Effect of Acid Rain in Soils - Tabatabai

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Effect of acid rain on soils

a b
M. Ali Tabatabai & R. A. Olson
a
Department of Agronomy , Iowa State University , Ames, Iowa
b
Department of Agronomy , University of Nebraska , Lincoln,
Nebraska
Published online: 09 Jan 2009.
To cite this article: M. Ali Tabatabai & R. A. Olson (1985) Effect of acid rain on soils, Critical
Reviews in Environmental Control, 15:1, 65-110, DOI: 10.1080/10643388509381727
To link to this article: http://dx.doi.org/10.1080/10643388509381727
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Volume 15, Issue 1 65
EFFECT OF ACID RAIN ON SOILS
Author: M. Ali Tabatabai

Department of Agronomy
Iowa State University
Ames, Iowa
Referee: R. A. Olson
Department of Agronomy
University of Nebraska
Lincoln, Nebraska
I. INTRODUCTION
Downloaded by [New York University] at 15:52 01 February 2015
Contamination of the biosphere with inorganic and organic chemicals has become a
subject of extensive concern in recent years. Among the various components of the
ecosystem, pollution of the atmosphere and soil and water resources has received the
most attention. Although point source pollution of the atmosphere and its effect on
agricultural crops, forests, soils, and surface water deserve the most attention, recent
publicity about acid rain has overshadowed the work on air pollution. The interest
within the scientific community in North America about the nature, causes, and effects
of acid rain increased rapidly within the past decade, and recently, the terms "acid
rain" and "acid precipitation" have become worrisome household words in the U.S.
The influence of industrial emissions on the health of humans and plants was first
observed by Evelyn1 in England in 1661. A recent review article by Cowling2 on histor-
ical perspectives of acid precipitation indicates that awareness of the acid rain problem
developed in many countries over more than a century ago. From work on the chem-
istry of rain in and around the city of Manchester, England, Smith3 was the first to
report on changes in precipitation chemistry in polluted air in the city to the country-
side. He reported the presence of (NH4)2CO3, (NH4)2SO4, and H2SO4 as one moves
from the fields at a distance to the suburbs and to the city. Although the term "acid
rain" was introduced by Smith in 1852,3 apparently without much scientific debate,
the current controversy would suggest that acid rain is a phenomenon of recent dec-
ades.
Although the term "acid rain" has been popularized by some scientists and the
media, the more inclusive atmospheric deposition is more appropriate. Atmospheric
deposition refers to materials — liquid, solids, or gases — that are deposited in wet or
dry forms from the atmosphere onto land and water surfaces. Wet deposition includes
materials incorporated in rain, snow, dew, fog drip, and sleet. Dry deposition includes
dry fallout of large particles such as sea salt, soil particles, fly ash, organic particles,
and aerosols or suspended compounds such as (NH4)2SO4 and NH4NO3. Gases such as
CO and oxides of S and N that are absorbed directly from the atmosphere by foliage,
soils, or bodies of water and other surfaces are also often included with dry deposi-
tion.4 Because it is much easier to sample and quantify than dry deposition, wet depo-
sition — material incorporated in precipitation — has received the most research atten-
tion and publicity. Dry deposition, especially near point sources (smokestacks and
feedlots), however, is a more serious environmental problem and must receive in-
creased attention.
The phenomenon of acid rain is not new. As long as water has been falling on the
surface of the earth it has probably contained varying amounts of oxides of C, N, and
S that decreased the pH of precipitation. This was certainly true at the early stages of
66 CRC Critical Reviews in Environmental Control
life formation when volcanism resulted in the widespread expulsion of elements into
the atmosphere.5 The acid rain phenomenon has been active for more than a billion
years.6 In addition to N2, O2, and CO2, normal air contains trace amounts of other
gases (e.g., CH4, N2O, CO, O3, NH3, NO2, and SO2). Natural airborne materials could
be acidic, basic, or neutral. The materials are produced by a variety of sources, includ-
ing animal- and man-derived contributions to the atmosphere from biological waste
production, domestic combustion, land use, deforestation, forest fires, desertification,
volcanic activity, and sea spray.7 The literature suggests that several hypotheses have
been accepted without much debate by knowledgeable scientists:
1. A pH of 5.6 could serve as a reference value for acidity of precipitation in un-

polluted atmosphere.
2. Relatively lower pH values, such as 4, result from anthropogenic strong mineral
acids.
3. The acidity of precipitation in the northeastern U.S. has been increasing during
recent years, and this is related to increased emission of anthropogenic acids to
the atmosphere.
4. Sulfate and/or nitrate in precipitation are a measure of acid deposition.7
In islands thousands of kilometers removed from industrial activity, and presumably

unaffected by it, rain with pH 4.7 is common. Soils having a pH of 3.5 are formed
without human participation in the process.6
Most of the allegations of the effects of acid rain on soils and crops are either based
on hypothetical and theoretical considerations or based on experiments with synthetic
acid rain under such extreme conditions — conditions that are highly unlikely to occur
even if rain acidity increases significantly. To my knowledge no in situ detrimental
effect of acid rain on soils or plants, attributed to increased anthropogenic deposition,
have been documented except for point sources (e.g., uncontrolled emission from in-
dustrial sources such as Sudbury, Ontario, Canada). Several sources of acidity contrib-
ute to the soil pH. These include H2CO3 formed from high CO2 concentrations in the
soil atmosphere produced from root and microbial respiration, acidity produced in
mineralization of organic N and S and from NHi-forming fertilizers, organic acids pro-
duced from litter decomposition, and atmospheric deposition. Therefore, the follow-
ing questions should be asked:
1. What is the pH of normal, unpolluted rain?

2. What are the sources of acidity in rain?
3. What is the significance of measuring the pH of rainfall?
4. What is the significance of H* activity in rainfall relative to those of other sources
that contribute H* to soil systems?
5. What are the sources of H* in soils?
6. What are the effects of pH on soil chemical and biochemical processes and on
plant nutrition?
7. What ranges of pH values are expected for agricultural and forested soils?
These and some other questions, will be discussed. At this point it becomes essential to
introduce the definition of pH and the significance of measuring rainfall and soil ac-
idity and the errors associated with these measurements.
II. DEFINITION OF pH AND SOIL REACTION
Soil pH is one of the most important parameters governing the chemical and bio-
chemical processes in soils. The soil reaction, whether acidic, neutral, or basic, would
significantly alter the solubility of various compounds, the relative bonding of ions to
exchange sites, the enzyme-catalyzed reactions, and the activity of various microorga-
nisms. The formation and transformation of clay minerals depends on soil reaction.
Consequently, plant growth is affected either directly or indirectly by the acid-base
reaction in soils.
There are three concepts of acid and base. These are as follows:
1. Acids are compounds that contain H and in aqueous solution produce H + , and
bases are those compounds that produce OH" in solutions. This concept was
developed by Arrhenius between 1880 and 1890. It is valid only for the definition
of acids because almost all acids contain H. The definition of bases under the
Arrhenius concept is, however, not necessarily valid because it is known that NH 3
and many organic substances exhibit characteristics of base compounds.
2. Acids are those compounds that are capable of donating protons. Therefore, by
definition, any compound that is capable of accepting a proton is considered a

base. This concept was developed in 1923 by Brçinsted and Lowry. According to
this concept, HC1 is an acid because it can donate a proton. After dissociation,
however, the remaining Cl~ is then a base because it can accept a proton. This
type of acid base is called a conjugate base of the acid HC1.
3. An acid is a compound that can accept an electron pair, and a base is a compound
that can donate an electron pair. This concept was developed by Lewis in 1923.
Reactions with clay minerals perhaps follow the Bronsted-Lowry concept more
and complex reactions involving organic matter apply only to the Lewis theory. 8
A combination of the Arrhenius and Br0nsted-Lowry concepts must be applied
to characterize the acid and alkaline conditions of soils. In acid soils, more H*
than OH" are present. The contrary is true in alkaline soils. The distribution of
H* and OH" in the soil solution is not homogeneous. Hydrogen ions usually are
adsorbed by soils more tenaciously than are the OH". Consequently, H ions are
concentrated at and near the negatively charged colloidal interfaces; therefore,
they become less concentrated as the outer portions of the water films are ap-
proached (double layer theory). Because OH" vary in number inversely with H + ,
this causes a higher p H in the outer moisture zones. Studies with chymotrypsin
in solution and adsorbed on kaolinite have shown the optimal activity occurs at
pH 7 and 9, respectively,' indicating the H* concentration on the surface of koal-
inite is 100 times greater than that in bulk solution at pH 9. Such variations in
pH of the soil colloidal and bulk solution have significant effects on enzyme-
catalyzed reactions and nutritional consequences in both microorganisms and
higher plants.
The term " p H " was introduced by S0rensen in 1909.1O The concept of pH is based
on the ion product of pure water, which dissociates very slightly: Kw = [H*] [OH] =
10"14 at 23°C, where Kw and [ ] indicate ion production of water and the activity of
each compound is indicated in moles per liter of solution, respectively. Since [H*] =
[OH"] in pure water at 23°C, each is equal to (lO" 14 )" 2 = 10"7. The pH of a solution is
defined as the negative logarithm to base 10 of the H* activity or the logarithm of the
reciprocal of the H* activity:
1
pH = -log,,,[H + ] = log,, (1)
[H + ]
Thus, the pH of pure water at 23°C is 7, whereas that of acid is <7 and that of a base
is >7. At 100°C the p H of pure water is 6 and at 0°C it is 7 . 5 . " Hence, it is essential
that p H measurements be made at about room temperature and that the pH meter be
adjusted to the temperature of the solution being measured. The sensing electrode
measures only the dissociated H*; therefore, undissociated H is not a part of the H*
activity and is not included in the pH measurement.
Temperature exerts two significant effects on pH measurements: (1) the electrodes
used vary in potential and (2) ionization in the sample varies. The first effect can be
compensated by an adjustment which is provided on most commercial instruments.
The second effect is inherent in the sample and is taken into consideration by recording
both the temperature and pH of each sample. This ionization, depending upon the
values of K, and K2 for H2CO3 as well as on Kw for H2O at various temperatures, is to
a significant extent related to the alkalinity of the sample. Increasing alkalinity reduces
the effect of temperature change on the pH. This affect is not a direct relationship and
can be quite pronounced even at low concentrations of alkalinity. Data for calculating,
by interpolation, the pH of natural waters at other temperatures than that of the meas-
urement are provided by Langelier.12 Information on the use and abuse of pH mea-
surements is available.13 Soluble acids are classified into strong acids (fraction disso-
ciated approaches 1) and weak acids (fraction dissociated is <1).
A number of compounds contribute to the development of soil reaction. Organic
and inorganic acids produced by the decomposition of soil organic matter and plant
litter are common soil constituents that may affect soil acidity. Also, respiration of
plant roots and microorganisms yields CO2 that will produce H2CO3 in water. Nitrifi-
cation of NH3 and NHt-forming fertilizers is a major source of acid in managed soils.
Water is another source of a small portion of H \ Depending on the soil environment,
a large portion of H* in soil is adsorbed by clay complexes as exchangeable H*, which
may dissociate into free H \ The degree of dissociation and ionization into the solution
determines the nature of soil acidity. Therefore, the exchangeable H* is defined as
potential or reserve soil acidity, which can be determined by titration. The H* is the
free acidity, which is measured and expressed as pH. Several factors, however, affect
the measured pH of soils. These include
1. The nature and type of inorganic and organic constituents that contribute to soil
acidity.
2. The soil to solution ratio.
3. The salt or electrolyte content.
4. The CO2 content.
5. Errors associated with equipment standardization and liquid junction potential"
A comprehensive treatment of the chemistry of soil acidity and lime effects in acid soils
has been prepared by Coleman and Thomas.14
III. SOIL FORMATION
In order to understand the relative effect of acid rain on soil, a brief summary of the
factors affecting soil formation is essential. A number of physical, chemical, and bio-
chemical processes are involved in soil formation and development. Hans Jenny15 de-
veloped the fundamental equation of soil-forming factors over 40 yeas ago, as follows:
s = f(cl,o,r,p,t ...) (2)
where cl, o, and r refer to the environmental factors of climate, organisms, and topog-
raphy, respectively. The remaining variables are p = parent material and t = time. The
dots indicate that, besides the variables listed, additional soil-forming factors may have
• Prairie
o Forest
4.0 _L
0 50 100 150 200 Cm
i |j i D O v O D y| \j Ul v O
Depth and Horizons
FIGURE 1. Comparison of pH values of soils developed un-

der prairie and under forest in Illinois. All other soil-forming
factors are identical. (From Jenny, H., Factors of Soil For-
mation, McGraw-Hill, New York, 1941. With permission.)
to be included in Equation 2. By holding the other factors constant, the effect of each
of these factors on certain soil properties is demonstrated.15 The effect of time on
CaCOj and H* concentration show inverse relationships; as CaCO3 is leaching out of
the soil system, the soil becomes more acidic. The amount of water percolating through
the solum greatly affects the process of soil formation. Considering rainfall as a factor,
several early investigators have shown that the percentage of N and percentage of clay
are positively correlated with the amount of rainfall, but soil pH is inversely correlated
with rainfall. Therefore, acidification of soils is a natural process.
Weathering of parent materials and the formation of soils is basically a combination
of destruction and synthesis. Two basic processes — mechanical and chemical — are
involved in soil formation and development. The former is disintegration and the latter
is decomposition. The disintegration process involves the effect of temperature (differ-
ential expansion on minerals, frost action, and exfoliation), erosion and deposition (by
water, ice, and wind), and influences by plants and animals. The decomposition proc-
ess involves hydrolysis, hydration, carbonation and related acidification processes, oxi-
dation, reduction, solution, and clay formation. Among the soil-forming processes,
the following have been defined and elaborated: calcification, podzolization, lateriza-
tion, salinization, desalinization, alkalization, dealkalization, and gleyzation, includ-
ing the formation of peat (highly acidic) and poorly drained soils.16
Similarly, by keeping the other factors constant, organisms have a significant influ-
ence on soil formation and properties. Figure 1 shows a classical example of the effect
of vegetation on pH of soils developed from loess under prairie (Grundy silt loam) and
forest (Rushville silt loam) in Illinois. In all horizons the pH is lower under timber than
under prairie. The lower A horizon and the upper B horizon are highest in acidity.
Near the zone of carbonate accumulation, the reaction becomes alkaline.
Cactus
arid
high evaporation Conifers
humid
^ / ^ .
Sage brush low evaporation
semiarid Short grass
subhumid
Permanently dry
substrata
Pedocals Pedalfers
o
Permanently moist substrata
FIGURE 2. Schematic diagram showing relation of climate and vegetation to soil development. (From
Thompson, L. M. and Troeh, F. R., Soils and Soil Fertility, 4th ed., McGraw-Hill, New York, 1978. With
permission.)
Soil is a dynamic system. Under natural environment, the upper layer of soil is es-
pecially subject to changes by many agents, including rainfall. This is the zone where
the plant roots are most active, where uptake of nutrients by plants is greatest with
concurrent release of ions from the inorganic and organic constituents to maintain the
chemical equilibria of the various components. Decomposition of organic matter in
this zone results in release of bases and inorganic and organic compounds, including
inorganic and organic acids. With time, these compounds significantly reduce the pH
of soils. Furthermore, each type of plant has its own subtle influence on soil properties,
especially pH, and the most dramatic differences are between grasses and trees. Some
of these differences are illustrated in Figure 2. Because of the magnitude of nutrient
cycling in the upper layers of soils and because of the extent of biological activities and
production of a variety of acids in this layer, the influence of rainfall constituents,
including acidity, other than point sources, should have no significant effect on soil
reaction. It is doubtful if the effect of acid rain with an annual pH = 4.2, such as that
in New York and Connecticut,1718 could be measured even in 100 years. Therefore, it
is not surprising that the field studies conducted in Sweden and Ontario, Canada
showed that podzol soils with pH values <5 changed little in pH during the period
from 1934 to 1973 in Sweden and from 1960 to 1978 in Canada.19-20
Most grassland soils are less acidic than forest soils because grasses thrive in drier
ecosystems where leaching is less intense than in forest ecosystems. Another important
factor is that grasses are generally more effective than trees at offsetting leaching by
recycling nutrient elements. The recycling process is especially significant for cations
such as Ca, Mg, K, and Na that are gradually leached from the soil. Grass leaves
generally contain more of these bases than tree leaves. Leaching these bases from soil
leads to soil acidification. Therefore, the A horizons developed under forests are usu-
ally acid. Their organic matter is more likely to be eluviated than that developed under
grass. In addition, certain compounds of Fe and Al are more soluble and leach much
faster in the acid conditions common under forests. The B horizons of forest soils may,
therefore, contain illuvial deposits of organic matter and/or Fe and Al compounds in

addition to or even in place of illuvial clay deposits. The extreme example of this is the
spodosol group.21
IV. SOURCES AND FORMS OF ACIDITY IN SOILS

