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Journal of the Air Pollution Control Association
ISSN: 0002-2470 (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/uawm16
Acid Rain Effects Research—A Status Report
Allen S. Lefohn & Robert W. Brocksen
To cite this article: Allen S. Lefohn & Robert W. Brocksen (1984) Acid Rain Effects Research—A
Status Report, Journal of the Air Pollution Control Association, 34:10, 1005-1013, DOI:
10.1080/00022470.1984.10465847
To link to this article: https://doi.org/10.1080/00022470.1984.10465847
Published online: 08 Mar 2012.
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Citing articles: 11 View citing articles
Acid Rale Effects Research—-A Status Report
Allen S. Lefohn
A.S.L. & Associates
Helena, Montana
Robert W. Brocksen
University of Wyoming
Laramie, Wyoming
International concern about acidic precipitation as a
possibly serious, widespread pollution problem with
severe ecological consequences has increased the pace
of acid rain research in the United States. Accompa-
nying this increased activity has been a consonant in-
crease in results that directly relate to clarifying many
of the hypotheses that were proposed in the middle
1970s. This paper focuses on these key working hy-
potheses and summarizes, from the most current
knowledge base, the available information on possible
impacts of acid precipitation on the aquatic and ter-
restrial ecosystem. Based on the finer resolution now
available, research questions are provided to help guide
the testing of new and refined hypotheses.
In the 1970s and early 1980s, considerable effort was made to
publicize the potential danger that acidic deposition might
cause to ecosystems in the United States.1
"9
Concern for the
ecosystem has focused primarily on aquatic and forest eco-
systems.10
"12
To assess possible impacts associated with acidic deposition,
several hypotheses have been proposed. Some of the more
important of these hypotheses are:
• Concentrations of hydrogen ions observed in wet depo-
sition are mostly associated with strong mineral acids.
• The amount of sulfate in atmospheric precipitation can
be used as a substitute for predicting the amount of hy-
drogen ion contained in precipitation.
• Episodic pH declines observed in surface waters result
from: a) snowmelt runoff that has been acidified by at-
mospheric deposition and b) heavy rains that wash dry
deposited acidifying material to surface waters.
• Forest ecosystems in the northeastern United States may
have been impacted as a result of acidic deposition.
• Agricultural crops may be at risk as a result of exposures
to acidic deposition and gaseous air pollutants.
• Aquatic ecosystems have been impacted by acidic depo-
sition.
• Mitigation strategies are available to ameliorate the
possible ecosystem effects of acidic deposition.
The physical and biological parts of the ecosystem interact
in a synergistic manner. For example, the transport of anions
such as sulfate and nitrate through the various soil horizons
is a function of the physical soil characteristics, ion exchange
rates, chemical valence state, biological uptake, and micro-
bially-mediated transformations. To properly describe cause
and effect relationships, it may be necessary to focus on the
complex ecological factors that require researchers to combine
broad scale terrestrial and aquatic survey activities with in-
dividual process oriented laboratory and field work. Ecosys-
tem level research may be required to properly place into
perspective the natural ecological processes that are perturbed
by man's actions. This insight can provide us with an estimate
of the elasticity of the natural ecosystem and its ability to
respond to ecological perturbations.
Assessing the effects of acidic deposition on the ecosystem
requires an understanding of the cycling of each of the im-
portant nutrients through the ecosystem. The nutrient
chemical form, its concentration, and spatial and temporal
distribution are important considerations that may require
quantification. Without this additional understanding, it may
be difficult to use field survey results to separate perceived
anthropogenically caused environmental effects from those
resulting from natural changes in nutrient cycling pro-
cesses.
This article focuses on these key working hypotheses and
summarizes, from the most current knowledge base, the
available information on possible impacts of acid precipitation
on the aquatic and terrestrial ecosystem and proposes addi-
tional research questions to help guide the testing of new and
refined hypotheses. Specific attention is directed at the pos-
sible importance of natural ecological processes in controlling
many of the environmental observations that have been at-
tributed to acidic deposition.
Wet Deposition
The definition of the natural pH for atmospheric precipi-
tation is an important consideration. Some confusion is evi-
dent when trying to define the natural pH of atmospheric rain
in the absence of anthropogenic emissions. Galloway et al.,13
in an attempt to define the chemistry of unpolluted rain, an-
alyzed chemical precipitation data fromfiveremote sites. Data
analyses were based on precipitation event samples taken
from December 3,1979 through May 1,1981. Average volume
weighted pH precipitation data indicated acidity that ranged
from pH values of 4.78 to 4.96. Charlson and Rodhe14
and
Guiang et al.15
have confirmed that background atmospheric
rainfall pH values for other sites range from 4.5 to above 5.6.
Galloway et al.,1
^ Keene et al.,16
and Keene et al.17
attributed
the measured acidity at the remote locations to both weak
organic (e.g., acetic and formic) and strong mineral (e.g., sul-
furic and nitric) acids derived from sources that are a result
of natural and anthropogenic processes.
Copyright 1984-Air Pollution Control Association
October 1984 Volume 34, No. 10 1005
"At present, scientific results support the conclusion that no direct
evidence exists that acidic deposition currently limits forest growth
in North America. However, results indicate that tree growth
reductions are occurring in widespread areas in regions where
rainfall acidity is generally high on a volume weighted annual
average."
Keene and Galloway18
have emphasized that the pH of at-
mospheric precipitation at a specific site depends upon the
chemical nature and relative proportions of acids (i.e., strong
versus weak) and bases in solution. Temporal changes in
precipitation pH are related to variation in concentrations of
alkaline materials (e.g., Ca2+
) in the atmosphere, relative to
acid content. To use pH 5.6 to represent the hydrogen ion
concentration of wetfall for all sites not heavily influenced by
anthropogenic sources, and then compare this value to pH
values recorded at geographic locations thought to be in-
fluenced by anthropogenic emissions, is inappropriate. A clear
understanding of anthropogenic contributions and the natural
pH variation in deposition acidity resulting from weak at-
mospheric acids and soil sources is required.
Sulfate in Precipitation as a Surrogate for Hydrogen in
Rainfall
The acidic deposition discussion has mostly focused on the
direct and indirect effects of atmospheric hydrogen ion de-
positions on vegetation, soils, and surface waters. However,
because of 1) the difficulty associated with developing
transport models for predicting regional hydrogen ion depo-
sition and 2) the assumption that atmospherically deposited
sulfate is equivalent to atmospherically deposited hydrogen
ion, much of the discussion about reducing atmospheric
loading of hydrogen ion has centered on sulfate reduc-
tion.10
Several authors have commented on using either sulfur or
hydrogen ion loading in precipitation for estimating the im-
pact of acidic deposition. Coote et al. ,19
while focusing on the
applicability of using these two chemicals for predicting
possible soil impacts, have commented "when sulfur alone is
used, then the neutrality of calcium, magnesium, sodium, and
other such salts of sulfur is ignored." Results reported by
Krupa and Pratt,20
-21
Pratt et al. ,22
and Sequeira23
'24
bring
into question the hypothesis that sulfate can be used as a
substitute for predicting possible precipitation acidity effects
on both the aquatic and terrestrial environments.
Pratt et al.22
collected rain samples during the summers of
1977 through 1980 at seven sites in the vicinity of a coal-fired
power plant in central Minnesota. The authors' analyses in-
dicated that the major anions (sulfate and nitrate) appeared
to be more closely associated with calcium, magnesium, so-
dium, and ammonium ions than with hydrogen ions. They also
indicated that the sulfate concentration was dependent upon
the concentration of the cations present in precipitation.
Sequeira24
analyzed chemical composition data from at-
mospheric precipitation for three high altitude World Mete-
orological Organization stations (Monte Cimone, Italy; Mauna
Loa, Hawaii; and Alamosa, Colorado). Simple linear and
multiple linear regression analyses indicated that sulfate was
strongly associated with alkali/alkaline earth elements (cal-
cium, potassium, and sodium). Of the three sites, hydrogen
and total sulfate were highly correlated only at Mauna Loa,
Hawaii.
Data reported by Gorham et al.25
for 33 National Atmo-
spheric Deposition Program (NADP) stations in 1980 and 49
in 1981 (sites east of 95° W), indicate that hydrogen ions in
precipitation are more closely associated with sulfate than
with nitrate and that a reduction in sulfate ions would result
in a reduction in hydrogen in wetfall. The investigators ex-
amined correlations between volume-weighted, mean annual
ionic concentrations in wet deposition across sites. Caution
should be exercised in using the results because the authors
did not calculate the variability between sulfate and hydrogen
and nitrate and hydrogen at each of the monitoring sites.
Using annually averaged wet chemistry monitoring data to
address the surrogate question appears inappropriate. To test
this hypothesis, statistical analyses should be performed using
weekly (NADP) or event (MAP3S/UAPSP) wet chemistry
data collected at each site.
The implications of the work by Krupa and Pratt,20
-21
Pratt
et al. ,22
and Sequeira23
'24
are that sulfate in wetfall at some
sites is associated with cations other than hydrogen. The
National Research Council26
noted that not all sulfates in the
air or in precipitation contribute to the acidity measured.
However, the assumption that sulfate ion deposition can be
equated with hydrogen ion deposition over large geographic
areas has been made by several groups.10
'27
Caution should
be exercised when attempting to apply the hypothesis over
large geographic areas to predict surface water chemical
changes resulting from atmospherically deposited sulfate.
Surface Water Episodic pH Depressions
One of the important observations associated with possible
acidic deposition effects on the aquatic system is the episodic
increase in hydrogen ion concentration in surface waters
during snowmelt and heavy runoff. It has been hypothesized
that 1) during the winter, acidic deposition in rainfall and
snow is collected by the snowpack and released during spring
runoff periods and 2) heavy storms cause flushing events that
result in acidic materials deposited on the soil (derived from
dry atmospheric deposition) being carried to surface wa-
ters.10
However, recent reports and articles by Everett et al.,28
Brocksen and Lefohn,29
Jones et al.,30
Krug and Frink,31
Richter,32
U.S./Canada,10
CARP,33
and Lefohn and Klock,34
Noggle et al.,35
and Krug et al.,36
have rekindled the possi-
bility that natural soil processes have a more important role
in defining stream water chemistry than generally acknowl-
edged. Lefohn and Klock34
reviewed data and reports derived
from ten watershed sites across the U.S. and found that nat-
ural soil processes appeared to play an important role at most
of the sites in defining the seasonal episodic activity and
aluminum concentrations measured in many of the surface
waters. Noggle et al.35
have shown that forest soils in the
Raven Fork and Straight Fork, North Carolina watershed play
an important role in defining surface water chemistries. Re-
sults from applying pH 5.7 simulated rain showed that Raven
Fork forest soils contributed weak acids, strong acids, and
aluminum to percolating water in the absence of acidic de-
position in precipitation.
