biogeochemical cycles: integration across the land- estuary-continental shelf-ocean continuum sybil...
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Biogeochemical Cycles: Integration Across the
Land- Estuary-Continental Shelf-Ocean Continuum
Sybil P. SeitzingerRutgers University
Institute of Marine and Coastal SciencesNew Brunswick, NJ
Major Topics
Global models of nutrient export from land to coastal oceans
Fate of N along the river – estuary – shelf continuum
- denitrification
Effect of nutrient sources and sinks on coastal ocean
primary production- 3-D hydrodynamic plankton model
DOM – opening the Black Box
Human Impacts at Global Scales
Global models of nutrient export from land to coastal oceans
N Inputs to Estuaries O rig inate from M any S ources
A tm ospheric D epos ition
U rban R uno ffSewage
Storm water
F ores t R uno ff
A g ricu ltu ra l R uno ffAnim al Waste
Fertilizer
E S T U A R Y
N
N
N
N
NN
N Forms: DIN – ammonia, nitrateDON – Black BoxPN
Watershed Sources of Nutrients to Coastal Ecosystems
Approach
Measured N Export by Range of Rivers
Model Predict N Export f(N Inputs to Watersheds)
+Spatially Explicit Global Data Bases
Spatial Pattern N Export Globally
Model Calculation of NO3 Export by Global Rivers
NO3 Export = f(Human Sewage , Fertilizer Use, Atmos. Dep. )
from Caraco & Cole, 1999
[0.4 x Water Runoff 0.8] x [Fert Use + Atmos. Dep.] )
( NO3 Export = 0.7 x Human x 1.85 kg N
Population person-1 yr-1 x Fraction
urban +
Bouwman et al. 1995
Fertilizer 1990kg N km-2 y-1
NOy 1990NOy Atmospheric Deposition - 1990
kg N km-2 y-1
Dentener and Crutzen, 1994
+ Gridded Data bases for:• Global population (U.N.)• Water runoff • Watershed delineation
Seitzinger & Kroeze, Global Biogeochemical Cycles 12:93-133, 1998
Measured (kg N km-2 y-1)
1 10 100 1000 10000
Mo
de
led
, N
-mo
de
l (k
g N
km
-2 y
-1)
1
10
100
1000
10000
Kazan and Back
Murray-Darling
YukonMackenzie
ZambeziOrange
Nile Niger ParanaZaire
AmazonUruguay
Colombia Orinoco
Volga
St. Lawrence
Mekong Mississippi
Huang (Yellow)Baltic Sea Rivers
VistulaMagdalena
DanubeDelaware
Loire
RhineYangtze
Rhone
Ganges
r2 = 0.85
1:1
Model vs. Measured
Model Predicted DIN Export by Rivers
kg N km-2 watershed y-1
Seitzinger & Kroeze, 1998
20 o
20 o
45 o
45 o
66 o
66 o
DIN Export by RiversTg N y-1
N. Hemisphere87%18.2
S. Hemisphere13%2.6
Equator
Seitzinger & Kroeze, 1998
20 o
20 o
45 o
45 o
66 o
66 o
0 o
Global Total 21
4.1
5.3 4.2
1.5
0.9
Tg = 1012g
DIN, World RegionsTg N y-1
Seitzinger & Kroeze, 1998
1.6U.S.
20 o
20 o
45 o
45 o
66 o
66 o
0 o
Tg = 1012g
Source Apportionment of DIN Export
Seitzinger & Kroeze, 1998
Precipitation
FertilizerSewage
FertilizerSewage
Precipitation
USA
Imagining the Future
Business-as-Usual Scenario
19
90
20
50
Fertilizer NO Point Source0
50
100
150
200
y
1990
2050
Deposition
Tg
N y
-1
Inputs, 1990 & 2050 to Global Watersheds
Kroeze & Seitzinger, 1998
Bouwman et al. 1995
Bouwman et al. pers. comm
1990
2050
Fertilizer, 1990 & 2050kg N km-2 y-1
Dentener and Crutzen, 1994
Dentener, pers. comm.
