247

CHAPTER 13. ACID RAIN

Acid rain was discovered in the 19th century by Robert Angus

Smith, a pharmacist from Manchester (England), who measured
high levels of acidity in rain falling over industrial regions of
England and contrasted them to the much lower levels he observed
in less polluted areas near the coast. Little attention was paid to his
work until the 1950s, when biologists noticed an alarming decline
of fish populations in the lakes of southern Norway and traced the
problem to acid rain. Similar findings were made in the 1960s in
North America (the Adirondacks, Ontario, Quebec). These
findings spurred intense research to understand the origin of the
acid rain phenomenon.

13.1 CHEMICAL COMPOSITION OF PRECIPITATION

13.1.1 Natural precipitation

Pure water has a pH of 7 determined by dissociation of H2O

molecules:

+ -
H 2 O ⇔ H + OH (R1)

Rainwater falling in the atmosphere always contains impurities,

even in the absence of human influence. It equilibrates with
atmospheric CO2, a weak acid, following the reactions presented in
chapter 6:

H2O (R2)
CO 2 ( g ) ⇔ CO 2 ⋅ H 2 O

- +
CO 2 ⋅ H 2 O ⇔ HCO 3 + H (R3)

- 2- +
HCO 3 ⇔ CO 3 + H (R4)

The corresponding equilibrium constants in dilute solution at 298 K

are KH = [CO2⋅H2O]/PCO2 = 3x10-2 M atm-1, K1 = [HCO3-][H+]/
[CO2⋅H2O] = 4.3x10-7 M (pK1 = 6.4), and K2 = [CO32-][H+]/[HCO3-]
= 4.7x10-11M (pK2 = 10.3). From these constants and a preindustrial
CO2 concentration of 280 ppmv one calculates a rainwater pH of
 248

5.7. Other natural acids present in the atmosphere include organic

acids emitted by the biosphere, HNO3 produced by atmospheric
oxidation of NOx originating from lightning, soils, and fires
(section 11.4), and H2SO4 produced by atmospheric oxidation of
reduced sulfur gases emitted by volcanoes and by the biosphere. A
comparative analysis of these different natural sources of acidity is
conducted in problem 13. 5. The natural acidity of rain is partly
balanced by natural bases present in the atmosphere, including
NH3 emitted by the biosphere and CaCO3 from suspended soil
dust.

When all of these influences are taken into account, the pH of

natural rain is found to be in the range from 5 to 7. The term acid
rain is customarily applied to precipitation with a pH below 5.
Such low pH values are generally possible only in the presence of
large amounts of anthropogenic pollution.

13.1.2 Precipitation over North America

Figure 13-1 shows the mean pH values of precipitation measured

over North America. pH values less than 5 are observed over the
eastern half. We can determine the form of this acidity by
examining the ionic composition of the precipitation; data for two
typical sites are shown in Table 13-1. For any precipitation sample,
the sum of concentrations of anions measured in units of charge
equivalents per liter must equal the sum of concentrations of
cations, since the ions originated from the dissociation of neutral
molecules. This charge balance is roughly satisfied for the data in
Table 13-1; an exact balance would not be expected because the
concentrations in the Table are given as medians over many
samples.

Consider the data for the New York site in Table 13-1. The median
pH at that site is 4.34, typical of acid rain in the northeastern United
States. The H+ ion is the dominant cation and is largely balanced
by SO42- and NO3-, which are the dominant anions. We conclude
that H2SO4 and HNO3 are the dominant contributors to the
precipitation acidity. Both are strong acids which dissociate
quantitatively in water to release H+:

- +
HNO 3 ( aq ) → NO 3 + H (R5)
2- +
H 2 SO 4 ( aq ) → SO 4 + 2H (R6)
 249

5.0 4.6

4.4
pH
4.2
4.4
4.6
4.6

5.0
20

SO42-
40
30
20

20

NO3- 20 30 40

10

40
NH4+ 20

10
Figure 13-1 Mean pH and concentrations of SO42-, NO3-, and NH4+ (µeq l-1) in
precipitation over North America during the 1970s.
 250

Table 13-1 Median concentrations of ions (µeq l-1) in precipitation at two

typical sites in the United States.

rural southwest
Ion
New York State Minnesota

SO42- 45 46

NO3- 25 24

Cl- 4 4

HCO3- 0.1 10

SUM ANIONS 74 84

H+ (pH) 46 (4.34) 0.5 (6.31)

NH4+ 8.3 38

Ca2+ 7 29

Mg2+ 1.9 6

K+ 0.4 2.0

Na+ 5 14

SUM CATIONS 68 89

As shown in Figure 13-1, SO42- and NO3- concentrations

throughout the United States are more than enough to balance the
local H+ concentrations. More generally, analyses of rain
composition in all industrial regions of the world demonstrate that
H2SO4 and HNO3 are the main components of acid rain.