Further support for the importance of naturally produced
hydrogen in soils is derived from work of Seip et al.37
The
authors studied the changes in concentrations of chemical
components in snowpack and runoff in several mini-catch-
ments in Telemark, Norway. In 1979, the investigators neu-
tralized snow with sodium hydroxide before the snow melting
period. When the H+
concentrations in runoff in 1978 and
1979 were compared, the authors reported that the average
hydrogen ion concentrations were similar, despite the neu-
tralization of snow in 1979. Rosenqvist et al.38
have estimated
1006 Journal of the Air Pollution Control Association
that the atmospheric acids in excess of carbonic acids in the
Numedal area (Norway) contributed about 5-15% ofthe total
acid formed in soil.
There is mounting evidence supporting the thesis that ad-
ditional research is necessary before scientists can ascertain
whether the pH events observed during snowmelt and heavy
autumn rains can be attributed to internal H+
sources or a
mixture of both internal and anthropogenic sources. Works
by Chen et al.39
and Newton and April40
stress the importance
of soils in defining lake chemistry. For specific sites, if the
observed pH events in surface water are a result of a combi-
nation of natural and anthropogenic sources, then an effort
must be made to quantify the relative contribution associated
with each.
Forest Decline
There has been concern that acidic deposition has damaged
forest systems. Recent surveys of forests in the eastern U.S.
have shown that there are symptoms of measurable decline.
The slowing growth indicates a broad regional phenomenon
observed in both young and old trees of several species. In
some high elevation areas, visible dieback of certain coniferous
tree species has also occurred.
Johnson et al.n
have reported possible acidic precipitation
effects on a forest ecosystem in the New Jersey Pine Barrens
area. Johnson and Siccama41
have suggested that the rela-
tionship between loss of vigor and drought is clear. Surveys
of vegetation effects, conducted in the 1970s, reflected levels
of ozone in the vicinity of the Pine Barrens that were capable
of causing impacts to vegetation.42
-43
Lefohn44
recently re-
viewed the EPA air quality data for a monitoring site in the
area and has reported that elevated levels of hourly averaged
ozone concentrations do exist during the spring and summer
months.
In the Northeast, work by Vogelmann12
has been cited as
possible evidence that acidic deposition has caused the decline
of red spruce on Camel's Hump Mountain, Vermont. Johnson
and Siccama41
do not support this hypothesis. The authors
conclude instead that current evidence suggests conifers are
primarily affected by drought. The authors believe that acidic
deposition could exacerbate drought stress, but that no con-
vincing evidence is available to show that acidic deposition
can be linked to the observed mortality. Siccama et al.45
have
concluded that the cause of the decline of red spruce is not
known.
To explain the reduced growth phenomenon, the following
set of working hypotheses has been proposed:46
• Gaseous air pollutants, such as ozone, are causing damage
to tree foliage, and either alone or by interacting with acid
deposition, affecting tree growth.
• Deposition of metals, alone or interactively with acid de-
position, is directly or indirectly affecting tree growth.
• Acid deposition is increasing the leaching of nutrients
from the foliage of trees at a rate rapid enough that uptake
and recycling of lost nutrients cannot maintain adequate
supplies of nutrients in the tree foliage.
• Acid deposition is acidifying soil water, increasing alu-
minum concentrations, and ultimately affecting root
growth and nutrient and water uptake.
• Nitrogen saturation of forest soils is changing the bene-
ficial relationship between trees and soil microorganisms
either directly or indirectly, resulting in nutrient and
water imbalances.
Krug and Frink31
have pointed out that soils beneath forest
stands proceeding through succession toward climax generally
become more acidic over time. The authors stated that the
recovery of landscapes in New England from earlier distur-
bances, such as tree harvesting, can result eventually in in-
creasing acid surface soil horizons and thickening and acidi-
fication of forest floors. Evidence to support such a hypothesis
has been provided by Troedsson.47
The investigator analyzed
soil pH data from 13,000 arbitrarily selected test plots from
the National Forest Survey in Sweden and found a strong
correlation between increasing forest age and increasing soil
acidity. The author concluded that the relationship between
the age of coniferous trees and soil pH was stronger than the
relationship between atmospheric depositions.
In addition to the change in soil environment, Krug and
Frink31
have discussed land use practices as a possible per-
turbing agent in affecting the natural nutrient cycling pro-
cesses that influence forest growth. Man's destruction of the
"old growth" forest environment tends to diminish soil pod-
zolization. In contrast, fire protection of forest stands may
enhance podzolization. Therefore, land use practices have the
potential for significantly influencing podzolization activity
and consequently, the soil environment in which trees grow.
Placing the comments of Krug and Frink into perspective, a
second set of hypotheses might be:
• Changes in soil chemistry that result from natural suc-
cession result in forest decline for specific species.
• Land use practices (e.g., tree harvesting and fire man-
agement) have impacted the soil environment in which
trees grow. Changes in soil chemistry are manifested by
modifying tree succession patterns.
While scientists attempt to identify the causes of the forest
decline, survey work is continuing. McLaughlin et al.48
have
described two large scale surveys sponsored by the federal
government. The first is a study of dieback of red spruce over
its entire range of occurrence in the eastern U.S. Approxi-
mately 32 stands of spruce have been sampled to document
the geographical extent of dieback, the degree to which die-
back was preceded by declining growth of both spruce and
associate species, and the association of these responses with
the past history of growth of these species at these sites. A
second program was initiated in 1982 to examine the combined
effects of acid rainfall and chronic gaseous pollution stress on
a variety of forest species distributed throughout the eastern
U.S. The project, entitled FORAST (Forest Responses to
Anthropogenic Stress), is assessing forest effects and the re-
sults will be incorporated into the 1985 National Acid Pre-
cipitation Program Assessment.
At present, scientific results support the conclusion that no
direct evidence exists that acidic deposition currently limits
forest growth in North America. However, results indicate that
tree growth reductions are occurring in widespread areas in
regions where rainfall acidity is generally high on a volume
weighted annual average.33
It is possible that through a
comprehensive environmental characterization effort, a
quantification of anthropogenically caused effects will be
documented.
October 1984 Volume 34, No. 10 1007
"Although liming does not always work as predicted, it is currently
the most well understood and applicable management tool for
enhancing fisheries in acidic waters."
Agricultural Crops
Simulated acid precipitation experimental studies on ag-
ricultural crops show positive, negative, and no effects.49
"52
Using artificial exposures, effects symptoms have been ob-
served.53
"64
At this time, it appears that rain with pH values
above 4.0 applied in a routine manner to the vegetation, does
not cause detrimental effects.
The frequency of occurrence of rain events below pH 4.0 is
important. Many investigators have commented on the epi-
sodic nature of rain chemistry.13
-14
'22
-24
'65
-68
The annual
volume weighted concentration of a specific ion may not
necessarily correlate with possible ecological impacts. John-
ston et al.57
have compared differences between plants grown
in greenhouses exposed to rain at a constant pH 3.2 level and
those exposed to rain that increased in pH from 2.8 to 4.0 with
a pH 3.2 mean. Results indicate a tendency for rain events
with a high peak level of acidity to cause greater deleterious
effects on bush bean plants (Phaseolus vulgaris L. cv 'Blue
Lake 274') than those rain events characterized by a constant
pH level.
Using actual rain chemistry data, Lefohn69
and Lefohn and
Benedict70
have evaluated the frequency of weekly reported
pH values for wet chemistry monitoring sites. For the majority
of events, even at sites experiencing annual volume weighted
pH values of 4.16, the pH values are mostly above 4.0. Sites
in the northeastern U.S. experienced a greater percentage of
precipitation events below 4.0 than did sites in other parts of
the country. However, weekly NADP samples varied over a
large pH range. Jacobson,52
after reviewing the U.S. Depart-
ment of Energy's MAP3S data for the Ithaca, New York and
Pennsylvania sites, states that"... a reasonable conclusion
is that there is a low risk of foliar injury to field-grown vege-
tation from exposure to current levels of acidity in precipita-
tion in the U.S." While these conclusions are preliminary in
nature, Lefohn and Brocksen,71
Irving,51
and Jacobson52
have
emphasized that additional research should include other
considerations such as exposure patterns and chemical con-
stituent identification (e.g., nitrate and sulfate).
Concern has been expressed about the possible effects on
crops from simultaneous exposures of gaseous air pollutants
(e.g., ozone) and acid precipitation. Results by Jacobson et
al.,72
Troiano et al.,5S
and Troiano et al.73
show that under
simulated acid rain and filtered and nonfiltered ambient ox-
idant conditions, ozone and acid rain tended to show inter-
active effects. Work by Norby and Luxmoore74
showed that
simulated acid rain and sulfur dioxide/ozone exposures did
not affect the response of soybeans to extremely low pH (2.6)
simulated acid rain exposures. Lefohn and Tingey75
have re-
cently summarized the frequency of the number of co-occur-
rences of SO2/O3, SO2/NO2, and O3/NO2 under ambient
conditions and state that vegetation research using gaseous
air pollutant mixtures should focus on the sequential ap-
pearance of the pollutants. It appears reasonable to propose
that combined acidic deposition and gaseous air pollutant
mixture exposures should stress the sequential patterns of
occurrence.
