United States
             Environmental Protection
             Agency
              Environmental Research
              Laboratory
              Corvallis OR 97330
EPA 600 3-80-014
  ary 1980
             Research and Development
&EPA
Effects of Sulfuric
Acid Rain on Two
Model Hardwood
Forests

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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology.  Elimination  of  traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

      1.   Environmental  Health Effects Research
      2.   Environmental  Protection Technology
      3.   Ecological Research
      4.   Environmental  Monitoring
      5.   Socioeconomic Environmental Studies
      6.   Scientific  and Technical Assessment Reports (STAR)
      7.   Interagency Energy-Environment Research and Development
      8.   "Special" Reports
      9.   Miscellaneous Reports

This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on the effects of pollution on humans, plant and animal spe-
cies, and materials. Problems are assessed for their long- and short-term influ-
ences. Investigations include formation, transport, and pathway studies to deter-
mine the fate of pollutants and their effects. This work provides the technical basis
for setting standards to minimize undesirable changes in living organisms in the
aquatic,  terrestrial, and atmospheric  environments.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                                   EPA-600/3-80-014
                                                   January  1980
EFFECTS OF SULFURIC ACID RAIN ON TWO MODEL HARDWOOD FORESTS:

       THROUGHFALL, LITTER LEACHATE, AND SOIL SOLUTION
                             by

                       Jeffrey J.  Lee
                    Terrestrial Division
         Con/all is Environmental  Research Laboratory
                     Con/all is, OR 97330

                             and

                       David E. Weber
                   Energy Effects  Division
             Office of Research and Development
            U.S.  Environmental Protection Agency
                   Washington, D.C.  20460
         CORVALLIS ENVIRONMENTAL RESEARCH LABORATORY
             OFFICE OF RESEARCH AND DEVELOPMENT
            U.S.  ENVIRONMENTAL PROTECTION AGENCY
                     CORVALLIS, OR 97330

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                                  DISCLAIMER

     This  report  has  been  reviewed by  the Con/all is  Environmental  Research
Laboratory, U.S.  Environmental  Protection  Agency,  and approved  for publica-
tion.   Mention  of  trade names  or  commercial  products  does  not  constitute
endorsement or recommendation for use.

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                                   FOREWORD

     Effective regulatory and enforcement actions by the Environmental Protec-
tion Agency  would be  virtually  impossible without  sound scientific  data on
pollutants  and  their   impact  on  environmental  stability  and  human  health.
Responsibility for building  this  data base has  been  assigned  to EPA's Office
of Research and Development and its lb major field installations, one of which
is the Corvallis Environmental  Research Laboratory.

     The  primary  mission  of  the  Corvallis  Laboratory  is  research on  the
effects  of environmental  pollutants   on  terrestrial,  freshwater,  and marine
ecosystems;  the  behavior,  effects and  control   of  pollutants  in  lakes  and
streams;  and  the development  of  predictive models  on the movement of pollu-
tants in the biosphere.

     This  report describes  the  effects  of simulated  sulfuric acid  rain on
experimental model hardwood  forests,  and compares the results  to  the predic-
tions of  a computer  simulation model.  This work was  undertaken as part of a
research  program at  CERL to  determine  the  effects of  acid   rain  on forest
ecosystems.
                                   Thomas A.  Murphy, Director
                                   Corvallis Environmental Research Laboratory
                                      m

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                                   ABSTRACT

     Simulated  sulfuric  acid  rain was  applied  to  model  forests  containing
either sugar  maple (Acer  saccharum)  or  red alder (Alnus rubra).   One  set of
four plots  (two  alder and two maple) received  a control  rain consisting of a
stock solution equilibrated with atmospheric C02 to approximately pH 5.6.  For
three sets  of  four plots,  sufficient H2S04 was added to the stock solution to
lower the  pH  to 3.0,  3.5, or  4.0.   Nozzles were used to apply simulated acid
rain at the rate of 2.8 mm/hr  (maple) or 3.7 mm/hr (alder) for three hours per
day, three  days  per week,  throughout the year.   Water samples were collected
above and  below the  canopy,   below the  litter layer, and  from  20-cm  and 1-m
depths below the surface of the soil.

     While  throughfall  chemistry was not very  different  from rain chemistry,
the  litter leachate  (the  actual  input  to  the  soil)  had consistently higher
concentrations  of  calcium and magnesium,  and higher pH, than the  acid rain.

     For the  first six  months,  sulfate absorption by the  soil  prevented any
apparent differences  in sulfate,  calcium,  or  magnesium  concentrations among
plots receiving  either acid or control treatments.  Sulfate concentrations on
plots receiving the  most  acid rain (pH 3.0)  then became increasingly higher
than  on  the  other plots  until,  after  three  years,  they  were  approximately
equal to sulfate concentrations in the rain.  Soil solutions corresponding to
the pH 3.5  and pH 4.0 treatments responded  similarly starting one year and two
years,  respectively,   after  initiation of  exposure  to acid  rain.   Increased
calcium  and magnesium concentrations  and  lowered pH  in 20-cm  soil  solution
occurred simultaneously  with  increased sulfate concentrations.  At a depth of
one  meter, no  acid rain  related  effects  were  evident  even  after  3.5 years
exposure to pH 3.0  sulfuric acid rain.

     Comparisons of the data  with the  predictions  of a  computer  simulation
model indicated  that  soil  properties obtained under laboratory conditions can
oe  used  with  established relationships  to predict cation  concentrations in
soil solutions  associated  with increased anion concentrations from acid rain.
However,  sulfate concentrations in the 20-cm soil solution increased consider-
ably faster than predicted by using laboratdry values in a Langmuir represen-
tation of sulfate absorption.

     This report covers a period from June, 1976 through August,  1979.
                                      IV

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                                   CONTENTS
Foreword	iii
Abstract	iv
Figures	vi
Tables	vii

     1.    Introduction	   1
     2.    Conclusions 	   3
     3.    Recommendations 	   4
     4.    Experimental Procedures 	   5
     5.    Results	8
     6.    Discussion	27

References	35

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                                    FIGURES

Number

  1.  pH of Throughfall vs. pH of Rain	9

  2.  Sulfate Concentration in Throughfall vs. Sulfate Concentration in
      Rain	10

  3.  Magnesium Concentration vs. Sulfate Concentration in Throughfall. .  .  11

  4.  Calcium Concentration vs. Sulfate Concentration in Throughfall.  ...  12

  5.  pH of Litter Leachate vs. pH of Rain	13

  6.  Sulfate Concentration of Litter Leachate vs. Sulfate Concentration
      of Rain	14

  7.  Magnesium Concentration vs. Sulfate Concentration of Litter Leachate  15

  8.  Calcium Concentration vs. Sulfate Concentration of Litter Leachate.  .  16

  9.  Sulfate Concentration of 20-cm Soil Solution vs. Time	18

 10.  Magnesium Concentration of 20-cm Soil Solution vs. Time	19

 11.  Calcium Concentration of 20-cm Soil Solution vs. Time	20

 12.  pH of 20-cm Soil Solution vs. Time	21

 13.  Magnesium Concentration vs. Sulfate Concentration of 20-cm Soil
      Solution	22

 14.  Calcium Concentration vs. Sulfate Concentration of 20-cm Soil
      Solution	23

 15.  pH vs. Sulfate Concentration of 20-cm Soil Solution	24

 16.  Calcium Concentration vs. Magnesium Concentration of 20-cm Soil
      Solution	25

 17.  pH of 1-m Soil Solution vs. Time	26

 18.  Simulated Time Series of Sulfate Concentration of 20-cm Soil
      Solution in Maple Plots 	  32
                                      VI

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                                FIGURES (cont.)

