Inorganic carbon in the ocean: Basics

Introduction
Equilibrium and Measurement
Biogeochemical Processes and the CO2 system
-- organic matter formation / destruction
-- CaCO3 precipitation / dissolution

Why study carbonate in the ocean?

(stating the obvious)
Life on earth is carbon-based!
pH is a key master variable for many processes - and carbonate
equilibria play an important role in determining ocean pH
HCO3- is the 3rd most concentrated anion in the ocean
The marine carbon cycle is a key factor in determining the fate of
anthropogenic CO2

And if the pursuit of knowledge isnt enough:

MC&G students: I guarantee youll have a carbonate question
on your general exam!

Carbon cycling in the ocean

(an overview)
Atmosphere
HCO3-

Land

CO2
Ocean

CO2 + H2O H2CO3

H2CO3*

H +

2+

HCO3

Ca

CO2 Corg
+ CO32 CaCO3 ( s )

HCO3 H + + CO32

Corg CO2
CaCO3 ( s ) Ca2+ + CO32

sediments
Corg CO2
CaCO3 ( s ) Ca2+ + CO32

Earth surface carbon cycle - Time Scales

Earth Surface Carbon Cycle - Time Scales

Increasing
Atmosphere
1

10

100

Fossil fuels 4,000

Time required to affect atmosphere (years)

1 to 3

420 18 ka
590 A.D. 1750
750 A.D. 1990

60

2 to 3

Terrestrial
biosphere
560

70
Ocean Surface 900

Deep Ocean
36,400

Active Soils
1,100

1,000
0.6

Old Soils
500
10,000

Figure by MIT OCW.

Sundquist, 1993

Deep ocean :
large reservoir!

0.4

Reactive Marine Sediments

3,000

100,000

1,000,000

Surface ocean
~ atmosphere

0.2

Earth's Crust

0.2

90,000,000

Largest reservoir:
long time scales

Dissolved Carbonate Equilibria

[

][

][

CO2 = H 2CO3* + HCO3 + CO32

H + ][HCO3 ]
[
K1 =
[H2CO3* ]
H + ][CO32 ]
[
K2 =
[HCO3 ]

K1, K2 known
-- 3 equations, 5 unknowns
Specify (or measure) 2 things - CO2, pH to get :

-3

Concentration (moles/kg)

2.0x10

H2CO3*

2-

CO3

HCO3
1.5
Seawater
pH

1.0

0.5

0.0
4

8
+
pH = - log(H )

10

12

-2

Speciation as (pH) on log-log plot:

A Bjerrum Plot

10

Concentration (moles/kg)

H2CO3*

2-

-3

10

CO3

HCO3

-4

10

-5

10

-6

10

Seawater
pH

-7

10

-8

10

4
H + ][HCO3 ]
[
K1 =
[H2CO3* ]

---->

8
+
pH = - log(H )

[
[

]
]

HCO

3
+ log
*
H 2CO3

{ }

log{K1} = log H

10

12

Are CO2 and pH an ideal pair to measure?

Sometimes, but note:
Water mass A
pHA
CO2A

Water mass B
pHB
CO2B

50 : 50 mix of A and B
CO2(mix)=0.5*CO2(A) + 0.5*CO2(B)
** Not true for pH !! **

How about a quantity that is related to the major ion

composition?
The charge balance in seawater:
Concentrations, [ci] (mmol kg-1), and charge concentrations, [qi] = zi . [ci] (mmol kg-1),
of conservative ions in seawater at S = 35.
Cations

[ci]

[qi]

Anions

[ci]

[qi]

Na+

467.8

467.8

Cl-

545.5

545.5

Mg2+

53.3

106.5

28.2

56.4

Ca2+

10.3

20.6

SO42Br-

0.8

0.8

K+

9.9

9.9

F-

0.1

0.1

Sr2+

0.1

0.2

Total

605.0

Total

.
.

602.8

Figure by MIT OCW.

An apparent excess of positive charge of ~ 2.2 mmol / kg

What are the missing anions?

