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Iron and Biogeochemical Cycles
Redfield Ratio
• C:N:P
• 106:16 :1 (Redfield, 1958)
• Could there be other essential
micro-nutrients?
-Trace metals such as Fe, Zn, Co
are important!
High Nutrient, Low (Medium)
Chlorophyll Regions
Why aren’t the nutrients being completely
utilized by phytoplankton?
Phosphorous Chlorophyll
Conkright et al., 1994 µm
SeaWiFs
Hypotheses
• Light
• Grazing
• Micronutrient limitation
In situ Fertilization experiments: Is iron limiting?
e.g.
Iron needed for enzymes that
facilitate electron transport, O2
transport and other important
functions.
‘Dissolved’ Iron distribution
Why are there so few measurements?
- Difficult to measure
Surface 1000 m
Iron Profile
What controls the distribution (vertically
and horizontally) of Iron?
Iron has a profile
between a typical
metal and nutrient
Metal
Nutrient
Sources of Iron
• Riverine
• Continental Shelves
• Dust
Riverine
• [Fe’] decreases
further from coast.
• This is due to
scavenging of Fe by
particles.
• We can conclude that
rivers are not an
important source for
the open ocean Boyle et al. (1977)
Scavenging: Iron sink
• Iron lost to the ocean by
scavenging – the
process of sticking onto
particles
• Rate of scavenging not
well-known
• loss=-ksc[Fe’][P]
Continental Shelves
1. Resuspension of sediments
can release Fe
2. When organic matter
decomposes, Fe can diffuse or
be bio-irrigated into the water
column
C106H263O110N16P1Fe.0001+138O2=106C
O2 +16NO-
3+H2PO-
4+0.0001Fe(OH)2
Estimate global flux of 0.2-9 x 1010
mol y-1
Is this Fe upwelled to the
surface before being
scavenged?
Active area of research
Results from flux
chamber experiment
(Elrod et al., 2004)
Aeolian-derived Iron
• Major source of iron
• How much of the iron is
soluble?
- 1-10%
Active area of research:
differences by provenance,
processing in cloud, surface
waters
• Flux: 0.2-1.2 X 1010 mol
y-1 (assuming 2%
solubility)
Annual Fe flux (mg Fe m-2 y-1)
Mahowald et al. (2003)
Iron Speciation : Complexation
ligand
of
strength
specifies
constant
stability
cond.
]
'
][
'
[
]
[
'
'
'






K
L
Fe
FeL
K
FeL
L
Fe
FeL
Fe
FeT
Iron Speciation : Complexation
• Inorganic iron: Fe2+, Fe3+,
Fe(OH)3
– Since ocean is oxidizing
medium, reduced iron (Fe2+)
concentrations are low.
– Most Fe2+ produced by
photochemistry, has a short
lifetime
• 99% of Fe found bound to
organic ligands
– Increases solubility of iron in
water column
ligand
of
strength
specifies
constant
stability
cond.
]
'
][
'
[
]
[
'
'
'






K
L
Fe
FeL
K
FeL
L
Fe
FeL
Fe
FeT
Complexation: Active areas of
research
• What is the structure of the ligand?
-messy organic molecular
structure
• How do organisms produce it?
-current research suggest marine
bacteria produce the ligands.
• How do organisms utilize FeL?
