&EPA
United States
Environmental Protection
Agency
Washington, D.C. 20460
EPA-600/9-79-036
July 1980
Office of Research and Development
ACID
RAIN
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OKO Acid precipitation has become one of the major environmental
problems of this decade. It is a challenge to scientists throughout
the world. Researchers from such diverse disciplines as plant
pathology, soil science, bacteriology, meteorology and engineer-
ing are investigating different aspects of acid precipitation.
What has this research shown? We know that acid rain can
damage property, fish, soil and some crops. We know that most
acids in precipitation are sulfuric and nitric acids. We know that
these acids can form in the atmosphere from substances emitted as
a result of fossil fuel combustion. We know that such substances
can travel hundreds of miles from source to deposition. And we
know that our fossil fuel power plants, industries and motor
vehicles emit large amounts of acid-forming pollutants. We do
not, however, understand exactly how these processes work. EPA's
research program, in conjunction with those of several other agen-
cies, is attempting to find answers to these questions.
Despite some unknowns, the preponderance of our evidence to
date points to the need to control the emissions of acid-forming
sulfur and nitrogen compounds. Given the potential for damage
from acid precipitation, prudence dictates that we act soon to avoid
far more serious problems in the future. EPA's regulatory stan-
dards for new power plants and motor vehicles are a major step in
the right direction. Further steps may be required in the near
future.
This background document tells what we know — and don't
know — about acid precipitation, I hope you'll find it both infor-
mative and interesting.
Stephen J. Gage
Assistant Administrator
for Research and Development
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ACID
RAIN
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MeiiiKiiiu has always valued the rain. Plentiful and timely
rains assure good crops and abundant water supplies.
Summer rains are refreshing. Spring rains help recharge
aquifers and cleanse groundwaters; autumn rains and winter snow
cleanse the air. With rain comes a sense of hope, vitality and a
promise of the future.
Over the last decades, however, in many areas of the nation and
the world, simple rainfall has taken on a new and threatening
complexity. In these locales the rain is no longer benign, for here
the rain must pass through an atmosphere polluted with sulfur
oxides and nitrogen oxides. Such atmospheric oxides do occur
naturally and have, in past partnership with the rain, become part
of nature's balance to help nourish plants and aquatic life. But it is
the oxides from the unnatural sources—man-made industries,
power plants, auto exhausts and other fossil fuel combustion
processes—that have disrupted that partnership and upset the
balance. The falling rain and snow now react with the oxide
pollutants to produce precipitation of new chemical properties,
often a mixture of sulfuricacid, nitricacid and water, a far cry from
"pure rain" or "clean snow." It has become acid precipitation—
acid rain.
There is so much acid in some rains that they do not meet
Environmental Protection Agency (EPA) water quality criteria for
aquatic life. Moreover, acid rain is a problem with national and
international ramifications as clouds of pollution drift between
cities, states, countries and continents, on the way to becoming
acid rain.
We know much about acid rain. We know that fish die or don't
reproduce when water is too acidic. We know about air transport
patterns and about the major sources of air pollution. We are
beginning to understand how plants and man-made materials
respond to add rain. But key questions remain to be answered, key
pieces of the acid rain puz/Ie are yet to be solved. Overall we need to
be able to tie the existing information to future data to form a
consistent, comprehensive, scientific description of the causes,
consequences and means to control acid rain.
Acid rain. While the name itself evokes concern, the term is a
misnomer of sorts because it excludes other means whereby acids
fall to earth; there is acid snow, acid sleet and hail, even cases of
acid fog. And there is another phenomenon: pollutants in dry
form fall to earth awaiting some future precipitation or other
moisture that may transform them into the same acids found in
acid rain. Both of these phenomena, precipitation and dry deposi-
tion, are part of the same problem which—rightly named—is acid
deposition. Nevertheless, acid rain is the name by which the prob-
lem is identified.
Acid rain is an issue that is currently of concern to many
government agencies and private businesses. The Department of
Agriculture, the Forest Service and the Fish and Wildlife Service
are studying, respectively, acid effects on crops, trees, and fish and
wildlife; the Geological Survey is trying to determine the effects on
water quality and the Department of Commerce is studying acid
rain effects on materials. The Department of Energy is involved
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with the problem because the acids are products of energy produc-
tion; the automobile industry and the electric power industry are
vitally concerned because sulfuroxides and nitrogen oxides are put
into the air by smoke stacks and auto exhausts. And at EPA all of
these effects are of interest because of our mandate to protect the
environment and the health and welfare of people.
This report is a gathering of what is known about acid rain. It
does not contain the complete answer because our understanding
of acid rain and its effects is still in its formative stages. It is EPA's
intent to enlarge and expand upon this body of knowledge and to
help provide the data and technology necessary to protect the
quality and productivity of our environment. In short, EPA is
determined to help define, avert, and solve the problems that
surround the acid rain phenomenon.
Rain tends to be naturally acidic because carbon dioxide in
the atmosphere reacts with rain to produce carbonic
acid. That amount of acidity is, however, sufficient to
dissolve minerals in the Earth's crust, making them available to
plant and animal life, yet not acidic enough to cause damage.
Other atmospheric substances from volcanic eruptions, forest
fires, and similar natural phenomena also contribute to the natu-
ral sources of acidity in rain. Still, even with the enormous
amounts of acids created annually by nature, normal rainfall is
able to assimilate them to the point where they cause little, if any,
known damage. It is mankind's contribution, however, that is
thought to throw off this acid balance and convert natural and
mildly acidic rain into precipitation with far-reaching environ-
mental effects.
ACID RAIN:
THE FACTS
COMBUSTION
OF
FOSSIL FUELS
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Measuring Acid Rain
The acidity of any solution, including rain or snow, is
measured on a scale known as a pH scale. This scale is
numbered from 0 to 14. A pH value of 7 is neutral, neither
acidic nor alkaline. Values lower than 7 are more acidic—vinegar,
for instance, with a pH of between 2.4 and 3.4. Values above 7, such
as for ammonia or lye, represent alkalinity.
The pH scale is a logarithmic measure, that is, each change of
one pH unit—say from 6 to 5—represents a tenfold increase in
acidity. Thus a drop from pH 6 to pH 4 represents a hundredfold
increase and drop from pH 6 to pH 3 represents a thousandfold
increase in acidity.
For rain or snow, acidity measurements reflect the balance of
positive and negative ions in the precipitation (see box). The ions
can come from a variety of compounds or elements (sulfur and
nitrogen oxides, hydrogen, carbon oxides, chlorine etc.) thus the
total acidity of precipitation must take into account all of the
sources of ions.
Lemon Juice
Vinegar
Mean pH of Adirondack Lakes-1975
"Pure" Rain (5.6)
Mean pH of Adirondack Lakes-1930's
Distilled Water
Baking Soda
678
NEUTRAL
10 11 12 13 14
BASIC
The pH Scale
The pH ("potential
hydrogen") scale is a
measure of hydrogen ion
concentration. Hydrogen
ions have a positive
electrical charge and are
called cations; ions with a
negative electrical charge
are known as anions. A
substance containing equal
concentrations of cations
and anions so that the
electrical charges balance
is neutral and has a pH of 7.
However, a substance with
more hydrogen ions than
anions is acidic and has a
pH less than 7; substances
with more anions than
cations are alkaline and
have pH measures above 7.
Thus, as the concentration
of hydrogen ions increases,
the pH decreases. But the
pH scale says nothing
about whether the cations
or anions are from natural
or manmade sources; a
hydrogen ion from an
industrial smokestack
measures the same on the
scale as a hydrogen ion
from natural minerals.
PH4
PH5
PH6
PH7
=Acid Content
Remember
The/ower the pH value,
the higher the acid content.
Each full pH unit drop
represents a tenfold
increase in acidity.
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£ £ T% ure" rain is defined as rain with a pH of between 5.6
•-^ and 5.7. These pH values take into consideration the
A amount of acidity created by the reaction of rainwater
with normal levels of atmospheric carbon dioxide. But the acid
precipitation that is of concern in this report is that rain (or snow,
sleet, or hail) with a pH of 5.6 or below.
This concern with acid rain is not without good reason. Recent
research shows that the average precipitation in most states east of
the Mississippi River lies between pH 4 and 5, with individual
storms having pH values well below these averages. Furthermore,
acid rains and snows have been observed in remote and wilderness
areas in both the eastern and western United States testifying to the
possible widespread dispersion of the phenomenon.
The questions are then: What are the hazards posed by an acid
rainfall? Who and what is threatened by it? What is necessary to
control it? And, how can control be accomplished?