A variety of sources contribute H* to soils. These include H2CO3 formed from high
CO2 concentrations in the soil atmosphere, H* formed in mineralization of native or-
ganic N and S, nitrification of N in NHî-forming fertilizers, organic and mineral acids
produced from litter decomposition, and addition in precipitation whether or not the
rain contains anthropogenic inputs.
Although the CO2 concentration varies somewhat from one location to another, it
makes up about 0.03% by volume of the atmosphere. Plant root and microbial respi-
ration increases its concentration in the soil atmosphere. The soil air often may contain
CO2 concentration exceeding 10% under certain circumstances, and CO2 concentra-
tions between 1 and 5% are very common.22"24 The relationship between water pH and
the H2CO3 system in natural waters, including soil moisture, is complicated, but in its
simplified form can be characterized by the proton condition:
[H+ ] = [HCO3-] + 2[CO|~] + [OH"] (3)
and the equilibrium concentrations:
-log[H + ] = -log[HCO3-] = 5.65 (4)
-log[CO2aq] = -log[H2CO.,] = 5.0 (as a nonvolatile acidity) (5)
-log[H2CO3] - 7 . 8 (6)
-log[COn = 8.5 (7)
CO2 dissolves in water, forming H2CO3 in direct proportion to the concentration (or
partial pressure) of CO2 in the surrounding air.
It is evident from the data in Table 1 that CO2 dissolved directly from the atmos-
phere or soil air lowers the pH of water markedly. It should be noted that soil water in
a pore containing 10% CO2 in the gaseous phase would be at pH 4.45 if it is not
buffered at a higher pH by the soil or neutralized by basic substances. Another source
of CO2 is that released when lime is added to acid-managed soils. Until this CO2 dif-
fuses out of the soil, the acidity is not completely neutralized.
Carbonic acid in soils dissolves various compounds and the H* released displaces
other cations from the cation exchange sites. Therefore, in addition to the direct effect
of H+, H2CO3 influences soil pH by the type of salts it generates.
The chemistry of flood water in rice fields has been studied extensively. The pH of
the flood water is largely determined by the chemical equilibria that exist between the
CO2 balance achieved by the aquatic biota and the various solutes, solids, and gases
in the water. Of particular interest in the shallow-water systems found in flooded rice
culture is the CO2 balance existing among the various submerged aquatic plant species,
particularly algal forms, which develop quickly into a large biomass. The photosyn-
thesis process decreases the net concentration of [CO2 „,] + [H2CO3] during favorable
daylight periods, but when respiration activity exceeds photosynthesis, both acidity
and the total concentration of dissolved carbonic acid increases. Water pH values
undergo diurnal changes, increasing by midday to values as high as 9.5 to 10 and
Table 1
EFFECT OF CARBON
DIOXIDE
CONCENTRATION ON
pH OF WATER
CO2 content (%) pH
0.03 5.65
0.30 5.22
1.0 4.95
10.0 4.45
Reproduced from McLean, E.

O., Methods of Soil Analysis —
Chemical and Microbiological

Properties, Agronomy 9, Mon-
ogr. Part 2, 2nd ed., Page, A. L.,
Miller, R. H., and Keeney, D.
R., Eds., American Society of
Agronomy, Inc., Crop Science
Society, and Soil Science Society
of America, Inc., Madison,
Wis., 1982, chap. 12. With per-
mission.
decreasing as much as 2 to 3 pH units during night. The pH of shallow flood water is

greatly affected by the total respiration activity of all the heterotrophic organisms and
by the gross photosynthesis of the species present.24 In other soils, such as acid Loui-
siana clay, where the flood water is not conducive to algal growth, the pH values
fluctuate between 6.8 at midday and 5.8 at night.24 Although the pH of flood water
and its diurnal changes is of significance to NH3 volatilization, if flood water pH stays
below pH 7, NH3 losses from broadcast application of NHi-containing fertilizers are
likely to be of little agronomic significance in lowland rice production. The pH of most
natural waters falls within the range of 4 to 9." The information available indicates
that the diurnal changes in pH of flooded soils are great enough to neutralize and mask
the effect of acid rain in such systems.
Another important source of acidity in soils is the acidity produced from minerali-
zation of native soil N and S and from nitrification of anhydrous NH3 and NH*,-forming
fertilizers added to managed soils. Anhydrous ammonia, urea, nitrogen solutions, and
ammonium nitrate are among the most used commercial N fertilizers. The total
amount of N fertilizers consumed in the U.S. in 1982 was over 11 million tons. The
harvested crop acreage in the same year was about 138 million hectare with an average
N application rate of 139, 57, and 44 kg/ha for corn, cotton, and wheat production.26
Also, intensification of forest management practices to increase productivity has re-
sulted in fertilization, especially on soils of low nutrient status. Application of N fer-
tilizers is one of the most potential cost-effective treatments, and most aggrading forest
ecosystems are N-limited.27 Increased biomass production due to addition of N fertil-
izers has been widely observed, but mass balance and 15N recoverey experiments indi-
cate that the efficiency of N fertilizer use in forest is much lower than commonly
observed for agricultural ecosystems.2' Therefore, N content of precipitation should
be beneficial to forest growth.
Anhydrous NH3 reacts in soils to yield 1 mol acidity per mole of N applied according
to the reaction:
NH, + 2O2 = H+ H2O (8)

The hydrolysis of urea by soil urease produces 1 mol of H2CO3 and 2 mol of NH3
according to the reaction:
(NH2),CO + 2H,0 = H2CO3 + 2NH3 (9)
Nitrification of the NH3 produced results in production of 2 mol of H+. The net reac-
tion is
H,O
(NH2)2CO + 4O2 •H2CO3 + 2H+ + 2NO3- (10)
At soil solution values P6 the H2CO3 produced hydrolyzes to H* + HCO3. This results
in greater acidification per mole of N for urea as compared with NH4NO3.
The effective acidity produced from any quantity of N fertilizer added to soil is only
a fraction of the total acidity. Thus, soil acidification accounts for only 9 to 50% of
the theoretical H* produced."^ The remainder of the acidity from fertilizer cannot be
accounted for by leaching from the surface soil. In soils with high cation exchange
capacity, NHî is retained by the surface soil until oxidized to NO3 and the resulting
acidity is rapidly exchanged with other positive ions on the exchange sites. Studies in
Iowa showed that the amount of acidity resulting from N fertilization was retained in
the surface soil (0 to 15 cm) with no acidification formed in the subsoil (below 30 cm).2'
Four reasons are given for the less-than-theoretical recovery of H* as soil acidity:
1. NHÎ that is nitrified, then denitrified produces no net H*.

2. For each mole of NO5 taken up by corn plants and recovered in the grain, there is
a neutralization of 0.95 mol of acidity by OH" or HCOl released from the roots.
3. The incorporation of NHJ-N in soil organic matter (immobilization) results in no
net H* production.
4. Slow neutralization of some of the acidity by reaction with primary minerals.2S-29
Extensive studies by Pierre and associates29-30 showed that crops vary in their mode
of uptake of N such that the measured net acidification by N fertilization for corn may
not apply to other crops. Unlike corn, which takes up most of the NO3 by exchange
with HCO3from the roots, crops such as buckwheat take up NO3 along with a charge-
balancing metallic cation. Buckwheat also releases specific amounts of acidity from the
roots such that the acidification generated after N fertilization may be greater than that
due to NHi oxidation. Oats are quite similar to corn in their uptake of N.31
Crops both nonlegumes and legumes, have a major effect on soil acidity. In the case
of nonlegume crops, soil acidity development can be predicted from the difference in
the amounts of excess base (EB) and N recovered in the harvest.31 EB is equal to the
difference between the sum of the cations and anions taken up by plants, (Ca + Mg +
K + Na) — (Cl + S + P), expressed in milliequivalent per 100 g; phosphorus is calculated
as monovalent and sulfur is calculated as divalent. Therefore, a crop that takes up N
in the form of nitrate and contains on a chemical equivalent basis a larger amount of
N than that of excess base (EB/N < 1.0) will leave basic ions in the soil and thus leave
the soil less acid. On the other hand, a crop that contains more excess base than N
(EB/N > 1) will leave in the soil the equivalent of the inorganic anions formerly asso-
ciated with the excess base and make the soil more acidic.31-32
Leguminous crops are one of the major sources of acidity in soils. Well-nodulated
legume plants get most of their N from the air through fixation, while they absorb their
bases from the soil. Therefore, they theoretically should increase the acidity of the soil
by an amount equivalent to the excess-base content of the crop if all the N was obtained
from fixation. However, legumes obtain some N from the soil; consequently, the ac-
idity produced from N fixation will be modified. In a recent survey of field-grown

crops, Pierre and Banwart32 found that the average EB:N ratio for eight common
legumes ranged from 0.48 to 0.76 and averaged 0.59. When harvested as hay, alfalfa
(Medicago sativa L.) and soybeans (Glycine max (L.) Merr.) had average EB:N values
of 0.61. Thus, assuming all the N in the crops was obtained by fixation, indicates that
the fixed N in the tops should produce 61% as much acidity as would be produced
from an equivalent amount of mineral acid. Indeed, N fixation from an annual yield
of 10 metric tons/ha of alfalfa would produce acidity in the soil equivalent to 600 kg
of CaCO3/ha (12 keq H+ per hectare).33 Nyatsanga and Pierre33 obtained relatively
good agreement between the amount of acidity developed in soils by alfalfa and soy-
beans and the theoretical amounts calculated from the N and excess base contents of
plants.
Similarly, mineralization of N from soil organic matter produces acidity, but the
release of N is dependent on the C:N ratio of the soil organic matter. Generally, when
the C:N ratio is <20 N is mineralized and when it is >20 N is immobilized. A recent
review by Keeney"indicates that the C:N ratio of the litter in most forest floors is
relatively high (in the range of 40 to 60:1) corresponding to total N concentrations of
0.6 to 1.4% (ash-free basis). Recently cultivated agricultural soils may show N miner-
alization, the rate of N release varying with soil, cropping conditions, and management
practices.
Another source of acidity in managed soil is the H* produced from application of S
fertilizers. The amounts of S fertilizers used in the U.S. in 1981 and 1982 were 1.9 x
106 and 1.5 x 106 tons, respectively. Of the total amount used in 1982, 3, 5, 20, and
71% were used in the West-North-Central, Mountain, South Atlantic, and Pacific re-
gions of the U.S., respectively.34 S déficiences have been detected in several regions of
the U.S. during the past two decades, and S fertilization is now required in many areas
to ensure satisfactory crop production.35 Other areas that have shown response to S
fertilization are in Australia, Africa, Asia, Canada, New Zealand, and South and Cen-
tral America.36 The factors responsible for the increased need for S fertilization have
been discussed by Coleman." They include increased use of high-analysis fertilizers
that contain little or no S, increased crop yields, decreased use of S as a pesticide, more
intensive cropping, and decreased gain of atmospheric S by soils and plants as a result
of decreased combustion of coal and other S-containing fuels. Several forms of S are
used as fertilizers. These include elemental S, ammonium sulfate, calcium sulfate, po-
lysulfides, and thiosulfates.36 The compounds are either acid in reaction or produce
H2SO4 upon oxidation in soils.38
Litter decomposition is another source of acidity, especially in forest soils. The re-
action and base content of litter are quite variable and depend on such factors as leaf
types in the litter, the base status of the underlying soil, and the degree of litter decom-
position. Most decomposing litter is acidic, with that from conifer being more acidic
than that from hardwood deciduous trees. Therefore, in mixed forests, hardwood litter
tends to increase the base content, improve the buffering capacity, and decrease the
acidity. Studies of litter from a wide range of North American trees have distinguished
three groups of litter: hypobasic, middle, and superantiacid types.39 These groups were
distinguished by their calcium oxide content (3.6 to 5.7, 2.2 to 3.1, and 0.3 to 2.1%,
respectively) and their acidity (pH 3.3 to 4.0, 4.1 to 4.5, and 4.6 to 5.9). Only a few
litter types have a pH above 4.5.39
A broad correlation between pH of soil and that of the tree leaves and litter has been
found.40 This was most noticeable with hardwoods. Acid soils had litter of similar
reaction but alkaline soil had litter wth a pH lower than that of the soil. The extent of
decomposition of leaves also affects their reaction. A significant change in pH takes
place during the initial phase of decomposition. Studies have shown that most Utter
becomes less acidic during the first 34 days of decomposition on soils. This initial
Table 2
SOME ALIPHATIC ACIDS AND PHOSPHORIC ACID IN FRESH AND
DECOMPOSED LITTER EXTRACTS
Percentage of acid in form specified*
Treatment litter" Malic Citric Malonic succinic Fumanc Glycolic Phosph

Fresh litter extract A 6.8 2.7 1.8 Tr 0 0.9 2.7
B 0.8 0.8 + Tr 0 Tr 0.8
C 1.3 3.9 0.3 + Tr Tr 3.6
D 0.5 1.0 Tr Tr 0 Tr 9.3
E 0.9 1.8 0 Tr Tr 0 0.6
Anaerobic decomposi- A Tr 1.6 0.4 8.6 0 0.4 0.7
tion of litter extract B 0 0.8 0 2.5 0 Tr 0.8
during 4 days C Tr 3.9 Tr 5.2 0 Tr 3.6

D Tr 0.3 0 2.5 0 Tr 9.3
E + 1.8 0 3.0 0 Tr 0.6
" A, Frax/nusexce/s/or.-B, Alnusglutinosa;C, Betula verrucosa;D, Fagus silvática;and E, Pinus silvestris.