Number                                                                    Page

 19.   Simulated Relationship of Calcium Concentration vs. Sulfate
      Concentration of 20-cm Soil Solution	33



                                    TABLES

Number

  1.   Chemical Analyses of Soil Used in Lysimeter Studies 	   6

  2.   Chemical Content of Precipitation and Throughfall  in a Sugar Maple
      Stand	28

  3.   Parameters Used in LEACH Soil  Solution Simulation  Model  	  30

  4.   Results of LEACH Simulation 	  33
                                      vn

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                                   SECTION 1

                                 INTRODUCTION

     Rainfall  over  large  portions  of  Europe  and  North  America has  become
increasingly acidic during the past thirty years.1-7  The increased acidity of
precipitation is primarily due to higher concentrations of sulfuric and nitric
acids  derived  from  the air  pollutants  sulfur dioxide  (S02)  and  oxides  of
nitrogen (NO ).  Although  precipitation  may  be acidified by  a  local emission
source, transport  over hundreds  and  even thousands of  kilometers  is common.
Acid precipitation  thus tends  to be regional  and  chronic.1'5'6'7   With  the
increased use  of fossil  fuels,  precipitation will  probably continue to become
more acidic.   Currently,  all states  east of the Mississippi  River  regularly
receive precipitation which  is  more acidic than the expected value  of pH 5.6
for  carbonic  acid  rain.3'5'6   In the northeastern  United States,  pH  4.2  is
typical of winter precipitation;  for summer  rains,  pH 3.5  is typical.6  Acid
precipitation  is  not  limited  to  the east,  but also occurs in the western
(j 5 8 »9 > 10

     The impact of acid precipitation on agricultural  and forest ecosystems  is
not  understood.   The  potential  effects  of  chronic,  long term, exposure  of
forest  soils  to acid  precipitation have been  identified as a  major concern
since,   compared to  agricultural  soils,  forest soils  are  relatively  unman-
aged.11>12'13   Increased  anion  loading  of  forest  soils  can^  theoretically,
cause  increased  concentrations  of  cations,  both bases and H ,  in  soil  solu-
tions,   and,  eventually, lead to  acidification of  soils.7'14-17   Leaching  of
bases  and  acidification of  soils by acid rain have been  observed,2'18-21  as
has  increased  mineral  weathering.22-25   Increased  soil  acidity was  thought  to
be a possible cause of decreased forest productivity in Sweden.26'27

     Before  reaching  the  forest soil,  precipitation  percolates through  the
forest  canopy  and  litter  layer.   Throughfall  from  canopies  of  deciduous
trees2'28-38 and leachates  from hardwood litter layers39 tend to  have  higher
pH values,  higher  Ca  and  Mg concentrations, and lower  volumes  than incident
acid precipitation.   Any study  of the effects of acid precipitation on forest
soils must consider the differences in quality and quantity between  precipita-
tion and  the actual input  to the soil,  the  litter  leachate.   Similarly,  any
study  of  biological  processes  in  forest litter  or  soil  must  consider  the
chemical environment  as determined  by  the litter  leachate  or  soil  solution.

     At EPA's  Con/all is Environmental  Research Laboratory in Oregon,  we  have
studied the effects of simulated sulfuric acid rain  on nutrient cycling in two
types of model hardwood forest ecosystems.40   As part of  this study,  rainwater
has  been  regularly  collected above  and below the  canopy,  below the  litter
layer,  and at two depths in the  soil during a period of more than three years.
In this paper, we report on the  chemical  changes in  acid  rain as it percolates

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though  the ecosystem.   The  concentrations  of  divalent  cations  (Ca    plus
Mg  , equivalent  basis)  and S04  in the soil solution 20 cm below the surface
are compared with the predictions of a computer simulation model, LEACH.17'41

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                                   SECTION 2

                                  CONCLUSIONS

     A well developed hardwood canopy and litter layer can significantly raise
the pH and increase concentrations of bases in rainwater.   This will result in
a decreased tendency for acid rain to acidify forest soils.

     Increased  anion  concentrations  in soil  solutions  will  cause increased
concentrations  of  cations,  generally including both bases  and hydrogen ions.
However,  sulfuric   acid  rain  might  not  cause  significantly  higher  sulfate
concentrations  in  soil  solutions until  the  ability  of  the soil  to  absorb
sulfate  is exhausted.   The response  of  soil solutions  to nitric  acid  rain
would be more rapid.

     Soil  properties  identified  under laboratory conditions can  be used  with
established relationships  to predict cation  concentrations  in soil solutions
associated with  increased  sulfate concentrations.   However,  using laboratory
values in  a  Langmuir  representation  of sulfate absorption does not accurately
simulate the time series of sulfate concentrations in these solutions.

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                                   SECTION 3

                                RECOMMENDATIONS

     The effects of  acid  precipitation on forest soils can only be adequately
studied in  an ecosystem  context.   Specifically, the  following must  be  con-
sidered:

     1.   Changes  in  rain  chemistry  caused  by passage  through canopy  and
          litter layer.

     2.   Effects of altered soil solution chemistry on uptake of chemicals by
          plants.

     3.   Effects  on other  soil  biological  processes  such  as decomposition,
          nitrogen  fixation,  nitrification, sulfur  oxidation/reduction,  etc.

     4.   Effects on weathering of minerals.

     5.   Role of  sulfate absorption by the soil in controlling the chemistry
          of the soil solution.

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                                   SECTION 4

                            EXPERIMENTAL PROCEDURES

     Each of  18  lysimeter  plots consisted ofal.5mxl.5mxl.2m water-
tight  enclosure  constructed  of fiberglass  covered plywood  and filled  to  a
depth  of  1.1  m  with  a forest  soil.   The soil (Bohannon series  of  the fine-
loamy,  mixed, mesic   family  of  Typic  Halpumbrepts)  was  obtained  from  the
Si us!aw  National  Forest,  Oregon,  and  formerly  had  supported  a red  alder-
Douglas-fir  community.   The  horizons  were  reconstituted  with  respect  to
litter, topsoil, and  subsoil  layers.   Each layer was mixed to minimize inter-
plot differences.  Soil properties are summarized in Table 1.

     In  1975,  36  tree seedlings were  planted in  each system.  Sugar maple
(Acer saccharum) was planted in 9 of the plots, and red alder (Alnus  rubra) in
the  other  9  plots.   The  model  ecosystems  also contained  herbs  and ferns
brought in  with  the forest soil.   Insects and tree frogs were observed on all
plots.  Each  plot  initially  received litter obtained from natural tree stands
of the corresponding species.   Subsequently, leaf fall  was collected  from each
plot and placed on the soil.

     Each plot received simulated acid rain at one of four acidities,  and each
treatment was  replicated.   All  plots received a  stock  solution approximating
npn-acidic  rain  containing  11  ueq/1  Ca  ,12 ueq/1 NH4 , 5 ueq/1 Na  _,  2 ueq/1
K ,  5  ueq/1 Mg  ,11  ueq/1  S04" ,  12 ueq/1  N03",  and  12 ueq/1 Cl  .   These
concentrations were based  on  a  seven  year  average  from Hubbard Brook,  New
Hampshire,42  after  elimination of estimated sulfuric  and  nitric acid compo-
nents.  One set of four plots  (two  alder and two maple)  served as  controls,
receiving only the stock solution equilibrated with atmospheric C02  to approx-
imately pH  5.6.   For  three sets of four  plots,  sufficient H2S04 was added to
the  stock solution  to lower the pH to 4.0, 3.5,  or 3.0.  One plot on each end
of  the row of plots  received only  deionized water, and served as  a buffer
plot.  Nozzles were used to apply simulated acid rain to the plots at the rate
of 2.8 mm/hr (maple) or 3.7 mm/hr (alder) for 3 hours per day 3 days  per week,
throughout  the  year.   Annual  rain  amounts  (131  cm for maple  and 173  cm for
alder)  approximated  those  of  areas  in  which  these  species  usually grow.
Application of  simulated acid rain  began the last week  of June, 1976.  Rain
was  interrupted  from December 6, 1977  to February 16,  1978  (32 rain  events)
clue  to winter damage to equipment.   Severe freezing  temperatures  prevented
nine rain applications during the winter of 1978-1979.