1990
2050
Atmospheric Deposition NOykg N km-2 y-1
1990 and 2050 DIN Export by Rivers
for World Regions
19
90
20
50
North South Africa Europe Former China, India0
2
4
6
8
10
12
14
16
America America USSR Japanin Asia & S.E. Asia
Tg
N y
-1
1990
2050
Kroeze & Seitzinger, 1998
Research Needs
Other forms (particulate, dissolved organic)
Other elements (P, C, Si…….)
Time varying (seasonal, daily….)
Finer spatial resolution input dataincluding hydrology
Enhanced global databases
Process-based models
Global NEWS
Nutrient Export from WatershedsUNESCO-IOC Workgroup
Other forms (particulate, dissolved organic)
Other elements (P, C, Si…….)
Time varying (seasonal, daily….)
Finer spatial resolution input dataincluding hydrology
Enhanced global databases
Process-based models – NASA IDS
Average SRP Yield by Watershed (kg P/km2/yr)
Harrison, Seitzinger & Caraco, in prep.
Major Topics
Global models of nutrient export from land to coastal oceans
Fate of N along the river – estuary – shelf continuum
- denitrification
Effect of nutrient sources and sinks on coastal ocean
primary production- 3-D hydrodynamic plankton model
DOM – opening the Black Box
Denitrification
NO3/2 N2O N2
Buria l
?
Denitrific a tion
N 2Ac ro ss She lf Tra nsp o rt
N -fixa tio n2
Rive r inp utsAtm osp hericDep osition
N N
N N
NN
Terrestria l &Estuarine Continental Shelf O ceanicRivers Estuaries Continental
ShelfOceanic
Denitrificationof terrestrial N sources
From Seitzinger & Giblin 1996
R ivers
O nw e lling
B uria l
A tm os. D ep .
D enitrifica tion
NET
North Atlantic
North AtlanticContinental Shelf N Budget
Sources:
Sinks:
Net Balance (onwelling?)
Estuarine/R iver A tm os. Dep
Denitrification Burial
(10 m ol N y )46-63
13
1432-9
10 -1
59-76
145-152
-72 to -97
(fro m Se itzing e r a nd G ib lin 1996)
46-63
13143
Connecting the Ocean Margin to Estuaries and Oceans
North Atlantic
72-97
020406080
100120140160
1 2 3 4
From Seitzinger & Giblin 1996
R ivers
O nw e lling
B uria l
A tm os. D ep .
D enitrifica tion
NET
North Atlantic
North AtlanticContinental Shelf N Budget
Sources:
Sinks:
Net Balance (onwelling?)
Estuarine/R iver A tm os. Dep
Denitrification Burial
(10 m ol N y )46-63
13
1432-9
10 -1
59-76
145-152
-72 to -97
(fro m Se itzing e r a nd G ib lin 1996)
46-63
13143
Connecting the Ocean Margin to Estuaries and Oceans
North Atlantic
72-97
N,
10
10 m
ol N
/y
River N
Sources Sinks
Atmos.Dep.
Denitrification
020406080
100120140160
1 2 3 4
From Seitzinger & Giblin 1996
R ivers
O nw e lling
B uria l
A tm os. D ep .
D enitrifica tion
NET
North Atlantic
North AtlanticContinental Shelf N Budget
Sources:
Sinks:
Net Balance (onwelling?)
Estuarine/R iver A tm os. Dep
Denitrification Burial
(10 m ol N y )46-63
13
1432-9
10 -1
59-76
145-152
-72 to -97
(fro m Se itzing e r a nd G ib lin 1996)
46-63
13143
Connecting the Ocean Margin to Estuaries and Oceans
North Atlantic
72-97
N,
10
10 m
ol N
/y
River N
Sources Sinks
Atmos.Dep.