' +, indicates small amount; Tr, indicates trace amount. The amounts of aliphatic acids were calculated as
percentage of dry weight of fresh litter extract. The extracts were obtained by anaerobic leaching of litter
during 1 day at 25°C.
Adapted from Nykvist, N., Stud. For. Suec.,3, 1, 1963.
decrease in acidity is almost certainly due to leaching of acidic solutes (e.g., organic
acids) in the cell sap.41'42 The extent of the increase in pH depends on the aeration of
litter, the length of leaching period, and susceptibility of the litter to decomposition.
Thus, under aerobic conditions, the pH of Fraxinusleachates increased from 5.6 to 7.6
in 24 hr and to 7.1 in 42 days. Under anaerobic conditions, the corresponding values
were 5.5 to 5.4. The low pH of litter and its increase during decomposition and leach-
ing is not surprising because work by Nykvist43 showed that in addition to leaching of
amino acids and sugars, a number of aliphatic acids and phosphoric acid were leached
from a variety of fresh litter and during anaerobic decomposition of litter during 4
days at 25°C (Table 2). Removal of the acids by leaching leads to an increase in pH of
the remaining litter. The most abundant of the aliphatic acids in the liter extracts are
calculated as a percentage of the amount of water-soluble substances in the fresh ex-
tracts. In addition to the organic acids, malic, citric, malonic, lactic, succinic, fumaric,
and glycolic, significant amounts of phosphoric acid have been detected in decompos-
ing litter. Formation of sulfuric acid and nitric acid in litter decomposition is also
possible.
The amount of water-soluble substances is greater when leaching takes place under
anaerobic conditions than when aerobic. Under aerobic conditions, the aliphatic acids
are rapidly decomposed by microorganisms and have disappeared almost completely
after a few days. Malic acid is also rapidly decomposed under anaerobic conditions.
Citric acid is more resistant, and in most extracts no decrease is noted after 4 days/ 3
Comparatively greater amounts of lactic and succinic acids are formed under anaerobic
conditions.
The total amount of water-soluble organic and inorganic substances leached from
ground litter during 1 day has been determined and expressed as a percentage of the
dry weight of the litter. The values determined after the first day of leaching are ash,
25; birch, 16; oak, 14; spruce, 14; alder, 13; pine, II; and beech, 8%. The water-
soluble substances are easily leached from leaf litter, especially that of alder, ash, and
birch, and are leached slowly from unground needles of pine and spruce litter. Leaf
litters of beech and oak are in an intermediate position in this respect.43
NEUTRALITY
Range in pH Range in pH
common for common for Attained
humid region arid region only by
mineral soils mineral soils alkali
mineral
•Extreme range in pH for— soils
most mineral soils
FIGURE 3. Extreme range in pH values for most mineral soils and ranges commonly found in humid
region and arid region soils. The maximum alkalinity for alkali soils is also indicated as well as the minimum
pH values likely to be encountered in very acid peat soils. (From Brady, N. C , The Nature and Properties
of Soils, 8th ed., Macmillan, New York, 1974. With permission.)
Two kinds of acidity are present in soils. The H* concentration of the soil solution
is designated active acidity. The H and Al ions held on soil colloids are referred to as
the reserve or exchangeable acidity of the soil. The relative magnitude of the two types
of acidity — active vs. reserve — is of vital practical importance. Conservative calcu-
lations indicate that the reserve acidity may be 1000 times greater than the active acidity
in a sandy soil and between 50,000 and 100,000 times greater for a clay soil high in
organic matter. The figure for a peat soil is likely to be even greater.22
The relative proportion of the adsorbed H and Al and the exchangeable bases of
soils are shown by the percentage base saturation. A low percentage base saturation
results in acid soils, whereas a percentage base saturation approaching 100 will result
in neutral or alkaline soils. In general, humid-region soils dominated by clay and hu-
mus are acid if their base saturation is much below 80%. In addition to base saturation,
the exact pH value of any soil is determined by at least two other factors: (1) the nature
of the colloidal material (both clay and humic materials) and (2) the kind of adsorbed
bases.
A marked change in pH clearly indicates a radical modification in the soil environ-
ment, especially in relation to the availability of plant nutrients. If the parameters of
this environment fluctuate too widely, higher plants and microorganisms will suffer
seriously before they could make adequate adaptation. However, no such changes are
expected from acidification of soil by acid precipitation.
V. SIGNIFICANCE OF SOIL pH
One of the most important parameters that affect soil chemical and biological prop-
erties is pH. Figure 3 shows the ranges of soil pH encountered under natural environ-
ments and the terms commonly used in describing soil reactions. For mineral soils the
pH ranges from 3.5 to perhaps 10 or above under certain conditions. Certain soils may
have pH values of 3. The other extreme is the pH of alkali soils, some of which may
reach pH values near 11. In general, the pH values of soil of humid and subhumid
regions ranges from 4 to slightly above 7, while soils from the arid regions have pH
values ranging from slightly below 7 to approximately 9. The surface and subsurface
layers of organic soils of the lower coastal plain of North Carolina often have pH
values <4 and may reach as low as 2.5.44-45
A. Effect of Acidity on Soil Chemical Properties

Soil reaction affects the chemistry of soil constituents and plant growth and devel-
opment in two ways: (1) through direct effect of H* and (2) indirectly through its
influence on nutrient availability and the solubility of some toxic elements. Several
nutrient elements (e.g., Fe, Mn, and Zn) become less available to plants as the pH of
soil is increased from 5 to 7. On the other hand, Mo is affected in the opposite way,
being more available at the higher pH levels. At low pH values (<5), Al, Mn, and Zn
can be present in sufficient concentration to be toxic to growth of some plants. At very
high pH values, the HCO3 is sometimes present in sufficient concentration to interfere
with the normal uptake of other ions."
The cation exchange capacity of soil (the ability of soils to adsorb cations) is signif-
icantly affected by pH. The adsorption of cations by soil is due to the negative charges
associated with colloidal surfaces. Two types of negative charges have been identified
on soil colloids: (1) permanent charges and (2) pH-dependent charges. The first type
of charge is associated primarily with the silicate clays. These charges are due to the
electrostatic forces resulting from isomorphous substitution within the clay crystals
(e.g., Al3* for Si4*). The negative charge sites are located mostly on the internal surfaces
and the cations adsorbd on these surfaces are exchangeable at all pH values. Perma-
nent charges are higher on the 2:1 type clay where ionic substitution is greater.
The second type of negative charge is not permanent, but is related directly to soil
pH. The quantity of charges is low in very acid soils and increases as the pH increases.
This type of charge is thought to be derived from several sources. Among these
sources, are hydroxyl groups associated with Si and Al at the broken edges and external
surfaces of clays. Another source is the carboxyl (-COOH) and phenol groups (R-OH)
associated with the humus colloids. The covalent-bonded hydrogen of these groups is
not dissociated at low pH values. As the pH increases, however, the hydrogen disso-
ciates, leaving a negative charge on the colloidal surface. In nature, the dissociation of
this type of hydrogen is replaced by metallic cations, which are, in turn, exchangeable.
Pratt and Bair46 made measurements on a number of soils that led to the average figure
of 15.8 meq/100 g of clay for the pH-dependent exchange capacity between pH 3 and
8 and 370 meq/100 g of organic matter for the same pH range. Apparently, therefore,
the phenomenon of pH-dependency of the exchange capacity of soils is predominantly
a property of the soil organic fraction of soils. A similar conclusion was reached by
Helling et al.47 in a study to assess the contribution of organic matter and clay to soil
cation exchange capacity as affected by pH (from 2.5 to 8). At low pH values there are
enough FT in solution to suppress the dissociation of the H associated with the func-
tional groups of soil organic matter.
In acid soils, the complex Al and Fe hydroxy ions formed are tightly adsorbed within
the crystal units of certain 2:1 type clays, particularly vermiculite. These ions block
some of the negative charge sites of the colloids, thereby reducing the cation exchange
capacity. As the pH increases, the complex ions are removed, forming insoluble
A1(OH)3 and Fe(OH)3 and thereby releasing the exchange sites for cation exchange.
This reaction leads to increase in pH-dependent charges. The chemistry of Al and its
solubility in water solution as affected by pH of the solution is discussed by McLean."
Under very acid conditions, high amounts of Al become soluble in the form of Al or
Al hydroxy cations. These complex cations become adsorbed even in preference to H*
by the permanent negative charges on the clay minerals. The adsorbed Al will be in
equilibrium with AP* in the soil solution, which contributes to soil acidity through
hydrolysis:
>100
ot:
<
o.
o 80
Bound H and AI Exchangeable bases
SOIL pH
FIGURE 4. General relationship between soil pH and the cations held by soil colloids. This diagram is for
average conditions. Any particular soil would likely give a modified distribution of the various pools of the
adsorbed cations. (From Brady, N. C , The Nature and Properties of Soils, 8th ed., Macmillan, New York,
1974. With permission.)
Clay-Al = Al3+
Al3+ + H2O = A1(OH)2+ H
The H+ thus formed produce very low pH values in the soil solution and are consid-
ered the major source of H* in most very acid soils. The pH for hydrolysis of Al3* and
production of A1(OH)2+ is 5; therefore, soil containing Al3* would be expected to be
well buffered at pH = 5. The pH of maximum buffering capacity, however, has been
shown to decrease with increasing concentration of Al. A fully H-saturated soil clay
may have a pH as low as 2.5, but it rapidly increases to about 3.5 as Al and other
cations are released by decomposition of clay minerals. This is the reason why forest
soils rarely have pH values as low as 3.5. Hence, it is unlikely that modest amounts of
acidity in precipitation, when compared with potential acidity from nitrification and
litter decomposition, will lower the pH of unmanaged soils below 3.5.5
The general relationship between soil pH and the cations held by soil colloids is
shown for a hypothetical soil in Figure 4. Under very acid conditions, exchangeable Al
ions and bound H and Al dominate. At higher pH values, the exchangeable bases
predominate, while at intermediate values Al-hydroxy ions such as Al(OH)2* and
Al(OH)i predominate. The effect of pH on the distribution of bases and H and Al in a
muck soil and the White Store series (dominated by 2:1 clay), both from North Caro-
lina, is shown in Figure 5. Permanent charges dominate the exchange complex of the
mineral soil, whereas the pH-dependent charges account for most of the exchange sites
in muck soils. Kaolinite and related clay have a distribution intermediate between those
of the two soils presented in Figure 5. Also, it is important to note that two forms of
H are shown. One is tightly held (bound hydrogen) by pH-dependent sites (covalent
bonding); the other is exchangeable, associated with permanent electrostatic charges.
From Figures 4 and 5, it is obvious that the factors responsible for soil acidity are far
from simple. At the same time, there are two dominant groups of elements in control
MUCK SOIL MINERAL SOIL (2:1 TYPE)
100 100
Bound H Exchangeable bases
Bound H 80
(and probably AI and Fe
in very acid range
Exchangeable bases
60 M
O)
40
E
<u
_ Q.
20
Exchangeable
Ex-
H + and A l 3 +
changeable*
H+ and A l 3 +
ET
6 3
SOIL pH SOIL pH
FIGURE 5. Relationship between soil pH and the proportion of the adsorptive complex satisfied by bases and by hydrogen and aluminum. The mineral
soil (right) is of the White Store series in North Carolina. Its properties tend to be dominated by 2:l-type clays. The muck soil (left) is also from North
Carolina. Note the dominance of the permanent charge in the mineral soil and the large pH-dependent charge in the muck soil. Soils dominated by l:l-type
clays have distributions intermediate between these two extremes. (From Brady, N. C , The Nature and Properties of Soils, 8th ed., Macrmllan, New York,
!ÍÍl!!!l|F u n gi Illllllllllllllll
;;|açténa arid äctmömycetg^i
si S g:
pH
FIGURE 6. Relationships existing in mineral soils between pH

on the one hand and the activity of microorganisms and the avail-
ability of plant nutrients on the other. (From Brady, N. C , The
Nature and Properties of Soils, 8th ed., Macmillan, New York,
of soil acidity; Al and H generate acidity, and cations such as Ca2*, Mg2+, K*, and Na*
counteract it. Therefore, the acid substances in precipitation are neutralized by the
accompanying basic cations. There is a significant input of cations (Na*, K+, Ca2*, and
Mg2*) in precipitation (see Sections VII. and VIII.C). The basic cations in precipitation
are directly offsetting and have the same effect as the limestone used in agricultural
practices to restore the base saturation to a high level.
The relationship between soil reaction and the acitivity of microorganisms and the
availability of plant nutrients is shown in Figure 6. The wide portions of the bands
indicate the zones of greatest microbial activity and the most readily availability of
plant nutrients. Considering the relationships as a whole, a pH range of approximately
6 to 7 seems to promote the most readily available plant nutrients. In general, if soil
pH is suitably adjusted for P, other plant nutrients, if present in adequate amount,
will be satisfactorily available in most cases.
The H ions deposited by precipitation are buffered in soils by reacting with soil
constituents. Under extreme acidification, as from the continuous fertilization with
anhydrous ammonia practiced in modern agriculture, some pH changes are observed
with time. Within the following ranges, important neutralization processes can be dis-
tinguished:48
1. Carbonic acid/carbonate buffer range (pH 6.2 to 8.6): H ions are consumed by
the dissolution of CaCO3. The buffering rate is up to 2 keq HVha/year.
2. Carbonic acid/silicate buffer range (pH 5 to 6.2): H ions are consumed by the
weathering of silicates and the buffer rate ranges from 0.2 to 2 keq/ha/year. If
strong acids (e.g., H2SO4 and HNO3) are produced at a rate exceeding the buffer
rate, the pH may drop temporarily below 5.
3. Cation exchange buffer range (pH 4.2 to 5): H ions are consumed by dissolving
A1OOH from weathered silicates with the formation of polymeric Al-hydroxy
cations. These Al-hydroxy polymers replace Ca2* and Mg2* at the colloidal sur-
faces. The buffering rate, the rate of dissolution of A1OOH, may vary according
to the weathering product available, but is probably small (approximately 0.2 keq
HVha/year).
4. AI buffer range (pH 3 to 4.2): H ions are consumed by formation of AI3* from
polymeric Al compounds. The buffer capacity is higher (except in quartz). The
buffer rate varies, but is often small (approximately 0.2 keq HVha/year).
5. Fe buffer range (pH 3 to 3.5): H ions are consumed by the formation of Fe ions
from iron oxides. The buffer rate is relatively high (approximately 2 keq HVha/
year).
It is generally considered that soils low in cation exchange capacity and base satura-
tion are the most sensitive to acid precipitation. However, this concept is not accepted
by a number of soil scientists. In Sweden, based on laboratory experiments and field
studies, it has been suggested that acidified soil with a pH <5 would be only slightly
affected by acid precipitation since most of the cation exchange sites are already oc-
cupied by H*. Calcareous soils with a very high buffering capacity would be the most
resistant, whereas noncalcareous sandy soils with a pH 6 would be the most sensitive.49
Recent studies indicate that that a pH change of 0.2 may be obtained in Minnesota
soils by acid precipitation in 137 years. This magnitude of change in pH is well within
the variation observed with seasons and different locations in the same field.28 Seasonal
and yearly variations of pH are very common in managed and unmanaged soils. Vari-
ations of pH with annual cumulative precipitation in acid forest soils are reported by
Crampton50 for the Belcarra Mountain in the rain forest of British Columbia in Can-
ada for 1975 to 1978. He found that a year when precipitation was great, 1976, pH
remained moderately constant across the mountain, values in horizon A ranging from
4.3 to 4.4 and in horizon B ranging from 4.8 to 5, the average difference between the
two horizons being 0.5 of a pH unit. For a relatively dry year, (1977) there were great
variations in pH across the mountain. For sandy loam sites supporting brunisols, both
A and B horizons were more acid than during a wet year, the difference in pH values
between the two horizons being 0.6. The difference in the pH of the two horizons in
sandy podzols was only 0.2.
Distinct effects of acid precipitation on well-buffered soils in the field have yet to be
recorded in Scandinavia."-51 Similarly, there is ample evidence indicating that the ac-
idity of precipitation in North America has not significantly affected pH of
soils.5I8-20-28 A number of reports speculate on the nature of the potential changes in
soils by acid rain, including loss of silicate structure and destabilization of clay min-
erals,52 gradual deepening of the lime-free layer,53 increased ratio of acid to base cat-
ions and reduced cation exchange capacity,54 increased rate of, or premature, podzo-
lization, 55 increased rate of leaching of nutrient cations from root zones,56
solubilization (mobilization) of toxic metals such as Al, Hg, and Pb,56 loss of Mo,
which affects the biological fixation of dinitrogen,57 and slowing of pedogenesis and
acceleration of naturally soil-acidifying processes.51 Theoretical treatments of other
potential, but hypothetical, effects of acid precipitation on soil chemical properties
have been prepared by McFee et al.,58 Norton,59 Oden,60 Reuss,"•" Tamm," and Wilk-
lander.19-52" With the exception of perhaps acidification of soils near point sources,65
it is doubtful if any of these potential detrimental effects of acid precipitation can be