Pure Rain
SulfuricAcid- 65%
NitricAcid- 30%
Other Acids- 5%
—
rim
TYPICAL NORTHEASTERN U.S. ACID RAIN COMPONENTS
In the eastern United States, the major component of acid rain
is sulfuric acid, comprising as much as 65 to 70% of the rain's
acidity. The second major component is nitric acid with a
presence of 25 to 30%; other acidity comes from other acids in trace
amounts. In the western United States, the acids in acid rains are
generally half nitric acid and half sulfuric acid, although in some.
western urban areas, as much as 80% of a rain's acidity can be
comprised of nitric acid. In either case, west or east, the major
components do not start in the atmosphere as acids. Rather, they
generally begin as sulfur oxides (SOX) and nitrogen oxides (NOX)—
gases emitted into the air primarily from fossil fuel combustion in
power plants, industry, and cars and trucks.
In the atmosphere, SOX and NOX—widely recognized as among
the major man-made pollutants—are transformed into sulfates
and nitrates, which then react with moisture in the air, forming
acids. Thus when it rains, it rains a solution of water and sulfuric
and nitric acid.
The Acids in Acid
Rain
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When Acid Rain Falls
-—-^ ain and snow as it falls through the atmosphere functions
1 9 as an air cleaner. When there is a long interval between
Mm. rains, sulfates and nitrates can accumulate in large stag-
nant air masses, making the eventual precipitation highly acidic.
Under certain conditions, these compounds may be buffered by
airborne alkaline particles. However, while such atmospheric buf-
fering is sometimes significant (two-thirds of the atmospheric
sulfates in Minnesota and Scandinavia are estimated to be neutral-
ized in this manner), usually it cannot nearly counter the acid-
forming compounds downwind of heavily polluted areas.
Solutions Containing
Acids or Bases
Buffering Agents
•r Bases |
•••••••••
I : *
•••••••••••••••••
••••••••••••••••*
••••••••*••••••••
Buffering
A substance has
buffering capabilities when,
coming into contact with a
solution that contains acids
or bases, it neutralizes the
acids or bases without
appreciably changing its
own nature.
Normal rainwater (pH
Acids or Bases
Neutralized
oo
ooo
oooo
ooooooooooooooo
oooooooooooooooo
OOOOQOOOOOOOOOOQO
oooooooooooooooo
ooooooooooooooo
oooo
ooo
5.6) is not highly buffered
and therefore is susceptible
to pH decreases.
Airborne alkaline
particles sometimes buffer
air pollutants. Soils, on the
other hand, can have an
enormous buffering
capacity.
These accumulation, dispersion, and neutralization pheno-
mena help cause seasonal differences in the acid deposition prob-
lem. During the summer months, air circulation is generally slow,
with a decrease in the dispersion and dilution of atmospheric
acids. Increases in automobile use and electrical generation to
operate air conditioners result in a high level of fossil fuel combus-
tion. Also, increased solar radiation and humidity combine to
speed the process that turns SOX in the air into sulfuric acid. Nitric
acid levels are also affected, but significantly less so, making the
acid in the summer rains more rich in sulfuric acid than at other
times. The result? Summer rains may be the most acidic.
Even so, there is not always a correlation between the pH of a
rainfall on a given day, and the potential it has for damage to the
environment. In cold climates, for example, acid substances from
acid snow can accumulate in the winter snowpack; thus, when the
snowpack melts in the spring, a winter-long buildup of acids
courses through soils, vegetation and surface waters. This type of
deferred release of acids over and above the gradual accumulation
of acids in streams and lakes can be particularly devastating, espe-
cially in the spring. Reproductive cycles can be interrupted or
thwarted, seed germination can be retarded and newly-hatched fish
fingerlings or other new life can be destroyed. The implications for
forestry growth, farm productivity or deciduous plant vigor are of
particular concern.
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Once the SOX and NOX compounds are released into the
atmosphere, two factors determine their geographic im-
pact. First is their residence time—the amount of time
before the compounds either descend to the earth as dry deposition
or react with moisture in the air to form acids or other concoctions.
Second is the distance the sulfates and nitrates can travel in that
time.
The residence time of sulfates and nitrates is generally up to
about four days, although they may remain aloft longer. Their
movement depends primarily on wind speeds. Under certain con-
ditions sulfate and nitrate compounds can stay aloft long enough
to cross continents, oceans, and international boundaries, creating
a situation in which the acid rain in one country is caused by the
emissions of another, but the recipient of this damaging rain
receives little or no benefit from the source initiating the pollution.
For example, in 1892, the New York State Legislature estab-
lished New York's scenic Adirondack Parkas "forever wild." But
in the 1950s, fishermen began to complain of fewer and fewer trout
in the park's more than 200 high lakes and streams. It was then
thought that predator yellow perch were responsible, but soon the
perch died out as well, as did new species introduced experimen-
tally to replace the native fish. For a while, beavers and the logging
industry bore the blame. It was not until recently, however, that
scientists discovered that the chief reason for the disappearance of
fish from half of the park's high elevation lakes was acidification
of the lake's water.
The acid rain condition in the "forever wild" Adirondacks
underlines the problem posed by the transport of pollutants from
the point of their creation to the point of their effect. Clearly this is
a problem that cannot be dealt with on a local level, and in
instances where the polluted atmosphere drifts across interna-
tional borders, not even stringent national controls can stave off
potentially severe damage.
It is the Adirondack's geographic misfortune that they lie
downwind of many large industrial areas; it is similarly Sweden
and Norway's misfortune to suffer the airborne pollution from
England and Germany. In a few short days and often less, prob-
lems of local origins become ones of international scope.
From Here to There
—The Transport of
Acid Rain
ADIRONDACK PARK
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Eastern Rain/
Western Rain
The region of the continental United States most affected by
acid rain is the Northeast, where pH levels of between 4.0
and 4.5 are commonplace. In recent studies, New York
City averaged a pH of 4.28; the Hubbard Brook Experimental
Forest in New Hampshire, a pH of 4.03; and in numerous areas in
the mountains of Pennsylvania, New York, and New Hampshire,
pH values ranged from 3.98 to 4.02. Specific individual storms
with pH levels of anywhere between 3.0 and 4.0 are not out of the
ordinary, and values less than 3.0 have been found.
Notably, the most rapid increase in acid precipitation in the
country seems to be in the Southeast, an increase paralleling the
expansion of Southeastern urban and industrial acitivities that
result in sulfur and nitrogen emissions. Here the trend is more
apparent than in the Northeast because the atmosphere in the
Southeast is just beginning to deteriorate and fewer acids are
required to cause a pH change. In 1979, four rains in North
Carolina were measured at pH 3.3.
pH greater than 5.5
pH between 5.0 and 5.5
pH between 4.0 and 5.0
pH less than 4.0
Bringing It All Back Home
In March, 1973,
thousands of school
children across the country
participated in an exercise
to discover the pH levels of
rainwater and snow in their
own area. The results of
this study and the map
generated from their data
reveal the following:
• the entire half of the
country east of the
Mississippi had
precipitation of pH 5.0 to
5.5;
• many pockets east of the
Mississippi have
precipitation with a pH of
between 4.0 to 5.0;
• west of the Mississippi
there are also a number of
pockets with precipitation
values of between pH 4.0
and 5.0.
While the study was not
scientifically rigorous, it did
serve to support what acid
rain watchers have
documented.
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West of the Mississippi, rains are generally neutral or even
alkaline. Colorado, the Los Angeles Basin, the San Francisco Bay
Area, Spokane, Tucson, and Portland are the known exceptions.
In these locations, as in the Northeast, precipitation ranges from
between pH 4.0 to 5.0. A recently completed two-year study in
Southern California showed the mean pH in Pasadena to be 3.9.
Most of this is thought to be due to nitric acid contributed by
automobiles and trucks.
The earliest known measurement of precipitation pH in the
United States was done in Brooklin, Maine, in 1939 when a
pH value of 5.9 was obtained during a single rainstorm.
Ten years later, during a 1949 summer rainfall in Washing-
ton, D.C., measurement of the pH of eight individual raindrops
established their mean pH value to be 4.2.
THE HISTORY OF
ACID RAIN
Over The Ages
The pH of precipitation
found preserved in glaciers
and continental ice sheets
has been shown to be
generally above 5.
In Greenland, ice that
originated as snow 180
years ago had a pH ranging
from 6 to 7.6.
Although pH levels were not reported until the late '50s,
precipitation data indicate that by mid-decade the rain in
the eastern United States had turned decidedly acidic. Dur-
ing the early '50s, a number of key developments took place that
brought this about.
First, there was an increased amount of fossil fuel combustion as
more electricity was generated, more automobiles were on the road
and more factories were built.