DenitrificationOnwelling
Terrestrial
Rivers
Estuaries Ocean Margins Oceanic
0
50
100
150
200
250
Rivers Estuaries Continental Shelf Oceanic OMZ Pelagic sediments
Den
itri
fica
tion
Tg
N/y
Integrating Landscapes to WaterscapesDenitrification – Global View
No 3 NH4
Phyto -p la nkton
C hlo
Zoo -p la nkton
De trita l N (sm a ll)
De trita l N (la rg e )
Nitrific a tio n
M ine ra li- za tio n
Up ta ke
Exc re tio n
Sinking
G ra zing
M o rta lity
Se d im e nt
N 2 NH4 No 3
De tritus (lg )
De tritus (sm )
O xic M ine ra liza tio nDe nitrific a tio n
Lo ss o ffixe d N
Dynamic Biogeochemical/Hydrodynamic Model of the MABK. Fennel et al. in prep.; ASLO 2004
• N Based Plankton Model Fasham et al. 1990
• Sediment Denitrification Seitzinger & Giblin 1996
No 3 NH4
Phyto -p la nkton
C hlo
Zoo -p la nkton
De trita l N (sm a ll)
De trita l N (la rg e )
Nitrific a tio n
M ine ra li- za tio n
Up ta ke
Exc re tio n
Sinking
G ra zing
M o rta lity
Se d im e nt
N 2 NH4 No 3
De tritus (lg )
De tritus (sm )
O xic M ine ra liza tio nDe nitrific a tio n
Lo ss o ffixe d N
Dynamic Biogeochemical/Hydrodynamic Model of the MABK. Fennel et al. in prep.; ASLO 2004
• N Based Plankton Model Fasham et al. 1990
• Sediment Denitrification Seitzinger & Giblin 1996
River N Inputs Across Shelf Transport
Time for the Movie !
Run denitrificationriverine
nutrients/PON
A no no
B yes no
C yes yes
2-yr simulations, starting from same initial condition in January 1994 after a 1-yr spinup
A 227 gC /m2 /y
B 184 gC /m2 /y20% reduction
from A
C 200 gC /m2 /y10% increase
from B
K. Fennel et al. unpubl.ASLO 2004
Denitrification
River Nutrients Annual Primary Production
A 227 gC /m2 /y
B 184 gC /m2 /y20% reduction
from A
C 200 gC /m2 /y10% increase
from B
K. Fennel et al. in prep.ASLO 2004
Denitrification
River Nutrients
Denitrification
River Nutrients
Annual Primary Production
A 227 gC /m2 /y
B 184 gC /m2 /y20% reduction
from A
C 200 gC /m2 /y10% increase
from B
Katja Fennel – [email protected]
River Nutrients
Denitrification
River Nutrients
Denitrification
River Nutrients
Research Needs
• 3-D hydrodynamic/biogeochemical models global estuaries and shelf (C,N,P, …..)
• Enhanced observation systems for coastal ecosystems (remote sensing, in situ)
• Nutrient-plankton-sediment dynamics
• Higher trophic levels
Advanced Analytical Capabilities
Major Topics
Global models of nutrient export from land to coastal oceans
Fate of N along the river – estuary – shelf continuum
- denitrification
Effect of nutrient sources and sinks on coastal ocean
primary production- 3-D hydrodynamic plankton model
DOM – opening the Black Box
DOM Compounds
DOM
DOM
DOMDOM
DOM
DOMDOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
• 100’s to 1000’s of different DOM compounds
Resource Utilization by Microbial Communities: Is it Chaos?
