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352 Environmental Chemistry

A possibly significant counteracting measure is modification of the Earth’s surface in a manner

to reflect light. This can potentially be done with appropriate kinds of vegetation in the form of for-
ests and grasslands and by agricultural practices that minimize exposure of light-absorbing freshly
cultivated soil. Again, the scale required to make any significant difference would be huge. Another
small effect might be had by designing surfaces (roofs and parking lot surfaces) of anthrospheric
structures to maximize reflection of solar radiation. Such a measure would favor reflective alumi-
num roofs over dark roofing and light-colored concrete over black asphalt for parking lot surfaces.
A good alternative is to cover roofs with solar cells to generate electricity.

13.6.3 ADAPTATION
Since global warming will in fact occur and neither minimization nor counteracting measures will
be sufficient to stop it, adaptation to climate warming will be required. Other than increases in
global temperature, there are many effects of global warming, suggesting a variety of adaptations.
It may be anticipated that adaptation to global warming will be one of the most significant activities
of green science and technology in the future.
Water shortages and drought constitute perhaps the most troublesome aspects of climate warm-
ing. Water, already in short supply in many parts of the world, will become more scarce. It will be
necessary to implement more efficient irrigation practices and to grow crops that require less irriga-
tion. One approach with significant promise is to grow crops on arid coastal lands irrigated with sea-
water. Plants that can grow in seawater are called halophytes and can produce 1–2 kg of dry biomass
per square meter of field area, which is about the same production as conventional crops such as
alfalfa. Some of the most productive plants that grow in seawater have relatively unattractive names
including glasswort, sea blite, saltbush, and salt grass. Though not producing grain, some of these
plants produce abundant forage that can be eaten by animals. One small problem is that because of
the high salt content of the forage, animals that consume it must drink significantly greater amounts
of freshwater. One saltwater plant that does produce abundant seeds is Salicornia bigelovii, which
rapidly colonizes new mud flats. With a salt content of less than 3%, the seeds are 35% protein and
30% highly polyunsaturated oil, similar to safflower oil in composition. The seeds contain bitter
saponins, which limit somewhat the amount of seed or meal left after extracting oil that can be fed
to animals. As a source of oils, production of oil-producing algae in saltwater ponds, such as those
filled with brackish groundwater, is a promising approach.
One of the greater adverse effects of global warming results from the effects of high tempera-
tures on people, particularly the vulnerable elderly and people who have to work outside. This was
illustrated tragically in 2021 as global temperatures reached record high levels around the world.
As global warming occurs, a major adaptation will need to be the installation of air conditioning
and other cooling measures in regions of the world where air conditioning in homes and commercial
buildings has been uncommon. This is particularly true in Europe where periods of hot weather are
becoming more common, though of shorter duration than in much of the United States, for example.
In addition to the installation of air conditioning, provision has to be made to provide sustainable
power for it. This includes a need for fuel turbine peaking facilities for electrical power generation
and for greater reserves of cooling water for nuclear power reactors.

13.7 ACID RAIN

Precipitation made acidic by the presence of acids stronger than CO2(aq) is commonly called acid
rain; the term applies to all kinds of acidic aqueous precipitation and deposition, including fog,
dew, hoar frost (frost deposited from air onto surfaces under cold conditions; frost on automobile
windshields is a good example), snow, and sleet. In addition to scavenging acidic species from the
atmosphere, wet deposition including rain and surface deposition of water scavenges many kinds of
pollutants, contributes to their transport, and may be analyzed for evidence of atmospheric pollution.
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In a more general sense, acid deposition refers to the deposition on the Earth’s surface of aque-
ous acids, acid gases (such as SO2), and acidic salts (such as NH4HSO4). According to this defini-
tion, deposition in solution form is acid precipitation, and deposition of dry gases and compounds
is dry deposition. Although carbon dioxide is present at higher levels in the atmosphere, sulfur
dioxide, SO2, contributes more to the acidity of precipitation for two reasons. The first of these is
that sulfur dioxide is significantly more soluble in water than is carbon dioxide, as indicated by its
Henry’s law constant of 1.2 mol L−1 atm−1 compared to a value of 3.38 × 10 −2 mol L−1 atm−1 for
CO2. Second, the value of Ka1 for SO2(aq)

SO2 (aq) + H 2 O ↔ H + + HSO3− (13.6)

[H + ] HSO3−
K a1 = = 1.7 × 10 −2 (13.7)
[SO2 ]

is more than four orders of magnitude higher than the value of 4.45 × 10 −7 for CO2.
Although acid rain can originate from the direct emission of strong acids, such as HCl gas or
sulfuric acid mist, most of it is a secondary air pollutant produced by the atmospheric oxidation of
acid-forming gases by reactions such as the following, both shown as overall reactions consisting
of several steps:

SO2 + 1 2 O2 + H 2 O → {2H + + SO24− }(aq) (13.8)

2NO2 + 1 2 O2 + H 2 O → 2{H + + NO3− }(aq) (13.9)