     The plots were -located  under a transparent (90% transmittance)  roof open
on  the ends and  sides.   Shade cloths  were positioned  over  the plots during
simulated rain events.   The  plots were thus subjected to ambient temperature,
relative  humidity,  and light  intensity except during  simulated rain  events.
The  facility  is  located on. the Schmidt  Research  Farm  of Oregon State Univer-
sity, near Corvallis, Oregon.
                                       5

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TABLE 1.   CHEMICAL ANALYSES OF SOIL USED IN LYSIMETER  STUDIES


Level

1
2
3
4
5

Original
Depth
cm
0-20
20-40
40-50
50-60
60-110


Salts
mmhos
cm
0.22
0.28
0.20
0.13
0.10

Organic
Matter
%
11.1
8.1
8.1
3.9
2.0


Total -N
%
0.30
0.24
0.26
0.15
0.08


N03-N


15.4
24.1
16.9
11.1
4.1


Zn S04-S

mg/kg


0.25 7.8
0.14 7.4
0.09 12.0
0.09 20.4


P


10
7
5
4
3


K Ca


204 1.0
254 2.2
218 0.9
138 0.6
114 0.6


Mg


0.43
0.93
0.40
0.40
0.74


Na
1/100 g
0.07
0.17
0.12
0.10
0.11
Cation
Exchange
Capacity


31.5
33.0
37.7
30.7
30.6

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     Polypropylene beakers  and  funnels (Nalgene) were used to sample rain and
throughfall  bi-weekly  for chemical analysis.   Ceramic  candles (Soil Moisture
Equipment Corp.) were joined to form 1.3 m tubes; seven such tubes were placed
parallel to  each  other 10 cm above the  bottom of each plot (100 cm below the
soil surface)  and  connected to a  five-gallon  glass  carboy (Kimble) above the
soil.   Two  30 cm  ceramic candles were  placed  23  cm below the  soil  surface
(Level   2 in  Table  1) and connected to a 500 ml polypropylene filtering flask
(Nalgene);  after  the soil  settled,  these were  approximately  20  cm below the
surface.  Porous ceramic  disks  (Coors) were cemented to polypropylene funnels
(Nalgene).  These were placed so that the ceramic disks were slightly above the
soil surface in the  litter layer, and  the funnels were  connected  to  500 ml
polypropylene  filtering  flasks  (Nalgene).   In all cases,  tubing  and fittings
were polypropylene and  stoppers  were Vikem  (Belart).    Litter  leachate  and
20-cm soil solution  were  sampled bi-weekly for  chemical  analysis by applying
vacuum  to  the filtering  flasks.   To  prevent soil saturation,  vacuum  was  ap-
plied to the ceramic at  100 cm  depth  whenever water could be  drawn from  the
soil; this solution was sampled fjj>r chemical analysis every four weeks.   Water
samples were analyzed for pH, Ca   , Mg  , S04  , and N03 .

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                                   SECTION 5

                                    RESULTS

     Changes  in  chemical  content  of water after  percolation  through various
layers  are  summarized in Figures  1  through 17.  Throughout this  set of fig-
ures, the same set of symbols is used to indicate the four rain pH treatments.
On several  figures,  a diagonal  line indicates  points  at  which concentrations
at two  locations within  a  plot (e.g.  rain and throughfall)  would  be equal.
There are  150 to  160 points for  each  rain treatment on each  figure,  for an
approximate total  of 600  points per figure.   In many  cases,  results from the
control   plots fell  over  an  extremely  narrow range.  Thus, what  appears  as a
single  plus (+) in  the  lower left of the  figures  frequently  represents many
independent measurements.

THROUGHFALL

     Figure  1 shows pH  and Figure 2  sulfate  concentration   of  throughfall
versus pH of  rain.    For both pH and sulfate, results fell  close to the line of
equality for  both alder (la, 2a) and maple (lb, 2b).

     Figure 3 shows  magnesium concentration and Figure 4 calcium concentration
versus  sulfate  concentration in throughfall.    Little  if  any tendency towards
increased  leaching of either  cation with  increased  sulfate concentration is
evident for alder (3a, 4a) or maple (3b, 4b).

LITTER  LEACHATE

     The pH of water that had percolated through the litter is  plotted against
the  pH  of  the incident rainwater  in Figure 5.  For all  sulfuric acid treat-
ments,  the  pH of  the  litter leachate  was considerably higher  than  the  pH of
the  incident  rain,   indicating partial  neutralization  of the  acid by  the
litter.   This effect was  stronger for alder litter (5a) than for maple litter
(5b), to the point  that  no  difference  in the pH  of  the  litter  leachate was
apparent between alder plots  receiving either pH  4.0 or  control  rain.   For
plots  receiving control  rain,  the  pH  of  the litter leachate typically was
somewhat less than the pH of the rain for alder and somewhat higher for maple.

     The concentrations of sulfate in litter leachate and in rain are compared
in Figure 6.   For  both alder (6a) and maple (6b) the concentration was gener-
ally greater  in  the  litter leachate than in the corresponding acid rain.   This
tendency was  most  pronounced for maple, especially for the pH  3.0 rain treat-
ment.
                                       8

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7.0
            X = 3.0
                                              + = 5.7
                                                          7.0
 7.0 r
                                                = 5.7
              3.0
                                               6.0
7.0
                                 4.0         5.0
                                       PH
                                      RAIN
Figure 1.  pH  of  throughfall vs.  pH of  rain.   Symbols refer  to nominal pH  of
           rain treatment.   Diagonal  line represents  points at which rain and
           throughfall  pH values would be equal.

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A.
B.
                      X = 3.0
                          ALDER
                        = 3.5    0
                                                        +• = 5.7
              Id**!
           8.0 r
                    1.0     2.0
                      3.0     4.0    5.0
                        SUi_FATt  MG/L
                            RAIN
6.0    7.0
                                                                      10*41
                                                                    8.0
                   1.0     2.0
6.0     7.0
                                                                   8.0
Figure 2.
                     3.0    4.0    5.0
                        SULFATE MG/L
                            RAIN
Sulfate  concentration  in  throughfall  vs.  sulfate  concentration  in
rain.  Symbols refer to nominal  pH of rain treatment.   Diagonal line
represents   points   at   which   rain   and   throughfall   sulfate
concentrations would be equal.
                                         10

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A.
         2.5
                      X = 3.0
                                      ALDER
                                      3.5     0 = 4.0
                                 =  5.7
B.
         2-0
THROUGH FAL
MAGNESIUM MG
!_i M
In ° ^
x
O
. + GO - x x
O x
-H- O XX
+0 - - xxx
n-f <2> ~ xx xxxxx
- -H-Q83D ~ -- xxx
d&f RS) _r_fi*Lfi*-jvQ XX X XX 3XX X X X
SSffiF) r-r^r- - XX X X XSIOBKXW jSO <38D
^SfiKcSx'XN

tpoft^» ^
	 1 —



•»*• xxx
XX
**• X XX
" * •" •«• X X XX
«•*»'• XX XXX X
•**•" X X XXXXXXX


*<«' • ' ' x xx xoooocxxxx x
	 1 	 1 	 1 	 | 	 , 	 , 	 ,
                   1-Q
2.0
                                                      B.O
                                    7.0
                                                                     8.0
 Figure 3.
                     3.0     4.0     5.0
                        SULFATE MG/L
                        THROUGH FALL
Magnesium  concentration vs.  sulfate  concentration in  throughfall
Symbols  refer to nominal pH value of rain treatment.