Second, in the past 30 years smokestack heights have increased
along with the size of the plants thereby putting pollutants higher
into the air. This permitted the pollutants to remain aloft longer
which, in turn, led to wider pollution dispersion. The local prob-
lems were abated; regional problems were intensified.
Decade of Transition
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And third, summertime atmospheric acid concentrations in
some regions became greater than winter concentrations, due
primarily, it is thought, to more power plant emissions and to
automobile exhausts.
It was not actually until the early 1970s, however, that the
Hubbard Brook Ecosystem Study indicated the acid precipitation
problem in North America. As a result, in the years that followed,
the sparse data gathered in the '50s and '60s were studied with new
interest. The first complete set of data on the pH of precipitation
for the entire United States was collected between 1959 and 1966 by
the U.S. Public Health Service and the National Center for Atmos-
pheric Research. These findings indicated pH levels of well over 7
in the western United States compared to levels of less than 4 in
New England; overall, eastern rains were shown to be surprisingly
acidic.
In the 1970s, pH readings showed that acid precipitation had
become commonplace throughout the eastern United States. Con-
sistently low pH readings of precipitation in rural New England,
hundreds of miles from urban industrial centers, were testimony to
the long-range transport of SOX and NOX.
1955-1956
1972-1973
pH above 5.00 pH 5.00 or below pH 4.52 or below pH 4.22 or below
THE WEIGHTED ANNUAL AVERAGE OF pH OF
PRECIPITATION IN THE EASTERN UNITED STATES IN
1955-1956 AND 1972-1973
Source: National Academy of Sciences, Nitrates: An Environmental Assessment, 1976.
UNDERSTANDING
ACID RAIN
EFFECTS
10
Data from an air pollution monitoring network in Europe
provided the first evidence of a regional acid rain problem.
Gradually, over the years from 1968 to the present, scientists
first in Europe then later in Canada and the United States came to
recognize that a number of key factors influenced the times and
places that acid deposition would have important effects. The
recognized factors include—climate, topography, geology, biota
and human activity.
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ICELAND
NETHERLANDS
PJTLOCHFIY
In Europe...
The lowest recorded pH
valuator an individual
storm was 2.4 on April 10,
1974 at Pitlochry, Scotland.
During that same April a
value of of 2.7 was reported
in Norway and 3.5 in
Iceland.
In 1967, a survey in the
Netherlands reported the
lowest annual pH
level—3,78,
The most important aspect of climate in estimating the
polennal effects of add rain is the amount and frequency
number of K'T" "" "^ °f *"> °f ra'"fa» a"d
number oi inches of ram per year. In drier climates such as the
western Untted States, windblown alkaline dust .abundant and
"
be more acd ' '" *< ™' P^P^ion tends to
De more acid. Seasonal timmg of rain and snowfall is also a kev
element ,„ the measure of potential actd precipitation effects Fo
example, , doses of ^ ^ V e« . Fo
W,nd direction and wind speed determine the direction and the
speed pollutants travel, and to some extent, exert control
eTarl^'10"- HUmid"y a"d «""'
speed at which gases convert to acids.
FACTOR: Climate
11
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FACTOR:
Topography/Geology
m he topography of an area, taken along with its geology
Th- * ™rked infiuence °n acid rain effec^ rivTai
A sensitive to acid precipitation are those with hard, crystal
,me bedrock and very thin surface soils. Here, in *e absence o he
buffering propert.es of soil, acid rams will have direc access to
su a wafers and their delicate ecosystems. Conversely a thick
somantle or one with a high buffering capacity helps keep acid
ram damage down. Mountainous areas generally have thm surface
^"±1^'i±. of water is also a consideration, with
heldwater lakes and streams espeaally vulnerable to acidification^
Lake depth, the ratio of watershed area to lake area, and he
Residence time of water in lakes all play a part in determmmg the
consequent threat posed by acid, The source of the acid (rams or
runoff) may also influence effects.
FACTOR: Biota
he kinds of trees and plants in an area, their height and
whether thev are deciduous or evergreen may all play a
_ part in the potential effects of acid ram. Without a dens
leafcanopv more acids may reach the earth to impact on soil and
a e, chemistries. Stresses on the plants will also affect the balance
oft alTosvstems. Additionally, the rate at which different types
of plants carrv on their normal life processes influences an area s
ratio of precipitation to evaporation. In locales with high evapora-
don rates acfds will concentrate on leaf surfaces. Another factor is
tha" Sf Utter decomposition may add to the acidity of the soil due
to normal biological actions.
FACTOR: Human
Activity
ny discussion of acid rain effects would be mcomplet . wUh-
out considering the chief pollution , >our ces-automobi e
smokestacks, and other emitters of the by-products of foss
fuel combustion. And a number of questions about these issues
must be posed What tvpe of fuel is being used? Is u high m sulfur
P
°f Generally speaking, the more fuel that is burned, the greater the
amount of ^undischarged to the air and the more severe the
12
about what types of poUution
i ~A r'l^-anfH rnaP Low-sulrur coair
h™^^^
frok are'effective in reducing the amount or concentrauon of
emissions, other means of addressing local pol lution p^blems
such as tall stacks, also determine the nature of remaining
exhaus s For example, tall stacks may discharge the same amoun
oSons as small stacks but, due to the stack height ^e—
remain aloft longer. Longer airborne times may be mon ^condu
cive to the spread of acid deposition. The tall stacks-400 to 1200
fit tail-now number more than 200 in the United States.
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The Canadian Sudbury
smelters have one of the
tallest stacks in the world,
nearfy a quarter mile high—
as high as the tallest
building in the world,
Chicago's Sears Tower.
A main concern, at
present, is the
transboundary exchange of
pollutants between Canada
and the United States.
Canada receives 2 to 4
times the amount of SOX
the United States gets from
Canada. NOX exchange is
11 times greater from the
United States to Canada.
Other questions to be posed involve location and size of urban
and industrial developments. How large and concentrated are
these settlements? Are they upwind or downwind from delicate
ecosystems or regions with little buffering capacity? Which way
does the wind usually blow? At what time of year are most pollu-
tants emitted? Unfortunately, the answers to these questions gen-
erally are the "wrong" ones when addressing the problem of man's
contribution to the effects of acid precipitation; urban and indus-
trial areas are often large and concentrated, many are upwind from
sensitive regions, and summer is when emissions are at their peak.
But not all of man's activities worsen the effects of acid rain. Use
of low-sulfur coal and installation of stack scrubbers help reduce
pollution emissions. Certain agricultural activities also help ame-
liorate the potentially harmful effects of the rain. Limed fields will
buffer the rain, and dustfall from windblown soil can neutralize
acids in the air. On the balance, however, the human contribution
to acid rain effects is a substantial increase in the intensity and
spread of effects.
13
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THE DAMAGES
DUE TO ACID
RAINFALL
Strange things have been happening. In the Adirondacks
many lakes no longer hold fish. In some cities, statues, cen-
turies old, lose their features. Tombstones in New England
have become illegible. In Sweden lakes turn a swimming-pool
blue—almost all their organic life erased. In parts of Pennsylvania
and North Carolina automobile finishes rapidly corrode. Some
house paints last only a few years.
The effects of acid rain are as pervasive as the rain itself with
water, fish, vegetation, stone, steel, paint, soil, and mankind all
affected to a greater or lesser degree. Exactly what are these effects?
And how extensive are they? As is the case with many environmen-
tal problems, there are no easy answers to these questions.
Effects on Aquatic
Ecosystems
It is in lakes or streams where the most dramatic effects of acid
rain have been clearly observed. It is known that low pH
precipitation can kill—fish eggs, salamander eggs, frog eggs-
entire lakes and streams can be put under stress, devastated, or
destroyed. Fish-food organisms are affected, causing not only the
demise of a lake or stream, but also the disappearance of the
animals that depended on the water body for sustenance. The
extent of change in acidity of a lake or stream is determined mainly
by the buffering capacity of the surrounding soil and the composi-
tion and size of the watershed in which the water resides. If the
watershed soil is alkaline—containing limestone or bicarbonate to
neutralize incoming acids—the lakes and streams will be acidified
less rapidly and the aquatic community will be far less susceptible
to harm.
14
Surface Area—^
-Watershed—
Lakes Most Susceptible to Acidification
1—are located downwind,
sometimes hundreds of
miles downwind, from
major pollution sources—
electricity generation, metal
refining operations, heavy
industry, large population
centers
2—are surrounded by hard,
insoluble bedrock with thin,
sandy, infertile soil
3_have low buffering
capacity due to the terrain
4—have a low watershed to
lake surface area ratio
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The Fish Population. Fishing is one of the major reasons many
people visit lakes and streams, thus changes in fish populations are
among the most obvious effects of acid precipitation. In Norway,
for example, poor catches of salmon were reported as early as the
turn of the century, with precipitous declines in catches observed
since the mid 1960's. These declines are now recognized to have
been largely caused by acid precipitation. Today, the salmon catch
in the country's highly acid southern rivers is practically nil, and
an overall decline of various species has been observed in many
Norwegian lakes and rivers.
