and sources of C Salonen et al. 1983 Tranvik 1988 del Giorgio and Peters 1993 Cole et al. 1994 Richey et al. 2002 Algesten et al. 2003 Einsele et al. 2001 Dean and Gorham 1998Dillon and Molot 1997 Duarte and Prairie 2005 Kling et al. 1991
  • 14. Recent publications Older publications Raymond et al. 2013 The lake as a microcosm with a “closed” C cycle The inland water C cycle is heavily influenced by import Thienemann 1925 Forbes 1887 Naumann 1932 Inland waters are substantial sinks and sources of C at global scale Inland waters are landscape sinks and sources of C Salonen et al. 1983 Tranvik 1988 del Giorgio and Peters 1993 Cole et al. 1994 Richey et al. 2002 Algesten et al. 2003 Cole et al. 2007 Einsele et al. 2001 Dean and Gorham 1998Dillon and Molot 1997 Duarte and Prairie 2005 Kling et al. 1991 Tranvik, Cole, Prairie, LO Letters 2018
  • 16. Atmosphere OceanLand Storage Freshwaters Cole et al. 2007, Ecosystems “active pipe”
  • 17. OceanLand Inland waters 0.92.9 1.4 0.6 Tranvik et al. Limnol. Oceanogr. 2009Gigatons per year
  • 18. Gigatons per year Drake et al. Limnol. Oceanogr. Letters 2018
  • 19. Fig 7.3 of IPCC 4th Assessment Report, 2007, WG I, “The Physical Science Basis” The Global Carbon Cycle, IPCC 2007
  • 20. Fig 7.3 of IPCC 4th Assessment Report, 2007, WG I, “The Physical Science Basis” The Global Carbon Cycle, IPCC 2007
  • 21. Fig 7.3 of IPCC 4th Assessment Report, 2007, WG I, “The Physical Science Basis” The Global Carbon Cycle, IPCC 2007 ?
  • 22. IPCC 5th Assessment Report, 2013, WG I, “The Physical Science Basis” The Global Carbon Cycle, IPCC 2013
  • 23. Literature review: Inland waters are hot spots of OC decay, half life ≈ 2.5 years Catalán et al. Nature Geoscience 2016
  • 24. OceanLand Inland waters Things that transform the organic matter Flocculation/Sedimentation Microbial mineralization Photochemical mineralization
  • 25. bacterial enzymes photons and photochemically produced reactive oxygen species OH OH OH OH HOOC HOOC OHO OH O COOH N OH NH O O - O O OH O OHOH OH C H3 O OH OH OH OH NH NH2 NH NH O O NH COOH COOH NH C H2 O C H2 NH2 CH3 H Fe 2+ O O O C H3O O O - OO - NH2 O CH 2OH O NH2 O NH2 CH 2OH O O NH2 OH OO C H3 O N C H2 H NH C H2 NH C H2 OH NO 2 O NH C H2 NH O C H2 COOH O NH OH OH O O O - O OH OCH 3OH OH C H2C H2OC O NHC C H2O - O O H O H O N O H O O NH C H C H2 COOH O C H2 C H2 NNH O H3CO O O O H3CO H O H CH 2OH O C H3 COOH H K + Si OH OH O H O H Fe 2+ Fe 2+ Fe O O H H O - O NH2 H O H Al + OH OH O O Al Si O H O O O O Si O O OH Fe 2+O H H . . . OH OH O O O O NHCH3 OH O - OH O OH OH OH NO2 OH OH O NH2 O OH O O N OH O C H2C H2 O NH OH NH2 O O - H H H OH OH O O H3CO OH O CH 2OH CH 2OH O O O O C H2 O OO CH 2OH OO C H2 O CH 2OH O O H HOH C H3 OH H H H OH OH O - O LMW labile organic C CO2
  • 26. ”Photo-oxidative production of DIC from DOC is a significant process in the carbon budget of temperate lakes”
  • 27. “UV has the potential to account for most of the DOC losses … and thus may play a significant role in regulating DOC concentrations in lakes”
  • 28. Photochemical mineralization of organic matter It is an easy an safe experiment to put some water in a thin quartz vessel under the sun or under some lamp Many nice experiments, especially in surface water on sunny days – but does it matter at larger scales?
