acid rain -- what do we know?

Illinois State Water Survey Department of Energy and Natural Resources -- (Reprinted 7-1-87)


This is the second in a series of pamphlets describing in popular language our research findings about water resources and weather in Illinois and current issues concerning them.

Elisabeth Panttaja Siebel is a graduate student in journalism at the U. of Illinois and a part-time Research Assistant at the Water Survey.

Richard G. Semonin is Assistant Chief of the Water Survey and former Head of its Atmospheric Sciences Section. He is also adjunct Professor of Meteorology in the Laboratory for Atmospheric Research at the U. oflllinois and serves on the Executive Committee for the National Atmospheric Deposition Program.


Acid rain is not new. it was first identified in 1872 by an English chemist, and Swedish meteorologists have been studying it since the 1950s. But only in the last few years has acid rain become a subject of intensive research in this country and a source of worldwide concern.

Acid rain is widely believed to have damaging effects on the environment --- from killing off fish and wildlife, to stunting forest growth and inhibiting agricultural production, to the erosion of buildings and statues. There is even some talk about acid rain threatening human health.

In 1980, President Carter's committee on Health and Environmental Effects of increased Coal Utilization called acid rain one of the major global environmental problems to face us in this decade, and public and private sectors have taken the problem to heart:

An automobile company recently issued a pamphlet describing how to treat paint damage caused by acid rain, and an Illinois farmer discovered that the warranty on his new roof would not be honored because the damage, the company said, had been caused by acid rain . . . .

The Illinois State Water Survey is the central data repository and research ooordinator for Illinois in matters related to water resources and weather. Its research and service programs encompass assessment and evaluation of ground, surface, and atmospheric water resources as to quantity, quality, and use. The Water Survey was founded in 1895 and in 1979 became a division of the lnstitute of Natural Resources (now the Department of Energy and Natural Resources).


What is Acid Rain?
Scientists measure the relative acidity or alkalinity of a substance on a so-called pH scale. with values ranging from 0 to 14. Very simply, pH is a symbol representing the concentration of hydrogen ions in a solution. Seven is the neutral point, at which a substance is neither acid nor alkaline. Distilled water has a pH of 7. Numbers greater than 7 refer to alkaline substances; numbers less than 7 to acids. Thus, ammonia has a pH of 12, while lemon juice has a pH of 2. The pH scale is logarithmic; meaning that for every whole number increment. there is a tenfold difference in the concentration of hydrogen ions.


Leyden note:
a "log scale" means that a pH of 3 is 10x more acidic than pH 4 --- and is 100 times that of pH of 5 (10 x 10). The Richter Scale of Earthquake intensity has the same "log" relationship between its numbers. So -- an EQ of 8 is 10x the power of EQ of 7. That's something to get all shook up about.

If you take a glass of distilled water and put it in a room at normal temperature, the water will react with carbon dioxide molecules in the air, creating a slightly acid solution. Its pH, formerly 7, is now 5.6.

Many early discussions 0 acid rain used the 5.6 pH value as the dividing line between acid and non-acid rain. This simple definition is no longer accepted and, in fact, no pH value has been agreed upon for use as the critical dividing line.

What is the pH value of precipitation unaffected by human activities?

Scientists have been trying to answer this question by measuring the pH values of the "purest" rainfalls they can find, but they have no easy answers. Some samples from the most remote parts of the world such as the Indian Ocean and the Amazon jungle have pH values between 4 and 5.31


Leyden note:
elementary schools in illinois -- including Mark Twain in Charleston, participate in an acid rain "watch" -- where they measure the acidity of the rain and via computer, send their data to a National Geographic collection depot in D.C. Elementary teachers had better know what this "stuff" is all about.
Not only do the pH levels of precipitation vary widely over relatively short time periods (and even within the same storm events), but they have also been shown to change significantly over relatively short distances.

In a study conducted by the Water Survey near St. Louis, Missouri, rain receptors were placed every three miles in a 900 square mile area. After fourteen rainfalls, the measurements taken at each receptor were averaged, and the resulting values in this one area ranged from 4.3 to 6.8. These findings suggest that determining what is natural and unnatural in the chemistry of precipitation is very complex. In addition, the pH measurement itself can often be a misleading guide to acidity.