DOM
DOM
DOMDOM
DOM
DOMDOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
B
B
B
B
BB
B
B
B
B
B B
•100’s to 1000’s different DOM compounds
•100’s+ different species of bacteria
chemical composition, sources, and bioavailability of DOM are not well known
Electrospray Ionization Mass Spectrometry – ESI-MS Molecular Level Analysis
Instrument• Soft ionization, no fragmentation• Mass range = 50-3000• Direct injection of sample (20 µl)• Positive and negative ionization
modes
(Rutgers LC/APESI-MS/CLND facilityAgilent 1100)
Data• mass to charge ratio (m/z), 50-3000• abundance• basic/acidic properties (+/- mode) of functional groups
m/z
50 150 250 350 450 550 650
abun
danc
e
0
10000
20000
30000
40000
50000
60000140000160000
m/z
Ion
Ab
un
dan
ce
ESI-Mass Spectra of Streams L and M
C) Stream L - ESI negative
m/z
200 400 600 800 1000 1200 1400 1600
Ion
abun
danc
e
1000
2000
3000
4000
5000
6000
7000
8000
300006000090000
120000D) Stream M - ESI negative
m/z
200 400 600 800 1000 1200 1400 1600
1000
2000
3000
4000
5000
6000
7000
8000
300006000090000
120000
Stream L Stream M
m/z m/z
Ion
Ab
un
dan
ce
Ion
Ab
un
dan
ce
Seitzinger et al. accepted L&O
1435 “compounds” 1751 “compounds”
71%
5%
24%
Both Stream L and M
Only Stream L
Only Stream M
Similarity in DOM Composition in 2 Streams
C) Stream L - ESI negative
m/z
200 400 600 800 1000 1200 1400 1600
Ion
abun
danc
e
1000
2000
3000
4000
5000
6000
7000
8000
300006000090000
120000
D) Stream M - ESI negative
m/z
200 400 600 800 1000 1200 1400 1600
1000
2000
3000
4000
5000
6000
7000
8000
300006000090000
120000
Stream L Stream M
m/z m/z
Ion
Ab
un
dan
ce
Ion
Ab
un
dan
ce
Seitzinger et al. accepted L&O
1435 “compounds” 1751 “compounds”
Bioavailability of DOM in Streams
• Spring-collected stream water• Inoculated with freshwater bacteria
local pond• Incubated in the dark for 12 days
Bacterial analysis: Bulk analysis: Molecular level analysis: 3H leucine incorp DOC ESI-MS
Time series samples (days 0, 2, 6, 12)
Bulk Measures of Bioavailability
Leu
cin
e in
corp
ora
tio
n (
nm
ol
l-1 h
-1)
0
2
4
6
8
10LM
Experiment Day
0 2 4 6 8 10 12
DO
C-C
(µ
mo
l L
-1)
0
2000
4000
6000
8000
10000
12000LM
Bacterial Production
DOC Utilization 51% Stream L 43% Stream M
similar in both streams
0 2 4 6 8 10 12
Co
nce
ntr
atio
n (
ion
ab
un
dan
ce u
nit
s)
500
1500
2500
3500
4500
5500
6500
191 L-1191 L-2
Experiment Day
Patterns of Change in Abundance of Individual “Compounds” - m/z
D) Stream M - ESI negative
m/z
200 400 600 800 1000 1200 1400 1600
1000
2000
3000
4000
5000
6000
7000
8000
300006000090000
120000
Experiment Day
0 2 4 6 8 10 12Co
nc
en
tra
tio
n (
ion
ab
un
da
nc
e u
nit
s)
500
1500
2500
3500
4500
5500
6500
Experiment Day
0 2 4 6 8 10 12Co
nc
en
tra
tio
n (
ion
ab
un
da
nc
e u
nit
s)
500
1500
2500
3500
4500
5500
6500
m/z 191 m/z 179 m/z 335
Bioavailability Experiment: Molecular Level Results
No
. o
f m
/z
0
200
400
600
800
1000
1200
Decrease inAbundance
NoChange
Increase inAbundance
New m/z
72
60
48
24
% o
f to
tal
m/z
12
Stream M
DOM
DOM
DOMDOM
DOM
DOMDOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
B
B
B
B
BB
B
B
B
B
B B
Resource Utilization by Microbial Communities- Is it Chaos?