Aquatic Ecosystems
The question of acid rain affecting aquatic systems has been
shrouded in confusion. While much of what we do know is
based on circumstantial evidence,27
there are some specific
statements that can be made concerning the possible impact
of acidic deposition on streams, rivers, and lakes. Work Group
I reviewed the empirical data available for assessing possible
acidic deposition impacts to the aquatic ecosystem.10
The
Work Group has identified the following geographic areas as
examples that can be cited for illustrating acidic deposition
chemical and biological effects: Algoma (Ontario), Mus-
koka-Haliburton (Ontario), Laurentide Park (Quebec), Nova
Scotia, Adirondack Mountains of New York, the Hubbard
Brook Ecosystem (New Hampshire), and Maine and New
England.
Some headwater lakes in the Algoma district of Ontario
have elevated sulfate, aluminum, and lead concentrations.10
The Work Group has examined fish surveys conducted in the
area and has indicated that the numbers of fishless lakes in-
crease with decreasing alkalinity. This district begins about
100 km from Sudbury, Ontario (a significant local point source
of sulfate and heavy metal emissions). Because elevated lead
concentrations have been observed, the elevated sulfate levels
observed in the lakes may have originated from Sudbury
emissions. In addition, the number of fishless lakes may be
associated with possible elevated levels of heavy metals de-
rived from Sudbury.76
Data for the Muskoka-Haliburton area of Ontario show a
loss of alkalinity for one lake. However, the Work Group
mentioned pH depressions in a number of lakes and streams.
A fish kill, moreover, was observed once during spring snow-
melt in one lake. Although acidification was the suspected
cause, the actual cause of the fish kill was not determined. As
discussed by CARP,33
it is possible that pH depression events
occurring during the spring snowmelt and during the fall rains
could consist of natural (internally generated hydrogen ions
in the soil) and, secondarily, anthropogenic sources. Jones et
al.30
discuss this possibility in their description of the Raven
Fork, North Carolina, investigation. The Work Group has
stated that it is difficult to include natural acid formation
criteria in regional sensitivity assessments because the data
base is so limited.10
Thus, at this time, it is impossible to at-
tribute the fish kill to an anthropogenically derived source.
Work by Evans, and Dillon76
suggests that elevated con-
centrations of lead in the sediments of lakes in the Mus-
koka-Haliburton region of southern Ontario originated from
the burning of fossil fuels in North America; elevated con-
centrations of lead are also found in lakes in the Algoma dis-
trict. Both regions, however, are relatively close to a large point
source of sulfate and heavy metal emissions at Sudbury, On-
tario (200 km from the Muskoka-Haliburton region and 100
km from the Algoma district). Nriagu et al.77
report that
230,000 kg of lead are emitted annually from the Sudbury
smelters; in comparison, Turner and Strojan78
report that
total atmospheric emissions of lead from coal combustion in
the U.S. amount to 54,000 kg annually. The maximum lead
concentrations reported in the sediments of lakes in the
Muskoka-Haliburton region, reported by Dillon and Evans79
and presented by the Work Group,10
are about 2.5 to 5.0 times
greater than those found in Adirondack lake sediments (128
fig lead per gram of sediment) by Davis et al.80
Thus, if lead
concentrations provide an indication of the origin of the lakes'
anthropogenically derived sulfates, local emitting sources in
Canada may be important in explaining some of the obser-
vations.
1008 Journal of the Air Pollution Control Association
Data for Laurentide Park, Quebec, have been reviewed by
Work Group I, who found that sulfate concentrations in sur-
face waters in Quebec decrease toward the east and north,
parallel with the deposition pattern. As discussed by Lefohn
et al.,81
sulfate concentrations did not correlate well with
calcium + magnesium — alkalinity concentrations. Most im-
portantly, there is no evidence of effects to fish populations
from elevated sulfate concentrations in Quebec lakes.10
Historical salmon catch records from Nova Scotian rivers
reportedly show reductions over the past 40 years.10
The At-
lantic Salmon Review Task Force,82
relying on commercial
Canadian salmon catch data for the years 1910 through 1977,
report that many Atlantic salmon stocks production areas in
Nova Scotia, New Brunswick, and St. John have been affected
by over-harvesting and industrial development. For example,
the Task Force reported that Atlantic salmon in the southwest
Nova Scotia area have been impacted by over-harvesting,
while in the southern New Brunswick-St. Johns area, the
salmon have been impacted by the "construction of the
massive Mactaquac hydro-electric development just above
tide-head ..." The Task Force appears to believe that the
development created additional demands on much of the
salmon's freshwater habitat or lifeline and that by the late
1960s, thereiwas little optimism for rehabilitation of stocks
in the river.
In addition to development activities, local air pollution and
natural hydrogen sources may be an important aspect of the
problem. The findings of Shaw83
-84
suggest that a substantial
part of the hydrogen concentration in the Nova Scotian
waterbodies appears to be related to local point sources. Results
reported by Watt et al.85
and Farmer et al.86
show that many
of the Nova Scotian rivers contain humic and/or fulvic acids
and that the contribution of these organic acids to total acidity
may be significant.10
Data for the Adirondack Mountains in New York have been
reviewed by the Work Group.10
The Group infers that losses
in fish populations at 180 lakes are attributable to acid rain
because a comparison of data from the 1930s with data from
recent surveys has shown that more lakes have become acid-
ified. Recent reviews of the problems associated with com-
paring data derived from two distinct time periods87
con-
cluded that there are many more questions that need to be
answered before one can consider the comparisons valid and
reliable. Retzsch et al.88
have suggested several possible al-
ternative explanations for the reported observations. The
authors report that the numbers of lakes and ponds stocked
have shown a relatively continuous decline. This decline, ac-
cording to the authors, may be the result of the closing of
stocking waters found to be unsatisfactory for long-term fish
survival.
While no biological impacts associated with aquatic or-
ganisms have been documented at the Hubbard Brook study
area in New Hampshire, Work Group I did state that the area
has experienced pH depressions of 1 to 2 units in streams
during snowmelt.10
Brocksen and Lefohn29
and Lefohn and
Klock34
have discussed possible reasons that pH depressions
could be attributed to natural occurrences. The authors stress
that additional research is necessary to separate the natural
from the anthropogenic contribution of hydrogen ion during
spring snowmelt and heavy runoff.
In the Maine and New England areas, the Work Group10
reported lake water pH declines based on comparisons with
historical information.80
'89
-90
No effects have been observed
on Atlantic salmon populations, nor have effects been ob-
served on fish in inland lakes. Marcus et al.87
have pointed out
that Davis et al.91
noted that cultural eutrophication had
apparently increased the daytime pH of a small but significant
portion of the surveyed lakes and that although the earlier
measurements were made using colorimetric methods, the
more recent values were determined with potentiometric
methods. Lefohn et al.92
have pointed out the problems as-
sociated with comparing pH values using different measure-
ment techniques. The work by Norton et al.89
examined
changes in surface water pH between the periods 1939-1946
and 1978-1980. The authors concluded that 85% of the lakes
appeared to be more acidic in the period 1978-1980 than in
1939-1946. Marcus et al.81
and Brown and Brocksen93
pointed
out that since the study only compared two points in time over
extended intervals, it was unclear whether the results obtained
represented actual trends or were artifacts of normal temporal
variations in surface water pH. Linthurst et a/.94
state that
lake acidification trends, as described for the above examples,
cannot be unequivocably related to acidic deposition.
In contrast to the suggested acidification of New England
surface waters reported by the above cited authors, Norvell
and Frink95
concluded that the pH and alkalinity in sensitive
(alkalinity less than 200 neq L"1
) lakes of Connecticut had not
changed significantly from 1937 to 1973. Inspection of the
atmospheric deposition maps presented by the Work Group10
shows similar deposition rates of hydrogen and sulfate ions
in Connecticut and other parts of New England. Thus, care
must be exercised when discussing the possibility of extrap-
olating the results from a local observation in order to predict
regional scale effects.
Both chemical and biological processes within a forest
ecosystem soil appear to play an important role in determining
the chemistry of surface waters. Swank and Fitzgerald96
have
shown that the metabolism of inorganic sulfate to organic
forms can be a major process in the sulfur cycle that influences
sulfate soil accumulation and mobility in forest ecosystems.
Vitousek and Matson97
have reported that measurements of
nitrogen-15 retention in the field demonstrated that microbial
uptake of nitrogen during the decomposition of residual or-
ganic material was one of the most important processes in
retaining nitrogen in the soil. Results reported by Johnson and
Todd98
showed that irrigation with sulfuric and nitric acid at
two and ten times the current annual hydrogen inputs over
a period of one year had no statistically significant lasting
effect on nitrogen in the soil or Al availability or P avail-
ability.
Using sulfate concentration measured in surface waters as
an indication of acidic deposition effects may be misleading.
Parnell99
showed that where bedrock sulfide concentrations
are significant, naturally derived sulfuric acid may cause ac-
celerated chemical weathering rates and low pH values in local
streams. The author stressed that where sulfidic rocks crop
out, this contribution may have previously been underesti-
mated by some investigators. The author stresses that caution
should be used in interpreting acid precipitation leaching and
weathering data from New England drainage basins underlain
by sulfidic schists. As discussed by Everett et al. ,28
sulfate
measured in surface waters may be more correlated to the
sulfur contained in minerals than the sulfate deposited from
atmospheric wetfall and dryfall.
October 1984 Volume 34, No. 10 1009
"Science is the search for truth. Our efforts may lead us down
several different paths, but our challenge is to search for data that
will provide a clearer picture of how the ecosystem responds to
both natural and man-made perturbations."
Mitigation Strategies
Acidic surface waters generally have unproductive fisheries
or, in some cases, are incapable of supporting any fish popu-
lations. This results from both the oligotrophic (nutrient poor)
status of these waters and the low tolerances ofmany desirable
fish species to the acidity.
Liming is defined as the addition of lime, limestone, or other
alkaline materials to acidic surface waters for neutralization.
Finely ground calcium carbonates and basic slags of the mono-
and dicalcium silicate types have been found particularly
useful in pH adjustments of acid lakes because their relatively
intermediate solubilities tend to extend the period of neu-
tralization.100
Historically, liming has been used to establish, restore, or
enhance fish production in acidified waters. As a fisheries
management technique, liming was first used in naturally acid,
brown water lakes.101
Subsequently, the technique has been
applied to reclaimed lakes impacted by acid mine drainages.