measured under natural conditions even in 100 years.
One of the few studies that has been carried out to assess the effect of acid precipi-
tation in a natural environment (without simulated acid rain) on chemical changes in
loess-derived soils is that reported by Ulrich et al." in the Soiling highlands in Germany
for 1966 to 1979. The soil in this region is highly acidic, pH (CaCU) ranging from 3 to
4 in 50 cm profiles, and the slight difference between years has been attributed to
seasonal variation. The data indicate that the gain in H ions in this ecosystem was in
the order of 1 keq/ha/year. Although the magnitude of H ion input is too small,
perhaps it is within experimental errors associated with this type of work, Ulrich et
al.66 concluded that acid precipitation has induced the soil internal H ion production,
partly by accumulation of organic matter poor in N and partly by probable change in
the type of N nutrition. Even though one expects to have high Al concentrations in
such soils, there is a concern that the Al concentration in soil solution is increasing to
toxic levels.
To study the effect of acid precipitation on mobilization of Al and organic C,
McColl et al.67 exposed intact core (12 cm; coniferous litter and mineral soils) of two
Sierra Nevada soils to 3-hr applications of 2 cm of simulated rain (pH 5.6, 4, and 3)
every 3rd day for a total of 3 weeks. Aluminum in the leachates was significantly
correlated (r2 = 0.51, p < 0.001) with dissolved organic carbon. Speciation of Al re-
vealed that more than 99% of the Al was complexed with organics which had pH-
dependent behavior similar to organic acids with pH values of approximately 5.5. The
results indicated that Al3* levels appeared to be controlled by complexation rather than
mineral dissolution or ion exchange mechanisms. A direct H+ interaction with the large
pool of Al in the litter and mineral soil could not account for the observed Al levels in
the leachates. Furthermore, as compared with simulated rain at pH 5.6, neither acid
treatments resulted in a change in leachate strong acidity. As compared with pH 5.6
and 4, the pH 3 treatment resulted in decreased organic carbon and Al in the leachates.
These results indicate that precipitation acidity can indirectly influence Al mobility
through its interaction with the large pool of organic carbon in the litter and organic
horizons of forest soils. While the detrimental effect of acid precipitation on soils is
yet to be convincingly demonstrated, the beneficial effect on agronomic crops, mainly
enhanced soil fertility due to N and S input, has been amply documented.68
One of the important reactions that occurs in acid soils is the formation of hydrous
oxides of Al and Fe. Formation of these oxides in acid soil leads to production of
positively charged surfaces that adsorb anions such as sulfate and nitrate. Adsorption
of sulfate by soil is negligible above pH 6.5 and increases with decreasing pH below
this value (below zero point of charge).6' Therefore, sulfate adsorption is greater in
acid soils containing large amounts of Al and Fe oxides, the former generally being
more important. The adsorbed sulfate may also be displaced by solutions containing
anions of greater coordinating ability according to the series.™" hydroxyl > phosphate
> sulfate = acetate > nitrate = chloride. Therefore, sulfate, whether from fertilizer,
organic matter, or atmospheric sources, can be adsorbed by acid soils. Interactions of
sulfate with soil are important in the S nutrition of plants and have received much
attention in recent years. Although the relationships involved are complex, a number
of phenomena have been elucidated and generally accepted.69 The observations and
associated factors may be summarized as follows:
1. Most soils have some capacity to retain sulfate, and subsoils commonly contain
greater amounts of adsorbed sulfate than do surface soils. This difference may
be due to a lower pH in the subsoil or to the saturation of adsorption sites in the
surface soils with phosphates or other anions.
2. There is a strong dependence of sulfate retention upon the equilibrium pH with

the retention increasing as the pH decreases.
3. Koalin minerals retain more sulfate than do montmorillonites.
4. Al and Fe hydrous oxides have a marked tendency to retain sulfate.
5. The amount of sorption is concentration dependent, and the sorbed sulfate is in
kinetic equilibrium with the sulfate in solution.
6. The amount of sulfate retained is influenced by the associated cation when added
as a salt and by the exchangeable cations of the soil. The effect is in the same
direction as the cationic lyotropic series and is over and above the effect of pH.
Sulfate adsorption has two significant roles in the S nutrition of crops. It is a source
of available S for plants, and it retards the rate of sulfate movement within the soil,
thus reducing leaching losses and modifying the distribution of the element within the
profile. Loss of S from soils by leaching varies from insignificant amounts to as much
as 320 kg S per hectare annually from soils treated with S fertilizers." Deficiencies of
S, attributable principally to losses by leaching, are often found on coarse-textured,
nearly neutral soils after periods of heavy rainfall. Percolating waters frequently lower
the sulfate content of surface soils, particularly those that have been limed and fertil-
ized with phosphate." The amount of adsorbed sulfate can vary from 1 ppm to several
thousand parts per million. Some strongly sulfate-adsorbing surface soils of Hawaii
contain >1000 ppm, and the subsurface soils contain >7,000 ppm, of adsorbed sulfate
S.74 The adsorbed sulfate is readily available to plants. 74 ' 6
B. Effect of Acidity on Soil Biochemical Properties

Soil may be looked on as a biological entity, i.e., a living tissue77 with complex
biochemical reactions. The effect of acidity on microbial processes and biochemical
reactions in soil have been studied extensively for many years, and the subject has been
reviewed several times.57-78'79
Six major microbial groups reside in soils systems: bacteria, actinomycetes, fungi,
algae, protozoa, and viruses. Limited information is available on viruses in soils, but
the other groups are found in all soils and have been studied in detail. The roles of
microbial processes in soils have been reviewed,57 but the relative effect of acid precip-
itation in natural systems is difficult to ascertain mainly because the magnitude of soil
acidification by precipitation is so slow that to make a meaningful comparison of mi-
crobial processes resulting from acid rain is very difficult, if not impossible. The rates
of microbial processes are not significantly affected by modest acidification. Even the
effect of a relatively high atmospheric pollutant on microbial activity in a natural sys-
tem is often difficult to determine. In a study by Wainwright,80 surface samples of a
brown earth soil, showing signs of podzolization, were transferred from an unpolluted
woodland site and exposed to heavy atmospheric pollution for a period of 1 year. The
polluted site was exposed to the smoke plume emitted from a works manufacturing
refrectory bricks where SO2 concentrations were high (125 /¿g/m3) and the vegetation
showed signs of pollution injury and was covered with a thin layer of soot from the
middle of the growing season. Although exposure resulted in a decrease in soil pH
from 4.2 to 3.7, no significant changes in microbial numbers, nitrification, respiration
rate, solubilization of insoluble phosphate, or the activity of a range of soil enzymes
occurred. The rate of ammonification was, however, higher in the exposed than the
control soil. As is expected from the degree of acidification (reduction in pH), the
microbial activity in the unpolluted soil was not substantially impaired by exposure to
heavy atmospheric SO2 and soot pollution.
Other studies with soils of higher pH values than that used by Wainwright80 showed
that nitrification could be inhibited in areas acutely polluted with SO2 and NO2 gases.
Labeda and Alexander81 reported that nitrification in Lima loam, pH 7.2, was not
affected by continuous exposure of the soil to 0.5 ppm of SO2 or to brief exposure to
higher SO2 levels. Such treatment did not increase the levels of soluble K, Mg, Ca, Mn,
Fe, and Al. However, intermittent exposure of another soil, Hudson silty clay loam of
pH 5, to SO2 reduced the rate of nitrate formation. Continuous fumigation of the soil
with 10 ppm of SOj decreased the rate of nitrification, and continuous fumigation with
as little as 1 ppm increased the quantity of soluble Mn and Fe. The total numbers of
heterotrophic bacteria and the numbers of nitrite-oxidizing autotrophs were similar in
the fumigated and unfumigated soils. The pH of the Hudson soil decreased to 4.9 and
4.6 after 12 days of incubation at 22°C in the untreated and fumigated samples, re-
spectively. Continuous fumigation of the alkaline Lima soil with 5 ppm NO2 inhibited
the rate of ammonium disappearance, led to greater rates of nitrate formation and
resulted in nitrite accumulation.
In another study, Francis82 adjusted the pH of a forest soil (pH 4.9) to 3 with 1 N
H2SO4 or to 7 with Ca(OH)2. The natural soil which received only distilled water served
as a control. He reported a decrease in CO2 production by acidification of the soil.
Ammonia formation in the pH-adjusted acid soil was about 50% less than that of the
natural acid soil. Little autotrophic and heterotrophic nitrifying activity was detected
in the naturally acid and the acidified forest soils. Increased rates of ammonification
and nitrification were observed in the pH-adjusted neutral soil. The rate of denitrifi-
cation was slow in acid soils, and at greater acidities, N2O was the predominant end
product. A similar observation on the effect of pH on the production of N2O was
recently reported by Koskinen and Keeney83 for silt loam soil maintained at various pH
levels (4.6, 5.4, 6, and 6.9) for 18 years in Wisconsin. The effect of acidity on nitrate
reduction and denitrification in lower coastal plain soils is substantial in soils with pH
values <4 and is of a similar level to that for moderately acidic soils (pH 4.4 to 5.4).
Limiting results in increasing the rate of denitrification; this increase appears to be due
to the high level of soluble organic C.45
Although extreme acidification such as that described by Francis82 is not expected
from acid precipitation in natural soil systems, he concluded that further acidification
of acid forest soils by acid precipitation may lead to significant reduction in the leaf
litter decomposition, ammonification, nitrification, and denitrification and thus re-
duce nutrient recycling in the forest ecosystem.
Using simulated acid rain, Strayer and Alexander84 exposed samples of forest soils
to a continuous application of 100 cm of rain (pH 3.2 to 4.1) at 5 cm/hr or to inter-
mittent 1-hr application of 5 cm, 3 times per week, for a total of 7 weeks. They found
the effect of acid rain was localized in the top 1-cm layer of the soil column. The
changes observed included a decrease in pH and glucose mineralization rates and an
increase in exchangeable Al and total and exchange acidity. Glucose mineralization in
the soils tested (pH values 4.4 to 7.1) was inhibited by the continuous exposure to
simulated acid rain at pH 3.2, but notât pH 4.1 Acid rain of pH 3.2 occurs in isolated
places during certain rainfall events, but no rain of such acidity is reported to occur in
natural environments on a continuous basis. Recent monitoring work shows that the
annual pH of precipitation in North America for 1980 ranged from 4.1 in a small area
in the northeastern U.S. to 6.5 in several areas of the U.S. and Canada.85 From the
results reported by Strayer and Alexander,84 it is obvious that acid rain, even with a
pH of 4,1, would not significantly affect several microbial processes in soils. Further-
more, agricultural and forested soils do not receive the total acidity in the surface layer
because the acidity in precipitation is modified by the vegetation cover before reaching
the soil surface. For example, the Ca content of precipitation collected beneath the
forest canopy may increase by five- to tenfold relative to that in the incoming precipi-
tation.8<8S The annual nutrient added to the forest floor is also affected by the type of
vegetation cover.89 Similar observations have been reported for agricultural crops and
soils.90 An additional fact is that surface soils and its cover change with time by erosion
as is the case in agricultural soils or accumulation of litter as in the case in forests.
Therefore, the acidity is intercepted and neutralized by various changing surfaces.
Soil as a system of humus and minerals contains both immobilized enzymes, stabi-
lized by a three-dimensional network of macromolecules, and occluded microbial cells.
A number of enzymes have been detected in soils." Enzyme reactions are highly af-
fected by pH. A number of factors control the effect of pH on enzyme-catalyzed re-
actions in soils. Changes in H* concentration influence enzymes, substrates, and cofac-
tors by altering their ionization and solubility. Variation in such properties as
ionization or solubility influence the rate of enzyme reaction rates. Enzymes, being
proteinaceous, exhibit marked changes in ionization from fluctuation in pH. Charac-
teristically, each enzyme has a pH value at which the rate is optimal, and at each side
of this optimum the rate is lower; thus, the catalytic action of the enzyme operates in
a somewhat restricted pH range. Acidification of soils may also increase the solubility
of metals, some of which (e.g., Cu and Zn) are known enzyme inhibitors.
Although acidification of soils by many processes (e.g., nitrification of anhydrous
ammonia added to soil) is expected to reduce enzyme activities, the degree of this
acidification is important. Very little information is available on the effect of acid rain
on the reaction catalyzed by enzymes in soils. In the work by Wainwright80 where the
pH was decreased from 4.2 to 3.7 after exposing the soil for 1 year to polluted air
containing SO2, no significant change in the activity of the following enzymes could be
detected: arylsulfatase, cellulase, dehydrogenase, acid phosphatase, rhodanese, and
urease. On the other hand, in a study in California, a Sierran forest soil (pH 6.4)
planted with Ponderosa pine seedlings was exposed to simulated rain (pH 2 to 5.6) with
ionic composition reflecting that found in northern California, corresponding to 15 cm
of precipitation over a 12-week period. Changes in microbial activity were most signif-
icant in the surface I-cm layer. The results showed that only the pH 2 input caused
inhibition of both respiration and enzyme activities. The overall microbial response to
the pH 3 and 4 acid regimes was one of stimulation. Although the response of the
individual enzymes was more varied, in surface soils receiving the pH 3 input, urease
activity was unaffected while arylsulfatase and phosphatase were increased and de-
creased, respectively.
The pH stability of urease, acid phosphatase, alkaline phosphatase, and phospho-
diestrase in soils was investigated by Frankenberger and Johanson.92 They first incu-
bated soil samples after adjusting the pH with H2SO4 or NaOH (from pH 1 to 13) for
24 hr and then measured the activity at the enzyme optimal pH under standardized
conditions. They found that, generally, the decline in enzyme activity in a pH profile
near the optimum pH range was due to reversible reactions that involved ionization or
deionization of acidic or basic groups in the active center of the enzyme-protein. Irre-
versible inactivation of the enzyme was particularly evident at the lower and higher
ranges of acid and alkaline conditions. The results showed that the pH stability of soil
enzymes are highly dependent on the soil used. The variation among soils may be
attributed to the diversity of vegetation, microorganisms, and soil fauna as sources
contributing to the enzyme activity and to the protective sites which allowed entrap-
ment of the enzyme within colloidal humus and organic-mineral complexes. Appar-
ently, the adherence of the enzyme-protein to the humic-clay fractions would allow
some resistence to pH denaturation.
Many leguminous plants grow poorly in soil of low pH, and increasing acidification
leads to declining legume vigor and ultimate elimination. The suppression of legumes
may be associated with toxic levels of Mn, Fe, or Al, but in some instances it may be
related to the low concentration of available Mo in soils.93 The marked effect of acidity
on N2 fixation and growth of red clover has been demonstrated when supplied with
ammonium at pH 4.2.'" From the reviews available on the effect of acidification on N2
fixation and growth of leguminous plants, it is not clear whether the nodulation proc-
ess or leguminous plants are also acclimated to acid environments. Several contradic-
tory reports are available on the effect of acid precipitation on N2 fixation by plants.
For example, by using simulated rain acidified with sulfuric acid (pH 3.2), Shriner95
reported the inhibition of Rhizobium nodulation of red kidney beans (Phaseolus vul-
garis) and soybeans (Glycine max) by an average of 73%. On the other hand, work by
Firestone et al.' 6 with barley (Hordeum vuigareL.) and clover (Trifolium sp.), grown
from seeds for 12 weeks in Yolo sandy loam soil and spray irrigated with simulated
acid rain (pH 5.6, 4, 3, and 2), showed significantly higher rates of N2 fixation activity
(on root weight basis) in the clover root from pH 2 irrigation than from the other pH
regimes. Nitrification activities in rhizosphere soil from barley receiving pH 2 irrigation
and from clover receiving pH 2 and 3 irrigation were lower than the higher pH treat-
ments. In unplanted soil, the pH of the irrigation water had little effect on nitrification.
Denitrification activity assayed in barley rhizosphere soil receiving pH 2 solution was
about twice that of the higher pH treatments. Clover rhizosphere soil exhibited very
little pH effect on denitrification and rates of N-gas evolution from unplanted soil were
so low as to escape short term analysis. Firestone et al.96 concluded that the effect of
acid inputs on activities assayed were partially mediated by the effect of treatment on
plant growth. In all studies of the effect of acidity on N fixation, apparently the aci-
dification by legume N fixation and other nutritional requirements of these plants is
totally ignored. As discussed before, leguminous plants produce significant amounts
of acidity (see Section V.A.) Therefore, acidification of soils by leguminous plants is a
natural phenomenon that exceeds, by many-fold, the acidity added by precipitation.
The effects of simulated acid precipitation on several microbial nitrogen transfor-
mations have been determined in both rhizosphere and nonrhizosphere soil and as a
function of depth in soil." The effects on productivity of five agronomic species and
two forest-tree species (not specified) were assessed under four pH regimes. The au-
thors report that after 3 months of treatment, they could not observe any direct effect
on microbial activity. In nonfertilized soils, plant productivity generally increased with
increasing treatment acidity. They interpreted this to fertilizer effect of the acids em-
ployed (HNO3 and H2SO«) and to increased availability of other nutrient ions resulting
from slight soil acidification. In soils fertilized with N and S, plant productivity was
reduced in the most extreme pH treatment (pH 2). Within the pH range of naturally
occuring atmospheric precipitation, only increases in plant productivity with greater
acidity were observed; microbial activity reflected plant productivity changes. It is ev-
ident that the effect of acid precipitation on plant growth and microbial activity in soil
is strongly dependent on soil characteristics.
To determine the effect of vesicular-arbuscular (VA) mycorrhizae on the response
of perennial grass to heavy metal and acidic deposition, perennial bunchgrass (Ehr-
harta calycin) was grown with and without VA mycorrhizal infection (Glomus fasci-
culatus) in a sandy soil exposed to a range of heavy metal and acidic treatments for 14
weeks.'8 Heavy metals (Cu, Ni, Pb, Zn, Fe, and Co) were applied in simulated acid
rain (pH 3, 4, and 5.6) at concentrations approximately equivalent to a range of ob-
served smelter effluents. To eliminate any P nutritional problem, the non-VA mycor-
rhizae infected plants were also treated with phosphate to offset enhanced uptake of
this nutrient due to mycorrhizal infection. The results showed that growth yields of
infected plants were half that of noninfected under the highest heavy metal and most
acid (pH 2) treatment, although yields were little different under the less extreme treat-
ments. Increased metal uptake, particularly with respect to Cu (3.3 times greater inter-
nal shoot concentration in mycorrhizal plant as compared with nonmycorrhizal) and
Ni (3.5 times), provided a possible mechanism for explaining the differences in ob-
served plant yields.
The information available indicates that several changes in microbial activities in soil
due to acidification are expected, but no generalizations are possible on the direction
of the effect. This is because the results obtained are totally dependent on the experi-
mental conditions, type of soils tested, and the degree of acidification. It is doubtful,
however, if any of the changes observed with simulated acid rain can be realized in
natural ecosystems in many decades.
VI. SOURCES AND FORMS OF ACIDITY IN PRECIPITATION
It is often assumed that the pH of natural (unpolluted) rainwater is controlled by the