On Sweden's west coast, 50% of the lakes have pH values of less
than 6.0, a decrease of almost 2.0pH units since the 1930s. Overall,
10,000 lakes have been acidified to a pH below 6.0 and 5,000 to a pH
below 5.0. Salmon populations in western Sweden have been dec-
imated, and in the central and eastern sections of the country, other
sport fish have been seriously affected.
Technician sampling lake water forpH levels
Add Lime
The addition of lime to
acidified lake ecosystems
has met with some
beneficial results. In
Scandanavia chalk added
to Swedish lakes has led to
increased phytoplankton
growth and improved fish
survival. Adding CaCO3
and Ca(OH)2 to two acidic
lakes in Sudbury, Ontario
increased pH, decreased
heavy metal concentrations
and caused a temporary
decline in chlorophyll.
Liming experiments in
Norway, however, indicate
that this practice would
only be feasible for small
ponds and streams.
The first North American studies linking lake acidification to
acid precipitation were made in Canada, especially southern
Ontario. Smallmouth bass, walleye, white suckers, northern pike,
lake trout, lake herring, perch, and rock bass have been eliminated
from many of the lakes. These effects were first detected in the
vicinity of the Sudbury metal smelters. Increases in lake acidity of
more than one hundredfold in the past decade have been observed,
and of the 150 lakes surveyed, 33 were classified as "critically acid"
(pH less than 4.5) and 37 were classified as "endangered" (pH of 4.5
to 5.5). It has been more recently estimated that 200 to 400 lakes
within a 50-mile radius of the smelters contain few or no fish
whatsoever.
15
-------
Normal fish development atpH 5.5
Abortive development at pH 5.0
FREQUENCY DISTRIBUTION OF pH AND FISH
POPULATION STATUS IN FORTY ADIRONDACK LAKES
GREATER THAN 610 METERS ELEVATION
Surveyed during the period 1929-1937 and again in 1975
5 6
PH
No Fish Present \
Source; Schof ield, C.L, "Acid Precipitation Effects on Fish," AMBIO. 1976.
In the United States, similar effects have recently been observed
in the Adirondack Mountains where more than half of the remote
mountain lakes at elevations greater than 2,000 feet demonstrated
pH values of below 5.0; of these lakes, 90% contained no fish. In
contrast, between 1929 and 1937, only 4% of these lakes had a pH of
under 5.0 or were devoid of fish. While there are numerous other
areas of poorly buffered surface waters in the eastern and midwest-
ern United States, up-to-date inventories of fish populations have
generally been lacking.
The most common cause of decline in fish populations is failure
in the reproductive cycle. Through a series of reactions induced by
lake or stream acidity, calcium levels of prospective mother fish are
lowered to a point where she cannot produce eggs. When eggs do
develop, they may not be passed from the ovary to be fertilized; even
when the eggs are fertilized, both eggs and the freshly hatched
larvae do not develop normally. Those few fish that do survive
continue to be plagued by the acid water, their systems so stressed
that their biochemistry is altered. Where there is year-round acid-
ity, the stress is acute. In lakes subject to highly acidic spring
thaws, where acids are released in sudden, intense bursts, the
already stressed fish tend to die in large numbers.
FREQUENCY DISTRIBUTION OF pH IN ADIRONDACK LAKES
16
193O-1938
320 Lakes
1969-1975
216 Lakes
Source; Schofield, C.L, "Acid Precipitation Effects on Fish," AMBIO. 1976.
-------
Precisely what kills these mature fish? It is known that a low pH
can lead to improper body salt and calcium regulation in fish,
which, in turn leads to altered metabolism of sodium and other
elements. It is also thought that indirect effects might be responsible—
specifically, the effects of the acids on the fish food and the result-
ing altered food supply. An examination of the stomachs of 825
perch from 49 different Swedish lakes indicated that shifts in
eating patterns did indeed occur, but no conclusive link between
food supply and the elimination of fish species was established.
However, a direct link was found between fish deaths and some
metals. For example, aluminum and manganese become mobile
and soluble in soil after an acid rain, therefore, the concentrations
of these materials increase in the soils. Runoff and leaching subse-
quently transfer the metals to the water in sufficient amount to
cause fish to die (see box).
Scientists were puzzled
to find heavy trout mortality
occurring in lakes whose
acidity was inadequate to
account for the damage. It
was then discovered that
there was a "second wave
of destruction" in the wake
of acid rain. The soil
surrounding the lakes
reacted with the acid in the
rain to release large
quantities of aluminum into
the lakes. Aluminum in that
form is deadly to fish. The
poisoned runoff moved
rapidly across the water
surface. In deeper lakes
with good oxygen supplies,
fish could find refuge at the
bottom. In shallower lakes,
however, fish were caught
in a deadly trap. They had
the choice of dying from
lack of oxygen at the
bottom, or from acids and
aluminum at the top.
Another metal, mercury, may produce lethal effects as a result of
acid rain. As lakes acidify, mercury goes into solution as highly
toxic organic methyl mercury. A clear correlation exists between
the acid level of lake and the mercury levels of its fish; the more acid
added to the lake's waters, the more mercury in the fish, up to the
point where the fish may begin to die. Those fish that survive
present a clear danger to man—mercury, at even extremely low
levels can be lethal once it is introduced into the food chain and
consumed by humans.
17
-------
Overall, the prognosis for fish in these acid lakes is not good, for
even the most resistant species are affected when the pH drops
below 5.0. Presently, scientists are at work developing a strain of
acid-resistant fish to replenish the depleted Adirondack lakes. But
how resistant? And what will they eat? The real answer it would
seem lies not in making a "better" fish, but in diminishing the
amount of acid pollutants in the air that result in this decimation
of fish populations.
Far more than the lives of fish, of course, are at issue in these
aquatic environments. Acid rain has interferred with the reproduc-
tion of frogs and salamanders. Dense mats of peat moss, ordinarily
a land plant, are turning up on the bottoms of highly acidified
lakes. This may upset nutrient balances between the lake's water
and bottom. Algal communities in lakes with a pH of under 6.0
contain fewer species, with a shift to more acid tolerant forms. The
growth of rooted plants and the rate of decomposition of organic
matter is being reduced by acids; there are more fungi, less bacteria,
and fewer species of aquatic invertebrates to be found in both the
sediment and in the water column. Thus, acid rain presents a
threat to much if not all of the aquatic community. Through many
complex and subtle mechanisms, acid rain is already changing a
significant and important portion of our environment.
18
Behold the Eastern Tiger
Salamanders!
They emerge on early
spring nights to woo and be
wooed in nearby ponds.
Sometime later the female
lays a mass of eggs
surrounded by a jelly-like
substance. The eggs hatch
in some 12 to 18 days.
Adulthood takes two years
to reach.
In acid ponds, however,
the Eastern Tiger
Salamander's nuptials often
go unrewarded and
populations are dwindling.
The jelly-like substance
surrounding the eggs
absorbs acid water and
embryo development is
impaired.
In laboratories, mortality
was 0.6% at a pH of 7, 0.9%
at a pH of 6, 44% at a pH of
5.5 and over 65% at pH
values lower than 5.
Embroyos die at late stages
of growth, with the greatest
number of deaths occurring
at the outer portion of the
egg mass. Eggs in the
center were protected from
acids by their outer
neighbors. Further
laboratory testing of field-
laid eggs demonstrated
almost identical results,
pointing to the conclusion
that acid precipitation is
definitely the factor in the
Eastern Tiger Salamander's
demise.
Through the realization
of the causes of these small
deaths comes the
recognition of the
pervasiveness of acid rain
on unprotected animal life.
-------
Beyond the food provided them through photosynthesis,
plants must obtain mineral nutrients to grow normally.
These substances are taken up from either the soil by roots
or from precipitation and dry deposition on leaves. Animals also
require mineral nutrients and obtain them at salt licks, in drinking
water or by eating plants or other animals.
Mineral and chemical nutrients enter the soil in two ways: by
weathering from parent rock or by wet and dry deposition from the
atmosphere. Once in the soil they are continuously recycled
through plants and animals back to the earth in the form of dead
organic matter—a constant process of regeneration.
Effects on Soil
Systems
Acid Rain Effects on Plants
and Soil
• Lesions reduce growth.