A pH value is derived from the relationships between four individual substances in a solution:

Calcium Sulfuric acid
Magnesium Nitric acid

(There are other chemicals that affect precipitation chemistry, but these are the major contributors to acid rain.) Calcium and magneslum are the two alkaline agents, and the degree to which they exist in a solution directly affects pH levels. Low levels of calcium and magnesium will result in a low pH reading, just as high concentrations of acid will. Thus, before an accurate interpretation of a pH reading can be made, the occurrence of all four substances must be measured and compared.

American Acid Rain Research

Prior to 1972, only two comprehensive rain sampling networks existed in this country, and those but briefly. The first consisted of 67 ste tions and operated from July 1955 to July 1956. This survey provided data on a variety of chemical constituents of rainfall in that year, but it failed to record pH.
A second and smaller sampling network provided data, including pH, for rainfalls from 1965-66.

In 1974, two scientists from Cornell University, Cogbill and Likens, decided to compare pH calculations they made on the chemistry measurements from the two national networks. They used information from the 1955-1956 network to calculate the pH values of rainfall for that year.

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The results showed average values of 4.3-5.0 over most of the northeast. To the west and south, however, the pH values were higher. Cog-bill and Likens drew a line ringing that part of the northeast in which the pH was less than 5.6. They called the pH = 5.6 line the "threshold level" and used it as a way of identifying the extent of acid rain.

The data from 1966 again showed average pH values of between 4.3 and 5.0 for the northeast, but this time the threshold level of 5.6 was picked up farther south than before, and extended westward beyond the area of their study, implying that the acid rain problem had spread over our midwestern states.

In 1976, Cogbill obtained measurements of pH from many sites in the northeast for 1972-73. In 1972-73. the average pH values of rainfall stayed about the same, but the threshold level had moved farther south into Florida and north into Canada, implicating the entire eastern half of the United States in an acid rain situation.

A The trend seemed clear: acid rain was gradually spreading cross the country.

It was an alarming report. Acid rain had been perceived as a serious problem in Europe for decades. It had been linked to high levels of gaseous pollutants in the atmosphere, and Scandinavian research had already suggested its harmful environmental effects. The study by Cogbill and Likens was the first time that a trend of increasing acidity had been identified in this country, and it marked the beginning of the American acid rain problem.


Illinois Studies


In 1977, the atmospheric scientists at the Illinois State Water Survey conducted some tests in lllinois very similar to what Cogbill and Likens had done in the northeast. They used data they had collected in 1954 and compared it with their own local data from 1960 and 1977. The pH for 1954 was 5.6; for 1960, 4.7; and for 1977, 4.3.
Again, the findings indicated an increase in acidity over the years.

But the drastic drop in pH from 1954 to 1960 was suspicious. What had happened in those six years to so radically affect the chemistry of precipitation ?

Richard Semonin, Assistant Chief of the Survey, and his colleagues went back to the data. This time they broke the compositions of the various rainfalls down into the four basic parts -sulfates, nitrates, calcium, and magnesium -and compared them. They observed that the amounts of sulfuric acid in rainwater had not increased over the years, and that while the amounts of nitric acid had increased, they had not changed significantly enough to explain the plunge in pH.
What the Survey scientists did notice was a substantial drop in the amounts of calcium and magnesium, the two alkaline substances (whose absence can make water acidic).

---- Ca + Mg --- Sulfate -- Nitrate --- pH


1954 -- 65 -------- 60 -------- 18 ----- 5.6
1980 -- 37 -------- 60 -------- 15 ----- 4.7
1977 -- 10 -------- 70 -------- 30 ----- 4.3
Micro equivalents per 1iter
When pH values for Illinois were broken down into their four basic parts, it became clear that the drop in pH over the years was due, not to an increase in acidity, but to a decrease in alkalinity.

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Semonin delved into other records for 1954 and discovered that it had been a year of severe drought that affected both the northeastern and midwestern states. Dust storms were a common hazard that year, and one record states that at times the blowing dust reduced the visibility to 1/8 of a mile.