dissociation of the H2CO3 produced from the dissolved atmospheric CO2, has a value
of 5.65, and that any decrease below this value is due to addition of acidic compounds
by human activity. It is true that under laboratory conditions, distilled, deionized water
in equilibrium with atmospheric CO2 may have a pH value close to this theoretical
value, but rainwater cannot and should not be compared with distilled water. The
chemical nature of rainwater collected in the field, and therefore its pH, is influenced
by a variety of reactions that take place before the sample is collected. Natural airborne
materials could be acidic, basic, or neutral. These materials are produced by a number
of sources. In addition to man's activities, these include animal wastes, domestic com-
bustion, land use, deforestation, forest fires, desertification, and volcanic activity. Re-
cent assessment based on acid-base consideration indicates that the relatively lower pH
values (e.g., 4) may not entirely or always be due to anthropogenic acids and that the
recent postulated temporal decrease in pH of precipitation in parts of the eastern U.S.
could well be related to a decrease in the alkalinity content relative to the acid content.7
Consideration of the cycling of water and sulfate through the atmosphere and the
amount and composition of sulfate aerosol expected to be scavenged by a given
amount of cloud water in remote locations indicates that, in the absence of basic ma-
terials (such as NH3 and CaCO3), average pH values of ~5 are expected to occur in
pristine locations. This value must vary considerably due to variability in scavenging
efficiencies as well as geographical patchiness of the S, N, and water cycles. Thus, pH
values might range from 4.5 to 5.6 due to variability of the S cycle alone.98
The form of acidity in precipitation is not clear, but in general two types of acidity
have been recognized, i.e., strong and weak acids. There is a large array of proton
sources in precipitation. Detailed chemical analyses of acid precipitation in the north-
eastern U.S. show the presence of the mineral acids H2SO4 and HNO3, weak acids
(e.g., organic acids and H2CO3), and Bronsted acids (e.g., dissolved Fe, Al and NH,)."
The concentration of these acids in precipitation is presumably due to air pollution.
The relationship to air pollution is based upon two assumptions: (1) that the pH of
precipitation without anthropogenic acidity would be 5.65 and (2) that precipitation
with a pH <5.65 must contain a strong acid of anthropogenic origin; the strong acid
usually suggested is H2SO4 generated by the oxidation of SO2. The assumption that the
H+ found in precipitation at the present time is due to the presence of the strong min-
eral acid H2SO4 or HNO3 has been evaluated. In one such evaluation,100 precipitation
samples were collected on event basis from December 1973 through May 1974 at a site
located in Allegheny County, Penn., 11.2 km due north of the confluence of the Mon-
ongahela, Allegheny, and Ohio rivers, at an elevation of 400 m above sea level. The
sampling station was situated in residential area so as to be unaffected by local sources.
A total of 26 precipitation samples were collected and analyzed for pH, free H* con-
centration, and total acidity. The pH values ranged from 4.12 to 5.62 with a median
value of 4.49. Comparison of the free H* concentration and total H+ concentration
showed that rain is a weak acid. The weak acid nature of rain casts doubt on the
concepts that the acidity of precipitation is increasing and that these increases are due
to strong acids such as H2SO4.100
In a similar study," precipitation samples were collected at a semi-urban community
(Ithaca, N.Y.), a forested area in the White Mountains (Hubbard Brook Experimental
Forest, New Hampshire), and a forested area in the Adirondack Mountains (Paul
Smith, N.Y.). Over 200 precipitation samples were analyzed from February to Septem-
ber 1975. It is unfortunate that the authors do not report the results obtained for
precipitation collected at the various sites; details of sources of acidity in precipitation
collected in Ithaca on July 11, 1975 are given as an example. However, the authors
report that precipitation from the two rural areas was consistently between pH 3.5 and
4.5; the free acidity between 80 and 100% of the total acidity, indicating low quantities
of weak and Bronsted acids. Samples from Ithaca had the same range of pH, but
apparently the free acidities were between 50 and 80% of the total acidity, indicating a
greater abundance of weak and Bronsted acids. The information available indicates
that low pH occurs in both semiurban and rural areas throughout the northeastern
U.S. Semiurban areas seem to have additional amounts of weak and Bronsted acids in
their atmosphere and therefore in their precipitation. As Tyree101 indicates, no cogni-
zance appears to have been taken of the fact that the percentage ionization of most
weak acids increases sharply as the concentration decreases.
The allegation that the recent increase in acidity (decrease in pH) in the northeastern
U.S. is due to H2SO4 produced from SO2 emitted into the atmosphere is not substan-
tiated. Studies show a striking 70% decrease in SO 2 ; since 1950 in precipitation at Ith-
aca, N.Y.17 This change is probably due to the shift in use from coal (high in S) to
natural gas (low in S).120 The drop in the S concentration in precipitation is difficult to
reconcile with the contended recent increase in acidity. This controversy has been stud-
ied in detail.103
There are several N compounds in the atmosphere. These include N2O, NO, NO3,
NH 3 , and ammonium (NH*4) and nitrate (NO3) aerosols. Large portions of the NH 3 and
NO, in the atmosphere may originate from biological processes, but the concentrations
of these gases in the air are greatly affected by industrial activities, automobile traffic,
and feedlot operations. 104106 Of the eight possible oxides of N (N2O, NO, N2O3, NO2,
N2O4, N2OS, NO3, and N2O6), only three are important constituents of the atmosphere.
Of N 2 O, NO, and NO 2 , the most plentiful is the relatively inert N2O. NO2 in the at-
mosphere, however, can react with water vapor to form HNO3, which in turn reacts
with NH 3 or particles in the air and forms nitrate salts such as NH4NO3, which are
brought down by precipitation. The major reactions involving the various gaseous N
compounds are oxidation reactions of both NH 3 and NO2 to form nitrates and neu-
tralization of NH 3 to form (NH4)2SO4 and NH4NO3 aerosols; the data available from
western U.S. suggests the presence of HNO3.107 Atmospheric particles are frequently
found to contain (NH4)2SO4 and NH4HSO4 and their formation from NH3 and SO2 is
probably a significant factor in the scavenging of SO2.108 The major sources for gas-
eous N compounds are biological action and organic decomposition in the soil, to a
lesser extent in the ocean. Only NO and NO2 are emitted as pollutants, at an estimated
annual worldwide rate of about 50 * 106 t.109 It has been estimated that on a global
basis about 99% of the total atmospheric N is derived from biological processes and
only 1% is derived from combustion.106 The residence times for all the N compounds
except N2O are only a few days. For N2O the residence time has been calculated to be
<200 years if there was no loss in the biosphere.110 Biological reaction, however, may
reduce the residence time to about 1 to 3 years.'09
Another source of nitrate in the atmosphere seems to be the fixation by lightning.
The idea that nitrogen is fixed by electrical discharge in the atmosphere was proposed
by Leibig in 1827."" A mechanism for the fixation of nitrogen by lightning has been
proposed.111 Hutchinson112 reexamined the data published by Finnel and Haughton in
1931 and 1932 and concluded that <50% of the nitrate found in precipitation at the
investigated location originated from lightning. However, studies on the relationship
between nitrate concentration in precipitation, collected on a daily basis, and the num-
ber of lightning flashes showed a very weak correlation,113 suggesting that lightning is
a minor source of nitrate in precipitation. Analyzing quarterly precipitation maps for
the U.S., Junge114 concluded that the amounts of nitrogen fixed by lightning can con-
tribute 10 to 20% of the amount of nitrate found in rain. There is, however, no direct
evidence for these estimates.
Plant tops appear to be major sources of organic and inorganic nitrogenous com-
pounds in the atmosphere. A number of nitrogenous compounds are evolved from
leaves of plants, including ammonia and some amines, oxides of nitrogen (NO and
NO2), hydrogen cyanide, and some alkaloids. An excellent review article on this subject
has been prepared.115 Although field measurements on the loss of nitrogenous com-
pounds from tops of plants were reported around the turn of the century, most of the
work in this field was done in the past three decades. Losses of nitrogen in the range
of 10 to 50 kg/ha annually from a variety of agronomic crops have been reported.115
The emission of nitrogenous compounds by plants should account for a significant
portion of organic and inorganic nitrogen in precipitation. Oxidation of the released
nitrogenous compounds in the atmosphere is very likely because in addition to other
photochemical reactions, such compounds can be oxidized by the hydrogen peroxide
(H2O2) in the atmosphere. The presence of H2O2 in rainwater and surface water116 is
believed to be the result of either rainout or washout from the gas phase or from the
chemical reactions with O3 or other reactions in the gas phase constituents in cloud
aerosols.117118 It is unfortunate that the forms and amounts of nitrogenous compounds
evolved from plants are not considered by many investigators in evaluation of the
amounts and/or potential acidity of these compounds in precipitation.
Another source of acidity in precipitation is S, which is always found in trace quan-
tities in the atmosphere. S enters the atmosphere as SO2, a variety of reduced gases,
H2SO4, and various sulfates (SO2;). In unpolluted air, S occurs primarily in three com-
pounds: SO2; in aerosols and SO2 and H2S gases. H2S in the air is normally oxidized to
SO2, which in turn is oxidized to SO3. SO3 dissolves in water droplets to form H2SO4,
which may react further to form sulfate salts such as (NH4)2SO4. Both the H}SO4 and
sulfate salts thus formed exist in air as an aerosol and are removed by precipitation
and to a lesser extent by gravitational settling. It is estimated that a given volume of
SO2 that enters the air is removed by these mechanisms as acid or salt in 5 to 14 days.119
There are several sources for atmospheric S. These include sea spray, H2S and vola-
tile sulfides released from marshlands and sea, and S released by burning S-containing
fuels. Also, plants appear to be natural sources of S in the atmosphere, because recent
work indicate that H2S is emitted from a variety of agronomic and horticultural plants,
including corn (Zea maysL.), soybean (Glycine max(L.) Merr.), cucumber (Cucumis
sativusL.), squash and pumpkin (Cucúrbita pepoL.), cantaloupe (Cucumis mdoL.),
and cotton (Cossypium hirsutum L.), when the roots are treated with sulfate.120
Junge's 121 work in 1960 on the S budget of the global atmosphere indicates that,
excluding the SO2; in sea salt particles, 30% of the atmospheric S is of anthropogenic
origin. Other estimates in 1963 indicate that the S released from sea spray and S-con-
taining fuels account for about 12 and 11%, respectively. The other 77% is released as
H2S from marshlands and sea.1"
An excellent review article on the inventory of the natural and man-made sources of
atmospheric S has been prepared.122 The main natural source of atmospheric S is from
biogenic activities. However, considerable uncertainty seems to exist about the nature
90 CR C Critical Reviews in En vironm en tal Con trol
and amounts of the principal reduced sulfur compounds released. Estimates for 1976,
made with :he aid of emission factors, indicate that man's activities generate about
40% of all atmospheric S emissions and, if it continues to increase at the present rate,
will exceed nature's contribution before the end of this century.122 Estimates on the
contribution of anthropogenic and natural sources to atmospheric S in parts of the
U.S. indicate that where anthropogenic emissions exceed >15 to 30 kg of S per hectare
per year, they tend to dominate the biogenic emissions. This appears to be the case for
industrial Ohio, Illinois, and New England. If 10% of the available biogenic S is re-
leased to the atmosphere, natural or quasinatural emissions may be a significant con-
tributor in air over Minnesota and Wisconsin, Florida, and perhaps the rural areas of
Virginia and remote parts of Arizona and Utah.123
Although natural sources with the exception of volcanoes are not significant direct
sources of SO2, there are a number of other sources that emit gaseous forms of S such
as H2S, CS2, COS, (CH3)2S, and others. Some of these gases, e.g., CS2, COS, and
(CH3)2S, are released to the atmosphere through microbial transformations of S com-