                              11

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A.
 B.
          7.0
          6.0
          5.0
                       X = 3.0
     ALDER
      3.5     0 = 4.0
                               +• = 5.7
         
-------
A.
                     X = 3.0
                        =  3.5    0  =  4.0    + = 5.7
B.
                                                                 7.0
Figure 5.
pH of  litter  leachate vs. pH of rain.  Symbols  refer  to  nominal  pH
value  of  rain  treatment.   Diagonal  line represents  points  at which
pH values of rain and litter leachate would  be equal.
                                        13

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A.
 B.
     ALDER
     3.5     0 = 4.0
                                                          = 5.7
          1.2
1.0     2.0
                        X  =  3.0
3.0     4.0     5.0
   SULFATE  MG/L
      RAIN
     MAPLE
  - = 3.5    0  =
                                                      6-0
                                         7.0
                                                       B-0
        Ul
1.0
                           2.0
                                                             7.0
                                  8-0
 Figure  6.
                     3.0     4-0     5-0
                        SULFATE MG/L
                           RAIN
Sulfate  concentration of  litter  leachate  vs.  sulfate concentration
of  rain.   Symbols  refer  to nominal  pH  value of  rain treatment.
Diagonal  line represents  points  at  which  sulfate concentrations of
rain and litter leachate would  be equal.
                                          14

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     The  variation  of magnesium  with  sulfate in litter  leachate  is  shown in
Figure 7; Figure 8 shows this variation for calcium.   Although the data points
shown  in Figures  7  and  8  were  scattered,  there  was  an  apparent  tendency
towards  increased  leaching  of  calcium  from  the  maple  litter  layer  with
increased sulfate concentrations (Figure 8b).

TWENTY-CENTIMETER SOIL SOLUTION

     Figures 9 through 12 show the time series of sulfate, magnesium,  calcium,
and pH  in solution  20 cm below the  soil  surface.   Week one, the last week in
June, 1976, was  the first week in which the plots received acid rain.   During
week zero, all plots received control rain.

     For  the  first  six  months,  there were  no  apparent  differences in sulfate
(9b), magnesium (lOb), or calcium (lib) concentrations in 20-cm soil  solutions
from maple  plots receiving  acid  rain or  control  treatments.   At that time,
sulfate  concentrations for plots  receiving  the most acid rain (pH 3.0) became
increasingly  higher than  for  the  other plots.  After three years,  sulfate
concentrations in  the 20-cm soil  solution became approximately equal  to the
concentrations in the rain.   Solutions corresponding to the pH 3.5 and pH 4.0
treatments responded  similarly  starting  one year and two years,  respectively,
after the initiation of  simulated  acid rain  exposures.   Magnesium  (lOb) and
calcium  (lib)  concentrations generally  followed  the sulfate  trend.   Figures
13b and  14b  show the relation between sulfate  concentrations  and  the concen-
trations  of magnesium and calcium;  the curves are "eyeball fits" to  the data.
Magnesium and calcium concentrations followed similar trends (16b).

     Dry  soil  conditions  prevented  extraction of 20-cm  soil  solution  samples
from the alder plots during  the early part of the experiment.   For the period
for which samples were taken,  the  patterns for alder  (Figures  9a,  lOa,  lla,
13a, 14a,  16a) were similar  to those  for maple.  There was, however,  greater
scatter  of the data points, and, especially for magnesium (lOa),  an indication
of seasonal trends.

     The  pH of the  20-cm soil  solution  followed  a  trend towards lower values
for both alder (12a) and maple (12b)  plots for all  treatments.   The lower pH
values  were  often  associated  with with  higher sulfate  concentrations  (15a,
15b).

ONE-METER SOLUTION

     The  pH  values   of  soil  solutions at  a depth of one meter did  not vary
greatly  during 3.5  years  (Figure  17).   For all plots,  sulfate concentrations
were generally below the sensitivity of the analytical method (3 mg/1).
                                      15

-------
A.
 B.
           1.0
            .B
        S-J
         01
            -B
              1.0  r
               .B
                       X =  3.0
                ALDER
                3.5    0 = 4.0
                                                            =  5.7
.2
                                          .6        .8
                                              MG/L
                                    LITTER LE«=ICHATE.
1.0
                         X = 3.0
                                        MAPLE
                                              0 = 4.0    1-  = 5.7
1.2
                                          .6       .8
                                      5ULFATE MG/U
                                    LITTER LErtCHATE
                                   1.0       1.2
 Figure 7.  Magnesium   concentration  vs.   sulfate  concentration   of  litter
            leachate.   Symbols  refer to  nominal  pH value of  rain  treatment.
                                          16

-------
A.
B.
                       X = 3.0
  ALDER
= 3.5    0   4.0
                                                        = 5. 7
l.G

1.4
1.2
UJ
I s 1-°
LlTTtR LE.AC
CALCIUM M<
i> cn a
.1
\

O
x
'+ x
0 x x
-*



-

+ 0 ^ X xx x
-1 8 ° J** "x x XX X XX>jf* * X
P.
,
.2 .4 .6
SULPATE
LITTER LE<
MAPLE
X = 3.0 *. = 3.5
1.6 r1 **:
1.4 -
1.2 -
x
Ul XX.,
I- x
f^l.O - x >
0° + x * >
a r^
UJ s x X x>
2|^^+xX 6X
W^.
+
n 1 	 1 	 1 	 1 	

1
.8 1.0 1.2
MG/L
0 = 4.0 •<- = 5.7
x

x
^^ 5t ^ ^
<*xxxxxx xv
SXX,M X X
^x H X
* xxX
x x
'x^xXx
xXx
X

                      .2
.4        .G        .8
    SULFATE MG/L
   LITTER LEACHATE
                                                         1.0
                              1.2
Figure 8.
           Calcium concentration vs. sulfate  concentration of litter  leachate.
           Symbols refer to nominal pH value  of rain treatment.
                                       17

-------
A.
B.
                       X  =  3.0
    ALDER
SOIL  SOLN 2CCM
* = 3.5    0 = 4.0
                                                            = 5.7
           B.O


           7.0


           6.0


          | 5.0


          U.O
         tn 3.0
           2.0


           1.0
              i

             0
                            50
                        X = 3.0
      100
  UJEEK (NUMBER

    MAPLE
 SOIL  SOLN 20CM
- = 3.5    0 = 4.0
                    150
                        = 5.7
           8.0
           7.0
           6.0
         UJ
         H4.0
         _
         in 3.0
           2.0
               10**1
                                                          X
                                                           x
      X
     x
-------
A.
           1.0
                       X = 3.0
               <=)LDER
            SOIL SOLN 20CM
            ^  =  3.5    0  =
                                                          =  5.7
            .8 -
B.
o
2 .6

•s.
1— 1
in
z
C£> .4
Z
X XX

X X
>« x
^ x>~ x
w
•H- x<$)x x
x -ff H,
*x * o**
(Sx >^x&x
X
5C<
x« x
ac-»< x
T x x
Xx
x^ 5A
X ?S V1 V^
x< xx
x *
            .2
                     xxV
-------
A.
                       X  =  3.0
           2.5
           2.0  •
         ol.5

         2
         ID
         i—i
         O

         
-------
A.
B.
          7.0
          6.0
          5.0
                      X  =  3.0
            ALDER
         SOIL SOLN 20CM
        ^ =  3.5    0  =
   + = 5.7
        I
        a
          4.0
          3.0
          2.0
                                             O
         7.0
         6.0
         5.0
50            100            150
          UJEEK (NUMBER
                                      MAPLE
                                   SOIL SOLN 20CM
                      X = 3.0     ^ =  3.5    0  =  4.0     +  = 5.7
        a.
         4.0
         3.0
         2.0
                          50
              100
          WEEK NUMBER
150
                                                                     200
200
Figure  12.   pH of  20-cm soil  solution  vs.  time  since beginning of  treatment.
             Symbols  refer  to nominal  pH value of rain treatment.
                                          21