And more recently, liming has been applied to surface waters
in regions receiving acidifying depositions.102
'103
Liming reduces adverse effects of acidification on fish
populations by increasing pH, hardness, and alkalinity levels
of surface waters. These increases reduce the toxicity of acid
waters by 1) reducing toxic hydrogen ion concentrations; and
2) complexing, precipitating, changing chemical speciation,
and inhibiting uptake of metals that are often enriched in
acidified waters. As a result, liming has been very beneficial
in restoring and enhancing the fishery potential of some
acidified waters.
The utility of liming is best illustrated by the Swedish ex-
perience.104
Sweden is undertaking an extensive lake program
to preserve and protect salmon, perch, and pike fisheries
threatened by acidification. During 1977 to 1979, about 700
lakes and rivers were limed. During the 1982 fiscal year, 1000
lakes were to be limed at a cost of six million dollars. The
program is expected to expand to an annual budget of 40
million dollars by fiscal year 1986 to include the liming of
20,000 lakes and streams.
Liming programs in North America have been much less
extensive. Liming was used to increase pH levels in several
acidic lakes near Sudbury, Ontario. However, fish introduc-
tions into these lakes failed because high toxic metal con-
centrations, derived from local smelter emissions, remained
in lake waters. New York state has used liming since the late
1950s to maintain trout populations in some acidic lakes.
Concurrently, considerable research on liming and its use-
fulness for protecting or restoring fisheries is being conducted
by a number of governmental and private institutions.
Although liming does not always work as predicted, it is
currently the most well understood and applicable manage-
ment tool for enhancing fisheries in acidic waters. Much po-
tential exists for increasing its usefulness, especially by com-
bining it with some of the alternative strategies that may be
available.
Liming is not a viable mitigative strategy for every surface
water. Where the inaccessibility of some acidic water bodies
may greatly increase costs or where liming may not reduce the
episodic aspects of snowmelts, etc., other alternative strategies
may be appropriate. And, in some instances, more than one
strategy may be applied to the same waters. Certainly there
is a need for evaluation and development of additional strat-
egies for restoring and enhancing the fisheries of acidic wa-
ters.
Modern agriculture, animal husbandry, and forestry
practices may provide insight into ways of accomplishing this.
Through selective breeding, introduction of new species, and
fertilization coupled with changes in land use practices, it may
be possible to increase the pH and alkalinity of acidic waters
and establish fisheries where they were once absent.
While liming is a proven management tool in some cases,
there remain questions with respect to toxic metal bioaccu-
mulation by fish, longer term chemical alterations, and the
need to lime with relative frequency. As stated previously,
there is currently a large research effort examining problems
associated with liming and if this mitigative strategy is to be
implemented, consideration must be given to the site specific
characteristics of the water body and its watershed.
Future Research Directions
Much effort has been directed toward surveying the nation's
aquatic and terrestrial resources. To separate perturbations
associated with anthropogenic sources from those derived
from natural occurrences, it will be necessary for researchers
to blend survey activities with process oriented efforts. To
assist in this endeavor, the following series of fundamental
questions are proposed:
• What will happen to the pH concentration in rainfall in
the amount of sulfate and nitrate in rainfall is modi-
fied?
• How much do natural acidification soil processes con-
tribute to the pH depressions that are observed in surface
waters during heavy rainfall and snowmelt events?
• What are the important pollutants (e.g., acidic deposition,
ozone, sulfur dioxide, etc.) in combination with natural
factors (e.g., forest succession, drought, infestation, etc.)
that may contribute to the observed forest decline?
• Do combinations of pollutants (e.g., acidic deposition,
sulfur dioxide, and ozone) adversely affect agricultural
crops?
• How many lakes are acidic because of acidic deposi-
tion?
• How many lakes are incapable of supporting fish because
of acidic deposition?
• How many lakes will become supportive of fish if acidic
deposition can be reduced?
• What other remedial measures (or combinations of mea-
sures) will make a lake supportive of fish?
The ecosystem may have the potential for ameliorating
anthropogenically derived stresses if a pollutant's concen-
tration, frequency of occurrence, time between occurrences,
and temporal exposure occur in a pattern that provides for a
homeostasis or hysteresis feedback response. For researchers
to provide answers to the questions raised, it will be necessary
for "alternative" hypotheses to be identified and seriously
addressed. The talents of an eclectic set of scientists will be
needed to probe beyond the obvious.
Conclusion and Recommendation
Recent publications underscore the tenuous nature of the
acid deposition effects data base. Based upon the most current
evidence the following conclusions may be drawn:
1010 Journal of the Air Pollution Control Association
• If the hydrogen ion that is deposited on a watershed is
believed to be the primary source of ecosystem pertur-
bation (recognizing that mobile aluminum is a secondary
product of the soil acidification process), then it is unclear
whether a reduction in atmospherically deposited sulfate
or nitrate would result in a similar reduction in deposited
hydrogen ion.
• While hot being able to quantify their contribution at this
time, naturally produced acids that are internally gener-
ated within the soil ecosystem may play a considerably
more important role in determining the acidification of
surface water bodies than previously believed. The acid-
ification process may involve a combination of natural and
anthropogenically derived acid sources.
• While reductions in tree growth are occurring in North
America and Europe, no direct evidence exists to link
acidic deposition with these observations. In fact, recent
hypotheses tend to focus on many factors as possible
agents that might significantly contribute to the observed
forest decline.
• Evidence is mounting that ambient exposures of acidic
deposition may not injure or reduce the growth of agri-
cultural crops.
• Aquatic waterbodies identified by Work Group I (based
on empirical observation) as having been acidified by acid
rain may be more affected by local point sources (e.g.,
Sudbury, Ontario) or naturally derived acid sources con-
tained within the soil.
• Mitigation techniques are presently under review, but
caution should be exercised so that possible biological
modifications resulting from chemical alteration can be
avoided.
Over the next several years, the pace of acid rain research
will be increasing. However, it is unclear whether the quality
of the data produced from this increased pace will show a
consonant increase. Increased federal spending is not neces-
sarily synonymous with obtaining answers more quickly. The
entropy of the universe tends to increase and with it, maxi-
mum randomness. Therefore, additional energies within our
funding institutions will have to be found to organize and in-
terpret new information. Science is the search for truth. Our
efforts may lead us down several different paths, but our
challenge is to search for data that will provide a clearer pic-
ture of how the ecosystem responds to both natural and
man-made perturbations.
As Resnick105
has stated:
"Successful problem-solving requires a substantial
amount of qualitative reasoning. Good problem-sol-
vers dp not rush in to apply a formula or an equation.
Instead they try to understand the problem situation;
they consider alternative representations and rela-
tions among the variables. Only when they are satis-
fied that they understand the situation and all the
variables in it in a qualitative way do they start to
apply the quantification that we often mistakenly
identify as the essence of 'real' science of mathe-
matics."
Careful work will be required to clarify our knowledge of
how acidic deposition may be impacting ecosystems. With well
founded hypotheses that are designed to lead to greater un-
derstanding of the complex processes associated with this
problem, we hope to learn more about those important pro-
cesses that affect our biosphere.
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93. B. J. A. Brown, R. W. Brocksen, "An Analysis of the Relationship
between Acid Deposition, Surface Water Acidification, and Loss
of Fisheries," in Atmospheric Deposition, Air Pollution Control
Association, Pittsburgh, PA, 1983.
94. R. A. Linthurst, J. Baker, A. M. Bartuska, "Effects of Acidic
Deposition: A Brief Review," North Carolina State University,
Raleigh, NC, 1983.
95. W. A. Norvell, C. R. Frink, "Water Chemistry and Fertility of
Twenty-Three Connecticut Lakes," Bull. Conn. Agric. Exp. Sta.,
# 759, New Haven, CT, 1975.
96. W. T. Swank, J. W. Fitzgerald, "Microbial transformation of
sulfate in forest soils," Science 223:182-184 (1983).
97. P. M. Vitousek, P. A. Matson, "Mechanisms of nitrogen reten-
tion in forest ecosystems: a field experiment," Science 225:51-52
(1984).
98. D. W. Johnson, D. E. Todd, "Effects of acid irrigation on carbon
dioxide evolution, extractable nitrogen, phosphorus, and alu-
minum in a deciduous forest soil," Soil Sci. Soc. Am. J. 48:664
(1983).
99. R. A. Parnell, Jr., "Weathering processes and pickeringite for-
mation in a sulfidic schist: a consideration in acid precipitation
neutralization studies," Environ. Geol. 4:209(1983).
100. O. Grahn, H. Hultberg, "The neutralizing capacity of 12 different
lime products used for pH-adjustment of acid water," Vatten
31:120 (1975).
101. W. E. Johnson, A. D. Hasler, "Rainbow trout production in
dystrophic lakes," J. Wildlife Manag. 18:113(1954).
102. P. J. Dillon, N. D. Yan, W. A. Scheider, N. Conroy, "Acidic lakes
in Ontario, Canada: characterization, extent and responses to
base and nutrient additions," Arch. Hydrobiol. Beih. Ergn.
Limnol. 13:317 (1979).
103. B. Bengtsson, W. Dickson, P. Nyberg, "Liming acid lakes in
Sweden," Ambio 9:34 (1980).
104. J. Fraser, D. Hinckley, R. Burt, R. R. Severn, J. Wisniewski, "A
Feasibility Study to Utilize Liming as a Technique to Mitigate
Surface Water Acidification," Report No. 1238-03-81-CR,
General Research Corporation, McLean, VA, 1981.
105. L. B. Resnick, "Mathematics and science learning: a new con-
ception," Science 220: 477 (1983).
Dr. Lefohn is President and Founder of A.S.L. & Asso-
ciates, 111 North Last Chance Gulch, Helena, MT 59601. Dr.
Brocksen is Director of the Wyoming Water Research Center
and Professor of Zoology at the University of Wyoming.