The Alkalinity
The missing anions: HCO3-, CO32-, B(OH)4The conjugate bases of the weak acids,
H2CO3 and B(OH)3

HA H + + A
acid

conjugate
base

Alkalinity (mol/kg) = the amount of strong acid that must be added to a

1 kg (sea)water sample to make its pH equal to that of the second
equivalence point of the dissolved CO2 system, pH = 4.3

Total Alkalinity:
seawater, pH = 8
2000
Contribution to PA (mol kg-1)

1770
1600
= PA = 2300 mol kg-1
1200
800
438
400
86
0

[HCO3- ]

2[CO23 - ] [B(OH)4- ]

-0.01

[OH -]

-[H+]

Figure by MIT OCW.

Practical Alkalinity:

PA = HCO3 + 2CO3 + B OH

( )4 + OH H +

What does the definition mean?

H2CO3

CO3

B(OH)4

B(OH)3

-4

10
Concentration (mol/kg)

2-

HCO3

-6

10

-8

10

pH = 8

-10

10

-12

10

Bjerrum Plot
for seawater

-14

10

8
pH

10

12

The titration of seawater with a strong acid (HCl)

Start

pH

A titration of seawater
with HCl

5
4
3

0.0

0.2

0.4
0.6
Va (ml HCl added)

0.8

1.0

8
dpH / dVa

pH

6
titration endpoint at
inflection of pH vs Va
curve

5
4
pH

0.0

0.2

0.4

Va (ml HCl added)

0.6

0.8

H2CO3

TA = HCO3 + 2CO32 + B OH + OH H +

( )

Concentration (mol/kg)

-4

10

2-

HCO3

CO3
B(OH)4

B(OH)3

-6

10

-8

10

-10

10

-12

10

Bjerrum Plot
for seawater

-14

10

10

12

pH

At the titration endpoint,

Concentrations during the titration:

[H + ]= 2[CO32 ]+ [HCO3 ]+ [B(OH )4 ]+ [OH ]

So: the moles of acid

added to reach the
endpoint = Alk

H+

Concentration (mol/l)

That is, the endpoint

Is the point at which
Alk = 0

-2

10

2-

10

2*[CO3 ] + [HCO3] + [B(OH)4] + [OH ]

-4

10

-6

10

-8

10

The H at which
alkalinity --> 0

-10

10

-12

10

6
pH

12

Alkalinity: A precise definition

Dickson, 1981 ; 19994

The total alkalinity of a natural water is thus defined as the number of moles of hydrogen ion
equivalent to the excess of proton acceptors (bases formed from weak acids with a
dissociation constant K <= 10-4.5 at 25C and zero ionic strength) over proton donors (acids
with K > 10-4.5) in one kilogram of sample.

Log [concentration (mol kg-1)]

-1

H+

-2

OH

-2.5

HCO3-

CO2

(1) predominant species

at pH = 4.5 does not contribute
to Alkalinity

CO32-

-3
-3.5
-4

HF

-4.5

B(OH)4

B(OH)3

HSO4-

-4
Log [concentration (mol kg-1)]

Remember:

SO42-

-1.5

pH

F-

NH+4

-5
H2PO4-

-6
-6.5

12

(2) How do you estimate pK for

an acid from this diagram?

NH3
H3SiO4-

H4SiO4

-5.5

10

PO43-

HPO24

H3PO4

-7
-7.5
-8

pH

10

12

Figure by MIT OCW.

Alkalinity
So we have:
Carbonate Alkalinity: CA = [HCO3-] + 2[CO32-]
Water Alkalinity = [OH-] - [H+]
Borate Alkalinity = [B(OH)4-]
For most applications, can use:
Alk = [HCO3-] + 2[CO32-] + [OH-] - [H+] + [B(OH)4-]
But in some applications, you need to add minor contributors, such as
NH3, PO43-, HPO42-, H3SiO4-, HS- ,
Remember, when you titrate a seawater sample to the 2nd CO2 endpoint,
The result is Titration Alkalinity, which includes all conjugate bases of weak
Acids in the sample. The approximation in the Alk expression above is the
Neglect of the contribution of minor constituents to the result.