-------
           1.0
            .8
        CM 2" .6
          uJ
        o 
-------
                        X = 3.0
     ALDER
     3.5     0
                          =  4.0     +•  = 5.7
        0
           2.5  r
           2.0
           1.5
               10**1
        tn 1-1
         o
        w 
-------
A.
B.
           7.0
           6.0
       O
       °   5.0
       O
       01
           4.0
           3.0
           2.0
       o
           7.0  r
           6.0  -
           5.0
       f=J  4.0
           3.0
           2.0
                        X = 3.0
                                         ALOER
                                       = 3.5     0 = 4.0
                                                   o
                                                              = 5.7
                        o

              0      1.0     2.0
                                                           _i	1_
                                   3.0     4.0     5.0
                                      5ULFATE MG/L
                                     SOIL  SOLN 20CM
                        X =  3.0
                                         MAPLE
                                    .*  = 3.5    0 =  4.0     +  = 5.7
                                     xxx
                                                    x  x
                                                    * x
                                    _l	U
                                                                           ao**i
                                                          6.0     7.0     B-0
                                                   _i	1	1	1
                     1.0     2.0     3.0     4.0     5.0     6.0     7.0    B.O
                                       SULFATE MG/L
                                      SOIL SOLN 20CM
Figure 15.  pH   vs.   sulfate  concentration of 20-cm  soil  solution.
             refer to nominal pH  value of  rain treatment.
                                                                               Symbols
                                            24

-------
                       X = 3.0
  ALDER

= 3.5    0
            = 4.0    + = 5.7
               10*»1
          2.0
       O _i

       eg ol.5
       in I-H
         o

       i=l Cl.O
       O O
       en
                        .2
.4          .6

MAGNESIUM MG/L

SOIL SOLN 20CM
                                                          .8
                               1.0
                       X = 3.0
   MAPLE

 = 3.5    0 = 4.0
                      =  5.7
2.5
2.0
2
O _l
o ^
csio 1.5
s:

_) 2
0 Z>
tn i-.
o
_J _!
ss1-0



.5

0

x
x

X
X
X
X X
X X
X X x XX
x* x x Xx * X
x x
X
^ x x a* x^ xx x* x
* *~ * •^yfe'jt x x
v^^^t^fz XX X
*^K^ ^ _ | 10**1Q
0 .2 .4 .B .8 1.0
                                   MAGNESIUM MG/L

                                   SOIL SOLN 20CM
Figure 16.   Calcium  concentration vs.  magnesium  concentration of 20-cm  soil

             solution.   Symbols  refer  to nominal( pH  value  of rain treatment.
                                          25

-------
A.
B.
          7.0
          6.0
                       X = 3.0
          5.0
        Q.
          4.0
          3.0
          2.0
            ALDER
         SOIL SOLN  1 M
        - =  3.5    0  =  4.0
                                                            = 5.7
                    O
                              O
                                            x±  A * -t-
                                                     + , +  •*•
                     ¥?**   ±*    x  _
                    x       i~        +K
                                                    O
                                                      O
          7.0
          6.0
50            100            150
          WEEK NUMBER
                                       MAPLE
                                    SOIL SOLN  1 M
                       X = 3.0 v.    A =  3.5    0  =  4.0     +  = 5.7
                                                                     200
          5.0
        a.
          4.0
          3.0
          2.0
                                 O
                                                Ox
                                                  06
                           50
              100
          WEEK NUMBER
150
200
Figure 17.   pH  of  1-m soil  solution  vs.  time  since beginning of  treatment.
             Symbols refer to nominal pH value  of rain treatment.
                                          26

-------
                                   SECTION 6

                                  DISCUSSION

     Eaton et  a^.35 determined  throughfall  chemistry in a^sugar^maple stand
receiving ambient acid rain (pH 4.1).   Their results for Ca  ,  Mg  ,  and S04 ,
summarized in Table  2,  indicated that partial neutralization  oc££irred+Hjn the
canopy,  and  that  throughfall  was  considerably enriched  in  Ca  , Mg   ,  and
S04 ,  compared to  incident precipitation.   These effects were  more pronounced
for trees with 40-65 cm dbh (diameter breast height) than for trees with 15-25
cm dbh.   Our results  for  small  maple trees  (less than 5 cm  dbh)  exposed to
simulated sulfuric acid rain at pH 4.0 were similar to theirs;  however,  we did
not observed increases in sulfate concentration caused by passage of rainwater
through the canopy.

     When  Fairfax  and  Lepp39  exposed maple (Acer  pseudoplatanus)  leaf  litter
to simulated sulfuric  acid rain  at pH 4.0, the resultant leachate had a pH of
5.2.    Calcium  concentration in  this  leachate was  13 times that  in  leachate
from litter exposed to deionized water (pH 6.8);  similar results were  obtained
for the  other hardwood  litters  they  tested.   We  also  found significant neu-
tralization of sulfuric acid by litter (Figure 5),  and that,  for maple litter,
higher calcium concentrations  (Figure 8b) were associated with  the more  acidic
treatments.  Thus,  when  acid  rain  falls  on  a hardwood  forest with  a well
developed canopy and  litter layer,  the actual  input to the soil will  probably
be considerably  less  acid than the incident precipitation.  Also,  precipita-
tion which  is  more  acid will  cause  more rapid leaching of cations  into the
soil.   These effects  could,  for  at  least a  few years,  tend to offset any
leaching of cations from the soil.

     Cronan et aJL43 observed  average sulfate  concentrations  of 8 mg/1 in soil
solutions beneath  a  coniferous  forest in New England;  they  attributed  76% of
cation leaching from the soil  to the presence  of sulfate anion.  For solutions
obtained from beneath a hardwood forest subject to  acid rain,  Koterba  et al.44
observed  an  average  sulfate  concentrations of  5  mg/1.   In  both cases,  the
soils had  been exposed to sulfuric acid rain for  approximately 30 years, and
to non-acidic sulfate  rain for  considerably longer.  The ability  of  the soil
to absorb  sulfate  probably has  been exhausted in that area.  While soil solu-
tions  in  areas  which  have only  recently begun to receive sulfuric acid rain
might  not  show an  immediate  response to increased sulfate  loadings, the re-
sponse to nitric acid rain would be more rapid.16'17'45

     The soil used  in  our experiment was a strong sulfate absorber.16  Figure
9b demonstrates  a  breakthrough  phenomenon as the  sulfate  absorption  capacity
of  the  soil was   approached.   As  expected  from the theoretical  work  of
Wiklander,14'15 Johnson  and Cole,16  and Reu^s,17   increased anion concentra-
tions caused increased concentrations of Ca   and Mg    and  lowered pH in the

                                       27

-------
TABLE 2.  CHEMICAL CONTENT  OF  PRECIPITATION AND THROUGHFALL IN A SUGAR MAPLE
          STAND


« ++
M3-
Mg
S04
PH
Precipitation
0.16 mg/1
0.03
2.7
4.1

Small
1.13
0.37
16.4
4.6
Throughfall
Trees* Large Trees*
mg/1 1.58 mg/1
0.40
25.2
4.9

  *  15-24  cm  dbh.
 **  40-65  cm  dbh.

 Adapted from Eaton  et  al.
35
                                        28

-------
soil  solutions  (Figures 13-15).   These changes were  not necessarily  due to
changes  in  the base saturation  of the soil, but were probably  the result of
increased ionic  strength of the soil solution.   The increased scatter of data
on  cation  concentrations for  alder plots was  probably due  to  variable N03
concentrations associated  with  symbiotic  nitrogen  fixation,  a characteristic
of  the genus  Alnus.   Although the  "sulfate  front"  presumably has moved down-
wards into  the soil,  it has not reached  a depth of 1  m; no effects attribut-
able to acid rain were observed in solutions extracted from this depth.