October 1984 Volume 34, No. 10 1013

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Acid Rain Effects Research A Status Report

  • 1. Full Terms & Conditions of access and use can be found at https://www.tandfonline.com/action/journalInformation?journalCode=uawm20 Journal of the Air Pollution Control Association ISSN: 0002-2470 (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/uawm16 Acid Rain Effects Research—A Status Report Allen S. Lefohn & Robert W. Brocksen To cite this article: Allen S. Lefohn & Robert W. Brocksen (1984) Acid Rain Effects Research—A Status Report, Journal of the Air Pollution Control Association, 34:10, 1005-1013, DOI: 10.1080/00022470.1984.10465847 To link to this article: https://doi.org/10.1080/00022470.1984.10465847 Published online: 08 Mar 2012. Submit your article to this journal Article views: 4935 View related articles Citing articles: 11 View citing articles
  • 2. Acid Rale Effects Research—-A Status Report Allen S. Lefohn A.S.L. & Associates Helena, Montana Robert W. Brocksen University of Wyoming Laramie, Wyoming International concern about acidic precipitation as a possibly serious, widespread pollution problem with severe ecological consequences has increased the pace of acid rain research in the United States. Accompa- nying this increased activity has been a consonant in- crease in results that directly relate to clarifying many of the hypotheses that were proposed in the middle 1970s. This paper focuses on these key working hy- potheses and summarizes, from the most current knowledge base, the available information on possible impacts of acid precipitation on the aquatic and ter- restrial ecosystem. Based on the finer resolution now available, research questions are provided to help guide the testing of new and refined hypotheses. In the 1970s and early 1980s, considerable effort was made to publicize the potential danger that acidic deposition might cause to ecosystems in the United States.1 "9 Concern for the ecosystem has focused primarily on aquatic and forest eco- systems.10 "12 To assess possible impacts associated with acidic deposition, several hypotheses have been proposed. Some of the more important of these hypotheses are: • Concentrations of hydrogen ions observed in wet depo- sition are mostly associated with strong mineral acids. • The amount of sulfate in atmospheric precipitation can be used as a substitute for predicting the amount of hy- drogen ion contained in precipitation. • Episodic pH declines observed in surface waters result from: a) snowmelt runoff that has been acidified by at- mospheric deposition and b) heavy rains that wash dry deposited acidifying material to surface waters. • Forest ecosystems in the northeastern United States may have been impacted as a result of acidic deposition. • Agricultural crops may be at risk as a result of exposures to acidic deposition and gaseous air pollutants. • Aquatic ecosystems have been impacted by acidic depo- sition. • Mitigation strategies are available to ameliorate the possible ecosystem effects of acidic deposition. The physical and biological parts of the ecosystem interact in a synergistic manner. For example, the transport of anions such as sulfate and nitrate through the various soil horizons is a function of the physical soil characteristics, ion exchange rates, chemical valence state, biological uptake, and micro- bially-mediated transformations. To properly describe cause and effect relationships, it may be necessary to focus on the complex ecological factors that require researchers to combine broad scale terrestrial and aquatic survey activities with in- dividual process oriented laboratory and field work. Ecosys- tem level research may be required to properly place into perspective the natural ecological processes that are perturbed by man's actions. This insight can provide us with an estimate of the elasticity of the natural ecosystem and its ability to respond to ecological perturbations. Assessing the effects of acidic deposition on the ecosystem requires an understanding of the cycling of each of the im- portant nutrients through the ecosystem. The nutrient chemical form, its concentration, and spatial and temporal distribution are important considerations that may require quantification. Without this additional understanding, it may be difficult to use field survey results to separate perceived anthropogenically caused environmental effects from those resulting from natural changes in nutrient cycling pro- cesses. This article focuses on these key working hypotheses and summarizes, from the most current knowledge base, the available information on possible impacts of acid precipitation on the aquatic and terrestrial ecosystem and proposes addi- tional research questions to help guide the testing of new and refined hypotheses. Specific attention is directed at the pos- sible importance of natural ecological processes in controlling many of the environmental observations that have been at- tributed to acidic deposition. Wet Deposition The definition of the natural pH for atmospheric precipi- tation is an important consideration. Some confusion is evi- dent when trying to define the natural pH of atmospheric rain in the absence of anthropogenic emissions. Galloway et al.,13 in an attempt to define the chemistry of unpolluted rain, an- alyzed chemical precipitation data fromfiveremote sites. Data analyses were based on precipitation event samples taken from December 3,1979 through May 1,1981. Average volume weighted pH precipitation data indicated acidity that ranged from pH values of 4.78 to 4.96. Charlson and Rodhe14 and Guiang et al.15 have confirmed that background atmospheric rainfall pH values for other sites range from 4.5 to above 5.6. Galloway et al.,1 ^ Keene et al.,16 and Keene et al.17 attributed the measured acidity at the remote locations to both weak organic (e.g., acetic and formic) and strong mineral (e.g., sul- furic and nitric) acids derived from sources that are a result of natural and anthropogenic processes. Copyright 1984-Air Pollution Control Association October 1984 Volume 34, No. 10 1005
  • 3. "At present, scientific results support the conclusion that no direct evidence exists that acidic deposition currently limits forest growth in North America. However, results indicate that tree growth reductions are occurring in widespread areas in regions where rainfall acidity is generally high on a volume weighted annual average." Keene and Galloway18 have emphasized that the pH of at- mospheric precipitation at a specific site depends upon the chemical nature and relative proportions of acids (i.e., strong versus weak) and bases in solution. Temporal changes in precipitation pH are related to variation in concentrations of alkaline materials (e.g., Ca2+ ) in the atmosphere, relative to acid content. To use pH 5.6 to represent the hydrogen ion concentration of wetfall for all sites not heavily influenced by anthropogenic sources, and then compare this value to pH values recorded at geographic locations thought to be in- fluenced by anthropogenic emissions, is inappropriate. A clear understanding of anthropogenic contributions and the natural pH variation in deposition acidity resulting from weak at- mospheric acids and soil sources is required. Sulfate in Precipitation as a Surrogate for Hydrogen in Rainfall The acidic deposition discussion has mostly focused on the direct and indirect effects of atmospheric hydrogen ion de- positions on vegetation, soils, and surface waters. However, because of 1) the difficulty associated with developing transport models for predicting regional hydrogen ion depo- sition and 2) the assumption that atmospherically deposited sulfate is equivalent to atmospherically deposited hydrogen ion, much of the discussion about reducing atmospheric loading of hydrogen ion has centered on sulfate reduc- tion.10 Several authors have commented on using either sulfur or hydrogen ion loading in precipitation for estimating the im- pact of acidic deposition. Coote et al. ,19 while focusing on the applicability of using these two chemicals for predicting possible soil impacts, have commented "when sulfur alone is used, then the neutrality of calcium, magnesium, sodium, and other such salts of sulfur is ignored." Results reported by Krupa and Pratt,20 -21 Pratt et al. ,22 and Sequeira23 '24 bring into question the hypothesis that sulfate can be used as a substitute for predicting possible precipitation acidity effects on both the aquatic and terrestrial environments. Pratt et al.22 collected rain samples during the summers of 1977 through 1980 at seven sites in the vicinity of a coal-fired power plant in central Minnesota. The authors' analyses in- dicated that the major anions (sulfate and nitrate) appeared to be more closely associated with calcium, magnesium, so- dium, and ammonium ions than with hydrogen ions. They also indicated that the sulfate concentration was dependent upon the concentration of the cations present in precipitation. Sequeira24 analyzed chemical composition data from at- mospheric precipitation for three high altitude World Mete- orological Organization stations (Monte Cimone, Italy; Mauna Loa, Hawaii; and Alamosa, Colorado). Simple linear and multiple linear regression analyses indicated that sulfate was strongly associated with alkali/alkaline earth elements (cal- cium, potassium, and sodium). Of the three sites, hydrogen and total sulfate were highly correlated only at Mauna Loa, Hawaii. Data reported by Gorham et al.25 for 33 National Atmo- spheric Deposition Program (NADP) stations in 1980 and 49 in 1981 (sites east of 95° W), indicate that hydrogen ions in precipitation are more closely associated with sulfate than with nitrate and that a reduction in sulfate ions would result in a reduction in hydrogen in wetfall. The investigators ex- amined correlations between volume-weighted, mean annual ionic concentrations in wet deposition across sites. Caution should be exercised in using the results because the authors did not calculate the variability between sulfate and hydrogen and nitrate and hydrogen at each of the monitoring sites. Using annually averaged wet chemistry monitoring data to address the surrogate question appears inappropriate. To test this hypothesis, statistical analyses should be performed using weekly (NADP) or event (MAP3S/UAPSP) wet chemistry data collected at each site. The implications of the work by Krupa and Pratt,20 -21 Pratt et al. ,22 and Sequeira23 '24 are that sulfate in wetfall at some sites is associated with cations other than hydrogen. The National Research Council26 noted that not all sulfates in the air or in precipitation contribute to the acidity measured. However, the assumption that sulfate ion deposition can be equated with hydrogen ion deposition over large geographic areas has been made by several groups.10 '27 Caution should be exercised when attempting to apply the hypothesis over large geographic areas to predict surface water chemical changes resulting from atmospherically deposited sulfate. Surface Water Episodic pH Depressions One of the important observations associated with possible acidic deposition effects on the aquatic system is the episodic increase in hydrogen ion concentration in surface waters during snowmelt and heavy runoff. It has been hypothesized that 1) during the winter, acidic deposition in rainfall and snow is collected by the snowpack and released during spring runoff periods and 2) heavy storms cause flushing events that result in acidic materials deposited on the soil (derived from dry atmospheric deposition) being carried to surface wa- ters.10 However, recent reports and articles by Everett et al.,28 Brocksen and Lefohn,29 Jones et al.,30 Krug and Frink,31 Richter,32 U.S./Canada,10 CARP,33 and Lefohn and Klock,34 Noggle et al.,35 and Krug et al.,36 have rekindled the possi- bility that natural soil processes have a more important role in defining stream water chemistry than generally acknowl- edged. Lefohn and Klock34 reviewed data and reports derived from ten watershed sites across the U.S. and found that nat- ural soil processes appeared to play an important role at most of the sites in defining the seasonal episodic activity and aluminum concentrations measured in many of the surface waters. Noggle et al.35 have shown that forest soils in the Raven Fork and Straight Fork, North Carolina watershed play an important role in defining surface water chemistries. Re- sults from applying pH 5.7 simulated rain showed that Raven Fork forest soils contributed weak acids, strong acids, and aluminum to percolating water in the absence of acidic de- position in precipitation. Further support for the importance of naturally produced hydrogen in soils is derived from work of Seip et al.37 The authors studied the changes in concentrations of chemical components in snowpack and runoff in several mini-catch- ments in Telemark, Norway. In 1979, the investigators neu- tralized snow with sodium hydroxide before the snow melting period. When the H+ concentrations in runoff in 1978 and 1979 were compared, the authors reported that the average hydrogen ion concentrations were similar, despite the neu- tralization of snow in 1979. Rosenqvist et al.38 have estimated 1006 Journal of the Air Pollution Control Association