-Light breaks down FeL so organisms
can grab the Fe’ Barbeau et al. (2004)
Forms of Iron
• Dissolved iron: <0.02
µm
• Colloidal: 0.02-0.4 µm
• Particulate: >0.4 µm
Active area of
research: Role of
colloidal matter
SJ-MP1-S16 (10 N)
0
500
1000
1500
2000
2500
3000
3500
4000
4500
0.0 0.5 1.0 1.5
Fe (nM)
depth
(m)
0.4 um F
0.02 um F
Data from Boyle, 10N (Atlantic)
dissolved
+ colloidal
dissolved
Biological Uptake of Iron
Oceanic
Coastal
•Oceanic species have higher growth rates at lower [Fe]
•They have adapted
•Their Fe requirement is lower (small Fe:C ratio)
•Oceanic species are smaller, so they have higher
surface area:volume ratio
Coastal
Oceanic
Sunda and Huntsman (1995)
Fe’
Putting it all together
biological
loop
dissolved
Fe
(< 0.4 mm)
biogenic export
lateral transport
and mixing
DUST
refractory dust
upwelling and
vertical mixing
mixed layer bottom
surface
remineralization
sediment-water interface
lateral transport
scavenging
& desorption
mixing
sedimentary deposition
scavenging
& desorption
Fe’ + L’  FeL
Fe’ + L’  FeL
Developing mathematical model to understand the
various processes affecting Fe
Model Results: Iron
Surface
1000 m
Observations
Model
Parekh et al. (2004b)
Link between dust flux and CO2?
Age (kyr)
Dust
Flux
(mg
m
-2
yr
-1
)
Atmospheric
CO
2
(ppm)
Figure from Gruber
from Martin (1990)
+dust  +Fe +bio. Productivity +Export +CO2 drawdown
Atmospheric CO2 Sensitivity to Increased
Dust Flux
• ‘Paleo’ dust estimate from Mahowald et al. (1999)
• Dust flux greater 5.5 times globally
LGM dust flux Present dust flux
Time series of total global primary production (GtC yr−1) for high
(solid line), medium (dashed line), and low (dash-dotted line) dust
sensitivity studies.
Model result
High Dust
Low Dust
Difference in primary production (gC m−2 yr−1) between high and low
dust sensitivity studies. Solid line is zero contour. Positive values indicate higher
production when aeolian dust supply is enhanced.
Low Dust
High Dust
Convergence of Macro Nutrients
in surface waters
Macro Nutrients
Export of Organic Matter
Changes in
Biogeochemical Cycling
Model result
The effect of
additional Fe is
quite small.
~11 ppm
ΔpCO2
(Pre-industrial -LGM)
=80 ppm
Iron Fertilization
• Adding Fe
artificially to
transfer CO2 from
atmosphere to the
sea
Open questions:
- How effective will
it be?
- Effect on marine
ecology?
End
Model IRON

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19-Iron.ppt

  • 2. Redfield Ratio • C:N:P • 106:16 :1 (Redfield, 1958) • Could there be other essential micro-nutrients? -Trace metals such as Fe, Zn, Co are important!
  • 3. High Nutrient, Low (Medium) Chlorophyll Regions Why aren’t the nutrients being completely utilized by phytoplankton? Phosphorous Chlorophyll Conkright et al., 1994 µm SeaWiFs
  • 4. Hypotheses • Light • Grazing • Micronutrient limitation
  • 5. In situ Fertilization experiments: Is iron limiting? e.g. Iron needed for enzymes that facilitate electron transport, O2 transport and other important functions.
  • 6. ‘Dissolved’ Iron distribution Why are there so few measurements? - Difficult to measure Surface 1000 m
  • 7. Iron Profile What controls the distribution (vertically and horizontally) of Iron? Iron has a profile between a typical metal and nutrient Metal Nutrient
  • 8. Sources of Iron • Riverine • Continental Shelves • Dust
  • 9. Riverine • [Fe’] decreases further from coast. • This is due to scavenging of Fe by particles. • We can conclude that rivers are not an important source for the open ocean Boyle et al. (1977)
  • 10. Scavenging: Iron sink • Iron lost to the ocean by scavenging – the process of sticking onto particles • Rate of scavenging not well-known • loss=-ksc[Fe’][P]