Consider now the data for the southwest Minnesota site in Table
13-1. The concentrations of SO42- and NO3- are comparable to
those of the New York site, indicating similar inputs of H2SO4 and
HNO3. However, the H+ concentration is two orders of magnitude
less; the pH is close to neutral. There must be bases neutralizing
the acidity. To identify these bases, we examine which cations in
Table 13-1 replace the H+ originally supplied by dissociation of
HNO3 and H2SO4. The principal cations are NH4+, Ca2+, and Na+,
 251

indicating the presence in the atmosphere of ammonia (NH3) and

alkaline soil dust (CaCO3, Na2CO3). Ammonia dissolved in
rainwater scavenges H+:

+ +
NH 3 ( aq ) + H ⇔ NH 4 (R7)

The equilibrium constant for (R7) is K = [NH4+]/[NH3(aq)][H+] =

1.6x109 M, so that[NH4+]/[NH3(aq)] = 1 for pH = 9.2. At the pH
values found in rain, NH3 behaves as a strong base; it scavenges
H+ ions quantitatively and NH4+ appears as the cation replacing
H+. Neutralization of H+ by dissolved soil dust proceeds similarly:

2+ 2-
CaCO 3 ( s ) ⇔ Ca + CO 3 (R8)
2- +
CO 3 + 2H ⇔ CO 2 ( g ) + H 2 O (R9)

The relatively high pH of rain in the central United States (Figure

13-1) reflects the large amounts of NH3 emitted from agricultural
activities (fertilizer use, livestock), and the facile suspension of soil
dust due to the semi-arid climate. Note from Figure 13-1 that
NH4+concentrations are maximum over the central United States.

13.2 SOURCES OF ACIDS: SULFUR CHEMISTRY

It has been known since the 1960s that the high concentrations of
HNO3 and H2SO4 in acid rain are due to atmospheric oxidation of
NOx and SO2 emitted by fossil fuel combustion. Understanding of
the oxidation mechanisms is more recent. The mechanisms for
oxidation of NOx to HNO3 were discussed in chapters 10 and 11,
and in problem 11. 8. Both OH (day) and O3 (night) are important
oxidants and lead to a NOx lifetime over the United States of less
than a day. We focus here on the mechanisms for oxidation of SO2
to H2SO4.

Sulfur dioxide (SO2) is emitted from the combustion of

sulfur-containing fuels (coal and oil) and from the smelting of
sulfur-containing ores (mostly copper, lead, and zinc). In the
atmosphere, SO2 is oxidized by OH to produce H2SO4:

SO 2 + OH + M → HSO 3 + M (R10)
 252

HSO 3 + O 2 → SO 3 + HO 2 (fast) (R11)

SO 3 + H 2 O + M → H 2 SO 4 + M (fast) (R12)

The lifetime of SO2 against reaction with OH is 1-2 weeks. A major

research problem in the 1970s was to reconcile this relatively long
lifetime with the observation that SO42- concentrations in rain are
maximum over SO2 source regions (Figure 13-1). This observation
implies that SO2 must be oxidized to H2SO4 rapidly; otherwise, the
emission plume would be transported far from the SO2 source
region by the time it was oxidized to H2SO4. Research in the early
1980s showed that most of the atmospheric oxidation of SO2
actually takes place in cloud droplets and in the raindrops
themselves, where SO2 dissociates to HSO3- which is then rapidly
oxidized in the liquid phase by H2O2 produced from self-reaction
of HO2 (chapter 11):

SO 2 ( g ) ⇔ SO 2 ⋅ H 2 O (R13)
- +
SO 2 ⋅ H 2 O ⇔ HSO 3 + H (R14)
H 2 O 2 ( g ) ⇔ H 2 O 2 ( aq ) (R15)
- + 2- +
HSO 3 + H 2 O 2 ( aq ) + H → SO 4 + 2H + H 2 O (R16)

Reaction (R16) is acid-catalyzed (note the presence of H+ on the

left-hand side). The rate of aqueous-phase sulfate formation is

d 2- - +
[ SO 4 ] = k 12 [ HSO 3 ] [ H 2 O 2 ( aq ) ] [ H ]
dt (13.1)
= k 12 K 9 K 10 K 11 P SO2 P H2O2

where the K’s are equilibrium constants. Acid catalysis is key to the
importance of (R16) for generating acid rain; otherwise, the reaction
would be suppressed at low pH because [HSO3-] depends inversely
on [H+] by equilibrium (R14) (see problem 13. 3). Substituting
numerical values in (13.1) indicates that reaction (R16) is extremely
fast and results in titration of either SO2 or H2O2 in a cloud;
measurements in clouds show indeed that SO2 and H2O2 do not
coexist. Reaction (R16) is now thought to provide the dominant
atmospheric pathway for oxidation of SO2 to H2SO4, although there
are still unresolved issues regarding the mechanism for oxidation
during the winter months when production of H2O2 is low.
 253