  • 4. that the atmospheric acids in excess of carbonic acids in the Numedal area (Norway) contributed about 5-15% ofthe total acid formed in soil. There is mounting evidence supporting the thesis that ad- ditional research is necessary before scientists can ascertain whether the pH events observed during snowmelt and heavy autumn rains can be attributed to internal H+ sources or a mixture of both internal and anthropogenic sources. Works by Chen et al.39 and Newton and April40 stress the importance of soils in defining lake chemistry. For specific sites, if the observed pH events in surface water are a result of a combi- nation of natural and anthropogenic sources, then an effort must be made to quantify the relative contribution associated with each. Forest Decline There has been concern that acidic deposition has damaged forest systems. Recent surveys of forests in the eastern U.S. have shown that there are symptoms of measurable decline. The slowing growth indicates a broad regional phenomenon observed in both young and old trees of several species. In some high elevation areas, visible dieback of certain coniferous tree species has also occurred. Johnson et al.n have reported possible acidic precipitation effects on a forest ecosystem in the New Jersey Pine Barrens area. Johnson and Siccama41 have suggested that the rela- tionship between loss of vigor and drought is clear. Surveys of vegetation effects, conducted in the 1970s, reflected levels of ozone in the vicinity of the Pine Barrens that were capable of causing impacts to vegetation.42 -43 Lefohn44 recently re- viewed the EPA air quality data for a monitoring site in the area and has reported that elevated levels of hourly averaged ozone concentrations do exist during the spring and summer months. In the Northeast, work by Vogelmann12 has been cited as possible evidence that acidic deposition has caused the decline of red spruce on Camel's Hump Mountain, Vermont. Johnson and Siccama41 do not support this hypothesis. The authors conclude instead that current evidence suggests conifers are primarily affected by drought. The authors believe that acidic deposition could exacerbate drought stress, but that no con- vincing evidence is available to show that acidic deposition can be linked to the observed mortality. Siccama et al.45 have concluded that the cause of the decline of red spruce is not known. To explain the reduced growth phenomenon, the following set of working hypotheses has been proposed:46 • Gaseous air pollutants, such as ozone, are causing damage to tree foliage, and either alone or by interacting with acid deposition, affecting tree growth. • Deposition of metals, alone or interactively with acid de- position, is directly or indirectly affecting tree growth. • Acid deposition is increasing the leaching of nutrients from the foliage of trees at a rate rapid enough that uptake and recycling of lost nutrients cannot maintain adequate supplies of nutrients in the tree foliage. • Acid deposition is acidifying soil water, increasing alu- minum concentrations, and ultimately affecting root growth and nutrient and water uptake. • Nitrogen saturation of forest soils is changing the bene- ficial relationship between trees and soil microorganisms either directly or indirectly, resulting in nutrient and water imbalances. Krug and Frink31 have pointed out that soils beneath forest stands proceeding through succession toward climax generally become more acidic over time. The authors stated that the recovery of landscapes in New England from earlier distur- bances, such as tree harvesting, can result eventually in in- creasing acid surface soil horizons and thickening and acidi- fication of forest floors. Evidence to support such a hypothesis has been provided by Troedsson.47 The investigator analyzed soil pH data from 13,000 arbitrarily selected test plots from the National Forest Survey in Sweden and found a strong correlation between increasing forest age and increasing soil acidity. The author concluded that the relationship between the age of coniferous trees and soil pH was stronger than the relationship between atmospheric depositions. In addition to the change in soil environment, Krug and Frink31 have discussed land use practices as a possible per- turbing agent in affecting the natural nutrient cycling pro- cesses that influence forest growth. Man's destruction of the "old growth" forest environment tends to diminish soil pod- zolization. In contrast, fire protection of forest stands may enhance podzolization. Therefore, land use practices have the potential for significantly influencing podzolization activity and consequently, the soil environment in which trees grow. Placing the comments of Krug and Frink into perspective, a second set of hypotheses might be: • Changes in soil chemistry that result from natural suc- cession result in forest decline for specific species. • Land use practices (e.g., tree harvesting and fire man- agement) have impacted the soil environment in which trees grow. Changes in soil chemistry are manifested by modifying tree succession patterns. While scientists attempt to identify the causes of the forest decline, survey work is continuing. McLaughlin et al.48 have described two large scale surveys sponsored by the federal government. The first is a study of dieback of red spruce over its entire range of occurrence in the eastern U.S. Approxi- mately 32 stands of spruce have been sampled to document the geographical extent of dieback, the degree to which die- back was preceded by declining growth of both spruce and associate species, and the association of these responses with the past history of growth of these species at these sites. A second program was initiated in 1982 to examine the combined effects of acid rainfall and chronic gaseous pollution stress on a variety of forest species distributed throughout the eastern U.S. The project, entitled FORAST (Forest Responses to Anthropogenic Stress), is assessing forest effects and the re- sults will be incorporated into the 1985 National Acid Pre- cipitation Program Assessment. At present, scientific results support the conclusion that no direct evidence exists that acidic deposition currently limits forest growth in North America. However, results indicate that tree growth reductions are occurring in widespread areas in regions where rainfall acidity is generally high on a volume weighted annual average.33 It is possible that through a comprehensive environmental characterization effort, a quantification of anthropogenically caused effects will be documented. October 1984 Volume 34, No. 10 1007
  • 5. "Although liming does not always work as predicted, it is currently the most well understood and applicable management tool for enhancing fisheries in acidic waters." Agricultural Crops Simulated acid precipitation experimental studies on ag- ricultural crops show positive, negative, and no effects.49 "52 Using artificial exposures, effects symptoms have been ob- served.53 "64 At this time, it appears that rain with pH values above 4.0 applied in a routine manner to the vegetation, does not cause detrimental effects. The frequency of occurrence of rain events below pH 4.0 is important. Many investigators have commented on the epi- sodic nature of rain chemistry.13 -14 '22 -24 '65 -68 The annual volume weighted concentration of a specific ion may not necessarily correlate with possible ecological impacts. John- ston et al.57 have compared differences between plants grown in greenhouses exposed to rain at a constant pH 3.2 level and those exposed to rain that increased in pH from 2.8 to 4.0 with a pH 3.2 mean. Results indicate a tendency for rain events with a high peak level of acidity to cause greater deleterious effects on bush bean plants (Phaseolus vulgaris L. cv 'Blue Lake 274') than those rain events characterized by a constant pH level. Using actual rain chemistry data, Lefohn69 and Lefohn and Benedict70 have evaluated the frequency of weekly reported pH values for wet chemistry monitoring sites. For the majority of events, even at sites experiencing annual volume weighted pH values of 4.16, the pH values are mostly above 4.0. Sites in the northeastern U.S. experienced a greater percentage of precipitation events below 4.0 than did sites in other parts of the country. However, weekly NADP samples varied over a large pH range. Jacobson,52 after reviewing the U.S. Depart- ment of Energy's MAP3S data for the Ithaca, New York and Pennsylvania sites, states that"... a reasonable conclusion is that there is a low risk of foliar injury to field-grown vege- tation from exposure to current levels of acidity in precipita- tion in the U.S." While these conclusions are preliminary in nature, Lefohn and Brocksen,71 Irving,51 and Jacobson52 have emphasized that additional research should include other considerations such as exposure patterns and chemical con- stituent identification (e.g., nitrate and sulfate). Concern has been expressed about the possible effects on crops from simultaneous exposures of gaseous air pollutants (e.g., ozone) and acid precipitation. Results by Jacobson et al.,72 Troiano et al.,5S and Troiano et al.73 show that under simulated acid rain and filtered and nonfiltered ambient ox- idant conditions, ozone and acid rain tended to show inter- active effects. Work by Norby and Luxmoore74 showed that simulated acid rain and sulfur dioxide/ozone exposures did not affect the response of soybeans to extremely low pH (2.6) simulated acid rain exposures. Lefohn and Tingey75 have re- cently summarized the frequency of the number of co-occur- rences of SO2/O3, SO2/NO2, and O3/NO2 under ambient conditions and state that vegetation research using gaseous air pollutant mixtures should focus on the sequential ap- pearance of the pollutants. It appears reasonable to propose that combined acidic deposition and gaseous air pollutant mixture exposures should stress the sequential patterns of occurrence. Aquatic Ecosystems The question of acid rain affecting aquatic systems has been shrouded in confusion. While much of what we do know is based on circumstantial evidence,27 there are some specific statements that can be made concerning the possible impact of acidic deposition on streams, rivers, and lakes. Work Group I reviewed the empirical data available for assessing possible acidic deposition impacts to the aquatic ecosystem.10 The Work Group has identified the following geographic areas as examples that can be cited for illustrating acidic deposition chemical and biological effects: Algoma (Ontario), Mus- koka-Haliburton (Ontario), Laurentide Park (Quebec), Nova Scotia, Adirondack Mountains of New