     To  better compare  the data  with  theoretical  predictions,  the  expected
response of soil  solution chemistry to acid rain was simulated using the LEACH
computer  model.17'41    Given  the  temporal  pattern of  chemical  content  and
amount of  rain,  this  model  uses  established soil  chemistry  rejatioijijhips £o
predict  the time series of soil  solution concentrations of  H  ,  Ca   ,  Al3 ,
SO   , Cl  ,  and HC03   in non-calcareous,   acid soils.  In  this model,  calcium
may  be  considered  to  be a  proxy for other cations, and  chloride  a proxy for
other  anions.   The  model   uses  the  Langmuir equation  for  the  relationship
between absorbed sulfate, S  , and  sulfate  in solution,  S ,
                           3.                            S

                                     SMAX  • S

                                Sa = SKLR  + S '


where S   is  in  moles/kg soil and S   is  in moles/1.  SMAX and  SKLR  are con-
stants Determined from laboratory  data.

     While  evapotranspiration  effects  are considered,  the model does not take
into  account the  weathering  of  minerals  by acids,  uptake   of  nutrients by
plants, or microbial alteration of chemical species.

     Soil parameters  used  for these simulations are listed in Table 3a.   Soil
solution data  obtained shortly after the  start of the experiment were used to
estimate the initial value of the  non-sulfate anion content of the soil  and to
translate  the lime  potential (LP)  vs.  base saturation  (BS) curve  for non-
montmorillonitic soils17 to  pass through  the point LP = 3.15, BS = 0.10.  All
other soil parameters were those obtained  from results  of laboratory analyses,
including those  listed under "Level 2" of Table  1.   Evapotranspiration rates
(Table 3b)  were  adjusted so that  predicted  values  of  soil water content were
consistent with the rates at which water was extracted from the plots.

     The chemical composition of the simulated "rains"  (Table  3d) approximated
those values  observed  for  the litter leachate.   The volume of rain (Table 3c)
was  set  equal to the  amount of  throughfall  for each month,  and  was  somewhat
less than the amount of rain applied to the experimental  plots.

     The simulated time series of  sulfate concentrations in the maple plots is
shown  in Figure  18.   Observed  sulfate  concentrations  (Figure  9b) increased
considerably  faster than predicted by the model.  For example, for the pH 3.0
treatment the  model predicts that a concentration of 40 mg/1  would be reached
only after  10 years;  this  concentration was actually reached in approximately
2  years.   Thus,  either  the  Langmuir parameters  obtained  under  laboratory
conditions  were  not relevant to field conditions, or the Langmuir formulation
may  not  be  an appropriate  representation  of  sulfate absorption  by this soil.

                                       29

-------
      TABLE 3.  PARAMETERS USED IN LEACH SOIL SOLUTION SIMULATION MODEL

3A.   Soil Parameters
         Thickness
         Bulk Density
         Field Capacity
         Wilting Point
         Cation Exchange Capacity
         Total Calcium*
         Total Sulfate
         Total Chloride**
         Partial Pressure C02
         Sulfate Absorption:  (see text)
                   SMAX
                   SKLR

 * Represents all bases.
** Represents all anions except  sulfate.
20.3 cm
0.84 kg/1
0.382 1 H20/l soil
0.193 1 H20/l soil
56.2 equiv/m2
3.350 moles/m2
0.042 moles/m2
0.004 moles/m2
0.001 atmosphere

0.811 x 10-2 moles/kg soil
0.800 x 10-3 moles/1
3B.  Daily Evapotranspiration  (mm H20)

        July  Aug   Sept  Oct   Nov   Dec   Jan   Feb   Mar   Apr   May   June

Alder   0.49  0.43  0.29  0.08 0.05  0.04  0.04  0.07  0.09  0.28  0.31  0.41
Maple   0.44  0.38  0.22  0.06 0.04  0.03  0.03  0.05  0.08  0.16  0.23  0.36

3C.

Alder
Maple
Rainfall Rate (cm/rain event)
July Aug Sept
0.7 0.6 0.7
0.5 0.6 0.6
Oct Nov
0.8 0.9
0.7 0.9
Dec Jan Feb
1.1 1.0 1.0
1.0 0.9 0.8
Mar Apr May
1.0 1.0 0.9
0.8 0.7 0.6
June
0.8
0.5

3D.







Chemical Composition

Nominal
pH
5.6
4.0
3.5
3.0
of Rain

Solution
pH
(5.6)
4.4
3.8
3.1

„++..++
Ca +Mg


10-5
1.75
4.76
9.64
12.03

S04"~


moles/1
0.55
5.55
32.17
50.60








 3E.   Chloride + Nitrate Content of Rain  (10-5  moles/1)

         July  Aug   Sept  Oct   Nov   Dec   Jan    Feb    Mar   Apr   May   June

 Alder   19.1   2.99  10.1   15.5  19.1   22.6   28.0   29.8   31.6  31.6  29.8  28.0
 Maple   1.20  1.20  1.20  1.20  1.20   1.20   1.20   1.20   1.20  1.20  1.20  1.20
                                        30

-------
     The  simulated  relationship  between  sulfate  concentration  and  calcium
concentration for  the maple  plots  is shown  in Figure  19a.   Four points ob-
tained  by summing  calcium and  magnesium concentrations  from the  curves  in
Figures 13b  and  14b are also shown.   The predicted and observed relationships
are quite similar.

     An attempt was  made  to simulate the effects  of  nitrogen fixation in the
alder plots by introducing a seasonal variation in the anionic content (repre-
sented  by Cl ) of  the simulated rain  (Table  3e).   This  induced  a seasonal
variation in anionic  concentration  of the simulated  soil  solution similar  to
that  observed   in  extracts  from  the  alder  plots,  but with higher  average
anionic content.  This  caused the predicted concentrations of Ca and Mg to  be
higher  than  the  observed  concentrations  (Figure  19b).   The variability  of
simulated anion  concentrations caused the  results to  be  more  scattered for
alder  (Figure  19b) than  for  maple  (Figure  19a);  this  same  tendency  was ob-
served in the data (Figures 13a and 14a vs.  Figures 13b and 14b).

     The  simulation  results demonstrate  that established relationships can  be
used to predict the response of cations in soil solutions to increased loading
of  anions due  to  acid rain.   In particular, the LEACH model is  an adequate
representation of those relationships.   Future efforts need to focus on simu-
lating  sulfate concentrations  more  closely.   Mineral  weathering  and  plant
uptake of nutrients also need to be considered.

     According to  the LEACH  simulations,  the changes  in  soil  solution chem-
istry (increased calcium and magnesium concentrations, lowered pH)  were almost
entirely  due to  increases  in  total  anion concentration rather than to changes
in  base  saturation.   An   example  is  the  simulation  summarized  in Table  4.
While  the predicted pH of the soil  solution dropped  from  5.3  to  4.9,  base
saturation was virtually  unchanged.   The change in pH was  associated with the
change  in sulfate  concentration.   The dependence  of  the pH of  a  solution  in
equilibrium with soil  on  the  ionic  strength  of the equilibrating  solution  is
well known to  those routinely performing soil analyses.  These results empha-
size the  need  to  distinguish between acidification of  soil  solution,  on the
one  hand,  and  acidification  of  soil   as  measured  by  decreases  in  base
saturation.14>15>17
                                       31

-------
CO
PO
        1976  '  1977 '  1978  '  1979  '  I960 '  1981  '  1982  '  1983  '  1984 '  1985  '  1986
     Figure 18.  Simulated Time Series of 20-cm  soil solution in maple plots.  Results were produced bv LEACH
               computer simulation model.