  • 29. Photochemical rate model, DOC > DIC Photon absorption rate (λ, z) = Spectral scalar irradiation (λ) * DOC absorption coefficient (λ) * Diffuse attenuation (λ, 0-z) Photoproduction rate (λ, z) = Photon absorption rate (λ, z) * Apparent quantum yield (λ, z) 𝑒−𝐾 𝑑(λ)𝑧 λ = Wavelength DOM= Dissolved organic matter z = Depth Kd = Diffuse attenuation coefficient Koehler et al. 2014
  • 30. Apparent quantum yield of DIC photoproduction, measured in the lab
  • 31. Absorbance and attenuation spectra Ø DOC absorbance spectra of 1086 lakes across Sweden, Riksinventering 2009 Ø Assuming that attenuation only due to absorption from dissolved organic matter and water
  • 32. Irradiance spectra, at each time point, at each lake Atmospheric radiative transfer model libRadTran Ø Absorption and scattering by atmospheric constituents Ø Using actual ozone and cloud profiles from 2009 for each spatial point Ø Hourly time scale Fichot and Miller 2010; Mayer et al. 2011
  • 33. Irradiance spectra, at each time point, at each lake Atmospheric radiative transfer model libRadTran Ø Absorption and scattering by atmospheric constituents Ø Using actual ozone and cloud profiles from 2009 for each spatial point Ø Hourly time scale Fichot and Miller 2010; Mayer et al. 2011
  • 34. Upscaling of photomineralization to the scale of Sweden • integration of photochemically active radiation over time Koehler et al. 2014
  • 35. Upscaling of photomineralization to the scale of Sweden • integration of photochemically active radiation over time • wavelength dependent depth attenuation of the photochemically active radiation Koehler et al. 2014
  • 36. Upscaling of photomineralization to the scale of Sweden • integration of photochemically active radiation over time • wavelength dependent depth attenuation of the photochemically active radiation • wavelength dependent photochemical reactivity of DOC Koehler et al. 2014
  • 37. Comparing model with photomineralization observed by Granéli et al. (1996)
  • 38. Depth profiles of DIC photoproduction example from two lakes, one day Brownwater vs. Clearwater lake ~10-fold difference in a350: 6.7 vs. 60.5 m-1 Similar DIC photoproduction: 26.9 vs. 25.5 mg C m-2 day-1 Photomineralization is photon-limited
  • 39. Annual course of DIC photoproduction, example from one lake, one year Clear-sky irradiances
  • 40. Annual course of DIC photoproduction, example from one lake, one year Clear-sky irradiances Cloud-corrected irradiances
  • 41. Annual total Swedish CO2-C emissions Photomineralization (this study): 0.1-0.3 Mtons C yr-1, i. e. 6-18% of total emissions* Hence, photochemistry is significant, but not the main driver of lake CO2 emissions *Algesten et al. 2003 Koehler et al. 2014
  • 42. OceanLand Inland waters Things that transform the organic matter Flocculation/Sedimentation Microbial mineralization Photochemical mineralization
  • 43. Sediment sequestration “Dystrophic“ lake sediment, fluffy and hopeless…
  • 44. The OC collected in sediment traps is to a large extent of terrestrial origin von Wachenfeldt and Tranvik Ecosystems 2008 Allochthony calculated from 13C
  • 45. CO2 DOC Plankton CO2 CO2 Light 100% C C ~ 50 % DOCPOC The OC settling onto the sediment can only to a minor extent be explained by particles imported from land Flocculation of DOC accounts for most of the OC found in sediments of boreal lakes von Wachenfeldt and Tranvik Ecosystems 2008, L&O 2008, 2009
  • 46. CO2 DOC Plankton CO2 CO2 Light 100% C C ~ 50 % DOCPOC Flocculation: • Microbial “triggering” of flocculation • Photochemical Fe redox effect von Wachenfeldt and Tranvik Ecosystems 2008, L&O 2008, 2009
  • 47. OceanLand Inland waters Whatever the things are that make the organic carbon dissappear – how fast do they act? Flocculation/Sedimentation Microbial mineralization Photochemical mineralization
  • 49. 154.2 192.9 226.9 254.9 292.9 326.8 369.2 429.2 505.1 561.1 655.1 0.0 0.2 0.4 0.6 0.8 1.0 9 x10 200 400 600 800 1000 1200 1400 1600 1800 m/z …but there are hundred thousands (or more!) components in the organic matter with different properties, some degrade slowly, some fast