  • 11. Continental Shelves 1. Resuspension of sediments can release Fe 2. When organic matter decomposes, Fe can diffuse or be bio-irrigated into the water column C106H263O110N16P1Fe.0001+138O2=106C O2 +16NO- 3+H2PO- 4+0.0001Fe(OH)2 Estimate global flux of 0.2-9 x 1010 mol y-1 Is this Fe upwelled to the surface before being scavenged? Active area of research Results from flux chamber experiment (Elrod et al., 2004)
  • 12. Aeolian-derived Iron • Major source of iron • How much of the iron is soluble? - 1-10% Active area of research: differences by provenance, processing in cloud, surface waters • Flux: 0.2-1.2 X 1010 mol y-1 (assuming 2% solubility) Annual Fe flux (mg Fe m-2 y-1) Mahowald et al. (2003)
  • 13. Iron Speciation : Complexation ligand of strength specifies constant stability cond. ] ' ][ ' [ ] [ ' ' '       K L Fe FeL K FeL L Fe FeL Fe FeT
  • 14. Iron Speciation : Complexation • Inorganic iron: Fe2+, Fe3+, Fe(OH)3 – Since ocean is oxidizing medium, reduced iron (Fe2+) concentrations are low. – Most Fe2+ produced by photochemistry, has a short lifetime • 99% of Fe found bound to organic ligands – Increases solubility of iron in water column ligand of strength specifies constant stability cond. ] ' ][ ' [ ] [ ' ' '       K L Fe FeL K FeL L Fe FeL Fe FeT
  • 15. Complexation: Active areas of research • What is the structure of the ligand? -messy organic molecular structure • How do organisms produce it? -current research suggest marine bacteria produce the ligands. • How do organisms utilize FeL? -Light breaks down FeL so organisms can grab the Fe’ Barbeau et al. (2004)
  • 16. Forms of Iron • Dissolved iron: <0.02 µm • Colloidal: 0.02-0.4 µm • Particulate: >0.4 µm Active area of research: Role of colloidal matter SJ-MP1-S16 (10 N) 0 500 1000 1500 2000 2500 3000 3500 4000 4500 0.0 0.5 1.0 1.5 Fe (nM) depth (m) 0.4 um F 0.02 um F Data from Boyle, 10N (Atlantic) dissolved + colloidal dissolved
  • 17. Biological Uptake of Iron Oceanic Coastal •Oceanic species have higher growth rates at lower [Fe] •They have adapted •Their Fe requirement is lower (small Fe:C ratio) •Oceanic species are smaller, so they have higher surface area:volume ratio Coastal Oceanic Sunda and Huntsman (1995) Fe’
  • 18. Putting it all together biological loop dissolved Fe (< 0.4 mm) biogenic export lateral transport and mixing DUST refractory dust upwelling and vertical mixing mixed layer bottom surface remineralization sediment-water interface lateral transport scavenging & desorption mixing sedimentary deposition scavenging & desorption Fe’ + L’  FeL Fe’ + L’  FeL Developing mathematical model to understand the various processes affecting Fe
  • 19. Model Results: Iron Surface 1000 m Observations Model Parekh et al. (2004b)
  • 20. Link between dust flux and CO2? Age (kyr) Dust Flux (mg m -2 yr -1 ) Atmospheric CO 2 (ppm) Figure from Gruber from Martin (1990) +dust  +Fe +bio. Productivity +Export +CO2 drawdown
  • 21. Atmospheric CO2 Sensitivity to Increased Dust Flux • ‘Paleo’ dust estimate from Mahowald et al. (1999) • Dust flux greater 5.5 times globally LGM dust flux Present dust flux
  • 22. Time series of total global primary production (GtC yr−1) for high (solid line), medium (dashed line), and low (dash-dotted line) dust sensitivity studies. Model result High Dust Low Dust
  • 23. Difference in primary production (gC m−2 yr−1) between high and low dust sensitivity studies. Solid line is zero contour. Positive values indicate higher production when aeolian dust supply is enhanced.
  • 24. Low Dust High Dust Convergence of Macro Nutrients in surface waters
  • 25. Macro Nutrients Export of Organic Matter Changes in Biogeochemical Cycling
  • 26. Model result The effect of additional Fe is quite small. ~11 ppm ΔpCO2 (Pre-industrial -LGM) =80 ppm
  • 27. Iron Fertilization • Adding Fe artificially to transfer CO2 from atmosphere to the sea Open questions: - How effective will it be? - Effect on marine ecology?
  • 28. End
  • 29.
  • 30.