Dust is made up of loose topsoil, rich in calcium and magnesium. It falls as solid particles and also mixes with drops of moisture in the atmosphere and falls as rain. When measured on the pH scale, that rain was unusually alkaline, and the corresponding pH value was unusually high. So Semonin recalculated all the original data from the 1955-56 network. Only this time, where the levels of calcium and magnesium had been unusually high, he substituted more typical values. He discovered that, while the pH values of the northeast remained roughly the same, the pH measurements for the south and mid west were much lower, and the 5.6 threshold level that Cogbill and Likens had observed ringing the northeast did not occur. Semonin's new maps showed average pH levels ranging between 4.3 and 5.0 all across the country. In Illinois, the rainfall pH figure has historically been around 4.4, a value consistent with what has been measured in the state this year. (pH levels since 1978 have been 4.3-4.5 all across the state.)

These findings cast serious doubt on the alleged trend in acidity from 1955-1972. In addition, many scientists argue that data used for acid rain trend analysis should come from the same sites and same type of receptors, and be derived using the same analytical techniques. In the Cogbill and Likens study, both the receptors and the chemistry used to measure the rain were variable. In addition, only ten stations are common to both 1956 and 1966 (for those ten common sites, the acidity increased at four, decreased at two, and remained unchanged at four) and only three stations are common to all three networks.




Environmental Effects of Acid Rain

The media have been instrumental in publicizing the environmental effects of acid rain. Filmstrips show how acid rain damages crops, magazine articles talk about the corrosion of buildings, arid newspaper stories point to "dead" lakes, victims of acid rain. Yet anyone wishing to dig beneath the surface of these reports will find that the scientific facts, when they are known, are neither so simple nor so clear.

The two most important potential hazards of acid rain are damage to aquatic ecosystems and decreases in agricultural production. The suggested effects of acid rain on lakes and fish are quite alarming and have received the most attention.


Effects on Lakes

The average pH of a freshwater lake is usually quite high - between 8 and 9.
When even "pure" precipitation has a pH of 5.6, one wonders how the lakes can maintain their low levels of acidity. There are two main reasons, and both have to do with soil: A lake's "watershed" is the geographical region surrounding the lake, and any precipitaton that falls in the watershed area ultimately drains into the lake. When the watershed is large, the rain travels a long distance before it reaches the lake, and the soil it passes over and through, usually rich in calcium and magnesium, acts as a buffering agent to neutralie the rain's acidity. The soil and rocks that make up the bottom and sides of the lake have the same buffering effect and help to maintain the lake's low level of acidity.

Lakes in the Adirondack region of New York and in various parts of southern Ontario and Ouebec, with their unusually low pH readings, have typically been singled out as examples of the harmful effects of acid rain. These lakes are virtually carved out of granite and do not have the benefit of large amounts of soil in their relatively small watersheds to act as buffering agents.

Do the geological characteristics of the Adirondack and Canadian lakes make them more vulnerable to outside acidification, or are these factors in themselves the cause of the low pH readings? The answer to this question is crucial to the study of acid rain's effects on acuatic ecosystems. Until we know the chemical history of these lakes, it is almost impossible to judge whether a low pH reading is natural or man- made.

At this moment, scientists are conducting chemical studies of the layers of sediment buried beneath the Adirondack lakes. They hope to uncover the historical data so necessary to determining whether or not the lakes have undergone chemical changes and what role, if any, acid rain has played in the process.

In Illinois, rivers and streams have been chemically tested for a period of years. Scientists have measured no trend of increased acidity, and no harmful environmental changes have been noticed. Illinois watersheds are large and well-buffered, and it is unlikely that high acid levels will ever pose a serious threat to our aquatic ecosystems.

Illinois watersheds are large and well-buffered, and it is unlikely that high acid levels will ever pose a serious threat to our aquatic ecosystems.


Leyden note:
Note that term, buffered ? How about "bufferin" - - the OTC drug for headaches; etc. Do you suppose there is a connection ? A buffered solution is one that essentially can maintain a constant pH ( unless severely chemically upset ).
Effects on Fish

Scientists usually consider the first danger signal of acidification to be a decrease in fish populations, and many people have suggested that acid rain is responsible for the complete disappearance of thousands of fish from our lakes, especially game fish such as trout which have been shown to be highly 'acid sensitive.'

Although very few studies have been carried out in natural settings, laboratory experiments have proven that large quantities of sulfuric acid released into fish tanks can affect the reproductive organs of fish, and in higher quantities, the acid can be lethal. Research has also shown that acid water is especially damaging to fish eggs and hatchlings and that acid in lakes and streams reacts chemically with surrounding rocks, releasing aluminum and mercury ions that can be harmful - and even deadly - to fish.