pounds in soils and animal manures.124 Also, (CH3)2S and CS2 are produced by aquatic
microorganisms. Although it seems likely that microorganisms are the major producers
of these gases in the atmosphere, a significant amount of these gases seem to be emitted
to the atmosphere by industrial or biological processes. Among these gases, COS has
been detected in emissions from volcanoes and fumaroles125 and in products emitted
from coal gasification plants.126 At present, not much is known about geographical
distribution and relative source strength of these gases nor how they are oxidized to
SOj in the atmosphere. It is believed that O3 plays an important role in oxidation of
H2S, CS2, and COS; OH radical plays the key part in the oxidation process.127128 Also,
it is possible that these gases are oxidized by other oxidents (e.g., H2O2) that are known
to occur in precipitation.117-118
VII. SIGNIFICANCE OF ACIDITY IN PRECIPITATION
As discussed in Section IV, soil acidification is a natural phenomenon in humid

regions. The acid inputs by precipitation were obviously present independent of man's
activities. At least five natural sources of H* are responsible for soil acidity:
1. Production of H2CO3 from the reaction of atmospheric CO2 with rainwater (CO2
+ H2O ** H* + HCO3) — Theoretically, this reaction, if it proceeds to completion,
would produce water with a pH value of 5.65. In surface and subsurface soils,
however, root and microbial respiration increase the concentration of CO2 in the
soil atmosphere to high levels (4 to 6% are common), that in equilibrium with
water produce pH values <5.
2. Mineralization and oxidation of naturally occurring organic N and S in soils and
litter.
3. Organic acids (e.g., acetic acid and formic acid) produced from decomposition
of litter and plant residues in unmanaged and managed lands43129 — Organic
acids accumulate because of the fermentation character of the microflora of wet
soils. Formation of organic acids is an important process in the development of
acid spodosols.
4. Oxidation of reduced S forms, such as pyrite — This source is very important in
acid sulfate soils130 and in coal mine operations.
5. Acid precipitation — Rainfall probably always contains small amounts of S and
N compounds. In the absence of alkaline-producing compounds, the reaction of
SO2 and the reactive N gases (NO and NO2) in the atmosphere with water produce
H2SO4 and HNO3, respectively. Natural sources contribute significant amounts
Table 3
MAGNITUDE OF ACID INPUTS RELATIVE TO SOIL CATION EXCHANGE
CAPACITY AND AGRICULTURAL OPERATION
H* input
(keq/ha/year) Re]
Acid input from 100 cm of precipitation at pH = 4.0 1

Wet deposition of acid at:
Adirondacks, N.Y. 0.76 132
Connecticut 0.72 5
Soiling, Germany 0.70 66
Welston, Mich. 0.25 133
Wet and dry atmospheric deposition of acidifying substances in Germany 1.52 66
Neutralization capacity of 50 kg CaCO3/ha 1
From N fixation in alfalfa with an annual yield of 10 t/ha 12 33
Potential acidifying effect of 140 kg of anhydrous ammonia applied to corn
100
Exchange capacity to a depth of 20 cm in a course mineral soil with bulk den- 130
sity of 1.3 g/cm3 and CEC of 5 meq/100 g
Exchange capacity of moderately dark silt loam soil with CEC = 15 meq/100 g 390
of the SO2 found in the atmosphere. A preliminary estimate of the mass of SO2
deposited in the stratosphere by the large eruptions of El Chichón volcano on
April 3 and 4, 1982 is 3.3 106 tons.131 Also, SO2 is probably formed from oxida-
tion of reduced S gases evolved from soil, marshes, and plants. These are some
of the reasons why the pH of precipitation in unpolluted areas varies from 4 to 6
and why some knowledgeable scientists were led to suggest that the pH 5.6 should
not be taken as a reference point in studies involving precipitation chemistry.7'8
The relative magnitude of addition of acidity from various sources and the relative
significance of these sources to other soil properties are shown in Table 3. In general,
the acidity produced from application of 140 kg of anhydrous ammonia per hectare in
1 year produces acidity that is equivalent to the acidity added by 100 cm of pH 4
rainfall for 100 years. The acidity produced from organic acid during litter decompo-
sition on forest soils is even greater than that added by N fertilizers. Furthermore, it is
well documented that the acidity of rainfall onto forests is removed on interception by
the vegetation cover, presumably through an exchange process.134 With near neutral
precipitation pH, the pH of throughfall, however, would be similar to that of the
incoming precipitation. The concentration of throughfalls with respect to the various
cations and anions present in plant tissues are much higher than those of the same
elements in the incoming precipitation,86'87 i.e., the concentration of sulfate, nitrate,
calcium, and potassium are much higher in throughfall than in the rainwater. Leaching
of nutrient elements by rainwater from agronomic crops has also been demonstrated.90
Apparently even when the pH values of precipitation, throughfall, litter solution, soil
solution, and drainage water are between 5.6 and 6.7, the pH of stemflow in Inga sp.
and Pentaclethra sp. are as low as 3.3 and 3.7, respectively.135
Application of anhydrous ammonia or ammonium-producing fertilizers to soils re-
sults in acidification of soils; oxidation of ammonium ions to nitrate by bacteria in soil
produces 2 mol of H* for every mole of N oxidized. The effect of this process in soils
has been studied for more than 50 years.136137 In soils that are poorly buffered with
respect to pH changes, heavy application of nitrogen fertilizer can produce conditions
of acidity that hinder agricultural production (Table 3). Addition of limestone is usu-
ally recommended to correct the problem. Recent work comparing acidification of
Minnesota soils by nitrogen fertilization and acid rain showed that in a typical corn-
soybean rotation, using 100 kg of N per hectare annually for corn production, a 0.25
unit pH drop (from 6.26 to 6.01) was obtained in Nicollet loam (Aquic Hapludoll) in
about 38 years.28 This much drop in pH of soil, however, is not significant because
such variation in pH values can be expected in soil samples obtained from the same
field. Furthermore, the small decrease in pH is not significant in terms of changing the
chemical and biological properties in such soils. Application of nitrogen fertilizers to
surface soils under the no-till management system causes greater acidification of the
soil surface as compared with fertilizer incorporation or injection of anhydrous am-
monia.138
Similar to the result reported from Minnesota,28 Wiklander19 could not support the
postulated cause of forest productivity losses in Sweden because he found no evidence
of pH changes in a podzol soil in Sweden over a 39-year period, from 1934 to 1973.
Wiklander19 further discussed the sensitivity of various soil types to acidic precipitation
and suggested that there would be no effect on calcareous soils which have a very high
buffering capacity, while acidified soils with a pH <5 would be only slightly affected
since most of the cation exchange sites are already occupied by H* (most forest soils
fall within this group). He considered sensitive soils to acidic precipitation to be non-
calcareous sand soils with pH values >6. No results of long-term studies are available
to support this last conclusion
In a study conducted by Linzon and Temple20 in Ontario, Canada, pH values of six
soil profiles were measured in 1978 and compared with those obtained in 1960. They
found that in most cases, the pH data were about the same for both years, and the
small differences were attributed to differences in techniques of pH measurement. The
only soil series which showed a definite decline was the Magnetawan series, in which
the pH of the Ao horizon was 5.7 in 1960 and 4.8 in 1978. Interestingly enough, this
soil was a dark brown silty clay loam, nonpodzolized, and was the only soil in the
original 1960 survey to have a pH >5 in all horizons. Because the original pH measure-
ment decreased with depth, not increased as with most other soils, Linzon and Tem-
ple20 questioned the original pH measurements of this soil profile. All the other soil
types were podzolized sandy soils, with pH values <5 in the upper horizons, and none
of these soils showed any significant change in pH over the 18-year period. From this
study, Linzon and Temple concluded that acidification of soils is not readily altered by
acidic precipitation and that drainage through these soils to rivers and lakes may be as
acidic as the incoming precipitation. They suggested that their findings may explain
why two nearby lakes both exposed to precipitation of the same pH may have different
lakewater pH values.
Another important cause of soil acidity is the fixation of atmospheric nitrogen by
leguminous crops (Table 3). For example, Nyatsanga and Pierre33 found that under
intensive cropping in the greenhouse the amount of N fixed by "Vernal" alfalfa during
a growth period of 167 days (3 cuttings) or by soybean (Glycine max) during a growth
period of 67 to 73 days was sufficient to lower the pH of the soils by more than 1 pH
unit. The two soils used in this experiment were Nicollet clay loam, an Aquic Haplu-
doll, and Wadena loam, a Typic Hapludoll, having pH values in 0.01 MCaCU of 4.63
and 4.58, respectively. On the basis of the data obtained from this experiment, Nyat-
sanga and Pierre33 concluded that N fixation from an annual yield of 10 metric tons
per hectare of alfalfa would produce acidity in the soil equivalent to 600 kg of CaCO3
per hectare (equivalent to 12 kg of H* per hectare annually). Thus, the acidity produced
in soils by N fixation is of considerable significance under certain cropping conditions.
Undoubtedly, significant amounts of acidity are produced from N fixation by other
plants species in forest ecosystems. The global biological N fixation by legumes (agri-
culture), grasslands, and forests has been estimated to be 35, 45, and 40 Tg year,
respectively. The estimated biological N fixation in aquatic systems ranges from 20 to
120 Tg year.110 It has been suggested that the acidity produced from N fixation process
may also have been an important factor in soil genesis and development.33
Black139 elegantly demonstrated the effect of N fertilization on tree growth and pro-
duction of acidity in soils. He shows a cross section of the trunk of a white ash tree
from Harvard Black Rock Forest in New York. In 1935, when the tree was apparently
50 years of age, the area where the tree was growing was treated with 969 kg ha of
nitrogen fertilizer as an equal weight of ammonium sulfate and sodium nitrate. No
fertilizer was applied subsequently. The cross section of the tree shows increased thick-
ness of the growth rings for a number of years after the fertilizer was applied. The
theoretical acidity produced in the soil by the ammonium sulfate in the fertilizer would
be equal to the acidity of 7655 cm of acid rain of pH 4. It would have required 3892
kg of calcium carbonate per hectare to neutralize this if the fertilizer had been pure
compound applied in the absence of vegetation. However, plants influence the effect
of nitrogen fertilizers on soil acidity because they absorb unequal numbers of cation
equivalents and anion equivalents. Nitrate is generally the anion absorbed in greatest
quantity. Most crop plants take up more equivalents of anions than of cations. As a
consequence, the acidity developed in the soil from nitrogen fertilization in the pres-
ence of most crops is less than the theoretical value. Data are available showing the
effect of different crops on the acidity produced in the soil by addition of ammonium
nitrate.30
Recently McFee and Kelly140 discussed the degree of pH shift in a typical midwestern
soil (cation exchange capacity = 20 meq/100 of soil) and concluded that if the pH of
precipitation was 4 and the annual input was 100 cm (40 in.) (see Table 3), the reduc-
tion in soil base saturation in the plow layer (20 cm) due to acid precipitation could be
19% in the 100 years. This would result in a decrease of a 0.6 pH unit. This decrease
in pH would occur only if there were no concurrent inputs of basic cations and if the
exchange of H+ was complete. It is well known, however, that there is input of basic
ions such as Ca2* and Mg2*. The acidifying effect of the H+ in precipitation is lessened
by accompanying neutral salts." Thus, the acidity of precipitation, such as that found
for rainfall in areas removed from point sources in the U.S. and Canada,85 should have
little or no effect on soil chemical and biological processes. An additional fact is that
the effect of H+ concentration in precipitation on soils cannot be assessed because
precipitation contains small amounts of NHÎ, and this ion has acidifying potential of a
similar magnitude to direct inputs common in rainfall. Therefore, the amount of ac-
idity added in precipitation, especially to agricultural soils, is insignificant in relation
to the acidity from other sources (Table 3; also see Section IV).
Soils vary in many properties even within a few square kilometers. Therefore, the
effect of acid precipitation, though not measurable within a lifetime, theoretically
would vary depending on the cation exchange capacity (CEC), percent base saturation,
mineral composition, texture class, and the type and nature of the soil organic matter.
The rapidity and direction of change induced by acid precipitation are strongly influ-
enced by these properties. Some of these properties are discussed by Wiklander19 and
Bache.54 Even with the complexity of the soil environment and the multitude of sources
of acidity in managed and unmanaged ecosystems, attempts have been made to cate-
gorize soil regions according to their sensitivity to acid rain. Though it is not possible
to derive any meaningful scheme of soil sensitivity rating, nevertheless, this type of
work has generated interest among ecologists. Soil scientists are aware of the fact that
variability within a soil and inclusion of other soils within mapping units severely limit
the interpretation that can be made of any sensitivity rating maps. In addition, there
are obviously many unknown or poorly defined rates of change in the field that com-
plicate predictions of susceptibility of soils to acid precipitation. For example, base
addition by dry deposition, cycling of the various nutrients, or degree of mineral
weathering are seldom known. With all these complex problems, McFee141 developed
a relatively simple scheme for grouping soil regions into sensitivity classes. After
grouping all soils that are calcareous or subject to frequent renewal by such events as
flooding into the nonsensitive group, he classified the others on the basis of their CEC.
He considered many of the potentially serious soil effects tied to changes in pH which
he believes are controlled by CEC. In this classification scheme, McFee141 grouped the
soils rather arbitrarily as "sensitive" if the CEC was low enough that 25 years of acid
precipitation (100 cm at pH 3.7 per year; condition which does not occur in nonpoint
source areas) would contain acid equivalent equal to 25% of the CEC in the top 25
cm. Soils with a higher CEC, in the range of 6 to 15 meq/100 g of soil were considered
"slightly sensitive". The same amount of acid input would equal only 10 to 25% of
their CEC. Others with higher CEC were considered "nonsensitive". Being aware of
the complex nature of soil problems, McFee141 carefully makes so many qualifying
statements as to make any classification scheme useless. For example, he concludes
that since agricultural manipulations are massive in their input compared to that of
acid precipitation, measureable effects are improbable on cultivated soils even in the
"sensitive" class. It is clear that since forest soils are usually acidic in reaction, meas-
ureable effects are not possible in such soils either.
Another classification scheme for acid precipitation sensitivity rating of soils is that
developed by Klopatek et al.142 This system utilizes the Geological Data Base of Oak
Ridge National Laboratories which is based on soil descriptions from the Soil Conser-
vation Service for "typical" soils of each county. The sensitivity criteria considered in
this scheme are CEC and percent base saturation. The more sensitive classes in this
scheme include those soils with low CEC (<12 meq/100 g of soil), with a pH >5.5 and
a medium to high percent base saturation (30 to 50%), and those with higher CEC (12
to 20 meq/100 g of soil) if their percent base saturation was 30 to 40%. This classifi-
cation scheme was criticized for including some cultivated soils, ignoring sulfate ad-
sorption, and including as sensitive some soils of relatively high buffering capacity.143
A third system of sensitivity classification was proposed by Wang and Coote144 rat-
ing agricultural lands to long-term acid precipitation in Canada. They considered CEC
and percent base saturation in determining the fraction of exchangeable bases leached
from the plow layer (15 cm) in 25 years with inputs of CaCO3 of 60 keq/ha/year. This
is about the same criterion proposed by McFee141 and Holowaychuk and Lindsay,145
except it is based on less input (1.2 vs. 2.0 keq/ha/year acid input) and includes percent
exchangeable bases. All these schemes of rating soils for sensitivity to acid precipitation
ignore acid consumption and weathering reactions, the recycling of bases by vegeta-
tion, the influence of accompanying basic cation inputs, acidification of soils by leg-
uminous plants, and the influence of fertilizers and lime.
VIII. DEPOSITION OF NUTRIENTS
A total of 16 elements are required for plant growth and development. These are
grouped into macro- and micronutrients. The macronutrients are those elements re-
quired in relatively large amounts, including N, P, K, S, Ca, and Mg. The micronu-
trients are those elements required in trace amounts, often referred to as trace ele-
ments, including Mo, Cu, Zn, Mn, Fe, B, and Cl. These elements are removed from
the atmosphere by dry and wet depositions. Although the chemistry of wet deposition
has received the most attention, significant amounts of nutrients, heavy metals, pesti-
cides, and other organic compounds are removed from the atmosphere by dry deposi-
tion. While it is relatively easy to determine the concentrations and amounts of inor-
ganic ions and organic compounds added by wet deposition, it is difficult to estimate
the quantities added by dry deposition. Atmospheric deposition of nutrients and other
CONCENTRATION (mg/l)
0.01 0.1 1.0 10 100
Cropland runoff
Non-cropland runoff
Drainage N
FIGURE 7. Range of inorganic nitrogen, sulfur, and phosphorus concentrations in natural waters.
chemicals is absorbed by soils, plants, and surface waters (lakes) without being washed
out by rain and snow. The proportion of dry to wet deposition depends on the distance
from the source of pollution and atmospheric humidity.
Water pollution by sulfate from nonpoint sources is usually not of concern; water
pollution by nitrate and phosphate from leaching, runoff, and erosion, especially from
managed land, can contribute to quality of lakes and streams, and therefore has re-
ceived the most attention. Thus, numerous reports are available on the concentrations
of N, P, and S in waters and sediments. This makes comparison of these elements in
waters derived from managed and unmanaged lands with those in precipitation possi-
ble. The usual ranges of values in concentrations and spatial rates are presented in
Figures 7 and 8.
For comparison of contribution of N and S deposition to requirements of crops of
these elements, the N and S contents of various crops are summarized in Table 4. The
rates of plant nutrients (N, P, and K) applied to agricultural soils in the U.S. from
1965 to 1980 are shown in Table 5. The more intensive corn production systems devel-
oped in recent years led to increases in the rates of application of N, P, and K fertil-
izers. Although S deficiencies have been reported in many parts of the U.S. and other
areas around the world (see Section IV), current deposition of S and that absorbed by
the aerial portions of plants seem to meet the requirements of many crops and perhaps
forest trees. This explains why world-wide need for S as a fertilizer has not paralleled
the need for N. Additions of macro- and micronutrients to soils will be discussed in
the following sections.
A. Macronutrients
The macronutrients that receive the most attention are N, S, P, K, Ca, and Mg. Of
these elements, only N and S and the micronutrient Cl can be present in gaseous forms,
salts in aerosols, and compounds associated with suspended particulates in the atmos-
phere. The other elements (P, K, Ca, and Mg) are present in the atmosphere in sus-
pended particulates.
SPATIAL RATE (kg/ha/yr)

