vvEPA
            United States
            Environmental Protection
            Agency
            Environmental Research
            Laboratory
            Duluth MN 55804
EPA-
May
600 3-80-044
1980
            Research and Development
Impacts of Airborne
Pollutants on
Wilderness Areas
Along the
Minnesota-Ontario
Border

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                RESEARCH REPORTING SERIES

Research reports of the Office ct Researon and Development U S Environmental
Protection Agency have been grouped into nine series  These nine broad cate-
gories were established to lac'hta'e further development and application of en-
vironmental technology  Elim nation of traditional grouping  was  consciously
planneo to ?oster technology tra::sfer and a maximum mterface in related fields
The nine  series are

      1   Environmental  Heailr Effects Research
         Env ron ne'>tai  Protec^on Technology'
         Ecological Research
         Environmental  Monitorinq
         Socioeronomic En^'Onmental Studies
         3c'e-!t'f ; jr '1  r-c'in>i,ai Assessment Reports (STAR)
         interage-.: y Energy-Environment Research ana  Development
          Speoia:  Reports
         Mi3f>?Hanecus Fieo('r!s

This report has been assigned to the ECOLOGICAL RESEARCH series This series
describes reseaicri 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 ot pollutants and their effects  This work provides the technical bas s
for setting stancards to minimise undesirable changes in living organisms in the
aquat.c  terrestnal and atmospheric environments

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            United States       Environmental Research     EPA-600 380044
            Environmental Protection    Laboratory         May 1980
            Agency         Duluth MN 55804

            Research and Development
&EPA     Impacts of Airborne
           Pollutants on
           Wilderness Areas
           Along the
           Minnesota-Ontario
           Border

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                RESEARCH REPORTING SERIES

Research reports of trie Office ot Research arid Development U S Environmental
Protection Agency have been grouped into nine series These nine broad cate-
gories were established to tac'htate further development and application of en-
vironmental technology  Elimination of traditional  grouping was consciously
planned to toster technology 'ranker and a maximum interface in related fields
The Cine series are

      1   Environmental He. aitn  Effects Research
      2   Env.ronmeMai Protect on Tecnnoiogy
      3   E c c! c ;'j > i' a I R e search
      4   Environmental Monitoring
      5   Soci^eoonomic E:,,' r )nmental  Studies
      6   Sc'er-'itu ar'd TVciinu:ai Assessment Reports (STAR)
      •7   Interface- ,< Energy-Environment Research and Development
      8    Special  ReooHb
      9   Miscellaneous Reocns

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 rnatena.s Problems are assessed for their long- and short-term influ-
ences Investigations mcluae formation transport and pathway studies to deter-
mine the fate o* pollutants and the^r ejects This work provides the technical basis
for setting standards to minimize undesirable changes in living organisms in the
aquatic  terrestrial and atmospheric environments

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&EPA
            United States
            Environmental Protection
            Agency
            Environmental Research
            Laboratory
            Duluth MN 55804
EPA-GOO 3-80-044
May 1980
            Research and Development
Impacts of Airborne
Pollutants on
Wilderness Areas
Along the
Minnesota-Ontario
Border
 EP 600/3


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                                                    EPA-600/3-80-044
                                                    May 1980
IMPACTS OF AIRBORNE POLLUTANTS ON WILDERNESS AREAS ALONG THE
                  MINNESOTA-ONTARIO BORDER
                          Edited by

                        Gary E. Glass
          Environmental Research Laboratory-Duluth

                             and

                       Orie L. Loucks
            The Institute of Ecology-Indianapolis
                     Project Coordinator

                        Gary E. Glass
          Environmental Research Laboratory-Duluth
                  Duluth, Minnesota  55804
              ENVIRONMENTAL RESEARCH LABORATORY
             OFFICE OF RESEARCH AND DEVELOPMENT
            U.S. ENVIRONMENTAL PROTECTION AGENCY
                  DULUTH,  MINNESOTA  55804

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                                  DISCLAIMER

     This report has been reviewed by the Environmental Research Laboratory-
Duluth, U.S. Environmental Protection Agency, and approved  for publication.
Mention of trade names or commerical products does not constitute endorsement
or recommendation for use.
                                       11

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                                   FOREWORD

     Many of the objectives  that drive  efforts  to  improve  our  environment are
local in nature and can be viewed  as  improvements  in the quality of  life.
For example, the opportunities  to  swim  in  rivers and lakes,  to catch  sport
fish in a beautiful lake, or  to camp  in a  wilderness area  are  certainly
valuable.  But these objectives are not necessary  for  our  biological
requirements.

     Other efforts for environmental  protection are  driven by  the necessity
to sustain the very existence of mankind.  Examples  of such  efforts are the
protection of the ozone layer,  preservation  of  our soil  for  food
productivity, the maintenance of our  forest  lands  for  production of wood
products, and the protection  of terrestrial  vegetation to  assure gas  balance
in the atmosphere.

     This report presents evidence to suggest  that the deposition of
atmospheric pollutants is not only threatening  a huge,  beautiful wilderness
area of the continent, but is also giving  rise  to  another  large geographical
area where forests may be endangered  for wood  production and sustaining the
atmospheric life-supporting  systems.

                                      Donald I.  Mount,  Director
                                      Environmental  Research Laboratory
                                      Duluth, Minnesota
                                     ill

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                                   ABSTRACT

     The goal of this study was to examine previously  unanswered  questions
concerning potential effects of the  proposed Atikokan,  Ontario power plant on
ecosystems in the Boundary Waters Canoe Area Wilderness (BWCA) and Voyageurs
National Park (VNP) of Minnesota by  using  the most  relevant  data  and
analytical methods.  The principal steps were to  focus  on:   (1) the ultimate
deposition of emissions from the plant  (rather  than only on  pollutant
concentrations), (2) the use of a time-varying  grid model with provision for
atmospheric transformations, and (3)  a  detailed review of  all  available data
from the region on atmospheric deposition  of pollutants, water quality, and
effects.  The results are considered  in relation  to a  review of responses by
terrestrial and aquatic organisms to  changes in the chemistry  of  this
environment.

     The sensitive aquatic and terrestrial receptors in the  BWCA-VNP region
are described quantitatively, and this  information  is  assessed in terms of
what is currently known about the impacts  of atmospheric pollutants.
Specific conclusions based on factual information,  probable  consequences, and
possible impacts of the proposed coal-fired power generating station at
Atikokan are presented.

     The study supports, in part, the conclusions reached  previously
concerning the predicted air concentrations of  sulfur  dioxide, but differs
significantly with the conclusions concerning the significance of future
impacts.  When, the total emissions from the proposed power plant  are
considered, the increased loadings of sulfuric  and  nitric  acids,  fly ash, and
mercury as an addition over and above other regional sources will, with high
probability, have significant consequences for  the  sensitive receptors in the
BWCA-VNP region, especially for the  future of sport fisheries  and other
aquatic resources.
                                       IV

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                                  CONTENTS

Foreword	iii
Abstract	iv
Figures	vii
Tables	ix
Acknowledgments  	  x

    1.  Introduction  	  1
             Background  	  1
             Uniqueness of the BWCA	3
             Structure of the study	5
    2.  Summary of Results and Conclusions  	  6
             Air-Quality Impacts 	  6
                  Conclusions of fact	6
                  Probable consequences  	  7
             Terrestrial Impacts 	  7
                  Conclusions of fact	7
                  Probable impacts  	  8
                  Possible impacts  	  9
             Aquatic Impacts  	  9
                  Conclusions of fact	9
                  Probable impacts  	  10
                  Possible impacts  	  11
    3.  Air Quality in the Boundary Waters  Canoe Area  (BWCA)	12
             Introduction	12
             Background Air-Quality Data Near the BWCA	14
             Atikokan Emissions  	  16
             Atmospheric Dispersion,  Transformation, and Deposition   ...  18
                  Plume chemistry	19
                  Dry deposition    	20
                  Wet deposition    	20
             Description of the Three-Dimensional Dispersion  Model  ....  27
                  Model formulation	27
                  Numerical solution  of the plume model   	  31
                  Meteorological data used  in the model	33
             Plume Model Results for  Atikokan   	  35
                  Atmospheric loadings  in the Quetico area	45
             Validation of the Model	46
             Summary Discussion of  the Atikokan Modeling Results  	  48
    4.  Potential Effects of Coal-Combustion Emissions  on the Terrestrial
        Biota of the BWCA	49
             Introduction and Goals   	  49
             Biological and Temporal  Characteristics of the Boundary
             Waters Canoe Area	50