• Litter accumulates, and
bacterial decomposition is
inhibited.
• Nitrogen fixation is
inhibited.
• Calcium, magnesium,
and potassium are leached
from the leaves and soil.
Often these nutrients are not in forms usable by plants, and
chemical transformations must take place to make them so. For
example, in order for plants to get at the nutrients contained in
dead organic matter, the material must first be broken down,
usually by bacteria and fungi. A key nutrient, nitrogen, is partly
replenished in the soil by microorganisms, which extract it from
the atmosphere.
Acid rain may disrupt this system of soil regeneration in two
fundamental ways. First, acids in rain could suppress the decay of
organic matter and the formation of nitrogen-fixing products on
the roots of legumes such as soybeans. Blue-green algae, another
nitrogen-fixing organism, ceases to function below a pH of 6.
Second, acids in rain may affect the storage function of soil.
Valuable nutrients like calcium and magnesium are bound to soil
particles and thus are protected from being rapidly washed into
groundwater. Normal rain can break these bonds to leach the soil
of these nutrients; acid rain, however, might greatly accelerate the
process and thus reduce the mineral stores of soils.
19
-------
In the already nutrient-poor woodland soils of Sweden, scien-
tists have observed a reduction in forest growth which they attrib-
ute to continued leaching of calcium and other nutrients from the
soil by acid rains. Similiar studies of North American forests,
however, are inconclusive. Continued acid rain could damage the
properties of soils, which in turn may eventually reduce plant
productivity, thus leaving forests without the food necessary to
grow as quickly and as vigorously as they have in the past. The
extent to which this could impact our forest products industry-
paper, or wood for homes, for example—is just not known.
Acid rain also causes plants to take up and hold greater amounts
of potentially toxic substances. It has been demonstrated that leafy
plants (such as lettuce) exposed to acid precipitation retain an
increased amount of cadmium. In this case, even if productivity is
not affected, the plants may be unmarketable and food supplies
diminished.
Acid Rain and
Vegetation
Acid rain could have direct impacts on plants. It may affect
young growing tissues and the process of photosynthesis.
Plants require their embryonic tissue throughout their lives
for the formation of new leaves and buds. When tissues are dam-
aged, a plant's developmental power is diminished, gross deforma-
tions occur {much like birth defects), vitality is sapped, and
chances for survival are lessened.
20
"Meanwhile, Back in the
Forest."
In forests, raindrops _
wash over three tiers of
foliage before reaching the
soil. What is the effect of
acid rain on this foliage?
Visual signs of injury
occur on plants where pH
values are 3 or less—brown
pockmarking after a few
hours and the pitting of
both faces of the foliage
after a day. These leaf
lesions reduce the area for
photosynthesis, limit leaf
growth, affect root growth,
decrease soil respiration
and affect germination of
conifer seeds. At
intermediate pH levels
where there are no visual
signs of damage, however,
significant reductions in the
weight of the leaves point
to other forces at play,
although it is not yet clear
what forces and how strong
they may be.
-------
Acid Rain and Vegetation
While some plants thrive
in acidic conditions, many
others do not. Early in this
century plots of timothy
grass were treated with
sulfuric acid solutions in a
pH range of 2.2 to 3.7. At
the end of three year's time,
the grass exposed to the
least acidic treatments
showed a decline in
productivity. The grass
exposed to the most acidic
treatment was dead.
More recently:
• Western pines sprayed
with sulfuric acid at a pH of
greater than 4.0 grew
needles half as large as
control pines, thus severely
diminishing their
photosynthetic capacity.
• Yellow birch seedlings 2
to 5 weeks old subjected to
a misting with sulfuric acid
at pH 3.0 showed the
younger plants to be more
susceptible to damage than
the older. More mature
yellow birches have also
been deformed by
exposure to acid rain.
• Tomato plants in Hawaii
exposed to low pH rain
showed decreases in pollen
germination and pollen
tube growth. Lower quality
and quantities of fruit
result.
• Kidney beans, pinto
beans, sugar maple and
yellow birch foliage
demonstrated pockmark
acid lesions when misted
with pH 3 solutions. The
threshold for bush bean
foliage was pH 2.5. Studies
of the yields for these
plants, however, showed
mixed results.
• Christmas tree farms in
West Virginia, downwind of
the Kyger Creek coal-fired
plant in Ohio, have suffered
extensive damage. Acid
rain or dry deposition has
been implicated, and the
disease afflicting the trees
has been duplicated in at
least two independent
laboratory studies using
sulfuric acid mists.
Even more important, however, are the possible effects on pho-
tosynthesis caused by acid rain. Photosynthesis is the process by
which plants convert sunlight into carbohydrate foodstuffs. It is
the chlorophyll in the plant that is charged with the task of
capturing the sunlight. Research has shown that chlorophyll
taken from plant tissue and placed in an acidic environment below
pH 3.0 becomes bleached and is no longer capable of performing
its functions. It has not yet been determined, however, whether
chlorophyll in the plant will react in a similar manner.
A second influence of acid rain on photosynthesis has been
definitely demonstrated—certain plants have shown a clear and
significant reduction in carbohydrate production as a result of
being exposed to acid. A decrease in carbohydrate producton can
result in alteration of those parts of the plant that are organs of
carbohydrate storage—seeds, fruits, roots, tubers, etc., which are
those plant parts most often used for food.
21
-------
But, not all acid rain effects on vegetation have been deemed
destructive. It is known, for example, that nitrogen and sulfur in
precipitation can, in limited concentrations, be a beneficial nut-
rient to some ecosystems. In fertilized agricultural systems the
nitrogen might only be equivalent to a small part of the amount
assimilated annually, but in pristine forests and in low-organic-
content lakes, the nitrogen input from acid rain might represent a
significant amount of the total nitrogen required. In fact, in a
typical loblolly pine forest in the southern United States, about
40% of the nitrogen comes from the atmosphere.
Acid Rain and Man
Made Objects
Sandstone sculptures erected in Germany in 1702 and photo-
graphed in 1908showed no noticeable deterioration, although
the sculptures were over two centuries old. By 1969, however,
they were substantially eroded. The interactions between the stat-
uary and air pollution (SOX, NOX, acid rain and dry deposition)
are thought to be chiefly responsible. Why?
When stone weathers, atmospheric gases dissolved in water or
water vapor react with the stone's surface to form a chemically
active solution. This solution and the products it forms then either
seep into the stone or mix on the surface with environmental soot
to form an ugly crust. When the crust is washed away by precipita-
tion it takes a layer of stone along with it. Statues lose their detail
and stone buildings are sapped of their structural integrity.
This weathering process is greatly accelerated when the atmo-
sphere contains SO2 or NOX and rains are acidic. The SO2 trans-
forms calcite in the stone into gypsum, which is much more
soluble in water. The resulting black sulfate crust—a mixture of
calcite, gypsum, fly ash, silica and other pollutants—is then easily
washed away by an acid rain and fresh stone is laid bare for further
attack.
22
-] Acid rain, or dry
deposition falls
Crust forms
Crust washes off
Layer of stone is
removed
-------
A link between corrosive damage to steel and SO2 has also been
established. In a recent study, different types of steel were exposed
to a variety of pollutants for between 4 and 64 months. The results
indicated thepresenceof SO2as themajorcauseof corrosion. Even
zinc, long used in galvanizing to protect metals such as steel from
corrosion, has itself been demonstrated to fall victim to industrial
air pollution where chiefly sulfates work to destroy its protective
covering.
Paint manufacturers have also acknowledged problems caused
by acid rain in many parts of the country. Industry spokesmen
attribute the problem directly to the chemical fallout of sulfuric
acid. Oil-based and automobile finishes have been demonstrated to
be particularly vulnerable.
The direct biological effects of acid rain on humans have yet
to be established. Some experiments investigating lung
responses to acids are currently underway to determine the
human body's tolerance to the effects of acid mists. And there are
other questions: What about acid rain and effects on human skin
or hair? At what pH level do we feel the acid? If acids cause burns
on leaves at pH 3, what pH level will cause burns on humans? Most
environmental health scientists believe that we are more threa-
tened by the pollutants we breathe than those that rain down on us.
The heavy metals released by acid rain, however, do present a
potential threat to human health. Recently researchers at Colorado
State University and the University of Southern Florida detected
minute amounts of mercury compounds in rainfall which could,
when the rain is too acidic, be converted into toxic methyl mercury.
Furthermore, it is thought that as drinking water reservoirs
acidify, concurrent increases in heavy metal concentrations may
exceed public health limits. In New York State, for example, water
from the Hinckley Reservoir has acidified to such an extent that
when the water comes in contact with household plumbing sys-
tems, lead from soldered joints passes into the water at concentra-
tions that exceed the maximum levels recommended by the New
York State Department of Health.