0.01 0.1 1.0 10 100
Precipitation ¡00000000*8000*900090000
PL •N
Cropland runoff
PC
Non-cropland runoff
Drainage
PL J
Cropland sediment V///////,
Non-croplandp
sediment
FIGURE 8. Range of spatial rates of inorganic nitrogen, sulfur, and phosphorus (total for sediments) in
natural waters and sediments.
1. Nitrogen
Most of the information available on N in precipitation is concerned with inorganic
N (NHi and NO!). Fractionation of N in precipitation in Indiana and Wisconsin indicates
the presence of significant amounts of organic N.147 The inorganic N added by precip-
itation varies not only among states, but also among sites within each state and during
storms. For example, Table 6 shows inorganic N deposition by precipitation during
1970 to 1980 at several sites in Arizona, Florida, Iowa, Michigan, Minnesota, Ne-
braska, and New York. Expressed in kilograms per hectare the total annual inorganic
N deposited varied from 3.5 in Florida to about 20 at one site in Nebraska. The
amounts of inorganic N (NOâ + NHi)-N deposited by precipitation in 1980 in North
America ranged from 0.5 to 7.5 kg/ha. 85 These are similar to those reported for Con-
necticut from 1929 to 1948 (3.1 to 7.4 kg/ha/year). 5 Generally, however, the amount
of inorganic N added by precipitation is small compared with that mineralized from
soil organic matter and added by fertilizers. The data indicate that precipitation adds
inorganic N equivalent to 3 to 10% of the N added as fertilizers for corn production
in many areas. This amount of N would be significant for crops that receive little or
no N fertilizers. Similarly, such amounts of N would be significant for forests, unim-
proved pastures, and rangeland production.
Seasonal variations in precipitation N concentration are not evident from the data
available in Iowa and other midwestern states.147 It has been shown, however, that a
large portion of the precipitation occurs during the periods before crops are established
and that precipitation during these periods accounts for greater surface runoff losses
of N. In a study of the contribution of precipitation N to surface runoff discharge,
Schuman and Burwell148 found that 69% of the N discharged to surface runoff from
Table 4
NITROGEN AND SULFUR CONTENT OF
VARIOUS CROPS
Nitrogen Sulfur
Crop Yield/acre (kg/ha) (kg/ha)
Corn 200 bushel 359 49

Grain sorghum 8000 lb 292 43
Wheat 80 bushel 168 25
Oats 100 bushel 112 22
Rice 145 bushel (6500 lb) 151 20
Soybeans 50 bushel 207 11
Peanuts 30001b 247 28
Cotton 2.5 bale 140 26
Tobacco 2800 lb 107 24
43
Alfalfa 6 tons 376

Clovers 4 tons 179 20
Grasses 4 tons 135 18
Potatoes 400 bushel 224 20
Cabbage 20 tons 146 41
Turnip 25 tons 128 43
Onions 20 tons 135 28
From Bixby, D. W. and Beaton, J. D., Sulphur-Containing Fertil-

izers: Properties and Applications, Tech. Bull. 17, The Sulphur In-
stitute, Washington, D.C., 1970. With permission.
Table 5
FERTILIZER CONSUMPTION IN THE
U.S. (kg/ha)
Period
Crop trient 1965 1970 1975 1980
Corn N 73 119 111 139

P 20 31 25 28
K 33 57 51 65
Cotton N 71 63 56 57
P 16 13 10 11
K 23 20 16 13
Soybeans N 1 3 3 5
P 3 5 5 8
K 6 13 13 23
Wheat N 17 27 32 44
P 6 7 7 8
K 5 5 7 7
Adapted from Hargett, N. L. and Berry, J. T., 1980 Fer-

tilizer Summary Data Bull. Y-165, National Fertilizer De-
velopment Center Muscle Shoals, Ala., 1980.
the sampled events could be accounted for by precipitation originated N on a wa-

tershed fertilized at 168 kg/ha, whereas 53% of the N discharged from a second wa-
tershed fertilized at 448 kg of N per hectare could be attributed to N originating in
precipitation. They concluded that, on an annual basis, the surface runoff N discharge
accounts for only 20% of that present in total incoming precipitation.
Junge114 conducted a nationwide survey of NH4-N and NO3-N in rainwater samples
of 60 sites in the U.S. during 1955 and 1956. He found an even distribution of both of
Table 6
AMOUNTS OF INORGANIC NITROGEN DEPOSITED BY
PRECIPITATION AT VARIOUS LOCATIONS
NO3N Total
State Site NHÎN (kg/ha/year) inorganic N Period
Arizona Tombstone 3.5 3.5 1975—1978

Florida Gainesville
(I) 1.2 2.3 3.5 1976—1977
(II) 1.5 2.8 4.3
Iowa Ames 6.0 6.0 12.0 1971—1973
(7.4) (3.0) (10.4)
Atlantic (5.7) (5.0) (10.7) (1980)
Boone 6.0 7.2 13.2
(7.1) (4.0) (11.1)
Charles City 7.2 6.0 13.2

Crestón 6.7 6.0 12.7
Eldora 5.0 4.8 9.8
Fairfax (7.6) (5.5) (12.1)
Guthrie Center 7.1 7.2 14.3
Sigourney (3.6) (8.9) (12.5)
Storm Lake (8.6) (5.5) (14.1)
Tripoli (8.8) (5.4) (14.7)
Michigan Pellston 3.1 4.0 7.1
Houghton Lake 2.1 3.2 5.3
Minnesota Lamberton — — 13.6 1975—1978
Morris — 5.8
Staples — — 6.3
Waseca — — 11.1
Nebraska Clay Center 4.9 3.6 8.5 1970—1972
Concord 13.7 5.8 19.5
Mead 8.0 5.2 13.2
North Plate 4.4 3.3 7.7
Scottsbluff 3.9 1.8 5.7
New York Aurora 3.3 4.3 7.6 1970—1971
Geneva 3.5 4.8 8.3
Ithaca 3.2 4.2 7.4
From Tabatabai, M. A., Agricultural Nonpoint Sources and Pollutant Processes, Schaller,
F. W. and Bailey, G. W., Eds., Iowa State University Press, Ames, 1983. With permission.
these forms of inorganic N in rainwater and found no correlation between these inor-
ganic N forms and agricultural activities. He did find, however, that areas having soils
of low pH values correlated with areas having low concentrations of NH4-N in rain-
water and that alkaline-soil regions seemed to be associated with high concentrations
of NH4-N in rainwater. No recent studies have been conducted to support this finding,
but the information available from the North Central Region does not support the
conclusion reached by Junge.147
2. Phosphorus
The concentration and accumulation of P by precipitation is small relative to that of
N. This is mainly because no P gases are emitted into, or exist in, the atmosphere. The
only sources of P in precipitation are airborne particulate matters, mostly dust. In
addition to the amounts of P added to soils and water surfaces by precipitation, a
significant amount of P is removed from the atmosphere as dry fallout between storms.
Estimation of the P added by fallout is difficult. It has been shown, however, that
most of the P in rain is associated with dust, a significant portion being organic in
Table 7
AMOUNTS OF PHOSPHORUS DEPOSITED BY
PO4-P
State Site (kg/ha/year)" Period
Arizona Tombstone 5.8 1978

Florida Gainesville
(I) 0.41 t 1976—1977
(II) 1.02 t
Iowa Ames 1.41 1980
Atlantic 0.87
Çoone 0.48
Fairfax 0.60
Storm Lake 1.37
Tripoli 1.28
Michigan Pellston 0.25 t 1973—1974
Saginaw 0.21 t
Houghton Lake 0.31 t 1974
Ottawa National Forest 0.46 t
Minnesota Cloquet Forestry Center 0.22 t 1975
Marcell Experiment Station 0.49 t 1971—1973
Nebraska Clay Center 0.60 1970—1972
Concord 1.20
Mead 0.40
North Platte 0.10
Scottsbluff 0.40
New York Aurora 0.06 1972
Geneva 0.05
Ithaca 0.05
Wisconsin Drummond 0.16 t
" t = total P.
From Tabatabai, M. A., Agricultural Nonpoint Sources and Pollutant Proc-

esses, Schaller, F. W. and Bailey, G. W. Eds., Iowa State University Press,
Ames, 1983. With permission.
nature.147 In general, storms blowing in from oceans are very low in P. P can also be
associated with fly ash and smoke, as indicated in the concentration of P in rain from
several sites in southern California.147 Comparison of results from several locations in
the U.S. indicates that total P concentration of precipitation in the Great Lakes area
and coastal regions is smaller than the soluble P in many inland areas. The yearly input
of 0.1 to 1 kg of P per hectare is very common, but P loading as low as 0.05 kg/ha
and as high as 5.8 kg/ha has been reported for sites in New York and Arizona, respec-
tively (Table 7). The amount of P added by precipitation is insignificant compared
with that present in soils and added fertilizers. The P loading by precipitation is signif-
icant, however, compared with concentrations of P in surface runoff, especially from
noncropland.
3. Sulfur
Continuous monitoring of the concentration of SO4-S in precipitation in Iowa and
Wisconsin indicated that it was seasonal and inversely related to the monthly precipi-
tation.149150 The greatest concentration of SO4-S was found during the fall and winter
when precipitation was low, and the least during the summer and spring when precip-
itation was high. In the north central U.S., the high concentration of SO4-S during the
Table 8
AMOUNTS OF SULFUR AND CHLORINE DEPOSITED BY
ci-
SO2;-S (kg/ha/
State Site (kg/ha/year) year) Period
Arizona Tombstone 4.1 1.7 1975—1978