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                 Plant community types	50
                 Long-term stability of  the BWCA  landscape   	   54
       Biotic Responses to Coal-Fired Power-Plant Emissions  	   55
            Residuals of concern   	   57
            Conifers (pines) and aspen	59
            Lichens and Bryophytes (sphagnum)  	   65
            Arthropods (insects)	69
            Amphibians	73
            Soils	73
            Nutrient Cycling  	   79
            Influence of affected  trees  on insect populations  	   82
            Bioaccumulation 	   83
       Application of Research Findings  to the Boundary Waters  Canoe  Area   90
            Significance for pines	91
            Significance for lichens	91
            Significance for insects	92
            Potential for the bioaccumulation  of  toxic materials   ....   92
            Significance for nutrient cycles	93
            Lake and watershed chemistry in relation to BWCA  soils   ...   93
   5.  Impacts of Acidification on Aquatic Ecosystems of the Boundary
       Waters Canoe Area (BWCA) and Voyageurs  National Park (VNP)  ....   98
            Introduction  	   98
            Characteristics of Lakes Vulnerable to Acidification   ....   99
                 Physical factors  in the  characterization of vulnerable
                 lakes	99
                 Chemical characteristics and  responses of vulnerable
                 lakes	104
                 Atmospheric acidification of  BWCA-VNP lakes   	  106
            Impacts Upon Aquatic Communities   	  113
                 Effects on microbiota   	  117
                 Effects on benthic plants  	  119
                 Effects on phytoplankton 	  121
                 Effects on invertebrates 	  121
                 Effect on vertebrates-fish 	  123
                 Effects on other  vertebrates  	  127
            Summary	127

References	129
Appendices

   A.  Wet Removal Rates for S02 Gas and  S0£ Aerosol	154
   B.  Simple Model Calculations of Emissions Applied to Atikokan  ....  167
   C.  Representative Analysis of  Coal and Fly Ash for Major and Trace
       Components	172
   D.  Data Pertinent to the Aquatic Ecosystems of the Boundary Waters
       Canoe Area	173
                                     VI

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                                     FIGURES


Number                                                                    Page

1   Map of the  study  area  showing  grid  for computer model ......... 13

2   Qualitative description  of  synoptic  situations envisioned for
      the model .............................. 22

3   Washout ratio as  a  function  of precipitation rate.   Curve 1
      represents predictions for intense convective storms or from
      clouds where tops  are  warmer than  0°C;  curve 2 represents
      predictions for storms where rain  develops without the
      assistance of an  ice-growth  stage; curve 3 is for storms where
      the ice-growth  process is  necessary for initiating precipitation . . 25

4  Sulfate concentrations  in surface  precipitation at Pennyslvania State
      University, September  1976 through January 1978.   The curve is
      an eyeball fit  to  individual data  points .............. 26

5   Schematic diagram of the parameters  used  in the grid model ...... 28

6   Computed annual average  concentrations due south of Atikokan
      for SC>2>  SO^, fly  ash,  and mercury ................. 38
7   Computed 24-h worst-case concentrations  due  south  of Atikokan
      for S02> S0£,  fly  ash, and  mercury  ................. 39

8   Computed 3-h worst-case concentrations due  south of Atikokan
      for S02> SO^,  fly  ash, and  mercury  ................. 40

9   Computed annual  and  seasonal  dry deposition  flux due south of
      Atikokan for SC^j  SO^, fly  ash,  and mercury.  There are only
      two seasons:   summer and winter.  Summer  is  defined as  the time
      when the snow  is not on the ground  ................. 43

10  Computed annual  and  seasonal. wet deposition  flux due south of
      Atikokan for SC^,  SO^, fly  ash,  and mercury.  There are two
      seasons:  summer is rain, and winter is snow ............ 44

11  Results of the sensitivity tests of the  grid model showing
      the influence  on SC>2 concentration  for a worst-case day ....... 47

12  Distribution of vegetation types in the  BWCA-VNP area and vicinity .  . 53
                                    vii

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13  Schematic diagram of regional material exchange  system  and
      biological response processes that may be anticipated  in  response
      to coal-fired power-plant emissions  	   56

14  General exchange relationships between pH and cations	78

15  Outline map of the areas of sensitive soils (shaded) within the
      Kawishiwi Area Soils Map	94

16  Sample sheet of the soil map of the Kawishiwi Area  showing
      sensitive soil areas (shaded) and the location of  six  potentially
      sensitive lakes (arrows) 	   95

17  Regions of North America containing lakes that are  sensitive
      to acidification by acid precipitation, based  on  bedrock  geology.
      Calcareous overburden will modify this picture somewhat	100

18  Rainy Lake drainage basin emphasizing major watershed areas and
      river-flow patterns toward U.S./Canadian border lakes.  Water-
      flow direction of Lake Superior, Hudson Bay, and Lake  of  the
      Woods watersheds is indicated	101

19  Profile of waters along the international boundary,  Lake Superior  to
      Rainy Lake Reservoir	102

20  Park boundaries outlined on the Rainy Lake drainage  basin.   November
      1978 EPA sampling sites	103

21  Percentage distribution of 85 BWCA-VNP lakes based  on the water
      alkalinity observed in November 1978	105

22  Relationship between pH and alkalinity in 85 BWCA-VNP lakes	108

23  Relationship between acid Loading and pH change  for  lakes in  Sweden
      in very sensitive and somewhat  less sensitive  surroundings  ....  110

24  Effect of acid addition on the pH of water from  selected BWCA-
      VNP lakes	112

25  Relationship between frequency and mercury concentrations of  walleye
      and northern pike taken from selected BWCA-VNP area lakes  ....  115

26  Regressions of log mercury concentration against total  length for
      brook trout sampled from acid drainage lakes and  limed, seepage,
      and bog lakes in the Adirondacks	116
                                     Vlll

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                                   TABLES
Number

 1  Summary of Available Data on Air Pollutants in the Boundary
      Waters Canoe Area and Adjacent Ontario 	   15

 2  Atikokan Power Plant Emissions  	   17

 3  Wind and Diffusivity Profiles	   30

 4  Model Parameters that are Species Dependent	   34

 5  Average Meteorological Data, International Falls, Minn., 1970-74  .   36

 6  Number of Periods Per Year When the S02 Concentration in the
      BWCA is Calculated to be in a Given Range due to the Atikokan
      Plume	41

 7  Virgin Upland Communities in the BWCA and the Importance of
      Stands, Types, Species, and Families  	   52

 8  Effects of S02 in Combination with Other Pollutants on Native
      Vegetation	   62

 9  Summary of Native Insect Responses to S02 and Other Pollutants  .  .   84

10  Potentially Sensitive Headwater Lakes in the BWCA	   97

11  The pH of Precipitation on the Laurentian Shield of Eastern North
      America	107

12  Calcite Saturation Indices (CSl) for 85 BWCA-VNP Lakes  	  109

13  Snow-meltwater Enrichment by Dissolved Components - Concentrations
      and Percentage of Total Mass Found in Melted Snow as a Function
      of the Percentage Melted (Average of Three Sites in BWCA-VNP).  .  114

14  Approximate pH at which fish in the LaCloche Mountain Lakes,
      Ontario,  Stopped Reproduction	126
                                     IX

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                                ACKNOWLEDGMENTS

                           Air Quality and Modeling

     This section was written primarily by Dr. K. W. Ragland (University of
Wisconsin-Madison) and Dr. B. C. Scott (Battelle, Pacific Northwest
Laboratories).  It does not  indicate endorsement by EPA or Battelle.  K.
Wilkening, C. Donovan, and H. Hull (University of Wisconsin-Madison) did much
of the computer work.  The cooperation of J. Bowman (Minnesota Copper-Nickel
Study) was most helpful.

                             Terresterial Impacts

     Edited by S. S. Smith and 0. L.  Loucks, University of Wisconsin-Madison,
and E. Preston, EPA Laboratory, Corvallis, Oregon from contributions provided
by a panel including J. Bromenshenk,  University of Montana, Missoula; J.
Chilgren, EPA Laboratory, Corvallis,  Oregon; S. Eversman, Montana State
University, Bozeman; C. C. Gordon, University of Montana, Missoula.
Additional help was provided by J. Lieberman and B. Patterson of the Minnesota
Copper-Nickel Study Group and P. Juneau,  Environmental Research Laboratory-
Duluth.
                                Aquatic Impacts

     Edited by J. Eaton, Environmental Research Laboratory-Duluth, and B.
Coffin, Minnesota Department of National Resources, from contributions provided
by a panel including E. Gorham, University of Minnesota,  Minneapolis; H.
Harvey, University of Toronto, Toronto, Ontario; G. R. Hendrey, Brookhaven
National Laboratory, Upton, N.Y.; D.  W. Schindler, Freshwater Institute,
Winnipeg, Manitoba; C. L. Schofield,  Cornell University,  Ithaca, N.Y.; G. E.
Glass, L. J. Heinis, L. Anderson, C.  Sandberg, T. Roush,  J. Use, J. Rogalla,
S. Kohlbry, and M. Brilla, Environmental Research Laboratory, Duluth,
Minnesota; S. Eisenreich, University of Minnesota, Minneapolis; and members of
the Minnesota Copper-Nickel Study Group.