-------
    A.
B.
CO
10
70


60


^ 50
o>
0
E
to 40
O

+o 30
o
20
10
°c
o
Alder
o
~ 0 ~"
o
o
o o
e
00
° 0
o A
o Oo
o
_ 0 ° 0 _
r ° *
o°6«f ° 0»°»0«
0^
o o 0
o
o
A
o
o
8

-------
                     TABLE  4.   RESULTS OF LEACH SIMULATION



PH
H+
Ca2+
A13+
S0|~
cr
HC03~
Base Saturation
Starting Value
5.3
5 ueq/1
102 ueq/1
0 ueq/1
48 ueq/1
55 ueq/1
3 ueq/1
12%
Ending Value
4.9
12 ueq/1
750 ueq/1
1 ueq/1
726 ueq/1
34 ueq/1
1 ueq/1
12%

     All values  except base  saturation  refer  to the soil solution  at  20  cm.
Simulation  used  values  in Table  3 for  maple plots, and was for  10  years.
                                        34

-------
                                  REFERENCES

 1.   Bolin, B. ,  L. Granat, L. Ingelstam, M. Johannesson, E. Mattsson, S. Oden,
     H.  Rodhe and C.  0.  Tamm.    1971.   Air pollution  across national bound-
     aries.  The  impact of  sulfur  in  air and precipitation.   Sweden's  case
     study for the  United Nations Conference on the Human Environment.  P. A.
     Norstedt and Sons, Stockholm, Sweden.  97 pp.

 2.   Braekke, F.  H.   1976.   Impact of acid precipitation on  forest and fresh-
     water ecosystems  in  Norway.   Research Report  FR6/76.   SNSF Project, As,
     Norway.   Ill pp.

 3.   Cogbill, C.  V.  and  G.  E.  Likens.   1974.   Acid  precipitation in north-
     eastern United States.  Water Resources Research 10:1133-1137.

 4.   Gambell, A.  W.   and  D.  W.  Fisher.   1966.   Chemical  composition of rain-
     fall, eastern North  Carolina and southeastern Virginia.  U.S. Geological
     Survey Water Supply Paper 1535-K.  41 pp.

 5.   Likens,  G.  E.  and F.  H. Bormann.   1974.   Acid Rain:   a serious regional
     environmental problem.  Sci.  184:1176-1179.

 6.   Likens,  G.   E.,  R. E.  Wright, J.  N. Galloway  and R.  J.  Butler.   1979.
     Acid rain.   Sci. Am.  241:42-51.

 7.   Forest Service.   1976.   Proceedings of the First International Symposium
     on Acid Precipitation  and  the  Forest Ecosystem.   USDA  Forest Service
     General  Technical  Report NE-23,  Northeastern  Forest  Experiment Station,
     Upper Darby, PA.  1974 pp.

 8.   Larson,  T.   V.,  R. J.  Charlson,   E.  J.  Knudson,  G.  D.  Christian  and H.
     Harrison.   1975.  The  influence  of a sulfur dioxide  point source on the
     rain chemistry  of a  single storm in  the  Puget Sound  region.  Water, Air
     and Soil Pollut. 4:319-328.

 9.   Liljestrand, H.  M. and J. J.  Morgan.  1978.  Chemical  composition of acid
     precipitation in  Pasadena, Calif.   Environ. Sci.  Techno!. J2:1271-1273.

10.   McColl,  J.  G.  and D.  S.  Bush.    1978.   Precipitation and throughfall
     chemistry in  the San  Francisco  Bay  area.  J.  Environ.  Qual. 7:352-357.

11.   Forest  Service. -  1976.  Workshop report  on  acid precipitation  and the
     forest  ecosystem.  USDA Forest  Service  General  Technical  Report NE-26.
                                       35

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12.   Galloway,  J.  N. ,  E.  B.  Cowling,  E.  Gorham  and W. W.  McFee.   1978.  A
     national  program  for assessing  the problem of  atmospheric deposition
     (acid rain).   A report to the Council on Environmental  Quality.  Natural
     Resource  Ecology  Laboratory,  Colorado   State   University,  Ft.  Collins.

13.   Electric  Power Research Institute  (EPRI).   1979.   Ecological effects of
     acid  precipitation.   Report  of  workshop  held  at  Gatehouse-of-Fleet,
     Galloway, U.K., September 4-7, 1978.  EPRI SOA77-403.

14.   Wiklander,  L.   1973.  The  acidification of  soil  by acid precipitation.
     Grundforbattring 26:155-164.

15.   Wiklander,  L.    1975.   The  role of  neutral  salts in  the  ion exchange
     between  acid precipitation and soil.  Geoderma  14:93-105.

16.   Johnson,  D.  W.  and D. W.  Cole.  1977.   Anion  mobility in soils:   rele-
     vance  to  nutrient  transport  from  terrestrial  to  aquatic ecosystems.
     USEPA,   Con/all is  Environmental  Research  Laboratory,   EPA-600/3-77-068,
     Corvallis, OR.   27 pp.

17.   Reuss,  J.   1978.  Simulation of  nutrient loss  from soils  due to rainfall
     acidity.   U.S.  EPA,  Corvallis Environmental  Research  Laboratory, EPA-600/
     3-78-053,  Con/all is,  OR.  44  pp.

18.  Crowther,  C.  and A.  G.  Ruston.   1911.   The   nature,  distribution  and
     effects  upon vegetation of atmospheric  impurities in and near an  indus-
     trial town.  J.  of Agric. Sci. 4:25-55.

19.  Overrein,  L. N.   1972.  Sulfur  pollution patterns observed; leaching of
     calcium  in forest  soil determined.   Ambio. 2:145-147.

20.  Nyborg,  M. and  McMinnon, Allen  and Associates, Ltd.    1973.  Atmospheric
     sulfur  dioxide:  effects on  the  pH and  sulfur  content  of rain and snow:
     addition of sulfur to surface waters, soil,  and crops;  and  acidification
     of  soils.   In:   D.  Hocking and  R. Reiter,  eds.,  Proceedings  of a workshop
     on  sulfur gas  research in Alberta.   Information Report NOR-X-72.   North-
     ern Forest Research Centre,  Edmonton, Canada.

21.  Cronan,  C.  S.   1979.   Effects  of acid precipitation  on soil  leaching
     processes  in high elevation  forests  of  the  northeastern U.S.   In:   H. H.
     Izard and  J. S.  Jacobson, eds.,  Scientific  papers  from  the public meeting
     on  acid precipitation, Lake  Placid,  NY.   May 4-5, 1978.  New York State
     Assembly,  Albany.

22.  Carroll, D.   1962.   Rainwater as  a  chemical  agent  of  geologic processes—
     a   review.   U.S.   Geological  Survey  Water  Supply  Paper 1535-G.    18  pp.

23.  Johnson, N.  M. ,  R.  C.  Reynolds and G. E.  Likens.   1972.   Atmospheric
     sulfur:    its  effect  on  the chemical  weathering  of  New England.    Sci.
     177:514-516.
                                        36

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24.   Norton,  S.  A.    1976.   Changes in chemical  processes  in soils caused  by
     acid precipitation.   In:   Proceedings of the first international  sympos-
     ium on acid  precipitation and the forest ecosystem.  USDA Forest  Service
     General Technical Report NE-23.

25.   Turk, J.  T. and N. E. Peters.  1979.  Acid rain weathering of a metasedi-
     mentary  rock basin,  Herkimer County, New York.   In:   H. H.  Izard and  J.
     S.  Jacobson,  eds.,  Scientific papers  from  the  public meeting  on acid
     precipitation,  Lake Placid, NY.  May 4-5, 1978.  New York State Assembly,
     Albany.

26.   Jonsson,  B. and R. Sundberg.  1972.  Has the acidification by atmospheric
     pollution  caused a growth  reduction in  Swedish  forests.   Research Note
     No. 20.  Department  of Forest Yield Research, Royal College of Forestry,
     Stockholm,  Sweden.  49 pp.

27.   Jonsson,  B.  and  R.  Sundberg.   1976.   Soil  acidification  by atmospheric
     pollution and forest growth.  In:   Proceedings of the First international
     symposium  on  acid precipitation  and the  forest  ecosystem.   USDA Forest
     Service General Technical Report NE-23.

