Chemistry for Everyone

Climate Change and Its Effect on Coral Reefs

Ralph E. Weston Jr.
Chemistry Department, Brookhaven National Laboratory, Upton, NY 119793-5000; weston@bnl.gov

The discussion of acidbase equilibria in general chemistry and physical chemistry texts usually extends to the treatment
of polyprotic acids, and a frequently used example is the
carbonic acid equilibrium (1). This system plays an important
role in the chemistry of the sea, and books on chemical oceanography typically devote a chapter to the discussion of the
carbonic acid system and the determination of the concentrations of the various species involved. In addition, the concentration of the carbonate ion is important in determining
the solubility of calcium carbonate, which in turn is related
to the formation of coral in tropical seas. (The reactions involved in these equilibria are presented in eqs 111.)
The intent of this article is to provide a specific example
of the way in which several concepts of elementary physical
chemistry encountered by students in their first chemistry
course (Henrys law of gas solubility, acidbase equilibria and
dissociation constants, and solubility products) apply to a realworld situation. To emphasize the timeliness of this topic,
recent concerns about the effect of projected climate change on
the health of tropical coral deposits are examined in detail.
The Dependence of Coral Health on Atmospheric
Carbon Dioxide
A worldwide, disastrous decline in the growth of coral
is being observed by marine scientists. Coral bleaching, coral
disease outbreaks, and algal overgrowth are all increasing in

frequency, intensity, and range (2). There are a number of

causes, some of them only local in effect, such as dust from
the fringe of the Sahara loading the coral with sediment.
Others are global in their range, such as enhanced UV radiation caused by the decrease in stratospheric ozone, and a
general increase in global mean temperature. The effect of
temperature is demonstrated strikingly by coral bleaching in
tropical areas where unusual seawater temperatures have led
to a series of intense El Nio events since the mid-1970s.
But one particular threat is the result of a change in the
chemical composition of seawaterspecifically an increase in
dissolved carbon dioxide due to the increased carbon dioxide
content of the atmosphere. As Figure 1 shows, the carbon
dioxide concentration in the atmosphere measured at the
Mauna Loa observatory in Hawaii has increased steadily since
these measurements were started in 1958. These data connect smoothly with the record of atmosphere carbon dioxide
concentrations derived from ice cores that are as much as 1000
years old. Since this increase is most marked in the last century,
it is attributed chiefly to the increasing use of fossil fuel as
an energy source.
Coral reefs depend upon the formation of calcium carbonate for their growth, and this in turn is related to the saturation
state, defined as = [Ca2+][CO32 ]/Ksp, where the brackets
indicate concentrations and Ksp is the solubility product
constant for either of the forms of calcium carbonate involved,
calcite or aragonite. A value of larger than unity indicates
400

Carbonic Acid Equilibria

Equilibrium Constants:
CO2(aq)

(1)

Hydration of carbon dioxide: CO2(aq) + H2O H2CO3

[H2CO3]/[CO2(aq)] = K0

(2)

CO2*, [CO2*]/[CO2(g)] = Kh

(3)

Henrys law: CO2(g)

where CO2* = H2CO3 + CO2(aq)

(4)

pCO2 / atm

Dissolution of carbon dioxide: CO2(g)

350

300

Dissociation of carbonic acid: CO2* + H2O H+ + HCO3

(5)
[H+][HCO3]/[CO2*] = K1
Dissociation of bicarbonate ion: HCO3 H+ + CO32
[H+][CO32]/[HCO3] = K2
Ionic product of water: H2O

(6)

H+ + OH, [H+][OH] = Kw (7)

Solubility product of CaCO3: CaCO3(s)

[Ca2+][CO32] = Ksp

Ca2+ + CO32

(8)

Conservation Equations:
Charge balance: 2[Ca2+] + [H+] = 2[CO32] + [HCO3] + [OH] (9)
Total carbon species: TCO2 = [CO32] + [HCO3] + [CO2*] (10)
Conservation of carbon species: [Ca2+] = TCO2

1574

(11)

250
1000

1200

1400

1600

1800

2000

Years
Figure 1. Atmospheric concentration of carbon dioxide for the past
millennium. Circles, from ice core samples at site DSS of the Law Dome
in Antarctica. Squares, from atmospheric measurements at Mauna
Loa, Hawaii. Ice core data from Etheridge, D. M.; Steele, L. P.;
Langenfelds, R. L.; Francey, R. J.; Barnola, J.-M.; Morgan, V. I. In Trends:
A Compendium of Data on Global Change; Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, Oak Ridge,
TN, 1998. Atmospheric data from Keeling, C. D.; Whorf, T. P. Scripps
Institution of Oceanography, University of California, La Jolla, CA,
July 1999. Available on the Internet at http://cdiac.esd.ornl.gov/
ndps/ndp001.html.