                1978 Data Report (Appendix D) - and Manuscript

     Compiled by G. E. Glass, L. J. Heinis, L. Anderson,  F. Boettcher, C.
Sandberg, B. Halligan, and T. Roush,  with acknowledgments of assistance from
the staff of the following organizations:

     USEPA Environmental Research Laboratory-Corvallis, D. Krawczyk
     USEPA Environmental Research Laboratory-Duluth, T. Highland, P. Gray, and
       B.  Halligan
     USDA Forest Service-Duluth, J. M. Ramquist, E. Marsolek, and B.
       Dovenmuehl

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     Freshwater Institute Winnipeg
     Minnesota Pollution Control Agency, J. Pegors and T. Musick
     University of Wisconsin-Madison, A. Andren
     University of Minnesota-Duluth, Lake Superior Basin Study Center
       Laboratory
     USDC Voyageur's National Park Director

     Comments and suggestions contributed by manuscript reviewers; W. Dickson,
W. R. Effer, J. H. Gibson, D. Lang, G. E. Likens, C. S. Mathias, J. Moody, G.
Robitaille, B. Smith (reviewer and editor), and R. F. Wright are gratefully
recognized.  The reviewers are, of course, not responsible  for any data or
information contained in the report.
                                     XI

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                                    SECTION  1

                                  INTRODUCTION

     The Boundary Waters Canoe Area Wilderness  (BWCA),  a wilderness  unit
within the Superior National Forest (Minnesota)  and  located  along 176 km  (110
miles) of the Minnesota-Ontario border,  occupies 439,093 ha  (1,085,000 acres)
of characteristic northwoods terrain.  The  area  varies  from  16 to 48 km (10
to 30 miles) in width.  Over 1,900  km  (1,200 miles)  of  streams,  portages,  and
foot trails connect the hundreds  of pristine,  island-studded lakes that make
up approximately one-third of the total  area.  Few wilderness  areas  have  been
the focus of as much persistent concern  for protection  from  human impacts  as
has the BWCA.

     The 1976 proposal by Ontario Hydro  to  build and operate a major
coal-fired power plant north of the Quetico-BWCA wilderness  complex  has led
to concern that air quality and ecosystems  in  the  area  could be  inadvertently
degraded, in spite of the years of  effort and  the  legislation  designed to
protect them.  Because of the important  natural  resources represented by  the
waters, forests, and air of the BWCA,  many  individuals,  legislators,  and
environmental organizations have  been  concerned  with possible  deficiencies in
the available data, methodology,  and scope  of  the  assessments  carried out
since the plant was first proposed.  These  concerns  have led to  the  decision
by the U.S. Environmental Protection Agency, in  cooperation  with State
agencies, universities, and other Federal agencies,  to  proceed with  the
present comprehensive study of potential impacts on  the  biota,  air,  and
water.  Additional data and new analytical  tools,  including  a grid model  that
computes pollutant transformation and  deposition,  were  available and
appropriate for a second-level analysis.

BACKGROUND

     Ontario Hydro, a crown corporation  established  by  the Ontario govern-
ment, requested in 1976 and received in  1977 Provincial  approval to  build  an
800-MW, coal-fired electric generating station near  Atikokan,  Ontario. The
site is approximately 20 km (12 miles) from the  northern boundary of Quetico
Provincial Park and about 55 km (38 miles)  from  that portion of  the
U.S.-Canadian border which forms  the northern  edge of the BWCA in Minnesota.

     Criticism of the project from  Canadian and  U.S.  environmental
organizations and individual scientists has centered on  the  proposed plant's
proximity to the Quetico-BWCA wilderness complex,  and on the omission from
the structure of any scrubber technology.   Concern also  has  been addressed to
the Ontario Hydro environmental analysis document, which,  critics said,
failed either to give substantial evidence  for  its claim that  no vegetation
damage would result from S02 emissions or to treat adequately  the problems
of acid precipitation and deposition of pollutants in the Quetico-BWCA
environment.

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     The Atikokan facility  is to be  staged  in  four 200-MW  units,  one  of which
is to be in service during  1984.  The boilers  for these units would burn
either low sulfur subbituminous coal  from Alberta or  lignite  from
Saskatchewan.  The proposed facility would  feature electrostatic
precipitators to control particulate emissions, but no  scrubbers  would be
used to minimize SC>2 emissions.  Planning  for  the Atikokan generating
station began in 1974; in 1976 Ontario Hydro published  an  environmental
analysis and supplementary  report dealing with  the project.  The  regulations
of the recent Environmental Assessment Act  of Ontario were not  applied
retroactively to the Atikokan generating station.

     United States-Canadian international negotiations  on  the Atikokan plant
began in August 1977.  At that time  the Canadian participants agreed  to
provide the U.S. Department of State with additional  information  for  a more
precise evaluation of the project's  potential  transboundary effects.
Technical studies were undertaken in each country of  the S02 concentrations
expected to originate from  this plant.  The results were exchanged  in late
December 1977.  With the additional  Canadian information and  in consultation
with the Department of State, the U.S. Environmental  Protection Agency
proceeded with its initial  review of the Atikokan proposal.

     During this period Minnesota congressional representatives and several
environmental organizations urged the Department of State  to  ask  Canadian
officials (1) to refer the matter to the International  Joint Commission
(IJC), with a moratorium on plant construction  (to allow a comprehensive
study of the plant and its  impacts), or (2) to  ask for  installation of the
best available scrubbers (90% efficient) similar to those  already used
extensively in Minnesota for new sources.

     The Department of State presented the  results of the  EPA initial review
at a second international negotiations meeting  held on  January  11,  1978.  The
EPA review included a literature survey on  acid rain  problems and projections
of S02 dispersal based on the standard Gaussian plume dispersion  model.

     At this January meeting the U.S. team  noted that results of  both
Canadian and U.S. modeling  studies  indicated that the concentrations  of S02
entering the BWCA from the Atikokan  plant occasionally  may be in  excess of
the Class I air quality standards permitted under the U.S. Prevention of
Significant Deterioration Criteria.  (Covering  classified  wilderness, Class I
is the most stringent standard.)  Also using the studies from both  countries,
the Canadians concluded at  the January meeting  that the predicted
transboundary impact of S02 emissions from  the  Atikokan generating  station
was below the threshold at which injurious  environmental effects  are  known to
occur.  Canadian officials  confirmed  that  the  plant would  meet  all  Canadian
environmental requirements.

     The U.S. negotiating team initially requested the  installation of 50-
percent-efficient scrubbers.  The Canadian  representatives indicated  that
they could not, at that time, accept  such  a requirement.   The negotiators
then focused on discussing  a referral to the IJC'that would not include a
construction moratorium, but would  feature  a program  to monitor effects of

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the plant.  The Department  of  State  submitted  proposed wording for such an
IJC reference, and  the Canadian Office  of  Foreign  Affairs  agreed to consider
the proposal.

     The U.S. team,  lead  by officials  of  the Department of State,  included
representatives from  the  State of Minnesota, the Environmental Protection
Agency, and the USDA  Forest Service, which manages the BWCA.   The  Canadian
team, headed by officials  from the Bureau  of USA Affairs of the Department of
External Affairs,  included  representatives of  the  Province of Ontario,
Environment Canada,  the Canadian Embassy  in Washington, and the Canadian
consulate  in Minneapolis.

     On February 22,  1978,  some members of the U.S.  negotiating team met in
Chicago to discuss  additional potential air quality  impacts such as acid
fallout.  Also present were staff of the EPA Office  of International
Activities, EPA Region 5;  scientists from  the  EPA  Environmental Research
Laboratory-Duluth  (Minnesota), and Environmental Research  Laboratory-
Corvallis (Oregon), and several universities;  and  representatives  from
conservation organizations  (National Parks and Conservation Association,
Friends of the Boundary Waters Wilderness,  and National Clean Air  Coalition).
At this meeting the data, methodology,  and scope of  the initial EPA study
were reviewed in detail,  especially  the following:  (1) the lack of realistic
simulation of meteorological and chemical  transport  and deposition processes
by a Gaussian plume model over the distance involved in the Quetico-BWCA
study; (2) the omission of  data on existing conditions covering sensitive
water quality, water-flow direction, and high  mercury levels  in fish; and (3)
the necessity that  contributions made  by  the Atikokan plant be assessed
against present background  levels and  all  planned  future sources in the area.
The consensus of those attending was that  the  Atikokan generating  station had
the potential to be a significant addition to  the  pollutants  in the BWCA area
for both air and water and  that a much  more comprehensive  study to assess its
significance should be undertaken.

     On March 20 the  Canadian Embassy  issued a diplomatic  note rejecting any
International Joint Commission reference,  citing as  its reason "the lack of
indiction of any potential  injury" to  the  U.S. side, such  injury potential
being "the traditional basis for considering transboundary pollution
questions" by the  IJC.  The Canadian team  also concluded that since the
existing studies predicted  that concentrations of  the pollutant of major
concern in the United States, sulphur  dioxide, would be far below  injurious
levels, there was no basis  for considering the installation of scrubbers.

     Subsequently,  the U.S.  Environmental  Protection Agency agreed to support
a limited additional  study  of potential impacts of the proposed Atikokan
power plant, for which this  report details results.   This  latest study  was to
be supported also  in  part by the Department of State; the  USDA Forest Service;
and the Minnesota Pollution Control Agency; and was  to be  coordinated by the
EPA Environmental Research  Laboratory-Duluth.