28.   Tamm,  C. 0.   1953.   Growth,  yield and nutrition in  carpets  of a forest
     moss  (Hylocomium splendens).  Medd.  Stat.   Skogsforskn.  Inst.  43:1-140.

29.   Madgwick, H. A.  I.  and J.  D.  Ovington.   1959.   The chemical composition
     of  precipitation in  adjacent forest and  open  plots.   Forestry 32:14-22.

30.   Voigt, G.   K.    1959.   Distribution  of  rainfall  under  forest   stands.
     Forest Sci. 6:2-10.

31.   Voigt, G. K.   1960.  Alteration of the composition of rainwater by trees.
     Amer. Midi. Nat. 63:321-326.

32.   Carlisle, A., A.  H.  F. Brown and E. J.  White.  1966.   The organic matter
     and  nutrient elements  in precipitation  beneath  a Sessile  Oak (Quercus
     petraea)  canopy.  J.  Ecology 54:87-98.

33.   Nihlgard,  B.   1970.   Precipitation, its  chemical  composition  and effect
     on  soil  water  in  a  beech  and  a  spruce  forest  in south  Sweden.   Oikos
     21:208-217.

34.   Henderson,   G.  W. ,  W.  F.  Harris,  D.  E.  Todd and  T.   Grizzard.   1972.
     Quantity and  chemistry of  throughfall  as influenced  by forest-type and
     season.  J. Ecology 65:365-374.

35.   Eaton, J.  S. ,  G.  E.  Likens  and  F.  H. Bormann.   1973.   Throughfall and
     stemflow chemistry in a northern hardwood forest.   J.  Ecology 61:495-508.

36.   Wood, T.  and F.  -H. Bormann.  1975.   Increases  in foliar leaching caused
     by acidification of an artificial  mist.   Ambio. 4:169-171.
                                       37

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37.  Wood, T.  and F.  H. Bormann.   1976.   Short-term effects of  an artificial
     acid rain upon the growth  and  nutrient relations  of Pinus  strobus  L.   In:
     Proceedings  of the  first  international  symposium on  acid  precipitation
     and  the forest ecosystem.   USDA Forest Service General Technical  Report
     NE-23.

38.  Mayer,  R.  and B. Ulrich.   1976.   Acidity of precipitation  as influenced
     by  the  filtering of  atmospheric sulfur and nitrogen  compounds—its  role
     in the  element balance  and effect on soil.   In:   Proceedings of the first
     international  symposium on  acid precipitation and the  forest ecosystem.
     USDA  Forest  Service  General  Technical  Report NE-23.

39.  Fairfax,  J.  A.  W.  and N.  W.  Lepp.   1976.   The effect  of simulated  acid
     precipitation  on cation  losses  from  a range  of  tree  litters.   In:   L.
     Karenlampi,  ed.,  Proceedings  of  the  Kuopio  Meeting  on  plant  damages
     caused  by  air  pollution,  August  16-18,   1976,   University  of  Kuopio,
     Finland.

40.  Lee,  J. and D.  E.  Weber.   1976.  A study  of  the effects  of acid  rain on
     model  forest ecosystems.   In:   Proceedings of the annual meeting  of the
     Air  Pollution  Control Assoc.   Portland, OR., June 1976.   17  pp.

41.  Hart, J.  W.   1978.   User manual for the LEACH acid rain simulation model.
     USEPA,   Corvallis  Environmental   Research  Laboratory,  Con/all is,   OR.
     CERL-046.

42.  Likens, G.  E. and  F.  H-.  Bormann.  1972.  Nutrient cycling in ecosystems.
     In:   Ecosystem  Structure and  Function,  p.  25-47.   Proc.   31st  Annual
     Biology Colloquim,  Oregon  State University Press,  Corvallis, OR.

43.  Cronan, C.  S. ,  W.  A.  Reiners,  R. C.  Reynolds   and  G. E.   Lang.   1978.
     Forest  floor leaching:   contributions from mineral, organic, and carbonic
     acids in New Hampshire subalpine forests.  Sci. 200:304-311.

44.  Koterba,  M.  T. ,  J.  W.  Hornbeck  and R.  S.  Pierce.    1979.   Effects  of
     sludge  applications  on  soil  water solutions and vegetation  in a northern
     hardwood stand.   J.  Environ.  Qual. 8:72-78.

45.  Johnson,  D. W.  and  D.  W. Cole.   1976.  Sulfate mobility  in an  outwash
     soil  in western Washington.   In:  Proceedings of the first  international
     symposium on  acid precipitation  and  the  forest  ecosystem.   USDA Forest
     Service General  Technical  Report NE-23.
                                        38

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
1. REPORT NO.
  EPA-600/3-80-014
                                                           3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE

  Effects of Sulfuric Acid Rain  on Two Model Hardwood
  Forests:   Throughfall, Litter  Leachate,  and Soil
  Solution
             5. REPORT DATE
              January  1980  issuing date
             6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)

  Jeffrey J. Lee and David E. Weber
             8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Environmental Research Laboratory
  U.S.  Environmental Protection  Agency
  200 S.W. 35th Street
  Corvallis, OR 97330
                                                           10. PROGRAM ELEMENT NO.
             11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
  Environmental Research  Laboratory
  U.S.  Environmental Protection  Agency
  200 S.W. 35th Street
  Corvallis, OR 97330
             13. TYPE OF REPORT AND PERIOD COVERED
                Final,  1975-1979	
             14. SPONSORING AGENCY CODE
                EPA/600/02
15. SUPPLEMENTARY NOTES
16. ABSTRACT
  Simulated sulfuric acid rain  (pH 3.0,  3.5, 4.5, and 5.6) was applied  to model forests
  containing either sugar maple (Acer saccharum) or red alder  (Alnus rubra).   Water
  samples were collected above  and below the canopy, below the litter,  and  from 20 cm
  and 1 m below the surface of  the soil.  While throughfall chemistry was not  very
  different from rain chemistry,  the litter leachate (the actual input  to the  soil) had
  consistently higher concentrations of  calcium and magnesium, and higher pH than the
  acid rain.  For the first 6 months, sulfate absorbtion by the soil prevented any
  apparent differences in sulfate, calcium, or magnesium concentrations in  the 20-cm
  soil solution among plots receiving acid or control rain treatments.   Sulfate concen-
  trations on plots receiving the most acid rain (pH 3.0) then became increasingly
  higher than on the other plots  until after 3 years, they were approximately  equal to
  sulfate concentrations in the rain. Twenty-cm soil solutions corresponding  to the pH
  3.5 and 4.0 treatments responded similarly starting respectively 1 year and  2 years
  after initiation of exposure  to acid rain.  Increased calcium and magnesium  concen-
  trations and lowered pH in 20-cm soil  solution occurred simultaneously with  increased
  sulfate concentrations.  No acid rain  related effects were evident in the 1-m soil
  solution even after 3.5 years exposure to pH 3.0 sulfuric acid rain.   Cation responses
  to increased anion concentrations followed those predicted by a computer  simulation
  model.  However, sulfate concentrations in 20-cm soil solutions increased considerably
17.
   aster than predicted by a
                                                              absorbtion.
                  DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS  C. COSATI Field/Group
  Rainfall, pollution, sulfuric  acid,
  sulfates, ecology, forest trees,  soil
  chemistry, and computerized  simulation
 Acid rain, bioyeochemica!
 cycles,  sugar maple,  red
 alder, and sulfate ab-
 sorbtion
06/F
07/B
18. DISTRIBUTION STATEMENT
  Release  to public
                                              19. SECURITY CLASS (ThisReport)
                                               Unclassified	
                                                                         21. NO. OF PAGES
20. SECURITY CLASS (This page I
  Unclassified
                           22. PRICE
EPA Form 2220-1 (Rev. 4-77)
                                            39

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