B
B
B
B
BB
B
B
B
B
B B
DOM
DOM
DOMDOM
DOM
DOMDOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOMDOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
DOM
High Degree of Similarity in Utilization of m/z’s between Replicate Flasks
0 2 4 6 8 10 12
Co
nce
ntr
atio
n (
ion
ab
un
dan
ce u
nit
s)
500
1500
2500
3500
4500
5500
6500265 L-1265 L-2379 L-1379 L-2191 L-1191 L-2
Experiment Day
Stream L
m/z 265Flask 1 2
Flask 1, concentration decrease(ion abundance units)
100 1000 10000 100000
Fla
sk B
, co
nc
entr
atio
n d
ecr
eas
e(i
on
ab
un
dan
ce
un
its
)
100
1000
10000
100000Basic compoundsAcidic compounds
High Degree of Similarity in Utilization of m/z’s between Replicate Flasks
Seitzinger et al. accepted L&O
Comparison Between Flasks and Between Streams
of m/z that Decreased
Flask 1, concentration decrease(ion abundance units)
100 1000 10000 100000
Fla
sk B
, co
nc
en
tra
tio
n d
ec
rea
se
(io
n a
bu
nd
an
ce
un
its
)100
1000
10000
100000Basic compoundsAcidic compounds
Between flasks same stream (L)
Stream M, concentration decrease(ion abundance units)
100 1000 10000 100000
Str
ea
m L
, co
nc
en
tra
tio
n d
ec
rea
se
(io
n a
bu
nd
an
ce
un
its
)
100
1000
10000
100000
Between streams (L and M)
Future Directions
• Identification of specific compounds
• Comparison of DOM chemical composition in time and space
- within and across aquatic (fw & marine) systems
• Effects of biological and physical complexity on patterns of DOM utilization
• Development of ecological theories of resource utilization by microbial communities
• Identification of compound-specific effects on aquatic organisms (e.g., HABs)
blankPopulation (persons km-2)
1990
2050
Lerner et al. 1988; updated to 1990 by Bouwman
Lerner et al. 1988; Bouwman, 1990; United Nations, 1996
Totals (Tg)
1990 21
2050 42
Model Predicted DIN Export by Rivers
Doubles by the Year 2050
DIN export doubles in 2050
Kroeze & Seitzinger, 1998
4 9 -5 7
7
8 6-22
9 .5 -1 8
4 7
5 .4
-24
Buria l
?
Denitrific a tion
N 2Ac ro ss She lf Tra nsp o rt
N -fixa tio n2
Rive r inp utsAtm osp hericDep osition
N N
N N
NN
Terrestria l &Estuarine Continental Shelf O ceanicRivers Estuaries Continental
ShelfOceanic
N2
N2
N2
North Atlantic
O nw e lling
B uria l
A tm os. D ep .
Entire Shelf Budget
N orth A tlanticC ontinental Shelf N B udget
S ources:
S inks :
N et B alance (onw elling?)
E stua rine /R ive r A tm os. D ep
D enitrif ication B uria l
(10 m o l N y )460-630
130
143020 -90
9 -1
590-760
1450 -1520
-720 to -970
Gulf of M exico
Northeast U.S.
Southeast U.S.D en itrifica tion
R ive rs /E stuaries
Regional Budgets
Modified from Seitzinger & Giblin 1996
Terrestrial
Rivers
Estuaries Ocean Margins Oceanic
Integrating Landscapes to Waterscapes
0
50
100
150
200
250
Rivers Estuaries Continental Shelf Oceanic OMZ Pelagic sediments
Den
itri
fica
tion
Tg
N/y
Check these blue numbers!!!
Terrestrial
Rivers
Estuaries Ocean Margins Oceanic
Integrating Landscapes to Waterscapes
0
50
100
150
200
250
Rivers Estuaries Continental Shelf Oceanic OMZ Pelagic sediments
Den
itri
fica
tion
Tg
N/y
Buria l
?
Denitrific a tion
N 2Ac ro ss She lf Tra nsp o rt
N -fixa tio n2
Rive r inp utsAtm osp hericDep osition
N N
N N
NN
Terrestria l &Estuarine Continental Shelf O ceanicRivers Estuaries Continental
ShelfOceanic
Terrestrial
Rivers
Estuaries Ocean Margins Oceanic
Integrating Landscapes to WaterscapesDenitrification – Global View
0
50
100
150
200
250
Rivers Estuaries Continental Shelf Oceanic OMZ Pelagic sediments
Den
itri
fica
tion
Tg
N/y