UNIQUENESS OF THE BWCA

     The Boundary Waters Canoe Area has been recognized as  a  unique resource
for many decades.   In 1930  the Shipstead-Newton-Newland Act was passed  to
                                       3

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protect its shorelines and water  levels  from dam building and drainage.  In
1948 passage of the Thye-Blatnik  Act  allowed condemnation and purchase by the
Federal government of private  lands  in  the  "roadless  area,"  as it was then
called.  President Truman issued  an  air  ban in  1950,  stopping the floatplane
flights into the "roadless area"  which  had  allowed  over-fishing of many
lakes.  The 1964 Wilderness Act designated  the  Boundary  Waters Canoe Area as
part of the National Wilderness Preservation System,  thus recognizing it as a
national resource of outstanding  quality that should  be  preserved in an
unimpaired condition so that the  forces  .of  nature rather than those of man
could predominate.  The act contained specific  provisions allowing certain
logging and motorized activity within portions  of the BWCA,  but otherwise
mandated specific wilderness protection.  Recently  passed legislation in the
1977-78 Congress now further limits  nonwilderness uses of the BWCA.

     It is difficult to describe  adequately the BWCA's significance to the
American public as a conservation,  scientific,  and  recreation resource for
the present and future.  It is the  only  lakeland canoe unit  of the U.S.
wilderness system and one of the  system's largest units  of any kind.
Embracing the largest remaining virgin  forest in the  east,  it attracts more
recreationists than any other  wilderness area in the  nation  and lies within
2 days' travel of nearly 50 million  people.  As the last large, unmodified
northern coniferous forest ecosystem in  the eastern United States, it has
become the focus of much education  and  demonstration  management in wilderness
ecology, animal behavior, vegetation history, nutrient cycling, and aquatic
ecosystems.

     The attraction of the area appears  to  be not any single factor, but a
combination of related ones:   fishing and camping in  a sought-for atmosphere
of wild, unpolluted landscape.  However,  the evergreen forests, clear water
and air, rock outcrops, and shallow  soils that  are  the conspicuous
ingredients of the BWCA landscape are all also  unusually sensitive to
regionally transported pollutants.   The  expansive and relatively unspoiled
terrestrial and aquatic ecosystems  in the BWCA  are  the major reasons for its
recognition as a unique resource  in  the United  States.  This recognition and
uniqueness have led to a protective  degree  of legislative and citizen
vigilence, and, indirectly, to recent monitoring of air  quality in
northeastern Minnesota.  Since August 8,  1977,  the  BWCA  has  been protected by
U.S. Clean Air Act amendments  that  guarantee maximum  "Class  I" protection for
parks and wilderness areas.  The  intent  of  a Class  I  status  is to assure
long-term maintenance of air quality over an area at  essentially the 1974-75
levels.  Class I applies to areas such  as the BWCA  in which  practically any
change in air quality would be regarded  as  signficant.

     Complementing the BWCA is Ontario's adjacent Quetico Provincial Park,
453,258 ha (1,120,000 acres) where  logging,  snowmobiles, and motorboats are
banned.  In 1973 the Ontario Provincial  Government  determined that Quetico
did not fit into any of the usual classifications for provincial parks and
declared it a "primitive wilderness."   The  importance of the BWCA to the
United States has been greatly augmented by the forward-looking decisions
made by Canadians in regard to the Quetico  Park, established simultaneously
in 1909 with the Superior National  Forest to create an international
sanctuary.  Approximately 90%  of  the people who visit and enjoy the resources

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of Quetico are U.S. citizens,  and  over  the  years  the Quetico-Superior (BWCA)
area has come to be viewed  as  a  single  air,  water,  biological,  and
recreational resource.

STRUCTURE OF THE STUDY

     This study has been  structured  to  capitalize on, rather than duplicate,
any of the previous assessments  of the  Atikokan power plant.  New data and
modeling approaches were  available from two major energy-impact studies
sponsored by the EPA, and results  of  an intensive study in the  northern
Minnesota area by  the State of Minnesota also were  becoming available.  These
results, together with the  previously available literature,  could be used in
conjunction with the  issues identified  during reviews of the previous
assessments to set a  new  standard  of  analysis and evaluation.

     Thus, the analysis and assessment  process incorporated in  this report  is
divided into three areas:   (1) air-quality  modeling (with multiple modeling
approaches for predicting air-pollutant concentrations and deposition); (2)
terrestrial effects (emphasizing transformation products of the S02 and the
receptors within the  BWCA);  and  (3)  aquatic effects (considering acid inputs,
due to all substances leaving  the  stacks at Atikokan, as well  as existing
conditions including  high levels of  mercury in fish and water  flow to the
border from both countries).   Each area involved  participants  from the two
principal research sites, Madison  (Wisconsin), and  Colstrip (Montana), and
other technical consultants and  required the assessment data from sources
throughout the region.

     The task of the  air-quality modeling group was (1) to determine what can
be predicted regarding the  route and  deposition of  the proposed emissions in
the region, by using  a regional  grid  model  with provisions for  chemical
transformations and deposition;  (2)  to  draw together information on current
background levels  of  air  pollutants  and all of the  emission sources in the
northwestern Minnesota region  and  adjacent  Canada;  and (3) to model all
current and proposed  emissions so  that  the  contribution of all  regional
inputs could be analyzed  in relation  to the total loadings in  the region.

     The goals of  the groups studying terrestrial and aquatic  effects were
(1) to characterize the sensitivity  of  the  components of the terrestrial and
aquatic ecosystems to the gaseous  and particulate pollutants;  and (2) to
summarize research results  available  on the responses of sensitive species as
well as to summarize  the  overall sensitivity of these associated ecosystems
to the current and expected levels of pollutants  reaching the BWCA.

     The assessment by these groups  proceeded around two principal workshops
and the preparations  and  follow-up for  each workshop.  Materials were
prepared for study prior  to a  problem-definition  workshop on each of the
three tasks (held  in April  1978).  Detailed data  summaries and  first drafts
of the final reports  were prepared during the spring and early  summer,
leading to an assessment workshop  (August 1978) where the findings of the
model output, assessment  of existing  conditions,  and a review  of existing
literature were evaluated by participants from all  groups.

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                                  SECTION  2

                     SUMMARY OF RESULTS AND CONCLUSIONS
     The goal of this study was  to use  the most  relevant  data  and  analytical
methods to examine previously unanswered questions  of  potential  effects from
the Atikokan power plant on ecosystems  in the  Boundary Waters  Canoe  Area
(BWCA) and Voyageurs National Park (VNP) of Minnesota.  The  approach has
been to focus on the ultimate deposition of emissions  from the plant (rather
than only on pollutant concentrations), to use a  time-varying  grid model with
provision for atmospheric transformations, and to review  in  detail  all
available data from the region on atmospheric  deposition  of  pollutants  and on
water quality.  The results are  considered in  relation to a  review of
responses by terrestrial and aquatic organisms to changes in the chemistry of
this environment.

     The study supports, in part, the conclusions reached previously
concerning the predicted air concentrations of sulfur  dioxide,  but differs
significantly with the conclusions concerning  the significance of  future
impacts.  When the total emissions from the proposed power plant are
considered, the increased loadings of sulfuric and  nitric acids,  fly ash, and
mercury as an addition over and  above other regional sources will, with high
probability, have significant consequences for the  sensitive receptors  in the
BWCA-VNP region, especially for  the  future of  sport  fisheries  and  other
aquatic resources.  Additional research will be  required  to  specify  these and
other possible impacts in detail.

AIR-QUALITY IMPACTS

     A time-varying grid model has been developed and  applied  to  the plume
from the proposed Atikokan generating station.   Preliminary  validation  steps
on the model have been carried out,  and a number  of  outside  reviewers have
examined the model assumptions and output.  Within  the  limits  of the
available data and the design specifications available to the  study, the
model performance provides a basis for  reasonable confidence in  the  projected
concentrations and deposition fluxes.

Conclusions of Fact

1.  By using the coal type (western  Canadian), sulfur  content  (0.8%), ash
    content (12%), and operating conditions agreed  upon by previous
    assessment studies, the emissions from the 800-MW  Atikokan generating
    station were computed to be  70,307  metric  tons/yr  (77,500  tons/yr)  of
    sulfur dioxide, 2,358 metric tons/yr (2,600  tons/yr)  of  fly ash, 41,630
    metric tons/yr (45,900 tons/yr)  of  nitrogen  oxides, and  0.9 metric
    tons/yr (1 ton/yr) of mercury.   Other volatile  components  of  coal,  such

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    as fluoride, arsenic, selenium, etc., will  be  emitted,  and  the  amounts
    will vary depending on the source of coal.

2.  The plume from the proposed Atikokan generating station will  be carried
    over the BWCA by NW to NE winds persisting  for 3-6  h.   For  the  base
    study-year, 1964, such conditions occurred  during 49  time-periods,  which
    totaled 910 h or 10.3% of the year.

Probable Consequences

1.  Model computations indicate that emissions  from the proposed  Atikokan
    stack reaching the 80-120 km BWCA region  contained  in the 35° south  sector
    will increase atmospheric deposition of sulfate by  about 0.9-1.4
    kg/hectare-year (ha-yr), fly ash by 18 g/ha-yr,  and mercury by  0.0016
    g/ha-yr.  These values will be added to the present 7-yr average atmospheric
    loading of  11 kg/ha-yr for sulfates.  Fly ash  deposition in the region  has
    not been measured, and mercury deposition based on  snow cores is at  most
    0.013 g/ha per snow season.

2.  The planned operation of the Atikokan facility represents a potential 30
    percent increase over probable unbuffered acid deposition even  after the
    prospective closing of the Steep Rock iron  ore processing facility.   If
    the iron mining operation is closed, and  only  half  of the Atikokan
    generating station is constructed (400-MW),  unbuffered  acid deposition  in
    the BWCA is expected to increase by 15 percent.