After this point, however, scientific consensus breaks down. Many scientists feel that the laboratory experiments are sufficient to establish the link between acid rain and decreased fish populations; other experts think that documented field studies are necessary to support these claims.


Until many more questions can be answered, it wlll remain difficult to efther prove or disprove the llnk between acid rain and changes in fish populations and aquatic ecosystems.
These latter scientists point to the fact that the pH levels of lakes vary naturally, and many species of fish that have lived in lakes for generations have experienced numerous changes in pH without being noticeably adversely affected. In addition, acid precipitation is not the only cause of a drop in pH, and not all drops in pH are harmful to fish.

The most radical changes in acidity usually occur during winter thaws or spring, when acids and other substances contained in snow are released rapidly into streams and lakes as melt-water. In Norway, there is at least one documented instance of a massive fish kill resulting from a radical drop in pH in a stream. Even in these dramatic instances, the connection between increased acidity and decreased fish populations is unclear.

In this country, there have been no reports of fish kills resulting from drops in pH. There have been reports of decreases in fish populations, but the cause is a matter of conjecture. The past twenty years has seen such varied atmospheric and climatological changes, and fish populations can be influenced by so many factors, that many scientists feel that a direct cause effect relationship . . . .


Leyden note:
Remember the 'what is science' discussion about -- cause - correlation and coincidence ? Hmmm - which is at work here ?
. . . . between acid rain and decreased fish populations is unrealistic. A lack of historical data compounds the problem, making it difficult to tell the exact extent to which game fish populations have decreased over time, and what other species, if any, have been affected.

Until many more questions can be answered, it will remain difficult, if not impossible, to either prove or disprove the link between acid rain and changes in fish populations and aquatic ecosystems.


Effects on Soil and Agriculture

In Illinois, the most critical aspect of the acid rain issue is its alleged harmful effects on soil and agricultural production. Here the scientific evidence comes almost exclusively from laboratory tests. Simulated acid rain has been shown to cause an impressive array of biological and chemical changes in plants and soils. Sometimes these changes are harmful, sometimes beneficial. Some results are even contradictory: Soybeans treated with acid water, for example, exhibited both decreases and increases in size and rate of growth.

Among other things, simulated acid rain causes lesions on foliage and slows the rate of many important microbiological processes in soil. It is also a good fertilizer and adds significant quantities of nutrients to both plants and soils.

In nature, actual economic damage to crops or soils due to polluted precipitation has been reported only rarely, and in most cases the evidence has not been considered scientifically reliable. Most scientists agree that examples of soil deterioration or crop damage caused by acid rain have not been found. Even if evidence of crop or soil damage did exist, it is unlikely that Illinois agricultural production would be affected. The Illinois soil is alkaline and wellbuffered, meaning that it has plenty of natural chemicals to offset high acidity levels should they occur.

Whether or not the net effect of acid precipitation will be harmful or beneficial in any geographic area seems to depend on a variety of interrelated factors, among them the chemical composition of the rainfall, its duration and intensity, and the general condition of the lakes and soils on which it falls.

Research suggests that acid rain is most likely to wreak ecological damage in areas with poorly buffered soils or lakes that are subjected to long and frequent rainfalls. Other areas are not likely to be affected by acid precipitation, and some regions may even enjoy ecological advantages caused by acid rain.


Is acid rain a problem or not ?

Unlike standard climatic variable which are continuously and exhaustively studied, information about acid rain is scare and incomplete. The lack of data precludes a firm conclusion, but the little that we do know indicates that changes in the acidity of rainfall may be much more subtle than initially conceived.

so far, evidence coming out of Illinois has questioned the alleged trend of increasing acidity and has suggest that at least some instances of radical rain chemistry change may have natural, not man - made, causes.

over the next few years as research findings from groups such as the National Atmospheric Deposition Program and the National Acid Precipitation Assessment Program become available, many of the unresolve issues will probably be decided. At this time, however, the questions are far more numerous than the answers, and as acid rain remains in the public spotlight, it is increasingly important to separate scienctific facts from speculations.


NOTE:
this report is dates may 1981; revised dec 1984; reprinted july 1987. That was almost a decade ago. You'll need more modern references to supplement this report. Pages 7-8 omitted: topic: The NADP - national atmospheric deposition program / NTN - national trends network

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