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Chemistry for Everyone

supersaturation, while a value less than unity implies that the

solid will dissolve in order to achieve equilibrium. In fact,
the upper layers of the worlds oceans are saturated or supersaturated with respect to calcium carbonate (3). The rates controlling the ionic equilibria cited in eqs 111 are very rapid,
and even the relatively slow hydration of carbon dioxide has
a half-life of less than one minute (4 ). On the other hand,
achievement of an equilibrium between a solid and ions in
solution is expected to be very slow.
Kleypas et al. (5) have combined physical chemical data
with databases containing global distributions of carbon
dioxide, sea surface temperature, and other relevant parameters
in order to calculate the global distribution of values with
atmospheric CO2 concentrations since 1880 and projected to
2100. Although even the worst case projections of the carbon
dioxide increase still give values of that are larger than unity,
there is a pronounced decrease. The authors cite several studies
indicating that a decreased saturation state leads to lower rates
of calcification and increased stress on the coral reef.
Equilibria in the CarbonateBicarbonateCarbon
Dioxide System
The statement addition of fossil fuel CO2 decreases
[CO32 ] (5 ) is at first glance counterintuitive, since one might
expect the increase in carbon dioxide to lead to a concomitant
increase in carbonate. So lets look at the equilibria involved (eqs
111). When carbon dioxide dissolves in water, only a very small
amount of carbonic acid is actually formed (K0 2 103).
Furthermore, since CO2(aq) and H2CO 3 are difficult to
distinguish experimentally, their concentrations are lumped
together as CO2*. The equilibrium constants tabulated in the
box are based on this convention.
The relative amounts of the three carbon-containing species are a sensitive function of the pH, as shown by Figure 2.
Such a diagram is sometimes known as a Bjerrum plot, and
it has the same form for any acidbase equilibrium but is
shifted along the pH axis according to the value of the pK s

(pK = log10 K ). Note that [CO2] = [HCO3 ] when the pH

equals pK1, and [HCO3] = [CO32 ] when the pH equals pK2.
Also indicated in this figure are the large shifts in the equilibria caused by the change in the equilibrium constants in seawater, which has an ionic strength of about 0.7 mol per kilogram of solution, principally due to sodium chloride. In the
pH region pertinent to seawater (pH = 8.08.2) the relative
amounts of dissolved CO2* and CO32 are very sensitive to the
pH, whereas the relative concentration of HCO3, the major
constituent in this pH region, does not change dramatically.
For example, if the total amount of carbon-containing species
is kept constant and the pH increases by 0.1 unit, the relative
concentration changes are HCO3, 3.3%; CO32, 21.7%; CO2*,
23.2%. It can also be seen from Figure 2 that an increase in
dissolved carbon dioxide concentration, directly proportional to
the atmospheric concentration, is commensurate with a decrease
in carbonate, but the bicarbonate concentration changes only
slightly. A very complete discussion of the calcium carbonate
watercarbon dioxide system is given elsewhere (4, 68).
Let us first consider the case where calcium carbonate
dissolves in pure water. In addition to the equilibria involving
only carbon dioxide and water, there are the additional
constraints of the solubility product, charge balance, and the
fact that all carbon species are formed from the carbonate
dissolving from the calcium carbonate (eqs 111). Since we
know that calcium carbonate is slightly basic, we can guess
that the concentrations of H+ and CO2* will be negligibly
small, thus simplifying eqs 911, which can then be combined to yield
[HCO3 ] = [OH ] = K w /[H+]

(12)

Substituting this concentration of bicarbonate into eq 6, we

obtain
[CO32 ] = K 2 K w /[H+]2

(13)

and from eq 8 this leads to

[Ca2+] = (K sp/K 2 K w)[H+]2

(14)

Now we can express eq 10 entirely in terms of [H+] in the form

(K sp/K 2 K w)[H+]2 = K 2 K w /[H+]2 + K w /[H+]

100

Percentage total carbon

CO2*

HCO3

CO3

80

[H+] = 1.10 1010; pH = 9.96

[HCO3 ] = [OH ] = 9.07 105
[CO32 ] = 3.85 105
[Ca2+] = 1.29 104
[CO2*] = 2.24 108

60

pH = pK 1

pH = pK 2

40

20

0
4

10

(15)