Measurements: Summary
CO2

(i) Titration + curve fitting

(ii) Acidify ; strip CO2 ;
Measure CO2 by gas chromatography,
Coulometry, IR analyzer

2 mol/kg

Calibration: reference seawater (Dickson)

Alkalinity

(i) Titration + curve fitting

(ii) Gran titration

2 mol/kg

Calibration: reference seawater (Dickson)

pH

(i) Electrochemical measurement

(ii) pH-sensitive dyes
Calibration: buffers for seawater

0.002 pH units

The more-than-I-ever-wanted-to-know section :

pH scales
(1)

Laboratory chemistry: the NBS pH scale

pH = log a

H+

** Defined relative to low-ionic strength buffers -abandoned for measurements in seawater

(2) Seawater: An analysis of [H+] in seawater yields

[H+]free + [HSO4-] + [HF]
[HF] is small; in order to determine [H+]free, need to know
K for HSO4- dissociation WELL.
They have decided it is better to define a new pH scale:
The Total pH scale :

H + = H +
+ HSO
4

T
free

Or the seawater pH scale :

H + = H +
+ HSO
4 + [HF]
T
free

pH scales, cont.
So that:
(1) pH measurements are reported on the pHT scale
(2) equilibrium constants are reported on the pHT scale

Can convert between the scales with KHSO4 and KHF

**The difference between pHsws and pHT is ~ 0.01 unit ~ 2% at pH 8

The difference between pHNBS and pHT is ~ 0.1 unit ~ 20% at pH 8
The precision of good pH measurements is ~ 0.002 pH units

On equilibrium constants
for calculations in seawater
Consider the reaction:

In an ideal solution:

HCO 3 H + + CO 2
3
+ 2
H CO

3
K=

HCO
3

In an ideal solution, all

concentrations --> 0, so there are no
ion-ion or ion-solvent interactions.

In a real solution, these interactions are important, so

On equilibrium constants
for calculations in seawater
HCO 3 H + + CO 2
3

Consider the reaction:

+ 2
H CO

3
K=

HCO
3

In an ideal solution:

In a real solution:

K=

In an ideal solution, all

concentrations --> 0, so there are no
ion-ion or ion-solvent interactions.

H + CO 2 H + CO 32

HCO 3 HCO 3

The are activity coefficients,

and are generally <1 for
ions in solution because of
electrostatic interactions between
ions and between and ions and
solvent .
In addition, some ions (esp. CO32) form complexes with other ions
in seawater.

Equilibrium constants for calculations in seawater

For a solution with the ionic strength of seawater (I = ci zi2 ~ 0.7), it is difficult to
calculate the values.
Therefore:
Constant ionic medium equilibrium constants are used. They are:
-- measured in solutions with the same proportions of major ions as
seawater
-- measured as functions of T and S
-- pressure dependence is calculated from thermodynamic data
So:

+ 2
H CO 3
T
T
K'=

HCO
3

The T denote total concentrations, including

complexes
And remember, for H+, the T denotes the total
pH scale.
These seawater constants are
available from the literature as (T,S,P)

Working with the carbonate system in seawater

CO2 = H2CO3* + HCO3 + CO32

Alk = HCO3 + 2CO3 + B OH + OH H + min or components

( )

+ B OH

[ ( ) ] ( ) = cons tan t Salinity

TB = B OH

HCO
H
3

K1 =

*
H2CO3

KB =

+
H B OH

4

( )
[B(OH )3 ]

+ 2
H CO3
K2 =

HCO3

KW = H + OH

Measure CO2, Alk, S ==>7 equations in 7 unknowns

==> you can solve for speciation!

Useful approximations for back-of-the-envelope

calculations
-

H2CO3

CO3

B(OH)4

B(OH)3

-4

10
Concentration (mol/kg)

2-

HCO3

At seawater pH,

-6

10

CO2 ~ [HCO3-] + [CO32-]

-8

10

Alk ~ [HCO3-] + 2 [CO32-]

-10

10

And

pH = 8

[CO32-] ~ Alk - CO2

-12

10

Bjerrum Plot
for seawater

-14

10

8
pH

10

12

The effect of biogeochemical processes on CO2 and Alk

(1)

The incorporation of CO2 into organic matter (I.e., production of o.m.)