Acid Rain and Effects
on Humans
Today the problem is still too elusive to quantify; there are
no hard dollar figures. The economic data on the amount
and extent of damage by acid deposition is very much
needed. Some important questions:
• How much will it cost to clean and preserve the statuary and
the buildings already weakened or marred by acid rain?
• How much of the tourist industry has been lost in the "forever
wild" Adirondacks? How many related industries suffer? What
other areas of the country are vulnerable?
Costs of Acid Rain
23
-------
• How much has acid rain already depleted the soil of nu-
trients? Which crops will suffer? Which farmers? Which related
industries?
• Can the forestry industry anticipate a steady decline in the
rate of forest regrowth and general forest productivity? What
about the price of paper? How will housing starts be affected?
Housing prices?
• How seriously are the life spans of cars and homes dimin-
ished by sustained acid rains?
• Will our food supply be diminished in the future?
• What will be the sustained loss to the sport fishing industry in
the higher elevations most affected by acid precipitation?
• What is the value of a child catching that first lake trout? How
shall we value his or her disappointment when fish can no
longer be taken from a lake?
Indeed, we do not yet know what will be lost and what the costs
will be. Nor do we yet know the most economically sound manner
of dealing with the problems caused by acid rain.
THE SOURCES
Acid concentrations in rain vary considerably in the U.S. In
the Northeast, sulfuric acid accounts for 65-70% and nitric
acid 30-35% of total acid in rainfall; near Denver, sulfuric
content is around 10%, while the nitric acid contribution soars to
80%. Both acids result from the by-products of the combustion of
coal, gasoline, and other fossil fuels. The primary purpose of this
combustion is for energy; the primary locations of this combustion
are in stationary sources such as electric utilities and in mobile
sources such as cars and trucks.
24
\
I '-•:&-<&: 4
/JIT" -~"-f ^-y
/A- "
'Vv-oV
Acid Rain Analysis
If you were to analyze a
single sample of even
highly acid rain, you would
be reassured to find that it
was almost totally water.
You'd also discover that the
actual acid components of
the rain were truly minute,
even relatively weak.
However, the amounts and
concentrations of acids we
detect and measure are far
greater than those acids
that occur naturally on the
earth's surface. Their
existence then leads to a
single and obvious
conclusion: these acids are
the leavings of some less
than natural phenomenon.
That unnatural
phenomenon is, to a great
extent, the combustion of
fossil fuels.
-------
The major man-made sources of SOX and NOX are largely
upwind of affected areas, and analyses of air-mass trajectories have
demonstrated a high correlation between acid rain and storm
tracks that have passed over areas where high levels of combustion
take place. Ironically, actions taken to reduce local pollution prob-
lems from this combustion (e.g., tall stacks) may have also con-
tributed to the acid rain problem. In the mid-fifties, for example,
when smog killed thousands in England, tall stacks were built by
polluters. The English air cleared but acid rain problems in Scan-
dinavia and Western Europe worsened.
The lessons: Without a clear and complete understanding of
how pollution spreads, new problems can be created as old ones are
solved; and, changing the distribution rather than the amount of
pollution may just shift the problem from one location to another.
GLOBAL HUMAN-CAUSED SOx EMISSIONS
14% Petroleum Refining and
Non-Ferrous Smelting
Petroleum Products
Combustion
70% C031 Combustion
NORTHERN HEMISPHERE
7% SOUTHERN HEMISPHERE
Estimates of total global annual emissions of sulfur, the
major acid rain constituent, vary widely, ranging anywhere
from 140 million metric tons to 220 million metric tons.
Estimates also vary between those man-made emissions from sta-
tionary sources and those from mobile and miscellaneous sources.
Furthermore, the literature cites some figures for SOX—the total
sulfur oxide category—while other figures refer onlyXto SO2, the
most common oxide (95-98%) resulting from the burning of fossil
fuels. Consequently, information based on the estimates is often
disparate and confusing. The following numbers, nevertheless,
represent a certain consensus in the scientific community.
Between 25% and 50% of total global SOX emissions released into
the atmosphere annually are man-made. Over the Earth's land
masses, however, these man-made sources may account for more
than 50% of the total annual sulfur released. Of these emissions,
70% result from coal combustion, 16% from petroleum products
combustion (primarily residual fuel oils), with the remaining 14%
accounted for by petroleum refining and nonferrous smelting.
SOX-How Much,
Where, Why
25
-------
Man-made SOX emissions in the United States during 1977
totalled 27 million metric tons. Of that amount, 75% originated
east of the Mississippi River, and of that, 92% was emitted in the
vicinity of the Ohio river valley as a result of fossil fuel combus-
tion. Of the 25% emitted west of the Mississippi River, fuel com-
bustion was responsible for 38% while industrial and mining and
smelting processes contributed the remaining 62%.
NOX—How Much,
Where, Why
A Coal is a Coal is a Coal.
Or is It?
Part of the problem
posed by an energy
program that depends on
America's plentiful coal
supply is that there is no
"typical" coal on which to
base combustion
technology or controls.
Each region's coal varies
widely in heat value per
ton, and moisture, ash, and
sulfur content. Many
Western coals, for example,
are lower in sulfur content
than Eastern coals. But
they are also lower in
heating content. Thus,
more Western coal has to
be burned to create the
same amount of heat.
But, those coals most
economical to burn to
reach a desired degree of
heat may not be the ones
which will produce the least
amount of sulfur in the air
and acid in the rain.
26
The same cautions that apply to the quantifying of SOX
emissions also apply to NOX only more so. Overall emis-
sions figures for NOX (man-made and natural) are diffi-
cult to come by and are often widely disparate. Estimates of the
human contribution to global NOX emissions range from a small
percentage to as much as half. It must be remembered, however,
that human NOX emissions are highly concentrated at specific
locales whereas natural sources (e.g. decaying matter) are widely
dispersed. The United States contributions to worldwide man-
made totals during 1977 was approximately 23 million metric
tons, again, mostly from the combustion of fossil fuels. There is
some disagreement about whether the major NOX sources are
stationary (industrial and utilities) or mobile (cars and trucks),
however, the best available figures show that of the U.S. total,
approximately 56% of NOX emissions result from stationary fuel
combustion, one half of that from the generation of electricity. The
balance resulted mostly from the exhausts of cars and trucks.
-------
In the future, it is estimated that stationary source emissions
could double with the increased use of coal for industrial power
generation. As it is, NOX emissions have greatly increased in the
last twenty years thus the role of NOX in the overall acid rain
problem has also been on the increase. The reason? Adequate
alternate fuels or control measures for stationary combustion sour-
ces have been available only for SOX and not for NOX emissions.
Thus, while many large operations show a decrease of sulfur
emissions, NOX levels are maintained, resulting in a change in the
nature of air pollution and of acid rain. And while man-made NOX
emissions may account for only a portion of total global emissions!
an important footnote to any NOX emission discussion is that in a
nationwide study of precipitation chemistry, it was found that the
nitrate components of acid rain were almost entirely the result of
human activity.
Mobile sources
44%
Stationary sources (50%
Electricity generation)
56%
TOTAL MAN-MADE NOx EMISSIONS IN THE U.S. IN 1977
After all the effects are measured and all the logistics and costs
of acid rain "cures" considered, it appears that the only
truly practical approach to the problem lies in reducing
SOX and NOX emissions. Many innovative schemes have been
suggested, from altering production and combustion to recovery
and conversion of sulfur. There are studies underway to estimate
the costs of various ways to reduce SOX and NOX emissions. These
costs, of course, must be weighed against the costs of damage due to
aad rain which are now only beginning to be understood.
Controlling the
Sources
27
-------
Currently, there are three general options for the further reduc-
tion of many SOX and NOX emissions. Some are costly, others not.
Energy conservation resulting in reduced fuel consumption.
Conservation via more efficient fuel use and through improved
thermal insulation, etc.
Desulfurization and denitrification of fuels or stack gases and
increased use of fuels naturally low in sulfur content or use of
technologies that reduce emissions.
Substitutions for fossil fuels by other alternatives.
Conservation, however, may achieve only slower emissions
growth rates and low-sulfur fuels are in short supply. Desulfuriza-
tion and use of low-NOx-producing technologies are viable con-
trol options now and will probably continue to be for some time;
substitutions of energy forms are also future solutions to problems
posed by SOX and NOX emissions.
SOX Control
A number of techniques to reduce SOX emissions are already
on the commercial market or are in developmental stages.