The constants we need, for pure water at 25 C, are K1, 4.47

107; K2, 4.67 1011; Kw, 1.00 1014; and Ksp (calcite), 4.96
109 (9). These can be substituted into eq 15 and it can be
solved graphically to yield the following concentrations:

12

pH
Figure 2. The relative amounts of dissolved carbon dioxide, bicarbonate, and carbonate. Solid lines, pure water at 25 C. Calculated with
pK1 = 6.350, pK2 = 10.331. The dashed lines indicate the relative
amounts of dissolved carbon dioxide and carbonate in sea water
with a salinity of 36.5 at 26 C with pK1 = 5.831, pK2 = 8.915.

We see that our approximations involving the neglect of [H+]

and [CO2*] in eqs 911 were justified.
Next question: Does adding an atmosphere of carbon
dioxide above the solution increase the solubility of calcium
carbonate, as asserted by Kleypas et al. (5)? We need the additional Henrys law constant Kh, which is 3.40 102 mol/kg
wateratmosphere (9). Equation 11 is no longer valid, because
some of the carbon species are derived from the carbon dioxide
atmosphere. However, eq 5 gives

JChemEd.chem.wisc.edu Vol. 77 No. 12 December 2000 Journal of Chemical Education

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Chemistry for Everyone

[HCO3] = K1[CO2*]/[H+]

(16)
+

Now we can express the quantities in eq 9 in terms of [H ],

yielding
(2Ksp/K1K2KhPCO2)[H+]2 + [H+] =

(17)

(2K1K2KhPCO2)/[H+]2 + (K1KhPCO2 + Kw)/[H+]

This equation can then be solved as before, and once [H+]
has been found, the other concentrations can be calculated.
The resulting dependence of the CaCO3 solubility on the
pressure of carbon dioxide is shown in Figure 3.
For the specific case of the present atmospheric concentration of carbon dioxide, 3.5 104 atm, the concentration
of dissolved carbon dioxide is 1.20 105 M, and the following
results are obtained:
[H+] = 5.13 109; pH = 8.29
[OH] = 1.93 106
[HCO3] = 1.03 103
[CO32 ] = 9.34 106
[Ca2+] = 5.31 104
[CO2*] = 1.20 105
The fact that this solution is more acidic than the system
without carbon dioxide makes sense; one of the more colorful
lecture demonstrations consists of showing the change in the
color of an acidbase indicator dissolved in neutral water as
one either breathes into the solution or tosses in a chunk of
dry ice. It is apparent that the solubility of calcium carbonate is
about four times greater in water in equilibrium with the
present atmospheric concentration of carbon dioxide than in
pure water.
The CarbonateBicarbonateCarbon Dioxide System
in Seawater
For accurate calculations, a number of corrections to this
simple picture are needed, which require a more detailed
knowledge of the constituents of seawater. Oceanographers
typically measure several relevant parameters in a seawater
6

[Ca+2] / (104 mol L1)

sample: temperature, salinity, pH, total inorganic carbon

(TCO2), total alkalinity (TA), and fugacity (f CO2) or partial
pressure ( pCO2) of dissolved carbon dioxide. The temperature
and salinity determine the relevant equilibrium constants, and
once these are specified any two of the last four variables
suffice to determine the concentrations of the inorganic
carbon species. The total alkalinity is defined as the amount of
hydrogen ion required to neutralize the anions of all the weak
acids present (7). After the carbonate and bicarbonate ions,
the most important contribution is that of borate, B(OH)4,
which is typically a few percent of the total alkalinity. The
concentration of this ion is usually calculated from the boric
acid dissociation constants and the total boron content, which
is linearly dependent on the salinity (10).
Equations relating these four parameters are given by
Skirrow (7 ) and in a Department of Energy publication (11).
In addition, a report by Lewis and Wallace (12) is available
online (13) with a detailed discussion of the equilibrium
constants needed for the determination of the concentrations
of the inorganic carbon species. Also available is a computer
program that can be downloaded. This program allows the
choice of several sets of equilibrium constants and the choice of
the two parameters to be used as input. The output contains
the concentrations of carbonate and bicarbonate and the partial
pressure of carbon dioxide, as well as the pH and the values of
for calcite and aragonite. As discussed above, surface ocean
water is usually saturated or supersaturated. In calculating , the
calcium concentration is assumed to be linearly proportional
to the salinity, as extensive measurements indicate (14 ).
However, the carbonate concentration is obtained by solving
the appropriate equilibrium equations.
To be thermodynamically rigorous the equilibrium
constants for the reactions of eq 111 should be given in terms
of activities. Thus, the partial pressure of carbon dioxide
should be replaced by its fugacity, which takes into account
that carbon dioxide is not an ideal gas. However, this is a very
small effect (0.30.4%) at the relevant pressures. The activities
for the ionic species are usually taken into account by putting
the necessary activity coefficients into the equilibrium
constants. Both K1 and K2 involve more ions in the numerator
than in the denominator, and since the activity coefficients
of ionic species are less than unity, one would expect the
equilibrium constants to be smaller in seawater than in pure
water. The major ionic species in seawater are sodium and
chloride ions, so the equilibrium constants are often tabulated
as a function of the salinity in parts per thousand (). This
is not a trivial correction, as Figure 2 indicates, since pK1
decreases by about 0.5 units in going from pure water to water
of 36.5 salinity and pK2 decreases by 1.4 units. To add a
further complication, different conventions have been adopted
by different authors in defining pH.