3.  The grid-model computations indicate that the  3-h S02 concentration
    would exceed the U.S. air-quality Class I regulations for protection of a
    wilderness area two times per year; the 24-h standard would be  exceeded
    three times per year.  The annual average S02  standard  would  not be
    exceeded.

4.  Two-thirds of the particulate matter reaching  the BWCA  from the Atikokan
    plume will be as SO^ rather than fly ash; and  most  of the sulfate
    deposition in the region will have been deposited initially as  S02,
    followed by transformation in situ.

5.  Approximately half of the SC^-plus-SO^ and  fly ash  and  two-thirds of
    the mercury deposition will occur during  the snow season.

6.  The amount of sulfur leaving the 100-x 100-km  region  by atmospheric
    transport would be as much as 70% of the  total emitted  from the proposed
    Atikokan power plant.

TERRESTRIAL IMPACTS

Conclusions of Fact

1.  The terrestrial ecosystems of the BWCA and  VNP are  dominated  by
    short-season species, two of which, white pine (Pinus strobus)  and
    trembling aspen (Populus tremuloides), are  known to be  particularly
    sensitive to the gaseous emissions of coal-fired generating stations.

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    The white pine  is  the  largest  and  most  long-lived of species in the BWCA
    (a lifespan often  over  250 yr),  and  is  essential  to the lake-edge and
    skyline features.

2.  Soils of the BWCA-VNP region  are mostly shallow (0-46 cm),  of glacial
    origin, coarse  textured, derived from  granites  and other acid bedrock
    types, low  in cations  and available  nitrogen,  and low in percentage base
    saturation.

3.  Geochemical weathering  of rocks  and  soils  has,  throughout the earth's
    history, been dominated by the weak  carbonic  acid formed from carbon
    dioxide and water.  The nitric and sulfuric  acid  components of
    atmospheric deposition  now being measured  in  the  BWCA-VNP are sufficient
    to modify the normal carbonic  acid weathering  of  these soils and create a
    geochemical cycle  in which dilute  nitric and  sulfuric acid  are
    important.

4.  A number of lichen  species are among the plants that are most sensitive
    to gaseous coal-combustion emissions and acid  particulates.  Lichens are
    an important part  of the BWCA-VNP  biota and make  up the principal plant
    cover on 5% of  the  land area.  Lichen  species  also have been shown to be
    an important source of  nitrogen  (through N fixation) in a number of
    nitrogen-limited coniferous forest areas.

5.  A number of insect  groups with strong  sensory  systems, particularly
    saprophagous and predaceous beetles, social bees  (pollinators),  and
    parasitic wasps, have been shown to  be  reduced  in abundance at very low
    concentrations  of  air pollutants,  apparently because of pollutant
    avoidance or disorientation.   Several  plant-feeding insect  groups have
    been shown to increase  rapidly when  the activity  of parasites or
    predatory control  insects is  reduced,  or the vigor of host-plant species
    is reduced, both of which have been  shown  to occur from gaseous  pollutant
    emissions.

Probable Impacts

1.  Given what  is presently known  on mobilization  of  toxic elements  by acid
    fallout, the increase in fallout of  sulfuric  and  nitric acid deposition
    from operation  of  the Atikokan generating  station must be viewed with
    considerable concern.   Some of the mobilized elements are toxic  to
    terrestrial vegetation  after  relatively small  changes in concentration
    are induced by  additional acid fallout. The  projected additions of H+
    through nitrate and sulfate represent  an increase of more than 25% over
    the presently unbuffered atmospheric acid  deposition and appear  likely to
    exceed soil buffering capacities.  These mechanisms lead to effects, as
    well, on small  lakes that could  begin  to receive  increasing amounts of
    nutrient and toxic  elements within a few years.  Detailed watershed
    geochemistry and mass balance  studies  will be  required to document such a
    response.

2.  Small additions of  acidity to  the  thin, rocky  soils common in the BWCA,
    coupled with the geochemical weathering changes that are probable, can be
    expected to have relatively rapid  and  irreversible effects  on outputs
                                       8

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    from the nutrient  cycles  of  these  ecosystems.   These changes will affect
    groundwater  quality  and produce  soil-mediated  changes in cycling rates
    within the ecosystems.  Although the net changes in cation leaching due
    to  lowered soil  pH are  difficult to predict,  H+ additions to some soils
    will facilitate  leaching  of  essential  plant  nutrients.

Possible Impacts

1.  The projected  ambient  concentrations of total  suspended particulates,
    S02> ozone,  and  acid particulates  from the proposed Atikokan plant may
    directly affect  the  growth and  reproductive  rates of sensitive pine
    species.  The  presence  of phytotoxic elements  by leaching of cations
    could produce  similar  effects.   The possibility of such effects increases
    as  other major point sources of  gaseous emissions are developed in the
    region.  Over  periods  of  100-200 yr (the lifespan of much of the
    vegetation)  even  small  effects  on  growth rates affect survival of
    the dominant species and  could have important  consequences on the
    composition  of the region's  vegetation.  Such  plant responses could be
    assessed as  part  of  long-term watershed monitoring.

2.  Although visible  effects  on  lichens that would be measurable within 5 yr
    are not anticipated  at  the projected pollutant levels,  slowing of growth
    rates for a  number of  species is probable and  could change the species
    composition  over  a period of a  few decades,  leading to  detrimental
    effects on nitrogen  fixation.

3.  The lower pH of  the  forest soils could amplify trace-element effects by
    making these elements more available in the  food chain,  and hence in
    small herbivores,  fish, and  birds  at the top  of the food chain.
    Long-term monitoring will be needed to assess  these effects.

4.  Effects on insects at  the proposed concentrations have  not yet been
    documented because work on the  insect  groups  is sparse  and has not
    focused on the threshold  for response.  Additional emissions and higher
    concentrations can be  expected  in  the  area in  the next  few years,  and
    effects are  known  for  the concentrations expected in the future.
    Mobilization of  toxic  elements  through insect  food chains to small
    mammals and  birds  is possible.   Since  pollutant injury  to sensitive pine
    species also is possible, increased insect damage may occur.  Additional
    studies of the effects  of low concentrations  of S(>2 on  the olfactory
    systems of pollinating  and parasitic Hymenoptera, predatory beetles,  and
    decomposer insects are  urgently  needed.

AQUATIC IMPACTS

Conclusions of Fact

1.  The BWCA and VNP are in a region comparable  in vulnerability to others
    that have already  been  severely  affected by  acid precipitation in Europe
    and North America.   Most  BWCA-VNP  surface waters have a poor buffering
    capacity, and many have a low pH (below 6.5) as well.

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2.  Precipitation  in the near vicinity  of  the  BWCA-VNP  is  strongly acid on
    occasion, and  the mean annual  pH of  precipitation  is near the  level where
    damage begins.

3.  Atmospheric acid sulfate  loadings  in the near  vicinity of the  BWCA-VNP
    are at levels  associated with  the onset of  severe  lake acidification in
    Scandinavian countries.

4.  Mercury levels  in fish, which  increase  as  lakes  acidify,  are  already high
    in some lakes  in and near the  BWCA-VNP.

5.  Most of the area within a 100-km (62-mile)  radius  of Atikokan  is in the
    Rainy Lake watershed and drains into the international waters  of the
    BWCA, VNP, and Quetico lakes.

6.  The varied, valuable fishery resource  of the BWCA-VNP  includes many
    species that have been reduced or eliminated by  acid precipitation
    elsewhere in the United States and  Canada.

7.  Increased metal concentrations, sufficient  themselves  to  cause problems,
    often accompany reduced pH.  As the  pH  is  lowered,  the forms  of metals
    present also become more toxic in most  cases.

Probable Impacts

1.  It is likely that vulnerable lakes  in  the  BWCA-VNP  and Quetico areas
    (poorly buffered headwater  lakes with  small watersheds and shallow soils
    of low buffering capacity)  are already  being affected  by  acidity from
    atmospheric sources.

2.  Although present atmospheric loadings  of acid-producing material are
    probably affecting some BWCA-VNP-Quetico lakes,  additional loadings from
    Atikokan will  accelerate  the rate of acidification  in  vulnerable lakes
    and endanger other lakes not presently  being acidified.  Long-term
    studies of lake-water and stream-water  chemistry in the BWCA  are needed.
    Special attention should be given to accurate  hydrological and chemical
    budgets of inputs, outputs, and storage  in  ecosystems  susceptible to
    damage by acidification to  define the  timing and magnitude of  the
    effects.

3.  Given the probable changes  in  the  existing  pH  levels of lake  water, we
    can project likely responses in the  aquatic biota:   reduction  in
    decomposition  of organic matter; undesirable accumulation of  certain
    nuisance algae; decreases in phytoplankton  species  numbers, diversity,
    biomass, and production per unit volume; elimination of some  species and
    simplification  of zooplankton  communities;  alterations in benthic plant
    and animal communities; and the loss of fish species preceded  by
    reproductive failure.  These changes will  occur  over different time
    spans:  for some lakes, several years;  for  others,  several decades.