  • 50. Degradability of organic carbon decreases over time, due to gradual loss of the more labile compounds, and Reactivity continuum Boudreau and Rudick, 1991; Koehler et al. 2012 Apparent initial age of DOC (a) Distribution of the intrinsic reactive types (ν) Decayconstant,k Time, t
  • 51. Data from 208 bioassays and 107 field studies Longer retention time -> slower decay
  • 52. Data in previous slide vs marine sediments The same general pattern of slower decay extends over 10 orders of magnitude Open symbols: Marine sediment OC decay (Middelburg 1989) Catalán et al. 2016
  • 53. DOC input/output budgets of 82 water bodies, mostly from Europe and North America
  • 54. DOC input/output budgets of 82 water bodies, mostly from Europe and North America Evans et al. 2017, Nature Geoscience
  • 55. Loss of DOC overestimated at long WRT, and underestimated at short WRT* PredictedremainingDOC *if an average decay rate is used Evans et al. 2017, Nature Geoscience
  • 56. Loss of DOC overestimated at long WRT, and underestimated at short WRT* PredictedremainingDOC *if an average decay rate is used Loss is faster in the beginning, before labile compounds are exhausted Evans et al. 2017, Nature Geoscience
  • 57. Loss of DOC overestimated at long WRT, and underestimated at short WRT* PredictedremainingDOC *if an average decay rate is used Loss is faster in the beginning, before labile compounds are exhausted Loss is slower in the end, when predominantly recalcitrant compounds remain Evans et al. 2017, Nature Geoscience
  • 58. Loss of DOC overestimated at long WRT, and underestimated at short WRT* PredictedremainingDOC *if an average decay rate is used Loss is faster in the beginning, before labile compounds are exhausted Loss is slower in the end, when predominantly recalcitrant compounds remain …and when loss is increasingly counteracted by new primary production Evans et al. 2017, Nature Geoscience
  • 59. OceanLand Inland waters Different molecular properties are lost at different rates Will this result in emergent patterns across aquatic environments? Flocculation/Sedimentation Microbial mineralization Photochemical mineralization
  • 60. Köhler et al. PloSONE 2013 Increasing water retention time Basin A: 0.07 years; Basin F: 2.8 years
  • 61. DOC half-life: 6.1 years Color (abs420) half life: 1.7 years Fe half-life: 0.6 years The DOC becomes “fresher”
  • 62. Köhler et al. PloSONE 2013 Increasing water retention time Basin A: 0.07 years; Basin F: 2.8 years Loss rate: DOC < Color < Fe Colored DOC lost by co-precipitation with Fe, and with photodecay
  • 63. 311.113615 367.139846 ESI_neg_Annsjon1x_Anne_20111110_000001.d: -isCID MS 0.0 0.5 1.0 1.5 2.0 8x10 Intens. 150 200 250 300 350 400 450 500 550 600 650 m/z Detailed analysis of DOC chemistry by ultra-high resolution ESI FT ICR MS
  • 64. Ultra high resolution mass spectrometry Kellerman et al. Nature Communications 2014 1000s of formula plotted in space of elemental ratios, H/C and O/C
  • 65. Spearmancorrelation -0.75 0.75 ESI-FT-ICR-MS, specific molecular formula Condensed “humic-type” DOC correlates negatively Aliphatic “algal-type” DOC correlates positively Water Residence Time Kellerman et al. Nature Communications 2014
  • 66. Spearmancorrelation -0.75 0.75 ESI-FT-ICR-MS, specific molecular formula Condensed “humic-type” DOC correlates positively Aliphatic “algal-type” DOC correlates negatively Mean Annual Precipitation Kellerman et al. Nature Communications 2014
  • 67. OceanLand Inland waters Yes, there is some apparent selective loss of compounds resulting in emergent patterns across the inland water continuum Flocculation/Sedimentation Microbial mineralization Photochemical mineralization
  • 69. • DOC in inland waters is a major agent in continental carbon budgets Take home message
  • 70. • DOC in inland waters is a major agent in continental carbon budgets Take home message • Transformations of DOC results in substantial emissions to the atmosphere and a significant sediment C sink
  • 71. • DOC in inland waters is a major agent in continental carbon budgets Take home message • The composition of organic matter is shaped by selective biogeochemical processes • Transformations of DOC results in substantial emissions to the atmosphere and a significant sediment C sink
  • 72. • Thank you for listening!