The Effect of Increased Carbon Dioxide on Coral

Formation

0
0

50

100

150

200

250

300

350

pCO2 / atm
Figure 3. The solubility of calcite as a function of carbon dioxide
partial pressure. The constants used in the calculation are given in
the text.

1576

Several studies, cited by Kleypas et al. (5), indicate that

the health of coral reefs shows a strong dependence on the
saturation state, defined by . Thus, it is interesting to see what
a typical value of this quantity is in tropical waters, where such
coral deposits exist. The necessary data can be found in the
paper by Lee et al. (15), which describes measurements made

Journal of Chemical Education Vol. 77 No. 12 December 2000 JChemEd.chem.wisc.edu

Chemistry for Everyone

during a cruise closely following the 20 W meridian and

ranging from 63 N to 5 S. The authors combine these data
with similar data from an earlier NOAA-sponsored cruise, to
obtain data appropriate to the tropical latitudes. For latitudes
of 20 S and 20 N, the following values are appropriate:
TCO2, 2050 mol/kg; pCO2, 3.6 104 atm; salinity, 36.5;
temperature 26 C. These parameters are used as input for
the CO2SYS program,1 with the following output:
TA
[HCO3]
[CO32]
[CO2*]
pH
pK1
pK2
arag
calcite

2435 mol/kg
1761 mol/kg
279 mol/kg
9.9 mol/kg
8.10
5.843
8.895
4.4
6.6

The value of the total alkalinity thus obtained is in good

agreement with values measured in situ (15). Kleypas et al.
calculated a value of 4.0 for arag in the tropics, and they
illustrated that no reefs are found in waters where the
aragonite saturation factor is lower than this.
Now we can look ahead to predict the consequences of
increased atmospheric carbon dioxide. In their calculations,
Kleypas et al. (5) assume a doubling to about 7.0 104
atmospheres, which has been predicted by some climate
modelers (16 ). We now repeat the calculation just described,
but with pCO2 and TCO2 as the input parameters, assuming
that the latter quantity includes the additional carbon dioxide
in solution corresponding to the increased atmospheric partial
pressure, since this gassolution equilibrium is maintained.
The output of this new calculation is:
[HCO3]
2

[CO3 ]
[CO2*]
pH
arag
calcite

1877 mol/kg
163 mol/kg
19.2 mol/kg
7.83
2.4
3.9

We see that the saturation value for aragonite has dropped

below the value of 4 that is considered a minimum for coral
reef health. Kleypas et al. obtained a value of 2.8 in their
2100 C.E. projection, and it is clear that the projected value
of the saturation constant is dangerously low, compared with
present values. Coral reefs are biologically diverse ecosystems
that are important to fisheries and for coastal protection, as
well as major tourist attractions in some areas. These simple
acidbase calculations indicate the threat to these complicated
systems posed by continued increases in anthropogenic carbon
dioxide emissions.
Acknowledgments
This work was carried out at Brookhaven National Laboratory under Contract DE-AC02-98CH10886 with the U.S.
Department of Energy and supported by its Division of

Chemical Sciences, Office of Basic Energy Sciences. I thank

Ernie Lewis, Joan Kleypas, and an anonymous reviewer for
helpful comments on this paper.
Note
1. For those who want to use the CO2SYS program to check
these calculations, the following options were chosen: constants,
option 1, Roy et al. (17 ); sulfate, Dickson (18); pH scale, total.

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Oxford University Press: Oxford, 1990; p 231.
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