4.  Likely increases in the acidity of  the  water will  increase the severity
    of seasonal events such as  acid flushing  in the  spring due to  snow melt.
    Even moderately buffered  lakes may  form a  shallow,  but highly  acid layer

                                      10

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    of water from acid meltwater.   This  condition will result in a reduction
    in the variety of insect  species  emerging  in the spring and cause death
    of exposed fish embryos.

    A reconnaissance survey of  the  biota and productivity at all trophic
    levels should be carried  out.   It  would  be followed by detailed,  long-
    term monitoring of population dynamics  and lake metabolism, with special
    attention to organisms and  processes sensitive to acidification,  in a
    series of lakes of differing  sensitivity to acid precipitation.  Studies
    currently going on in Scandinavia  and  the  Adirondacks can serve as
    models.

5.  Increased acidity is likely to  result  in detrimental levels of aluminum
    and of other trace elements in  the lake  water by increasing leaching and
    creating more toxic  forms of  these elements.  Detailed studies of
    precipitation chemistry in  the  BWCA-VNP  are needed on a long-term basis
    (10-20 yr) .  Special attention  should  be given to loadings of acid,
    sulfate, nitrate, and heavy metals to  define these changes.

6.  The projected additions of  mercury and of  acid to the Rainy River water-
    shed are very likely to aggravate  an existing problem of mercury levels
    in fish tissues.  Additional  data  will be  required to define the precise
    changes and sources.

Possible Impacts

1.  Fish populations in  the most  susceptible lakes of the BWCA-VNP and
    Quetico could be eliminated by  acid  precipitation.  Some populations may
    be lost within a few years, and  in many  other lakes within a few
    decades.

2.  The productivity and biotic diversity  of the aquatic communities  in these
    lakes is likely to be severely  reduced over a period of one to several
    decades.  Some of the most  vulnerable  lakes may already have experienced
    reductions in pH levels and undergone  corresponding biological changes.
    The paucity of historical base-line  data makes such an analysis very
    difficult to perform at this time.

3.  It is possible that  these changes  and  others (e.g. ground-water quality),
    will not be reversible within the  foreseeable future,  even if the acidity
    of precipitation is  substantially  reduced.
                                     11

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                                  SECTION  3

            AIR QUALITY IN THE BOUNDARY WATERS CANOE AREA  (BWCA)
INTRODUCTION

     Air quality in the BWCA of Minnesota  can be  degraded  by  a combination of
large emission sources within 80-160 km  (50-100 miles)  of  the  area  and
long-distance transport of pollutants which  are accumulated during  certain
periods in the Midwestern United States  and  Canada.   Degradation  may occur by
increasing ambient air concentrations of air pollutants and by the  resulting
flux of these pollutants to the ground either by  dry  deposition or  by removal
via rain or snow.

     The air-pollutant concentrations or deposition,  or both,  may cause
damage to vegetation and animal groups such  as insects  and degrade
visibility.  The deposition fluxes potentially may  cause damage to  fish and
animals via the water and soil.  If the  concentrations  and deposition rates
are low enough (i.e., within some theoretical assimilative capacity for the
region), no significant damage will occur.   Since the BWCA is  a U.S.
wilderness area, the most sensitive effects  must  be considered.  To assess
the effects of future increased pollutant  loadings  and  concentrations,
careful estimates of the emissions near  the  BWCA, the transport,  and the
deposition are needed.

     The objective of this section on air  quality,  therefore,  is  to develop
and utilize a grid-type model of air pollution dispersion  to  assess the
ambient air concentrations and deposition  fluxes  in the BWCA  due  to emissions
from the proposed Atikokan generating station.  Attention  will  be focused  on
sulfur dioxide, sulfate aerosol, total fly ash particulates,  and  mercury.

     The study area contains the BWCA and  the Quetico Provincial  Park (Figure
1).  The Atikokan generating station will  lie 80-120 km north  of  the BWCA.
Sources of pollutant emissions due to present electric  power  generation,
mining activity, and industrial and municipal sources that may have an  impact
on the BWCA are considered as regional contributors to  the current  air
quality and atmospheric loadings.  Most  of these  sources are  outside the grid
considered in this report.

     The BWCA-Quetico area has a cool continental climate  characterized by
short, warm summers and long, cold winters:  mean annual temperature 2°C
(36°F); mean July temperature, 17°C (63°F);  mean January temperature, -15°C
(6°F).  The average annual precipitation is  71 cm (28 in.), 64% of  which
occurs as rain from May through September, the growing  season.  Annual  mean
snowfall is about 152 cm (60 in.), and the ground is  usually  snow covered
from mid-November to mid-April.
                                      12

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     The BWCA's landscape has  a generally  slight  but  locally rugged relief
left by preglacial erosion of  the Canadian  Shield.  Elevations  above sea
level range from 341 m (1,119  ft) at  Crane  Lake  to 680 m (2,232 ft) in the
Misquah Hills; local differences in elevation  range from 30  to  150 m.   The
land is heavily wooded, and  16.7% of  the BWCA  consists of lakes and streams.

BACKGROUND AIR-QUALITY DATA  NEAR THE  BWCA

     The BWCA currently has  especially  clean air.  The available monitoring
data near the BWCA are summarized in  Table  1.  The Fernberg  Road site,
presented in the table, is a remote site at the  edge  of  the  BWCA that  has
been monitored by the Minnesota copper-nickel  study.  Monitoring data  for
sulfur dioxide, suspended particulates, and bulk  deposition  are available
from February to December 1977 and ozone from  May to  December  (Valentine,
Minnesota Pollution Control  Agency, personal communication,  1978).

     The sulfur dioxide levels at Fernberg  during 1977 never exceeded  the
threshold level of the instrument, which was 10 yg/m^ (4 ppb),  and only
once exceeded this level during 1978.

     The suspended particulate matter,  as measured by a  high volume sampler,
yielded an annual arithmetic average  of 15  yg/nr*  and  an  annual  geometric
average of 11 yg/m .  There  were 53 days of data, taken  approximately  once
per week.  The maximum 24-h  reading was 66  yg/m  , which  occurred on May 1,
1977.

     The ozone data were recorded at  Fernberg  for 5,384  h from  May to
December 1977.  The arithmetic average  of  all  hourly  values  was 0.030  ppm,
and the geometric average was  0.027 ppm.  The  maximum hourly readings  were
0.100 ppm and 0.101 ppm, which occurred during the afternoons  of May 28 and
July 19, 1977.

     Since the ozone concentrations are due to long-distance transport, it is
instructive to compare the Fernberg site with  another site at  Cloquet, Minn.,
west of Duluth.  At Cloquet  the ozone readings followed  a pattern similar to
that at the Fernberg site, but were slightly lower.   The peak reading  on July
19 was 0.070 ppm rather than 0.10 ppm,  for  example.   The highest reading was
0.097 ppm on August 20.  The Cloquet  site  probably records lower ozone
readings than Fernberg because of scavenging of  the ozone by local sources of
nitric oxide from automobiles.

     The ozone measurements  indicate  that  the  Fernberg  site  is  probably
representative of the region.  It is  assured that the SC>2 -and particulate
readings are representative.   These data indicate that  the ambient SC^ from
regional sources is converted  to sulfates,  or  the SC>2 is deposited out
before it reaches the Fernberg site instrument.   The  total deposition  of
sulfate (wet plus dry) measured by the  Minnesota  copper-nickel  study south of
the BWCA was 10-15 kg/ha-yr  during the  2-yr period  1976-78.

     In addition, Ontario Hydro has monitored  air and precipitation quality
at five sites near Atikokan.   Continuous monitoring of  S02>  Og, and NOX
started in July 1975 (Ontario  Hydro 1976).  The  Nym Lake site,  which is

                                      14

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    TABLE  1.   SUMMARY OF AVAILABLE DATA ON AIR POLLUTANTS IN THE BOUNDARY WATERS
                          CANOE AREA AND ADJACENT ONTARIO

Pollutant
Location
Level
recorded
Averaging
period
MINNESOTA (near BWCA)
S02
°3

03
Suspended
particulates


Bulk 804
deposition
Bulk 804
deposition
Fernberg Road3
Superior Nat'l Forest
Fernberg Road3
Superior Nat'l Forest

Cloquet, Minn.3
Fernberg Road3
Superior Nat'l Forest


BWCAb
Minnesota Copper-Nickel3
Project Area
< 10 Mg/m3
~ (4 ppb)
0.10 ppm
0.03 ppm
0.097 ppm
66 Mg/m3
15 Mg/m3
11 Mg/m3
1.5 kg/ha
10-15 kg/ha-yr
Individual hourly
readings Feb. -Dec. 197
Hourly maximum
May-Dec. 1977
Average May-Dec. 1977
Hourly maximum
May-Dec. 1977
24- hr maximum
Feb. -Dec. 1977
Annual arithmatic
average Feb. -Dec. 1977
Annual geometric
average Feb. -Dec. 1977
Average 304 snow
loading, 65 sites,
March 1978
Range 1976-78
ONTARIO (near Atikokan)
S02
°3
NOX
NOX
NOX
Bulk 804
deposition
Bulk 504
deposition
Nym Lakec
Nym Lakec
Nym Lakec
Nym Lakec
Nym Lake0
0.02 ppm
(50 Mg/m3)
0.10 ppm
0.01 ppm
0.03 ppm
0.10 ppm
Atikokan Region0 4 and 7
kg/ha-yr
Experimental Lakes'1 7-14 kg/ha-yr
Region (Kenora) (10.9 kg/ha-yr)
Hourly maximum
1975-76
Hourly maximum
1975-76
Summer average
1975
24-h maximum
1975
Hourly maximum
6/75-4/76
1971-77
Average
a Minnesota Pollution Control Agency (1978).
b Glass, G. E., L.
unpublished data
J. Heinis , L. Anderson, C
(1979).
. Sandberg, and
F. Boettcher,
c Ontario Hydro (1976).

d Schindler, D. W., unpublished data, ELA  Research  Station (1978).
                                          15

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located 17 km SSW of  the  generating  station  site  near  the  Quetico boundary,
is the most remote site from  the  Steep  Rock  mines  and  will be  briefly
reviewed (see Table 1).   The  total deposition  of  sulfate measured at two
sites was 4 and 7 kg/ha-yr.