York, the Hubbard Brook Ecosystem (New Hampshire), and Maine and New England. Some headwater lakes in the Algoma district of Ontario have elevated sulfate, aluminum, and lead concentrations.10 The Work Group has examined fish surveys conducted in the area and has indicated that the numbers of fishless lakes in- crease with decreasing alkalinity. This district begins about 100 km from Sudbury, Ontario (a significant local point source of sulfate and heavy metal emissions). Because elevated lead concentrations have been observed, the elevated sulfate levels observed in the lakes may have originated from Sudbury emissions. In addition, the number of fishless lakes may be associated with possible elevated levels of heavy metals de- rived from Sudbury.76 Data for the Muskoka-Haliburton area of Ontario show a loss of alkalinity for one lake. However, the Work Group mentioned pH depressions in a number of lakes and streams. A fish kill, moreover, was observed once during spring snow- melt in one lake. Although acidification was the suspected cause, the actual cause of the fish kill was not determined. As discussed by CARP,33 it is possible that pH depression events occurring during the spring snowmelt and during the fall rains could consist of natural (internally generated hydrogen ions in the soil) and, secondarily, anthropogenic sources. Jones et al.30 discuss this possibility in their description of the Raven Fork, North Carolina, investigation. The Work Group has stated that it is difficult to include natural acid formation criteria in regional sensitivity assessments because the data base is so limited.10 Thus, at this time, it is impossible to at- tribute the fish kill to an anthropogenically derived source. Work by Evans, and Dillon76 suggests that elevated con- centrations of lead in the sediments of lakes in the Mus- koka-Haliburton region of southern Ontario originated from the burning of fossil fuels in North America; elevated con- centrations of lead are also found in lakes in the Algoma dis- trict. Both regions, however, are relatively close to a large point source of sulfate and heavy metal emissions at Sudbury, On- tario (200 km from the Muskoka-Haliburton region and 100 km from the Algoma district). Nriagu et al.77 report that 230,000 kg of lead are emitted annually from the Sudbury smelters; in comparison, Turner and Strojan78 report that total atmospheric emissions of lead from coal combustion in the U.S. amount to 54,000 kg annually. The maximum lead concentrations reported in the sediments of lakes in the Muskoka-Haliburton region, reported by Dillon and Evans79 and presented by the Work Group,10 are about 2.5 to 5.0 times greater than those found in Adirondack lake sediments (128 fig lead per gram of sediment) by Davis et al.80 Thus, if lead concentrations provide an indication of the origin of the lakes' anthropogenically derived sulfates, local emitting sources in Canada may be important in explaining some of the obser- vations. 1008 Journal of the Air Pollution Control Association
  • 6. Data for Laurentide Park, Quebec, have been reviewed by Work Group I, who found that sulfate concentrations in sur- face waters in Quebec decrease toward the east and north, parallel with the deposition pattern. As discussed by Lefohn et al.,81 sulfate concentrations did not correlate well with calcium + magnesium — alkalinity concentrations. Most im- portantly, there is no evidence of effects to fish populations from elevated sulfate concentrations in Quebec lakes.10 Historical salmon catch records from Nova Scotian rivers reportedly show reductions over the past 40 years.10 The At- lantic Salmon Review Task Force,82 relying on commercial Canadian salmon catch data for the years 1910 through 1977, report that many Atlantic salmon stocks production areas in Nova Scotia, New Brunswick, and St. John have been affected by over-harvesting and industrial development. For example, the Task Force reported that Atlantic salmon in the southwest Nova Scotia area have been impacted by over-harvesting, while in the southern New Brunswick-St. Johns area, the salmon have been impacted by the "construction of the massive Mactaquac hydro-electric development just above tide-head ..." The Task Force appears to believe that the development created additional demands on much of the salmon's freshwater habitat or lifeline and that by the late 1960s, thereiwas little optimism for rehabilitation of stocks in the river. In addition to development activities, local air pollution and natural hydrogen sources may be an important aspect of the problem. The findings of Shaw83 -84 suggest that a substantial part of the hydrogen concentration in the Nova Scotian waterbodies appears to be related to local point sources. Results reported by Watt et al.85 and Farmer et al.86 show that many of the Nova Scotian rivers contain humic and/or fulvic acids and that the contribution of these organic acids to total acidity may be significant.10 Data for the Adirondack Mountains in New York have been reviewed by the Work Group.10 The Group infers that losses in fish populations at 180 lakes are attributable to acid rain because a comparison of data from the 1930s with data from recent surveys has shown that more lakes have become acid- ified. Recent reviews of the problems associated with com- paring data derived from two distinct time periods87 con- cluded that there are many more questions that need to be answered before one can consider the comparisons valid and reliable. Retzsch et al.88 have suggested several possible al- ternative explanations for the reported observations. The authors report that the numbers of lakes and ponds stocked have shown a relatively continuous decline. This decline, ac- cording to the authors, may be the result of the closing of stocking waters found to be unsatisfactory for long-term fish survival. While no biological impacts associated with aquatic or- ganisms have been documented at the Hubbard Brook study area in New Hampshire, Work Group I did state that the area has experienced pH depressions of 1 to 2 units in streams during snowmelt.10 Brocksen and Lefohn29 and Lefohn and Klock34 have discussed possible reasons that pH depressions could be attributed to natural occurrences. The authors stress that additional research is necessary to separate the natural from the anthropogenic contribution of hydrogen ion during spring snowmelt and heavy runoff. In the Maine and New England areas, the Work Group10 reported lake water pH declines based on comparisons with historical information.80 '89 -90 No effects have been observed on Atlantic salmon populations, nor have effects been ob- served on fish in inland lakes. Marcus et al.87 have pointed out that Davis et al.91 noted that cultural eutrophication had apparently increased the daytime pH of a small but significant portion of the surveyed lakes and that although the earlier measurements were made using colorimetric methods, the more recent values were determined with potentiometric methods. Lefohn et al.92 have pointed out the problems as- sociated with comparing pH values using different measure- ment techniques. The work by Norton et al.89 examined changes in surface water pH between the periods 1939-1946 and 1978-1980. The authors concluded that 85% of the lakes appeared to be more acidic in the period 1978-1980 than in 1939-1946. Marcus et al.81 and Brown and Brocksen93 pointed out that since the study only compared two points in time over extended intervals, it was unclear whether the results obtained represented actual trends or were artifacts of normal temporal variations in surface water pH. Linthurst et a/.94 state that lake acidification trends, as described for the above examples, cannot be unequivocably related to acidic deposition. In contrast to the suggested acidification of New England surface waters reported by the above cited authors, Norvell and Frink95 concluded that the pH and alkalinity in sensitive (alkalinity less than 200 neq L"1 ) lakes of Connecticut had not changed significantly from 1937 to 1973. Inspection of the atmospheric deposition maps presented by the Work Group10 shows similar deposition rates of hydrogen and sulfate ions in Connecticut and other parts of New England. Thus, care must be exercised when discussing the possibility of extrap- olating the results from a local observation in order to predict regional scale effects. Both chemical and biological processes within a forest ecosystem soil appear to play an important role in determining the chemistry of surface waters. Swank and Fitzgerald96 have shown that the metabolism of inorganic sulfate to organic forms can be a major process in the sulfur cycle that influences sulfate soil accumulation and mobility in forest ecosystems. Vitousek and Matson97 have reported that measurements of nitrogen-15 retention in the field demonstrated that microbial uptake of nitrogen during the decomposition of residual or- ganic material was one of the most important processes in retaining nitrogen in the soil. Results reported by Johnson and Todd98 showed that irrigation with sulfuric and nitric acid at two and ten times the current annual hydrogen inputs over a period of one year had no statistically significant lasting effect on nitrogen in the soil or Al availability or P avail- ability. Using sulfate concentration measured in surface waters as an indication of acidic deposition effects may be misleading. Parnell99 showed that where bedrock sulfide concentrations are significant, naturally derived sulfuric acid may cause ac- celerated chemical weathering rates and low pH values in local streams. The author stressed that where sulfidic rocks crop out, this contribution may have previously been underesti- mated by some investigators. The author stresses that caution should be used in interpreting acid precipitation leaching and weathering data from New England drainage basins underlain by sulfidic schists. As discussed by Everett et al. ,28 sulfate measured in surface waters may be more correlated to the sulfur contained in minerals than the sulfate deposited from atmospheric wetfall and dryfall. October 1984 Volume 34, No. 10 1009
  • 7. "Science is the search for truth. Our efforts may lead us down several different paths, but our challenge is to search for data that will provide a clearer picture of how the ecosystem responds to both natural and man-made perturbations." Mitigation Strategies Acidic surface waters generally have unproductive fisheries or, in some cases, are incapable of supporting any fish popu- lations. This results from both the oligotrophic (nutrient poor) status of these waters and the low tolerances ofmany desirable fish species to the acidity. Liming is defined as the addition of lime, limestone, or other alkaline materials to acidic surface waters for neutralization. Finely ground calcium carbonates and basic slags of the mono- and dicalcium silicate types have been found particularly useful in pH adjustments of acid lakes because their relatively intermediate solubilities tend to extend the period of neu- tralization.100 Historically, liming has been used to establish, restore, or enhance fish production in acidified waters. As a fisheries management technique, liming was first used in naturally acid, brown water lakes.101 Subsequently, the technique has been applied to reclaimed lakes impacted by acid mine drainages. And more recently, liming has been applied to surface waters in regions receiving acidifying depositions.102 '103 Liming reduces adverse effects of acidification on fish populations by increasing pH, hardness, and alkalinity levels of surface waters. These increases reduce the toxicity of acid waters by 1) reducing toxic hydrogen ion concentrations; and 2) complexing, precipitating, changing chemical speciation, and inhibiting uptake of metals that are often enriched in acidified waters. As a result, liming has been very beneficial in restoring and enhancing the fishery potential of some acidified