These techniques are categorized by the stage at which they
occur in the energy-production process:
• Pre-combustion—here the sulfur content is removed before
the fuel is burned; techniques include coal cleaning, coal gasifi-
cation, and desulfurization of liquid fuels;
• Combustion—the sulfur content is removed during combus-
tion, as in fluidized-bed combustion;
• Post-combustion—sulfur emissions are removed after com-
bustion, as in stack or flue gas desulfurization systems or
scrubbers.
Some of these techniques such as coal cleaning and flue gas
desulfurization are in full scale use, while others such as fluidized-
bed combustion are still being tested in small scale applications.
The future of SOX control from traditional fuel sources lies in the
perfection of these techniques.
NOX Control
28
or reducing NOX emissions from stationary combustion
sources, the only practical means commercially available in
the United States today involves modification of furnace and
burner design and/or modification of operating conditions. The
modifications generally attempt to reduce the combustion temper-
atures because at lower flame temperatures less NOX is formed.
The combustion modification techniques now available include
staging combustion, precisely controlling air, injecting water dur-
ing combustion, recirculating flue gases, and/or by altering design
of firing chambers.
-------
Mobile combustion sources of NOX are currently being reduced
through a variety of approaches. To date the primary technique for
reducing automobile NOX emissions has been by lowering com-
bustion temperatures in the engine. Today, however, most atten-
tion is being focused on catalytic removal of NOX from exhaust
using a 3-way system that reduces carbon monoxide, hydrocar-
bons, and NOX simultaneously.
The long-range transport of acid rain constituents across
state and national boundaries presents a tough and chal-
lenging legal problem. Historically, most state and federal
laws regulating SOX and NOX emissions from stationary sources
assume that a cause and effect relationship can be established
between emissions and pollution, i.e., that pollution in a locale
can be traced to a specific emissions source in the same general
locale. Local laws with local provisions for enforcement do not
take into account the damage caused in states (or countries)
hundreds of miles downwind of pollution sources.
The existing Clean Air Act is structured around a similar cause
and effect supposition that air pollution can be related to a particu-
lar source or to a well defined group of sources. But, in the case of
acid rain, there is no clear cut relationship between specific emis-
sions and the acid rain. That is, even though the types of emissions
that lead to acid rain are known, it is currently not possible to
accurately trace individual emissions that cause acid rain back to
their origin.
How, then, is this regional air pollution to be controlled? What
is the best control strategy? And what is the appropriate legal
mechanism to use? These are some of the key questions with which
EPA and other environmental regulatory groups will be grappling
for the next few years.
The Clean Air Act has, in recent years, evolved to address the
interstate problem of pollution. In 1970, the Clean Air Act gave
individual states primary enforcement responsibility. Each state
was required to set up State Implementation Plans (SIPs) with
emissions limitations sufficient to meet national ambient stan-
dards. States, however, were responsible only for controlling pol-
lution within their own borders. For this reason, it is now common
to find emission limitations of one state to be more lax or stringent
than those of a neighboring state. The 1977 Clean Air Act amend-
ments added requirements that SIPs contain provisions prohibit-
ing any source in the state from preventing attainment or mainte-
nance of a national standard in another state or from interfering
with another state's efforts to prevent deterioration of air quality or
to protect visibility. These provisions, however, still rely primarily
on the state-based SIPs for enforcement. Any given state is only
able to enforce its SIP requirements against sources within its own
boundaries. The 1977 amendments also provide that affected states
can petition the EPA Administrator to control pollution. The
major problem facing EPA, however, is how to demonstrate that
one or several out-of-state sources are responsible for impermissi-
THE LEGAL
ISSUES
29
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States Take Action
In 1979, New York State,
along with other states
protested a proposed
relaxation of emission
limits pertaining to two
Ohio river power plants. In
the protest, a New York
official asks that air be
regarded as "a flowing river
which can transport
contaminants from one part
of the nation to another.
Airshed boundaries must
be reevaluated to make
sure all states live up to the
same clean air goals."
30
ble air quality violations. Several questions arise concerning such
a demonstration. For example, how can the demonstration be
made? Will the demonstration withstand a scientific and legal
challenge? And isn't it possible that the effects experienced in the
Adirondacks are the cumulative effects of emissions from a number
of sources in a number of states and nations? The demonstration,
in any event, is hard to make. If an acceptable demonstration is
made, however, some action must be taken against the polluter.
To control acid rain EPA must determine how to best use the
existing mechanisms of the Clean Air Act in order to develop a
control strategy that will deal effectively with interstate pollution
impacts.
One possibility is better monitoring of SO2 emissions, which
will permit improved enforcement of emissions limitations.
Another possibility is establishing federal regulatory requirements
for review of interstate impacts of SIP provisions. Yet another
option is developing national ambient air quality standards for
nitrates or sulfates, two precursors of acid rain. However, it is not
clear if there are sufficient scientific data upon which to base such
standards. Moreover, even if data were available, standards for
these pollutants would have to be established through the lengthy
standards-setting process. Estimates are that it would take five to
ten years before any emission reductions could be achieved. A
fourth option is for EPA to establish new source performance
standards for pollutants for which EPA has not set ambient stan-
dards and then establish control requirements for emissions of
these pollutants from existing sources. In this way, existing sour-
ces of emissions of total sulfur, a pollutant which includes sulfur
dioxide and for which EPA has not set ambient air quality stan-
dards, might be regulated. EPA is reviewing these and other
options to determine which are most appropriate to address the
acid rain problem.
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In Sweden ...
Researchers have
calculated that 70% of the
sulfur in the atmosphere in
the southern part of the
country comes from human
activity. . .
. . . and 77% of this sulfur,
it is thought, comes from
sources outside Sweden.
The Clean Air Act deals with the question of international air
pollution. It permits the Administrator of EPA to trigger a revision
of a State Implementation Plan if the Administrator or Secretary of
State has reason to believe that emissions in a state cause or con-
tribute to air pollution that may reasonably be anticipated to
endanger public health or welfare in a foreign country. The plan
must be revised to the extent it is inadequate to prevent or elimi-
nate the endangerment. A reciprocity clause limits the section's
application to those foreign countries that have given the United
States essentially the same rights of pollution control as the United
States has given these countries under the international air pollu-
tion provision of the Clean Air Act. In addition, through agencies
like the United Nations Economic Commission for Europe (ECE)
and bilateral negotiations, the problems caused by transboundary
air pollution between the United States and Canada may be
resolved.
Acid rain research is presently being conducted by many
governmen t agencies and by private industry. Those directly
involved include in addition to EPA: the Electric Power
Research Institute, the Forest Service, the Fish and Wildlife Ser-
vice, State Agricultural Experiment Stations, the Geological Sur-
vey, the National Science Foundation, the National Oceanic and
Atmospheric Administration, the Department of Energy, the Ten-
nessee Valley Authority, and many research institutions, universi-
ties, and industry groups.
EPA AND ACID
RAIN RESEARCH
31
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Within EPA, two overall themes provide a framework for ongo-
ing research and development. One, EPA must communicate to
Congress and to the public the effects of acid rain, with special
attention paid to the ecologic and economic consequences of con-
tinued high levels of acid precipitation. Two, EPA must continue
to generate additional information that can be used to develop air
quality control strategies and options.
In his second environmental message, President Carter identi-
fied acid rain as a major global environmental problem and pro-
posed a multiagency 10-year plan for research into the subject. The
plan establishes an Acid Rain Coordinating Committee consisting
of seven federal agencies. The Committee is co-chaired by repre-
sentatives from the U.S. Department of Agriculture and from EPA.
The 10-year plan is for vital research; vital because today acid
rain knowledge is insufficient to provide a thorough understand-
ing of the nature of the problem. What is known, however, is that
acid rain is a global problem that results in a key inequity: the
populace of one state or country enjoys the economic and indus-
trial benefits that are derived from energy production, while those
in other locales and not benefitting must pay the price of the
consequent pollution. As international boundaries are crossed, the
resolution of such inequities grows more and more complex.
Currently, EPA is working together with many other agencies to
gather and interpret the scientific information necessary to dem-
onstrate the impacts of acid rain and to establish which controls
would be most effective in alleviating these impacts. These pro-
grams are designed to: (1) monitor the sources and deposition of
acid-causing pollutants, (2) discover and model the means of
transportation in the atmosphere including the chemical reactions
that take place in the air and (3) determine the environmental
effects that are caused when acids rain upon piants, animals,
property and people. EPA has published a summary of its acid rain
research program (see Research Summary Acid Rain, EPA-600/
8-79-028).