     The minimum detectable SC>2 level of  10  ppb was  observed  for short
times on 25 different days, and the  levels never  exceeded  25 ppb (50 yg/m^)
during the 10-month period reported.  Ozone  levels reached maximum levels of
0.100 ppm on 2 consecutive days during  July  1975  and were  generally similar
to those at the Fernberg  site.  When the  ozone was high, the sulfur dioxide
was usually not above threshold level of  the instrument.   The  NOX levels
typically averaged 5  ppb  during June and  10  ppb during July, August,  and
September.  On occasion the concentration reached  an hourly value of 0.100
ppm; however, these high  values did  not correspond to  either high 03 or
high S02 levels.  It  appears  that the S02 is due  primarily to  local
mining activities, and that the 0^ levels are  due  to  long-distance
transport.  The elevated  NOX  levels  may be due to  local  sources.

     Measurements of  bulk deposition of sulfate,  wet-plus-dry  fall, have been
carried out at three  locations in the vicinity of  the  BWCA (Table 1).  The
longest record, at the Experimental Lakes Area (ELA)  lakes 180 km northwest
of Atikokan, shows an average recent sulfate deposition  of 10.9 kg/ha-yr.
The average pH of the rainfall here  during 1974-77 is  4.86.  The
presettlement pH for  rainfall in  this area appears to  have been 5.7 (cf.
carbonic acid equilibrium and data for  1955-56 shown by  Galloway and Cowling
(1978).  Data from the ELA show that 70%  of  the nitrate  and sulfate in the
current rainfall is in a  neutralized form.   Thirty percent is  in the acid
form, and the H+ ions were assumed to divide between SO^ and N03 on
a 2:1 ratio.  This information yields an  estimate  of 7.6 kg/ha-yr of
neutralized sulfate and 3.1 kg/ha-yr of acid sulfate producing the net
depression in pH.  Thus,  depending on the historic potential of atmospheric
constituents to neutralize anthropogenic  acid, presettlement  loadings of
sulfate must lie between  0 and 7.6 kg/ha-yr.  For  purposes of  further
comparison a value of 4 kg/ha-yr  will be  used.

ATIKOKAN EMISSIONS

     The proposed Atikokan generating station  consists of  four 200-MW units
burning sub-bituminous or lignite coal  from  Saskatchewan with  a sulfur
content not to exceed 0.8% and a  maximum  ash content of  12%  .
Electrostatic precipitators for fly  ash removal are  to be  employed.  The
potential emissions were  calculated  with  the assumption  of an  overall thermal
efficiency of 36% and a full  load (Table  2).   The  emission factors were
obtained as follows.  For sulfur  dioxide  38S is the  current EPA handbook
(EPA-AP-42) value for pulverized  coal boilers.  The  sulfate emission factor
of 1.2 corresponds to the assumption that 2% of the  sulfur is  emitted
directly as sulfate.  Mercury is  assumed  to  go entirely  up the stack
(Billings et al. 1973).   The  nitrogen oxide  emission  factor  is based on the
  Fry, R.J. (Manager of Air Pollution  and Environmental  Contaminants
     Division, Environmental Protection  Service,  Ontario).   Letter I.M.
     Goklany, U.S. Environ. Prot. Agency, Region  V,  Chicago,  Oct.  14,  1977.

                                     16

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                  TABLE  2.  ATIKOKAN  POWER  PLANT  EMISSIONS3
            Item
High
Low
Heating value (BTU/lb)
Sulfur content (% weight)
Ash content (% weight)
Mercury content (% weight)
Sulfur dioxide emission factor (Ib/ton)
Sulfate emission factor (Ib/ton)
Total particulate emission factor0 (Ib/ton)
Mercury emission factor (Ib/ton)
Coal rate (full load) (tons/h)
Sulfur dioxide emissions (g/s)
Sulfur dioxide emissions (tons/yr)
Sulfate emissions (g/s)
Sulfate emissions (tons/yr)
Total particulate emissions (g/s)
Total particulate emissions (tons/yr)
Mercury emissions (g/s)
Mercury emissions (tons/yr)
NOX emission factor (lb/lb6 BTU)
NOX emissions (g/s)
NOX emissions (tons/yr)
7,500
0.8
12.0
2 x 10~5
38 Sb
1.2S
0.085A
20Hg
583
2,230
77,500
67
2,325
75
2,600
0.029
1.01
1.2
1,323
45,900
6,500
0.4
6.5
2 x 10~5
38S
1.2S
0.085A
20Hg
506
969
33,700
29
1,010
35
1,226
0.025
0.89
1.2
955
34,500

a If 36% thermal efficient and a  full  load  at 800-MW  are  assumed,  the  heat
  input rate is 7.59 x 109 BTU/h.

b S, A, and Hg are percentage by  weight, e.g.,  S =  0.8.

c Assuming 99.5% removal  in precipitator.
                                     17

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current U.S. emission  standard, which  reflects  current  boiler technology.
There are to be four stacks each  198 m high with  a 3.8-m exit diameter.  The
stack gas-flow rate  is 288 m^/s and  the  exhaust temperature is 408°K.
Representative coal  analysis  is given  in Appendix C.

     In addition,  the  Steep Rock  Iron  Mines at  Atikokan currently emit an
estimated 14-27,000 metric tons/yr (15-30,000  tons/yr)  sulfur dioxide and
10-18,000 metric tons/yr  (10-20,000  tons/yr) particulates.   The Caland Ore
Company at Atikokan emits an  estimated 254 metric tons/yr (280 tons/yr)
sulfur dioxide and 1,490  tons/year particulates.   Only  the  main stack of the
Steep Rock Iron Mine facility, which is  91 m high,  will possibly influence
the BWCA directly, since  the  other stacks  are  short.  These emission sources
are reportedly being closed in the near  future  and hence are not considered
in this modeling effort.

ATMOSPHERIC DISPERSION, TRANSFORMATION,  AND DEPOSITION

     A realistic air-quality  model to  meet the  objective of this study must
consider a number  of physical and chemical processes.   Consider a parcel of
air emitted from a tall stack.  The  advection  caused by the wind diffuses
laterally and vertically  at a rate that  depends on the  amount of turbulence
in the air.  The turbulence depends  on the wind speed and net heat flux.  The
vertical spread is constrained by an inversion  layer which  moves up or down
depending on the net heat flux and overall pressure patterns in the
atmosphere.  If the  inversion is  low,  the  plume will rise above the
inversion, and pollutants will not reach the ground unless  there is
precipitation.  The wind  speed, wind direction, and heat flux are continually
changing as the parcel of air is dispersing within the  region, and hence a
time-dependent model is more  appropriate than  a steady-state model.

     Certain pollutants within the plume can undergo chemical reaction as
they are being transported, such  as  the  conversion of  sulfur dioxide into
sulfate aerosol.   The  reaction rate  depends on  the concentration of the
reacting species as  well  as other species  in the  air and on the intensity of
the sunlight.  As  part of the parcel diffuses  to  the ground, it is partially
removed by dry deposition at  the  surface depending on  the type of surface and
type of pollutant.  When  precipitation occurs,  pollutants are scavenged at a
rate related to the  amount and type  of precipitation.   The  precipitation,
which is usually more  acidic  because of  the pollutants, is  deposited on the
ground.

     Plume modeling  is often  done with a so-called Gaussian plume model, such
as the EPA CRSTER  (Guldberg 1977) model.   Since this type of model is not
time dependent and does not include  pollutant  transformation, or wet and dry
deposition processes,  the Gaussian plume models are more appropriate to
smaller regions.   For  a study such as  this a grid-type  model based on
numerical solution of  the general, time-dependent diffusion equation is more
appropriate because  the meteorological,  chemical, and  deposition processes
can be more realistically simulated.

     Before describing the modeling  work,  a general discussion of chemical
reactions in the plume and dry deposition  processes is  presented.

                                     18

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Plume Chemistry

     The  primary  gases  emitted from the stack of a power-plant plume are
nitrogen, carbon  dioxide,  and  water vapor.   The release of these gases from
the regional  sources  will  not  have a direct known effect on the BWCA.  Carbon
monoxide  and  low  molecular weight  hydrocarbon emissions are considered to be
small and thus will not  be considered.   Sulfur oxides, nitrogen oxides, total
particulate matter, halogens,  and  mercury will be discussed below.