Florida Gainesville
(I) 8.0 11.8 1976—1977
(II) 9.0 22.7
Iowa Ames 16.8 (2.2) 1971—1973
(7.1)
Atlantic (6.0) (4.8) (1980)
15.6
Boone (1.1)
(6.1)
Charles City 13.2 —
Crestón 16.7 —
Eldora 17.3 —
Fairfax (17.1) (2.3)
Guthrie Center 16.1 —
Sigourney (16.1) (12.6)
Storm Lake (5.7) (3.4)
Tripoli (15.3) (5.1)
Michigan Antrim 9.0 — 4/59—3/61
Clinton 10.3 —
Ingham 14.0 —
Kalamazoo 13.5 —
Ottawa National Forest 8.1 —
Pellston 6.0 —
Saginaw Bay 22.7 —
Minnesota Cloquet Forestry Center 2.1 — 1975
Marcell Experiment Station 5.6 — 1978—1979
Nebraska Alliance 5.7 — 1959—1960
Auburn 13.1 —
Hasley 7.3 —
Lincoln 9.2 —
Red Cloud 6.1 —
Pierce 4.6 —
Valentine 4.6 —
New York Aurora 16.4 — 1970—1971
Geneva 11.5 —
Ithaca 13.0
From Tabatabai, M. A., Agricultural Nonpoint Sources and Pollutant Processes, Schaller, F. W.
and Bailey, G. W., Eds., Iowa State University Press, Ames, 1983. With permission.
fall and winter could be due to home and business heating. The low concentrations
during the spring and summer could be due to washing by precipitation and to lower
concentrations of S gases in the atmosphere resulting from direct absorption of SO2
and other gases by exposed soil and plant surfaces. These processes of addition and
removal of S gases to and from the atmosphere seem to play major roles in the ob-
served seasonal concentration of SO4-S in precipitation in many areas of the U.S.
The amounts of S deposited by precipitation at several sites in Arizona, Florida,
Iowa, Michigan, Minnesota, Nebraska, and New York are reported in Table 8. Ex-
pressed in kilograms per hectare, the annual addition of S ranges from 2 at Cloquet
Forestry Center in Minnesota to 23 at Saginaw Bay (industrial) in Michigan. Precipi-
tation S contributions at 3 sites in New York are very similar to those found in Iowa
and some sites in Michigan and Nebraska. The annual rates of deposition in North
America for 1980 ranged from 0.5 to 10 kg/ha.85 The concentration of S, and therefore
its accumulation, does not seem to have changed significantly in the north central
region of the U.S. For example, the average addition of S by precipitation during 1971
to 1973 in Iowa (16 kg/ha) and during 1969 to 1971 in rural areas of Wisconsin (17 kg/
ha) is similar to that reported over a half century ago.149150 Erdman151 estimated the
annual precipitation-originated S in Ames, Iowa in 1923 to be 17 kg/ha, and recent
estimates for this site are 17 (1971 to 1973) and 7 kg/ha (1980). These annual rates are
similar to those reported for Zhejiang province in China (13 to 27 kg/ha) and Russia
(10 to 22 kg/ha).152153 The least amount of S deposition in Russia is in tundra and
increasing in order through forest zone, forest-steppe, and steppe. Harper's154 sum-
mary of the data available before 1942 indicated that rural areas of the U.S. were
receiving precipitation-originated S in amounts similar to those found currently in
many areas.
As is true of N, the data available for S in precipitation in Iowa indicate that between
60 and 80% of the S is deposited during the spring and summer.14' The amount of S
(2 to 20 kg/ha annually) added by precipitation in most rural and forested areas of the
U.S. is important to forestry and crop production, especially of agricultural crops.
Laboratory and greenhouse experiments have shown that many soils of the U.S. do
not contain sufficient plant-available S to meet crop requirements for this element, yet
no S deficiency symptoms have been reported.35 Since it is known that soils and plants
absorb SO2 directly from the atmosphere, it is believed that the S requirements of crops
in many areas are met in this manner.155 A study in Wisconsin showed that under
optimum yield 44% of the S in alfalfa is derived from atmospheric sources.148 It has
been estimated that between 3 and 16 kg of S per hectare are lost by tile drainage in
Iowa, but little information is available about losses by surface runoff from cropland
and noncropland.155
4. Basic Cations
Precipitation may contain K, Na, Ca, and Mg. These elements originate mainly in
particulate and dust materials suspended in the atmosphere. Information on these nu-
trients in precipitation is available from several sites in North America and England
(Table 9). The cations in this group of nutrients are highly reactive with clay and or-
ganic matter in soils, and it is very unlikely that they contribute to amounts found in
surface runoff. The Ca and Mg in the atmosphere should act as neutralizing agents for
any H2SO4, HNO3, and HC1 produced from S, N, and Cl gases. Also, these basic
cations in precipitation directly reduce the effect of acidity by restoring the base satu-
ration of soils.
B. Micronutrients
Micronutrients and other trace elements and heavy metals in precipitation originate
from various sources. These include industrial activities, automobile traffic, volcanic
activities and fly ash, and soil particles. In contrast to organic compounds, only a few
metals in the atmosphere are in the vapor phase. Of the various elements detected in
the atmosphere (Table 10), only mercury (Hg) has a sufficient vapor pressure at am-
bient temperature to be present in the vapor phase. These metals may be removed from
the atmosphere by either wet or dry deposition as other pollutants are. The amount of
metal in either wet or dry deposition is directly related to the concentration of the metal
in the atmosphere.
/. Chlorine
As is the case with Na+, the concentration of Cl" is high in the coastal regions because
Table 9
AMOUNTS OF BASIC CATIONS DEPOSITED BY
Basic cation deposition,

kg/ha/year
State, province,
or country Site K Na Ca Mg
Arizona Tombstone 1.0 0.8 6.1 0.7

England — 1.4 17.0 3.5 2.2
Florida Gainesville
(I) 2.4 5.3 5.0 1.4
(II) 3.1 9.9 9.8 2.2
Indiana Indianapolis 1.2 2.6 6.9 —
Iowa Ames 2.7 1.2 4.9 1.4
Atlantic 3.2 2.0 6.9 1.5

Boone 1.1 1.5 4.4 1.7
Fairfax 1.4 1.6 11.5 1.1
Sigourney 3.5 10.0 14.6 3.8
Storm Lake 3.9 2.0 6.6 2.9
Tripoli 2.8 4.0 12.8 3.7
Michigan Pellston 2.7 6.3 10.5 1.7
Minnesota — 1.1 1.1 3.5 0.7
New Hampshire Hubbard Brook 0.7 1.6 2.7 0.6
New York Aurora 1.1 1.0 4.8 0.8
Geneva 0.4 0.8 3.3 0.6
Ithaca 5.6 1.4 6.5 1.5
Ontario — 0.7 0.8 8.5 3.0
Oregon H. J. Andrews 0.2 1.8 5.0 1.0
Tennessee Walker Br. 3.4 4.0 14.2 2.2
Note: The data for England, Indiana, Minnesota, New Hampshire, On-
tario, Oregon, and Tennessee are from Reference 140. All others
are from Reference 158. The data for Iowa are the actual deposi-
tion in 1980; those reported in Reference 158 were calculated by
using the long-term annual average (80 cm) of precipitation.
Table 10
TRACE ELEMENTS AND HEAVY
METALS FOUND IN
PRECIPITATION
Aluminum Al Lead Pb
Antimony Sb Manganese Mn
Arsenic As Mercury Hg
Bromine Br Molybdenum Mo
Cadmium Cd Nickel Ni
Cerium Ce Scandium Se
Cesium Cs Selenium Se
Chromium Cr Silver Ag
Cobalt Co Thorium Th
Copper Cu Vanadium V
Iron Fe Zinc Zn
From Tabatabai, M. A., Agricultural Nonpoint

Sources and Pollutant Processes, Schaller, F. W.
and Bailey, G. W., Eds., Iowa State University
Press, Ames, 1983. With permission.
Table 11
ESTIMATED DEPOSITION OF
MICRONUTRIENTS BY PRECIPITATION
Deposition Number of
Micronutrient Site (g/ha/year) references
Cobalt Rural <l,000 1

Copper Remote 0.01—0.7 4
Rural 10—74 8
Urban 160—600 3
Manganese Remote 6.2 1
Rural 21—500 4
Urban <l,000 1
Molybdenum Rural <10 1
Zinc Remote 0.01—25 3
Rural 40—11,000 9
Urban 350—15,800 5
From Tabatabai, M. A., AgriculturalNonpoint Sources and

Pollutant Processes, Schaller, F. W. and Bailey, G. W.,
Eds., Iowa State University Press, Ames, 1983. With per-
mission.
these ions are associated with sea spray.1" The deposition rate may range from 2 to 22
kg of Cl" per hectare per year (Table 8).
2. Trace Metals
The concentration of the micronutrients Co, Cu, Mn, Mo, and Zn in precipitation
varies with locations in remote, rural, and urban areas. J " In general, the concentra-
tions of these elements are lowest in remote areas and highest in urban areas. Estimated
deposition of micronutrients by bulk precipitation (wet and dry deposition) is reported
in Table 11. The concentrations and amounts of micronutrients in precipitation should
be considered rough estimates since most of the data seem to have been obtained by
extrapolation from few measurements. Other problems related to the information
available on metal concentrations and rates of deposition are:
1. Observation periods range from as short as 1 month to as long as 2 years.

2. Collection frequencies range from event sampling to monthly and even yearly
sampling.
3. Collector designs differ.
4. Sample treatment (filtered vs. unfiltered) and analytical methods vary.
5. Distinctions between remote, and particularly between rural and urban, sites are
subjective.
Micronutrient additions by precipitation to soils are small relative to the amounts

present in soils. It is very doubtful if the micronutrients present in precipitation would
significantly alter the quality of runoff water from managed and unmanaged land.
However, the potential effect of metals in dry and wet deposition on noncropland
deserves investigation, especially in urban areas and areas close to industrial activities.
The amounts of micronutrients in the above ground portion of some major field
crops (alfalfa, corn, cotton, soybeans, and wheat) at near-average yields are estimated
at <0.2 kg/ha of B and Cu, <0.6 kg/ha of Mn and Zn, and <2.2 kg/ha of Fe. The
concentration of Mo in the tissues of these crops are not well known, but its removal
by crops is estimated to be <0.03 kg/ha.1S9
Major sources of micronutrient additions to soils are crop residues and litter in man-
aged and unmanaged soils. Other major sources of these elements in managed soils are
fertilizers, farmyard manures, and municipal wastes. Crop removal and erosion of
surface soil contribute to the main micronutrient losses. Plant availability of all mi-
cronutrients except Mo increases with increasing soil acidity, but a large fraction of the
increased uptake usually would be recycled to soils with the return of the crop residue
in managed land15' or litter in forest soils. The concentrations of Pb, Cu, and Zn,
along with organic matter of the forest floor at Camel's Hump, Vt., increased between
1966 and 1980.160 Although, in general, the soil pH in the organic horizon increased
within this same period, the increases in concentration of these elements have been
attributed to atmospheric deposition rather than to nutrient cycling.
Changes in soil pH due to acid precipitation are minimal in most agricultural soils
because of the relatively high buffering capacities of these soils, and most forest soils
are naturally acid in reaction. Modern farming practices such as liming and return of
crop residues, especially under the minimum tillage and no-till systems, also may ov-
erride depositional effects. Therefore, micronutrient cycling in most agroecosystems
should not be significantly affected by acid precipitation. It is evident that since the
chemistry and mobility of the micronutrients are directly related to significant changes
in pH of the soil, it is important to document the acidification of soils by acid precip-
itation before meaningful studies can be conducted to assess the impact of acid precip-
itation on micronutrient cycling in soil systems.
IX. CONCLUSIONS
Soil formation is an acidifying process that involves dynamic chemical and biochem-
ical equilibria. Chemical weathering involves hydrolysis, hydration, oxidation-reduc-
tion, carbonation, and solution of compounds and elements found in the parent ma-
terials. The sources of acidity in soils include H2CO3 formed from high CO2
concentrations in the soil atmosphere produced from root and microbial respiration,
acidity produced in mineralization of organic N and S, N fixation by leguminous
plants, NHî-forming fertilizers, organic acids produced from crop residue and litter
decomposition, and addition in precipitation. Additions of acidity in precipitation to
soils are insignificant in comparison with the acidity produced in natural processes and
by agricultural soil amendments.
Although reports indicate that in recent decades the acidity of rain and snow has
increased sharply over wide areas, 1 " this conclusion has been questioned.103 The infor-
mation available to this time indicates that acid rain has not adversely affected soils.
The mean annual pH of precipitation in Connecticut is 4.2, which is one of the lowest
in North America, and recent studies indicate that there is no evidence of damage to
agricultural crops and little or no reason to believe that the forests in that state have
been adversely affected to date.18 While this may be true for acid rain, dry deposition
and acid dew and fog formation162164 near point source pollution sites may cause
greater acidification of soils and therefore deserve investigation. Inorganic constituents
in the atmosphere are derived from a variety of sources. Studies on the impact of land
use on the acidity and trace element composition of precipitation in the north central
U.S. suggest that soil sources dominate for major ions, and to some extent for trace
elements, corresponding to the prairie-agricultural areas of western Minnesota and
eastern North Dakota.165 The same study indicates that in the forested region of north-
eastern Minnesota, the soil function is less important and anthropogenic sources are
dominant for most trace elements, SO2* and NO^. Soil-derived cations (NH*4, Ca2*, and
MgI+) partially neutralize precipitation acidity in proximate agricultural lands.
The addition of trace elements and heavy metals by acid precipitation to soils is not
significant relative to the amounts present in soils and added in fertilizers, animal man-
ure, and municipal sludges. Significant acidification of soils may lead to a greater
mobility of these elements in the environment. This has been demonstrated by using
artificial rainwater acidified to pH values 4.2, 3.2, and 2.8."'
The pronounced intrinsic buffering capacity provided by soil minerals and organic
matter tends to minimize changes in pH of soils receiving acid precipitation. The
amounts of N and S added by precipitation are beneficial to agricultural, forested, and
unmanaged soils. The amounts of other macro- and micronutrients added to soils in
precipitation are insignificant compared with those present in soil systems. Studies on
the effects of natural acid precipitation on agricultural and forested ecosystems should
be encouraged. Acidification of soils by simulated acid rain will not provide the infor-
mation needed.
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Effect of Acid Rain in Soils - Tabatabai

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This article was downloaded by: [New York University]

On: 01 February 2015, At: 15:52

Critical Reviews in Environmental

Effect of acid rain on soils

To link to this article: http://dx.doi.org/10.1080/10643388509381727

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EFFECT OF ACID RAIN ON SOILS

Author: M. Ali Tabatabai

1. A pH of 5.6 could serve as a reference value for acidity of precipitation in un-

In islands thousands of kilometers removed from industrial activity, and presumably

1. What is the pH of normal, unpolluted rain?

II. DEFINITION OF pH AND SOIL REACTION

definition, any compound that is capable of accepting a proton is considered a

III. SOIL FORMATION

s = f(cl,o,r,p,t ...) (2)

Depth and Horizons

FIGURE 1. Comparison of pH values of soils developed un-

therefore, contain illuvial deposits of organic matter and/or Fe and Al compounds in

IV. SOURCES AND FORMS OF ACIDITY IN SOILS

[H+ ] = [HCO3-] + 2[CO|~] + [OH"] (3)

and the equilibrium concentrations:

-log[H + ] = -log[HCO3-] = 5.65 (4)

-log[CO2aq] = -log[H2CO.,] = 5.0 (as a nonvolatile acidity) (5)

-log[COn = 8.5 (7)

CO2 content (%) pH

Reproduced from McLean, E.

Chemical and Microbiological

decreasing as much as 2 to 3 pH units during night. The pH of shallow flood water is

NH, + 2O2 = H+ H2O (8)

(NH2),CO + 2H,0 = H2CO3 + 2NH3 (9)

1. NHÎ that is nitrified, then denitrified produces no net H*.

idity produced from N fixation will be modified. In a recent survey of field-grown

Treatment litter" Malic Citric Malonic succinic Fumanc Glycolic Phosph

during 4 days C Tr 3.9 Tr 5.2 0 Tr 3.6

" A, Frax/nusexce/s/or.-B, Alnusglutinosa;C, Betula verrucosa;D, Fagus silvática;and E, Pinus silvestris.

Adapted from Nykvist, N., Stud. For. Suec.,3, 1, 1963.

A. Effect of Acidity on Soil Chemical Properties

FIGURE 6. Relationships existing in mineral soils between pH

it is doubtful if any of these potential detrimental effects of acid precipitation can be

2. There is a strong dependence of sulfate retention upon the equilibrium pH with

B. Effect of Acidity on Soil Biochemical Properties

VI. SOURCES AND FORMS OF ACIDITY IN PRECIPITATION

It is often assumed that the pH of natural (unpolluted) rainwater is controlled by the

(CH3)2S, are released to the atmosphere through microbial transformations of S com-

VII. SIGNIFICANCE OF ACIDITY IN PRECIPITATION

As discussed in Section IV, soil acidification is a natural phenomenon in humid

Acid input from 100 cm of precipitation at pH = 4.0 1

VIII. DEPOSITION OF NUTRIENTS

SPATIAL RATE (kg/ha/yr)

Corn 200 bushel 359 49

Alfalfa 6 tons 376

From Bixby, D. W. and Beaton, J. D., Sulphur-Containing Fertil-

Crop trient 1965 1970 1975 1980

Corn N 73 119 111 139

Adapted from Hargett, N. L. and Berry, J. T., 1980 Fer-

the sampled events could be accounted for by precipitation originated N on a wa-

Arizona Tombstone 3.5 3.5 1975—1978

Charles City 7.2 6.0 13.2

Arizona Tombstone 5.8 1978

From Tabatabai, M. A., Agricultural Nonpoint Sources and Pollutant Proc-

Arizona Tombstone 4.1 1.7 1975—1978

Basic cation deposition,

Arizona Tombstone 1.0 0.8 6.1 0.7