CO2 --> Corg + O2
CO2 = -1
Alk = 0
and a small (usually negligible) increase in Alk due to NO3- assimilation, Alk = (16/106))* mol Corg formed

(2)

The precipitation of CaCO3

Ca2+ + CO32- --> CaCO3
CO2 = -1
Alk = -2

How do these processes affect the ability of the ocean to take up CO2 from the atmosphere?
Taking into account Henrys law relating [CO2] in the water to the PCO2 in equilibrium with
the water,

[CO 2 ] = K H PCO 2

System approaches equilibrium after

Perturbation: lower ocean [CO2] -->
ocean absorbs CO2

Contours of [CO2] vs. Alk and CO2

2450
30

20

10

Total Alkalinity

2400

40

form Corg

2350

50
60

2300
20

50
30

70 80
90

20
form CaCO3

2250
2050

2100

2150
2200
TCO2

2250

2300

o.m. formation:
decrease [CO2]
CaCO3 pptn:
increase [CO2]

Biogeochemical processes and the carbonate system

How do decomposition and dissolution processes affect the carbonate system?
(3) Organic matter dissolution reverses (1),
Corg + O2 --> CO2 +
CO2 = +1
Alk = 0
(and, as before, theres a small drop in Alk due to NH3 oxidation to NO3-)
(4) CaCO3 dissolution reverses (2),
CaCO3 --> Ca2+ + CO32CO2 = +1
Alk = + 2

How do these processes affect the [CO32-] of seawater as it ages during its transit through the
deep sea?

Contours of [CO32-]
2450
280

Contours of [CO23]

260
220

Total Alkalinity

2400

Dissolve CaCO3

240
200

180

120

140

2350

80

Dissolve CaCO3:
increase [CO32-]

100

2300

60

oxidize Corg

160

120

100

Oxidize o.m.:
decrease [CO32-]

80

40

2250
2050

2100

2150

2200

2250

2300

TCO2

Question: what can you use this contour plot for if you have actual data?

OBSERVATION
Geosecs North Atlantic North of Equator

2
3

Alk

4
5

DEPTH (kM)

1
DEPTH (kM)

Geosecs North Pacific North of Equator

0
2
3
4
5
6

6
7
2.20

2.25

2.30

2.35

2.40

2.45

7
2.20

2.50

2.25

2.30

Talk (10-3 EO/KG)

Geosecs North Atlantic North of Equator

TCO2

4
5

2
3
4
5
6

7
1.9

2.0

2.1

2.2

2.3

1.9

2.4

2.0

2.1

Geosecs North Atlantic North of Equator

2.3

2.4

Geosecs North Pacific North of Equator

CO32-

4
5

DEPTH (kM)

DEPTH (kM)

2.2

TCO2 (10-3 M/kG)

TCO2 (10-3 M/kG)

3
4
5
6

6
7

2.50

2.45

Geosecs North Pacific North of Equator

2.40

Talk (10-3 EO/kG)

DEPTH (kM)

DEPTH (kM)

2.35

7
0

100

200

CO3= (10-6 M/kG)

NORTH ATLANTIC

300

100

200

300

CO3= (10-6 M/kG)

NORTH PACIFIC
Figure by MIT OCW.

Using data and theory to calculate relative rates

of organic matter oxidation and carbonate dissolution
see Broecker and Peng, Tracers in the Sea
2500

North Indian and

Pacific Bottom Waters
1 Mole CaCO3
1 Mole ORG C
1 15
1
DALK
= 2= .93
DSCO2
2
2 105

ALKN (meq/kg)

2450

Antarctic Surface
Water

2400
1 Mole CaCO3

2350

Deep
Water

Antarctic Deep
Waters

4 Moles ORG C
4 15
1
DALK
= x 2- x
= .29
DSCO2
5
5 105

WSBW
CPDW
NIBW
NPBW
NADW

North Atlantic Deep

Water (2.5 oC)

Surface
Water
ANTARCTIC
S.INDIAN
S.PACIFIC
N.PACIFIC
S.ATLANTIC
N.ATLANTIC

2300
Temperate Surface
Water

2250
1900

2000

2100

2200

2300

2400

2500

DSCO2N (mmol/kg)
Figure by MIT OCW.

And

Weve shown how biogeochemical processes affect CO2 and Alk in

the ocean
Weve started to show how distributions of CO2 and Alk can be used
To learn about biogeochemical processes
Weve not discussed the biological and chemical processes that control
formation and decomposition of organic matter
formation and dissolution of CaCO3
Those discussions will follow