waters. The utility of liming is best illustrated by the Swedish ex- perience.104 Sweden is undertaking an extensive lake program to preserve and protect salmon, perch, and pike fisheries threatened by acidification. During 1977 to 1979, about 700 lakes and rivers were limed. During the 1982 fiscal year, 1000 lakes were to be limed at a cost of six million dollars. The program is expected to expand to an annual budget of 40 million dollars by fiscal year 1986 to include the liming of 20,000 lakes and streams. Liming programs in North America have been much less extensive. Liming was used to increase pH levels in several acidic lakes near Sudbury, Ontario. However, fish introduc- tions into these lakes failed because high toxic metal con- centrations, derived from local smelter emissions, remained in lake waters. New York state has used liming since the late 1950s to maintain trout populations in some acidic lakes. Concurrently, considerable research on liming and its use- fulness for protecting or restoring fisheries is being conducted by a number of governmental and private institutions. Although liming does not always work as predicted, it is currently the most well understood and applicable manage- ment tool for enhancing fisheries in acidic waters. Much po- tential exists for increasing its usefulness, especially by com- bining it with some of the alternative strategies that may be available. Liming is not a viable mitigative strategy for every surface water. Where the inaccessibility of some acidic water bodies may greatly increase costs or where liming may not reduce the episodic aspects of snowmelts, etc., other alternative strategies may be appropriate. And, in some instances, more than one strategy may be applied to the same waters. Certainly there is a need for evaluation and development of additional strat- egies for restoring and enhancing the fisheries of acidic wa- ters. Modern agriculture, animal husbandry, and forestry practices may provide insight into ways of accomplishing this. Through selective breeding, introduction of new species, and fertilization coupled with changes in land use practices, it may be possible to increase the pH and alkalinity of acidic waters and establish fisheries where they were once absent. While liming is a proven management tool in some cases, there remain questions with respect to toxic metal bioaccu- mulation by fish, longer term chemical alterations, and the need to lime with relative frequency. As stated previously, there is currently a large research effort examining problems associated with liming and if this mitigative strategy is to be implemented, consideration must be given to the site specific characteristics of the water body and its watershed. Future Research Directions Much effort has been directed toward surveying the nation's aquatic and terrestrial resources. To separate perturbations associated with anthropogenic sources from those derived from natural occurrences, it will be necessary for researchers to blend survey activities with process oriented efforts. To assist in this endeavor, the following series of fundamental questions are proposed: • What will happen to the pH concentration in rainfall in the amount of sulfate and nitrate in rainfall is modi- fied? • How much do natural acidification soil processes con- tribute to the pH depressions that are observed in surface waters during heavy rainfall and snowmelt events? • What are the important pollutants (e.g., acidic deposition, ozone, sulfur dioxide, etc.) in combination with natural factors (e.g., forest succession, drought, infestation, etc.) that may contribute to the observed forest decline? • Do combinations of pollutants (e.g., acidic deposition, sulfur dioxide, and ozone) adversely affect agricultural crops? • How many lakes are acidic because of acidic deposi- tion? • How many lakes are incapable of supporting fish because of acidic deposition? • How many lakes will become supportive of fish if acidic deposition can be reduced? • What other remedial measures (or combinations of mea- sures) will make a lake supportive of fish? The ecosystem may have the potential for ameliorating anthropogenically derived stresses if a pollutant's concen- tration, frequency of occurrence, time between occurrences, and temporal exposure occur in a pattern that provides for a homeostasis or hysteresis feedback response. For researchers to provide answers to the questions raised, it will be necessary for "alternative" hypotheses to be identified and seriously addressed. The talents of an eclectic set of scientists will be needed to probe beyond the obvious. Conclusion and Recommendation Recent publications underscore the tenuous nature of the acid deposition effects data base. Based upon the most current evidence the following conclusions may be drawn: 1010 Journal of the Air Pollution Control Association
  • 8. • If the hydrogen ion that is deposited on a watershed is believed to be the primary source of ecosystem pertur- bation (recognizing that mobile aluminum is a secondary product of the soil acidification process), then it is unclear whether a reduction in atmospherically deposited sulfate or nitrate would result in a similar reduction in deposited hydrogen ion. • While hot being able to quantify their contribution at this time, naturally produced acids that are internally gener- ated within the soil ecosystem may play a considerably more important role in determining the acidification of surface water bodies than previously believed. The acid- ification process may involve a combination of natural and anthropogenically derived acid sources. • While reductions in tree growth are occurring in North America and Europe, no direct evidence exists to link acidic deposition with these observations. In fact, recent hypotheses tend to focus on many factors as possible agents that might significantly contribute to the observed forest decline. • Evidence is mounting that ambient exposures of acidic deposition may not injure or reduce the growth of agri- cultural crops. • Aquatic waterbodies identified by Work Group I (based on empirical observation) as having been acidified by acid rain may be more affected by local point sources (e.g., Sudbury, Ontario) or naturally derived acid sources con- tained within the soil. • Mitigation techniques are presently under review, but caution should be exercised so that possible biological modifications resulting from chemical alteration can be avoided. Over the next several years, the pace of acid rain research will be increasing. However, it is unclear whether the quality of the data produced from this increased pace will show a consonant increase. Increased federal spending is not neces- sarily synonymous with obtaining answers more quickly. The entropy of the universe tends to increase and with it, maxi- mum randomness. Therefore, additional energies within our funding institutions will have to be found to organize and in- terpret new information. Science is the search for truth. Our efforts may lead us down several different paths, but our challenge is to search for data that will provide a clearer pic- ture of how the ecosystem responds to both natural and man-made perturbations. As Resnick105 has stated: "Successful problem-solving requires a substantial amount of qualitative reasoning. Good problem-sol- vers dp not rush in to apply a formula or an equation. Instead they try to understand the problem situation; they consider alternative representations and rela- tions among the variables. Only when they are satis- fied that they understand the situation and all the variables in it in a qualitative way do they start to apply the quantification that we often mistakenly identify as the essence of 'real' science of mathe- matics." Careful work will be required to clarify our knowledge of how acidic deposition may be impacting ecosystems. With well founded hypotheses that are designed to lead to greater un- derstanding of the complex processes associated with this problem, we hope to learn more about those important pro- cesses that affect our biosphere. References 1. G. E. Likens, F. H. Bormann, N. M. Johnson, "Acid rain," En- vironment 14: 33 (1972). 2. G. E. Likens, "Acid precipitation," Chem. Eng. News 54: 29 (1976). 3. C. V. Cogbill, G. E. Likens, "Acid precipitation in the north- eastern United States," Water Resources Res. 10: 1133 (1974). 4. C. L. Schofield, "Acid precipitation: effects on fish," Ambio. 5: 228(1976). . 5. J. N. Galloway, G. E. Likens, "Calibration of collection proce- dures for the determination of precipitation chemistry," Water, Air, Soil Pollut. 6: 241 (1976). 6. J. N. Galloway, E. B. Cowling, E. Gorham, W. W. McFee, "A national program for assessing the problem of atmospheric de- position (acid rain)," National Atmospheric Deposition Pro- gram, Natural Resources Ecology Laboratory, Fort Collins, CO, 1978. 7. G. E. Likens, R. F. Wright, J. N. Galloway, T. J. Butler, "Acid . rain," Sci. Am. 241:43 (1979). 8. G. E. Likens, T. J. Butler, "Recent acidification in precipitation in North America," Atmos. Environ. 15:1103 (1981). 9. E. B. Cowling, "Acid precipitation in historical perspective," . Environ. Sci. Technol. 16:110A (1982). 10. "United States—Canada Memorandum of Intent on Trans- boundary Air Pollution," Final Report, prepared by the Impact Assessment Work Group 1,1983, (Draft). 11. A. H. Johnson, T. C. Siccama; D. Wang, R. S. Turner, T. H. Barringer, "Recent Changes in Patterns of Tree Growth Rate in the New Jersey Pinelands: A Possible Effect of Acid Rain," University of Pennsylvania, Philadelphia, PA, 1981. 12. H. W. Vogelmann, "Catastrophe on Camel's Hump," Natural History, November 1982. 13. J. N. Galloway, G. E. Likens, W. C. Keene, J. M. Miller, "The composition of precipitation in remote areas of the world," J. Geophys. Res. 87:8771 (1982). 14. R. J. Charlson, H. Rodhe, "Factors controlling the acidity of natural rainwater," Nature 295: 683 (1982). 15. S. F. Guiang, III, S. V. Krupa, G. C. Pratt, "Measurements of S(IV) and organic anions in Minnesota rain," Atmos. Environ. (1984), in press. 16. W. C. Keene, J. N. Galloway, J. D. Holden, Jr., "Measurement of weak organic acidity in precipitation from remote areas of the world," J. Geophys. Res. 88: 5122 (1983). 17. W. C. Keene, J. N. Galloway, J. D. Holden, Jr., "Organic Acidity in Precipitation from Remote Areas of the World," in Pro- ceedings of the 3rd Annual National Symposium on Recent Advances in Measurements of Pollutants in Ambient Air and Stationary Sources, U.S. EPA, Research Triangle Park, NC, 1984. 18. W. C. Keene, J. N. Galloway, "Organic acidity in precipitation of North America," Atmos. Environ. (1984), in press. 19. D. R. Coote, D. Siminoyitch, S. Shah Singh, C. Wang, "The Significance of Acid Rain to Agriculture in Eastern Canada," Land Resource Research Institute, Contribution No. 119, 1981. 20. S. V. Krupa, G. C. Pratt, "Rainfall Chemistry in Minnesota and West-Central Wisconsin—Final Report 1981," prepared for Minnesota/Wisconsin Power Suppliers Group, 1983. 21. S. V. Krupa, G. C. Pratt, "Rainfall and Aerosol Chemistry in Minnesota and Wisconsin—Final Report 1982," prepared for Minnesota/Wisconsin Power Suppliers Group, 1983. 22. G. C. Pratt, M. Coscio, D. W. Gardner, B. I. Chevone, S. V. 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Bengtsson, W. Dickson, P. Nyberg, "Liming acid lakes in Sweden," Ambio 9:34 (1980). 104. J. Fraser, D. Hinckley, R. Burt, R. R. Severn, J. Wisniewski, "A Feasibility Study to Utilize Liming as a Technique to Mitigate Surface Water Acidification," Report No. 1238-03-81-CR, General Research Corporation, McLean, VA, 1981. 105. L. B. Resnick, "Mathematics and science learning: a new con- ception," Science 220: 477 (1983). Dr. Lefohn is President and Founder of A.S.L. & Asso- ciates, 111 North Last Chance Gulch, Helena, MT 59601. Dr. Brocksen is Director of the Wyoming Water Research Center and Professor of Zoology at the University of Wyoming. October 1984 Volume 34, No. 10 1013