Conversion of organic nitrogen into N

2
in
the oceans:
where does it happen?
and how?
Yuan-Hui (Telu) Li
Department of Oceanography
University of Hawaii at Manoa
Outline
1. Nitrogen cycle in the oceans:
2. Three end-member mixing model and the
aerobic partial nitrification hypothesis.
3. Nitrate deficits by the aerobic partial
nitrification and the anoxic denitrification.
4. Conclusions
5. Acknowledgement

+5

NO
3
-
NO
3
-

Anammox
+3

NO
2
-

NO
2
-

+2

NO NO

+1

N
2
O N
2
O

N
2
0

N
2
fixation N
2
-1

NH
2
OH NH
2
OH

-3

NH
4
+

PON

DON

NH
4
+

Uptake &
ammonification
Oxidation
state
[Anoxic]
Dissimilative
reduction
(Denitrification)
[Oxic]
Dissimilative
oxidation
(Nitrification)
Air
Gas
exchange
?
Assimilative
reduction
Air
1. Nutrient cycle in the ocean:
Redfield Ratios and Nitrification by
nitrifying bacteria [oxic]:

138 O
2
+ (CH
2
O)
106
(NH
3
)
16
(H
3
PO
4
)

H
2
PO
4

+

16 NO
3

+ 106 CO
2
+ 17 H
+
+ 122 H
2
O

A P\ A N\ A C
org
\- A O
2
= 1\16\106\138
or
r
p
= - A O
2
/ A P = 138
r
n
= - A O
2
/ A N = 8.63
r
c
= - A O
2
/ A C
org
= 1.30
phytoplankton
Denitrification by denitrifying bacteria [anoxic
and suboxic]
phytoplankton
94.4 NO
3
-

+ 93.4 H
+
+ (CH
2
O)
106
(NH
3
)
16
(H
3
PO
4
)
H
2
PO
4

+

55.2 N
2
+ 106 CO
2
+ 177.2 H
2
O

A P\- A N\ A C
org
\ A N
2
= 1\94.4\106\55.2

Anaerobic ammonia oxidation (anammox) by
anammox bacteria:

NH
4
+
+ NO
2
-
N
2
+ 2 H
2
O

2. Three end member mixing model (Li and Peng, 2002)

1 = f
1
+ f
2
+ f
3
(1)
u = f
1
u
1
+ f
2
u
2
+ f
3
u
3
(2)
S = f
1
S
1
+ f
2
S
2
+ f
3
S
3
(3)
O
2
+ r
n
NO
3
= (NO) = f
1
(NO)
1
+ f
2
(NO)
2
+f
3
(NO)
3
(4)
O
2
= o
0
+ o
1
u + o
2
S - r
n
NO
3
(4a)
where, r
n
= -AO
2
/ ANO
3
Similarly
O
2
= A
0
+ A
1
u + A
2
S r
p
PO
4
(5a)
where, r
p
= -AO
2
/ APO
4
Also:
DA = |
0
+ |
1
u + |
2
S + |
3
O
2
(6a)
where, r
c
= 1/(|
3
0.5/r
n
); r
c
= -AO
2
/ AC
org

DA = (DIC Alk/2)

-70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70
7
8
9
10
11
12
13
14
Latitude
-
O
2
/
N
i8
i9
geosecs
-70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70
8
10
12
14
16
18
Latitude
N
/
P
i8
i9
geosecs
-70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70
110
130
150
170
190
Latitude
-
O
2
/
P
i8
i9
geosecs
Redfield ratio
Redfield ratio
Redfield ratio
Indian
2a. Aerobic Partial nitrification
hypothesis:
Unidentified bacteria have evolved in a
low oxygen (but oxic) and high nitrate
environment (such as in oxycline, marine snow
and fecal pellets, sediments) to utilize both
oxygen and nitrate as terminal electron
acceptors during oxidation of organic matter,
and convert some organic nitrogen into N
2
,
N
2
O, and NO.
N

(
u
m
o
l
/
k
g
)
u
u
u
3. Nitrate deficit by partial nitrification (dN) and
denitrification (dN)

N
a
= 16(P - 0.16)
N
b
= -3.223 + 16.772P + 0.574 P
2
- 0.465 P
3

When N
b
s N s N
a

dN = N
a
- N ;
When N < N
b

dN = N
a
- N
b

dN = N
b
- N ;