Chemical reactions such as these play a dominant role in determining the nature, transport, and
fate of acid precipitation. As the result of such reactions, the chemical properties (acidity, ability
to react with other substances) and physical properties (volatility, solubility) of acidic atmospheric
pollutants are altered drastically. For example, even the small fraction of NO that does dissolve in
water does not react significantly. However, its ultimate oxidation product, HNO3, though volatile, is
highly water soluble, strongly acidic, and very reactive with other materials. Therefore, it tends to be
removed readily from the atmosphere and to do a great deal of harm to plants, corrodible materials,
and other things that it contacts.
Although emissions from industrial operations and fossil fuel combustion are the major sources
of acid-forming gases, acid rain has also been encountered in areas far from such sources. This
is due in part to the fact that acid-forming gases are oxidized to acidic constituents and deposited
over several days, during which time the air mass containing the gas may have moved as much as
several thousand kilometers. It is likely that the burning of biomass, such as is employed in “slash-
and-burn” agriculture, evolves the gases that lead to acid formation in more remote areas. In arid
regions, dry acid gases or acids sorbed to particles may be deposited with effects similar to those
of acid rain deposition.
Acid rain spreads out over areas of several hundred to several thousand kilometers. This classifies
it as a regional air pollution problem compared to a more local air pollution problem for smog and a
global one for ozone-destroying CFCs and greenhouse gases. Other examples of regional air pollution
problems are those caused by soot, smoke, and fly ash from combustion sources and fires (forest fires).
Acid precipitation shows a strong geographic dependence, as illustrated in Figure 13.7, represent-
ing the pH of precipitation in the continental United States. The preponderance of acidic rainfall in
the northeastern United States, which also affects southeastern Canada, is obvious. Analyses of the
movements of air masses have shown a correlation between acid precipitation and prior movement
of an air mass over major sources of anthropogenic sulfur and nitrogen oxides emissions. This is
particularly obvious in southern Scandinavia, which receives a heavy burden of air pollution from
densely populated, heavily industrialized areas in Europe.
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354 Environmental Chemistry

FIGURE 13.7 Isopleths of pH illustrating a hypothetical, but typical, precipitation–pH pattern in the lower
48 continental United States. Actual values found may vary with the time of year and climatic conditions.

Acid rain has been observed for well over a century, with many of the older observations from
Great Britain. The first manifestations of this phenomenon were elevated levels of SO2− 4 in pre-
cipitation collected in industrialized areas. More modern evidence was obtained from analyses of
precipitation in Sweden in the 1950s, and of US precipitation a decade or so later. A vast research
effort on acid rain was conducted in North America by the National Acid Precipitation Assessment
Program, which resulted from the US Acid Precipitation Act of 1980 and data are still being col-
lected regarding levels of acid rain.
Table 13.2 shows typical major cations and anions in pH 4.25 precipitation. Although actual val-
ues encountered vary greatly with time and location of collection, this table does show some major
features of ionic solutes in precipitation. From the predominance of sulfate anion, it is apparent that

TABLE 13.2
Typical Values of Ion Concentrations in Acidic Precipitation
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sulfuric acid is the major contributor to acid precipitation. Nitric acid makes a smaller but growing
contribution to the acid present. Hydrochloric acid ranks third.
Ample evidence of the damaging effects of acid rain exists. The major effects are the following:

• Direct phytotoxicity to plants from excessive acid concentrations. (Evidence of direct or

indirect phytotoxicity of acid rain is provided by the declining health of Eastern US and
Scandinavian forests and especially by damage to Germany’s Black Forest.)
• Phytotoxicity from acid-forming gases, particularly SO2 and NO2, that accompany acid
rain.
• Indirect phytotoxicity. One of the most harmful effects of acidic precipitation is the dis-
solution of Al3+ from soil at levels that are harmful to plants.
• Destruction of sensitive forests.
• Respiratory effects on humans and other animals.
• Acidification of lake water with toxic effects to lake flora and fauna, especially fish
fingerlings.
• Corrosion of exposed structures, electrical relays, equipment, and ornamental materials.
Because of the effect of hydrogen ion:

2H+ + CaCO3(s) → Ca2+ + CO2(g) + H2O

Limestone, CaCO3, is especially susceptible to damage from acid rain.

• Associated effects, such as reduction of visibility by sulfate aerosols and the influence of
sulfate aerosols on physical and optical properties of clouds. (Intensification of cloud cover
and changes in the optical properties of cloud droplets—specifically, increased reflectance
of light—resulting from acid sulfate in the atmosphere may even have a mitigating effect
on greenhouse warming of the atmosphere.) A significant association exists between acidic
sulfate in the atmosphere and haziness.

Soil sensitivity to acid precipitation can be estimated from the capacity of the soil to exchange
cations (cation exchange capacity). Soil is generally insensitive if free carbonates are present or if it
is flooded frequently. Soils with a high cation exchange capacity are also insensitive because the soil
acts as a buffer by taking up H+. Soils with relatively low cation exchange capacities are sensitive if
free carbonates are absent and the soil is not frequently flooded.
Forms of precipitation other than rainfall may contain excess acidity. Acidic fog can be espe-
cially damaging because it is very penetrating. The pH of the water in the particles in acidic fog
is often much lower than that in acid rain. Another source of precipitation often containing the
ammonium, sulfate, and nitrate ions associated with atmospheric acid is acid rime. Rime is frozen
cloudwater that may condense on snowflakes or exposed surfaces. Rime constitutes up to 60% of
the snowpack in some mountainous areas, and the deposition of acidic constituents with rime may
be a significant vector for the transfer of acidic atmospheric constituents to the Earth’s surface in
some cases.

13.8 STRATOSPHERIC OZONE DESTRUCTION

Stratospheric ozone, O3, serves as a shield to absorb harmful ultraviolet radiation in the strato-
sphere, protecting living beings on the Earth from the effects of excessive amounts of such radia-
tion. The two reactions by which stratospheric ozone is produced are

O2 + hv → O + O (λ < 242.4 nm) (13.10)

O + O2 + M → O3 + M(energy-absorbing N 2 or O 2 ) (13.11)