32
NATIONWIDE ACID PRECIPITATION MONITORING STATIONS
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EPA's function in future acid rain research will be to ensure
coordination among federal agencies and state and private research-
ers; EPA will also help to plan the roles for research and for
amelioration and regulatory policies. Additionally, EPA's techni-
cal role will be to collect data, conduct experiments, and arrive at
the scientific conclusions needed for future acid rain decisions.
President Carter also spelled out the need for public participa-
tion in the acid precipitation issue when he directed the Acid Rain
Coordinating Committee to "actively solicit public involvement
in us planning and reviews of the research results of the Commit-
tee's program . . ." This directive will help to ensure that future
research directions by EPA and other agencies will speak directly
to the needs and best interests of the American people. It also serves
as an impetus to EPA to communicate its research information in a
manner that will support public debate about this important
problem.
Future research on acid precipitation and its effects in the
United States must be built upon past data and on previous
efforts to study the problem both in North America and
abroad. Past EPA research relevant to acid rain includes programs
to help discern how atmospheric sulfur products move long dis-
tances, technology development programs to devise means to con-
trol the sulfur at the source, investigations into the effects of acid
rain, and establishment of networks for rainwater collection and
analysis to monitor pollution dispersion.
Many specific decisions about research and development efforts
will need to be made in the future. Building on already available
data some potential research directions are:
• Investigation of the causes of the widespread acidification of
rain in the eastern United States over the past 20 years;
• Exploration of the rate at which rainfall is becoming more
acid and the rate at which the problem is becoming geographi-
cally more widespread;
• Examination of the quantitative contributions of various
acids, especially nitric acid, to the overall acidity of rainfall;
• Investigation into the relative extent to which the acidity of
rainfall in a region depends on local emissions of sulfur and
nitrogen oxides versus emissions transported from distant
sources;
• Survey of the continent-wide extent and severity of acidifica-
tion of aquatic and terrestial ecosystem;
• Collection of baseline data to establ ish the point of departure
for monitoring and measuring the effects of continued acid
precipitation;
• Determination of the pH tolerance of aquatic organisms,
forest and orchard trees and agricultural crops;
• Development of diagnostic tests for acid injury to plants and
animals and man;
Potential Research
Directions
33
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• Continuation of whole ecosystems studies for further infor-
mation on nutrient cycling chemical budgets;
• Examination of synergistic effects of pH and heavy metals,
disease, etc.;
• Investigation of the mechanism of toxicity of acid precipita-
tion to fish and other aquatic organisms;
• Studies on the impact of acidic snowmelt on stream and lake
biogeochemistry;
• Analyses of economic damage to sensitive ecosystems and
materials.
ACID RAIN
TOMORROW
34
With oil in short supply in the United States and many of
our foreign oil sources becoming less secure and ever
more expensive, the rush is on to exploit our national
coal reserves. Whatever energy plan is ultimately adopted, it will
include the burning of coal—and a lot of it. What does this mean to
acid rain?
As utilities convert to coal, SOX emissions could be reduced,
remain somewhat constant or increase, depending on a number of
variables. The technology exists to burn coal cleanly, and a
number of control alternatives are possible, ranging from low-cost
coal cleaning to the installation of stack gas scrubbers. Early
retirement of existing oil-fired plants and replacing them with
new, better controlled, cleaner coal-fired plants would yield a net
reduction in emissions.
Today also, a number of oil-fired plants are capable of burning
coal. These can be converted back to coal without an increase in
regional SOX emissions provided the best available control tech-
nology is applied during the conversion. At today's oil prices, in
fact, it is estimated that it costs more to run many existing plants
with oil than it would cost to convert them to coal and install good
pollution control equipment.
Equally important is the question of the nitrogen oxides that
will be emitted from these plants—old and new, converted or
not_and from cars and trucks in the future that continue to burn
fossil fuels. Less is known about NOX emissions effects, yet, NOX is
a key constituent of acid rain. And with increased fossil fuel com-
bustion, and less stringent controls in force than for sulfur, there
will probably be relatively more NOX in our rain in the future.
The future? We have already seen acidified lakes no longer able
to support fish populations and other aquatic life. We have seen
the faces of buildings and the faces of statues lose their integrity.
We have, after all, already witnessed a rainfall in this country of
pH lower than 3.0, a rain more acid than vinegar. Without a firm
commitment both to developing improved pollution control
methods and to applying those methods rigorously, the problems
of the past could be a prelude to an acid rain future.
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Research Summary Acid Rain, EPA-600/8-79-028, prepared by the
Office of Research and Development/ Environmental Protection
Agency (October 1979)
A companion document to this Decision Series report, the Sum-
mary offers a complete but concise description of the EPA acid rain
research program. The three major program categories-
environmental effects, monitoring and atmospheric processes-
are described and individual projects are listed.
A National Program For Assessing The Problem of Atmospheric
Deposition (Acid Rain), prepared by the National Atmospheric
Deposition Program, (December 1978)
A study funded by the President's Council on Environmental
Quality, the report sutnmariz.es the issues facing researchers and
regulators. Background information chapters are authored by
noted experts; research programs are recommended. A good source
of accurate up-to-date scientific information.
Environmental Effects of Increased Coal Utilization: Ecological
Effects of Gaseous Emissions from Coal Combustion, EPA-600/7-
78-108, an Interagency Energy /Environment R&D Program Report
prepared by the EPA's Environmental Research Laboratory, Cor-
vallis, Oregon (June 1978)
A brief evaluation of air pollution impacts from coal combustion
on ecosystems and the environment. Acid precipitation is specifi-
cally considered. The report provides a preview of potential effects
as more coal is burned in America.
The Multistate Atmospheric Power Production Pollution Study
-MAP3S, DOE/EV-0040, prepared by the U.S. Department of
Energy, Office of Health and Environmental Research (July 1979)
A very detailed report about work which has taken place to under-
stand the transport, transformation and fate of air pollutants from
energy activities. An excellent annotated bibliography covers the
literature on the subject.
Proceedings of the First International Symposium on Acid Precip-
itation and The Forest Ecosystem, prepared by the U.S. Depart-
ment of Agriculture, Forest Service, Northeast Forest Experiment
Station, (1976)
A collection of scientific papers given at the symposium. Although
somewhat dated, many of the controversies that remain today are
evident in some of the differences between the papers. Some of the
papers are by foreign scientists, particularly from Sweden and
Norway.
Scientific Papers from the Public Meeting on Acid Precipitation,
by the Science and Technology Staff, New York State Assembly
(May 1978)
This set of papers is essentially an information update on acid
precipitation. Unfortunately, the general conclusion is that quan-
titative data are still lacking. The papers are for the most part,
short and readable.
35
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Proceedings: Advisory Workshop to Identify Research Needs on
the Formation of Acid Precipitation, EPRI EA-1074, prepared by
Sigma Research, Inc. for the Electric Power Research Institute,
Palo Alto, California, (May 1979)
A brief review of current information about the formation of acid
rain and some recommendations of research needed to gain a better
understanding of the problem. Relevant research projects now
underway are listed.
Ecological Effects of Acid Precipitation, EPRI EA-79-6-LD, pre-
pared by the Central Electricity Research Laboratories of England
for the Electric Power Research Institute, Palo Alto, California,
(December 1979)
A set of papers from a small group of scientists who have been
engaged in research about acid rain. Uncertainties about current
acid rain information are identified and crucial data gaps are
pinpointed.
Acid Rain, preprint 3598, by the American Society of Civil Engi-
neers, Environmental Impact Analysis Research Council for their
1979 Convention in Boston, (April 1979)
A collection of six talks given at the Convention. All six are
interesting, credible and very readable and give a nice overview of
the subject.
36
Credits for this report:
Richard Laska, Mark Schaefer, Dave Myers, Tom Parker, Bill
Wells, Phyllis Dorset, Jean McLean, Ken Altschuler, Marja
Wicker, Barry Scott-Walton
Cover photo by: Steve Snyder
Photo page 22 by: Ray Ellis
Technical reviews:
Professor Gene Likens, Cornell University; Professor Ellis Cowl-
ing, North Carolina State University; Dr. Robert W. Brockson,
Electric Power Research Institute; Dr. Gary Glass, EPA-Duluth;
Mr. John Backman, EPA-Research Triangle Park; Mr. Danny
Rambo, EPA-Corvallis; Mr. Dennis Tirpak, EPA-Washington,
D.C., Ms. Lydia Wegman, Office of General Counsel, EPA-
Washmgton, D.C., Mr. Ralph Luken, Office of Policy Analysis,
EPA-Washington, D.C.
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Additional copies may be obtained by writing to:
Publications
Center for Environmental Research Information
US EPA
Cincinnati, Ohio 45268
for sale from:
Superintendent of Documents
US Government Printing Office
Washington, D.C. 20402
Stock No. 055-000-00198-7
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