N* by Deutsch et al (2001):
N* = (N - N
a
)
N
a
= 16(P - 0.181)
-N* ~ dN + dN
i7n
(mol/kg)
u
u
u
u
u
u
Additional support for the aerobic partial nitrification hypothesis:

1. Schmidt et al (2004) showed that a wild-type of Nitrosomonas
europaea in chemostat cell cultures can produce nitrogen gases (N
2
,
NO, and N
2
O) during aerobic (O
2
~ 125M) oxidation of ammonia,
using genes encoding reduction enzymes such as nitrite reductase,
nitric oxide reductase etc. For example,
NH
4
+
(ammonia monooxygenase) NH
2
OH (hydroxylamine
oxidoreductase) NO
2

(nitrite reductase) NO (nitric oxide
reductase) N
2
O (not yet identified nitrous oxide reductase) N
2
.

2. Aerobic and anaerobic ammonia oxidizing bacteria are coupled in
suspended organic particles in a low-oxygen (O
2
~ 5 M) CANON
reactor (Nielsen et al., 2005) to produce N
2

3. Codispoti et al. (2001) estimated the excess N
2
in the water
column of the Arabian Sea, using the Ar/N
2
ratio in the water
column and in the air. They found that the excess N
2
is
substantially greater than the N
2
produced by the
denitrification process.
2. The aerobic partial nitrification must be performed by yet
unidentified bacteria, which may have evolved in low oxygen and high
nitrate environments (such as oxyclines, marine snows, fecal pellets,
bottom sediments etc) to utilize both oxygen and nitrate as terminal
electron acceptors during oxidation of organic matter. Direct proof is
urgently needed.
Conclusions
1. The dN (nitrate deficit by partial nitrification) maximum coincides
with the P and N maximums, lies within the oxycline below the
oxygen-depleted denitrification zone, and is in contact with the
continental slope sediments. In contrast, dN (nitrate deficit by
denitrification) maximum lies within the denitrification zone, is always
associated with a nitrite maximum in the water column, and intersects
the continental shelf or upper slope sediments.
Acknowledgement: Ms Lauren Kaupp patiently
showed me how to use the Ocean Data View
program, which was provided by Dr. Reiner
Schlitzer. Discussions with Drs. James Cowen,
David Karl, Marcel Kuypers, Fred Mackenzie,
Hiroaki Yamagichi and Wajih Naqvi were most
fruitful.
Many thanks to Professor Yoshiki Sohrin for kindly
inviting me here. This work is supported by a NOAA
grant to Y.H. Li and T.H. Peng.


u
-dN\O2
=(61)\130
u
u
u
u
r
p
= -O
2
/P; r
n
= -O
2
/N; r
p
/r
n
= N/P
V* = Red Sea
IV*w = W Equat. Indian Central
IV*e= E Equat. Indian Central
III* = Equat. Indian P Max.
V = South Indian Central
IV = Sub-Antarctic Oxygen Max.
III = Antarctic Intermediate
II = Circumpolar Deep
I = Antarctic Bottom
u
u
Redfield ratios:
P\N\C
org
\-O
2
= 1\16\106\138; (CH
2
O)
106
(NH
3
)
16
(H
3
PO
4
)

Antarctic Indian Ocean:
P\N\C
org
\-O
2
= 1\(151)\(832)\(1349)
Deep equatorial Indian Ocean:
P\N\C
org
\-O
2
= 1\(101)\(945)\(1307)

Average remineralization ratios for the warm water mass:
P\N\C
org
\-O
2
= 1\(15.60.7)\(1109)\(1598)

Andersons (1995) remineralization ratios and phytoplankton
formula:
P\N\C
org
\-O
2
= 1\16\106\150; (C
106
H
48
)(H
2
O)
38
(NH
3
)
16
(H
3
PO
4
)


1. The remineralization ratios (P\N\C
org
\-O
2
) of organic
matter in the oxygenated regions of Indian Ocean change
systematically with latitude and depth.

2. The average remineralization ratios for the Indian warm
water masses (potential temperature u > ~ 10) are
P\N\C
org
\-O
2
= 1\(15.60.7)\(1109)\(1598).
These are comparable to the traditional Redfield ratios
P\N\C
org
\-O
2
= 1\16\106\138,
and are in good agreement with Andersons (1995) values of
P\N\C
org
\-O
2
= 1\16\106\150
within the given uncertainties.
5. Conclusions