13.3 EFFECTS OF ACID RAIN

Acid rain falling over most of the world has little environmental
effect on the biosphere because it is rapidly neutralized after it falls.
In particular, acid rain falling over the oceans is rapidly neutralized
by the large supply of CO32- ions (chapter 6). Acid rain falling over
regions with alkaline soils or rocks is quickly neutralized by
reactions such as (R9) taking place once the acid has deposited to
the surface. Only in continental areas with little acid-neutralizing
capacity is the biosphere sensitive to acid rain. Over North
America these areas include New England, eastern Canada, and
mountainous regions, which have granitic bedrock and thin soils
(Figure 13-2).

Figure 13-2 Regions of North America with low soil alkalinity to neutralize acid rain.

In areas where the biosphere is sensitive to acid rain, there has been
ample evidence of the negative effects of acid rain on freshwater
ecosystems. Elevated acidity in a lake or river is directly harmful to
fish because it corrodes the organic gill material and attacks the
calcium carbonate skeleton. In addition, the acidity dissolves toxic
 254

metals such as aluminum from the sediments. There is also ample

evidence that acid rain is harmful to terrestrial vegetation, mostly
because it leaches nutrients such as potassium and allows them to
exit the ecosystem by runoff. Although NH3 in the atmosphere
neutralizes rain acidity by formation of NH4+, this acidity may be
recovered in soil when NH4+ is assimilated into the biosphere as
NH3 or goes through the microbial nitrification process (section
6.3):

+ microbes - +
NH 4 + 2O 2 → NO 3 + 2H + H 2 O
(R17)

The benefit of neutralizing acid rain by NH3 may therefore be

illusory.

Beyond the input of acidity, deposition of NH4+ and NO3- fertilizes

ecosystems by providing a source of directly assimilable nitrogen
(section 6.3). This source has been blamed as an important
contributor to the eutrophication (excess fertilization) of the
Chesapeake Bay; a consequence of this eutrophication is the
accumulation of algae at the surface of the bay, suppressing the
supply of O2 to the deep-water biosphere. Recent studies of
terrestrial ecosystems in the United States show that increases in
NH4+ and NO3- deposition do not stimulate growth of vegetation
but lead instead to accumulation of organic nitrogen in soil. The
long-term implications of this nitrogen storage in soil are unclear.

13.4 EMISSION TRENDS

Emissions of SO2 and NOx in the United States and other industrial
countries have increased considerably over the past century due to
fossil fuel combustion. Since 1970, however, emissions in the
United States and Europe have leveled off due to pollution control
efforts. Emissions of SO2 in the United States have decreased by
25% since 1970, while NOx emissions have remained flat.
Technology for SO2 emission control is expensive but readily
available (scrubbers on combustion stacks, sulfur recovery during
oil refining). The control of SO2 emissions in the United States was
initially motivated by the air quality standard for SO2 (SO2 is a
toxic gas) rather than by concern over acid rain; the original Clean
Air Act of 1970 did not include acid rain under its purview. The
 255

revised Clean Air Act, which now targets acid rain, mandates a
further decrease by a factor of 2 in SO2 emissions from the United
States over the next decade. Similar steps to further decrease SO2
emissions in the future are being taken in European countries. By
contrast, SO2 emissions in eastern Asia are on a rapid rise fueled in
large part by the industrialization of China and India relying on
coal combustion as a source of energy. A serious acid rain problem
may develop over eastern Asia in the decades ahead.

In the United States, the SO2 control measures to be achieved under

the revised Clean Air Act will provide significant environmental
relief over the next decades but cannot be expected to solve the acid
rain problem. First, current forecasts indicate little decrease in NOx
emissions over the next decade. Second, a reduction of acid levels
by a factor of 2 is not enough to make rain innocuous to the
biosphere (note that decreasing [H+] by a factor of 2 increases the
pH by only 0.3 units). Third, acid rain is in part a cumulative
problem; as the acid-neutralizing capacity of soils gets depleted the
ecosystems become increasingly sensitive to additional acid inputs.

Recently, there has been considerable interest in the possibility that

reductions of SO2 emissions to combat the acid rain problem might
have negative side effects on climate. As discussed in section 8.2.3,
there is evidence that anthropogenic sulfate aerosol at northern
midlatitudes has caused regional cooling, perhaps compensating in
a complicated way for the effect of greenhouse warming. Could
reductions in SO2 emissions expose us to the full force of global
warming? This is an interesting research question which should
not, however, discourage us from going ahead with SO2 emission
reductions. We do not understand climate well enough to play
with radiative forcing effects of opposite sign and hope that they
cancel each other.