     Most of  the  sulfur  in the combustion chamber is oxidized to SC^ although
a small percentage  is oxidized to  803 in the combustion chamber and reacts
with water vapor  in the  stack  to form sulfuric acid.  Approximately 2% of the
sulfur  is in  sulfate  form  in the plume  close to the stack (Forrest and Newman
1977a,  b) .  There is  general agreement  that SC>2 continues to react in the
plume and form sulfate  aerosol as  the plume diffuses (Gillani et al.  1978,
Schwartz  and  Newman 1978).  Recent studies  by Husar et al. (1978) found that
during  noon hours the S02  conversion rate was 1-4% per hour, whereas at night
the conversion rate was  below  0.5% per  hour in the Labadie plume, which is from
a 2,400-MW coal-fired power plant  near  St.  Louis.  The sulfate aerosol which  is
formed  is primarily in  the light-scattering size range (0.1-1 ym) so that
visibility is reduced by sulfate formation.  The mechanism for sulfate
conversion can be photochemical or heterogeneous reactions in combination with
particulate matter  in the  plume.  Although  theories exist for rapid conversion
of SC>2  to sulfates  in the  plume, the exact  mechanisms have not been
established.

     Nitrogen oxide (NO)  is formed in the combustion chamber from nitrogen in
the supply air and nitrogen bound  in the coal.  Nitrogen oxide is generally
converted to  nitrogen dioxide  (N02) in  the  plume as ambient ozone
diffuses  into the plume.

      The NO/N02  ratio  in  a plume  is difficult to model, and hence it is
customary to  model NOX,  which  is NO plus N02 weighted as N02.

     Particulate  matter  in the form of  fly  ash is emitted from the stack in
mostly  submicron  size.   The fly ash serves  as condensation nuclei for aerosol
formation.  The particulate matter can  also serve as a catalyst for sulfur
dioxide reactions.  In  our modeling work we assume that the particulate
matter  represents the fly  ash  only; the sulfate aerosol is modeled separately.

     Mercury  in coal  is  believed to be  vaporized in the combustion chamber
and emitted as a  vapor.  It is possible that part of the mercury may condense
on the  fly ash as the plume cools.  For modeling purposes, however, mercury
should be considered  in  the vapor  phase.  Coal also contains trace amounts of
chlorine, fluorine, and  bromine, which  can  form the acids HCl, HF, and HBr and
particulates  containing  these  elements.   These components were not considered
in detail because of  lack  of information concerning their environmental
behavior.
                                      19

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Dry Deposition

     Dry deposition of  gases  occurs  by  absorption and  adsorption on
vegetation, soil, and surface water.  Dry  deposition  of particulates occurs
by impaction onto the surface material.  The  dry deposition flux of any
species can be determined by multiplying the  concentration of that species
near the ground by the  effective  deposition velocity.   The deposition
velocities have been determined experimentally  and have been shown to depend
on the rate of diffusion and  the  characteristics of the underlying surface.
Frequently a deposition resistance  is used, which is  the inverse of the
deposition velocity.  The total resistance is the sum of the aerodynamic
resistance and the surface resistance.

     Calculation of the aerodynamic  resistance  will be discussed later.  For
S02 the surface resistance of tall  forest  lands,  which is  the majority of
the surface in the BWCA during summer,  is  generally agreed to be about
0.5 s/cm (Chamberlain 1966, Shepherd  1974).   The surface resistance of snow
to SC>2 is about 3 s/cm  (Whelpdale and Shaw 1974,  Dovland and Eliassen 1976).
Also, the atmosphere tends to be more stable  over snow,  and hence the
deposition velocity of  SC>2 to snow  is considerably lower than to summer
vegetation.

     The dry deposition velocity  of  particles is strongly  dependent on
particle size.  Most of the sulfate mass lies in the  0.1-  to 1-ym-diameter
range for which the deposition velocity  is not  expected to exceed 0.1 cm/s
(Anon. 1978).  Hence we have used a  surface resistance of  5 s/cm for both
winter and summer for sulfate aerosol.  Fly ash emitted from the stack is
also predominantly in this size range,  and hence a deposition velocity of 0.1
cm/s has been used.

Wet Deposition

     The concentration  of sulfate in  precipitation is  a consequence of
several cumulative processes occurring within and beneath  the clouds.
Brownian motion, phoretic attachment, inertial  impaction,  and nucleation all
serve to remove the sulfate aerosol  from the  air and  attach it to the cloud
and precipitation elements.  However,_Brownian  and phoretic attachment
mechanisms cannot place sufficient  SO^ mass into the  cloud water to
account for observed concentrations,  and inertial impaction of subcloud
sulfate is of second-order importance when compared to other removal
mechanisms (Scott and   Laulainen  1979).

     Since sulfate particles  are  generally soluble and are quite small, and
the majority of mass is distributed  over particles with diameters less than
1.0 pm (Harrison et al. 1976), they  should be effective as cloud condensation
nuclei.  Indeed, if as Weiss et al.  (1977) claim, the  major portion of the
aerosol with diameters  between 0.1  and  1.0 pm is sulfate,  then the airborne
sulfate aerosol could be responsible  for nearly all of the cloud droplets
appearing in continental clouds.

     Sulfate may be generated within  the cloud  and precipitation water
through the oxidation of absorbed SC>2 •  The oxidation  processes appear to

                                      20

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be temperature  dependent  and  often appear to rely on the presence of metal
catalysts.  Laboratory  and  theoretical  work also suggests that oxidants such
as 02> O-j,  and  ^02  are  capable of producing substantial quantities
of sulfate  in cloud  water  (see  e.g.,  Levy et al. 1976 for an extensive
literature  survey).

     Both the oxygen and  ozone  transformation mechanisms are pH dependent and
begin to decrease  substantially in importance as the pH decreases to less
than 6 for  G£ reactions  and 4.5 for 63  reactions.  The hydrogen peroxide
mechanism is relatively  insensitive to  acidity,  but few measurements of
tropospheric ^2^2  exist  to  determine the contribution to S0£ by this
oxidant.  Ammonia  can also  play an important role in aqueous phase S02
oxidation by neutralizing  some  of the ^SO^ that is formed and reducing the
acidity.  However, recent  solubility measurements by Drewes and Hales (1979)
imply that  oxidation mechanisms based upon the presence of ammonia proceed more
slowly than previously  thought.

     Fortunately some evidence  is beginning to accumulate suggesting that it
is not necessary to  consider  in-cloud conversion of SC>2 to SO^ in order
to predict  the  sulfate  concentration in precipitation.  Recent observations
by Scott and Laulainen  (1979),  and modeling efforts by Scott (1978) have
suggested that  for certain  precipitation events, the sulfate concentration in
precipitation is determined largely by  the sulfate concentration in the air
flowing into the storm  system.   Scott suggests that the sulfate concentration
in precipitation is  inversely proportional to the precipitation rate and
strongly dependent upon  the type  of storm system producing the precipitation.

     The removal of  soluble,  submicron, pollutant aerosol from clouds appears
to be accomplished primarily  by large collector  particles,  such as snowflakes
or raindrops, sweeping  downward through the cloud and capturing the small
cloud droplets  containing high  concentrations of the aerosol.  The final
concentration in the precipitation reaching the  ground is dependent upon two
features; first, the initial  concentration in the collector particles as they
start their descent  through the region  of the cloud where accretion of cloud
droplets is the primary growth  mechanism,  and secondly,  the concentration of
pollutant in the cloud  water  accreted by the collector particles.

     The solubility  of  sulfate  particles makes them extremely effective as
cloud condensation nuclei.  The sulfate concentration in the collected cloud
droplets depends upon the amount  of cloud water  condensed about each
activated sulfate  particle  which,  in turn, depends upon the number of
available aerosol, their size,  and the  intensity of the updraft velocity
within the  cloud.

     The model  of  sulfate removal  by Scott (1978),  considers the three basic
precipitation systems illustrated  in  Figure 2.   In the first case (Figure
2a),  the Bergeron  or  ice growth  process is primarily responsible for
precipitation development.  Ice  crystals nucleate in the upper portions of
the cloud,   grow rapidly  to  precipitation sized particles, aggregate with each
other, and  accrete tiny cloud droplets.   Even if melting should occur before
the ice particles  reach cloud base,  the hydrometeors are large enough so that
accretion of small cloud droplets  continues to be the primary growth

                                      21

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             la) BERGERON CLOUD
       IE
       o
            2 -•
            0 -L
                                           	0UC
                     7

                     POO
                           /«   o  ?••.••£
                               v
              (b) WARM OR MARITIME CLOUD
                              —V"
                              *
       x
       o
#**•-  o°09o
                        , trajectory
    of air flowing into the storm (solid lines);  — ->, motion
    of hydrometeors relative to the storm (dashed lines).  The
    vertical scale represents typical cloud depths.
                               22

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mechanism*.  The  sulfate  incorporated into the precipitation is assumed to be
predominantly  that  advected  through the cloud base.  This first case
represents  a situation  where the collector particle (snow) is relatively
pollutant free when it  begins  to accumulate liquid water.  The ice nucleation
is  in an environment  subsaturated with respect to water and upon nuclei with
lattice structures  similar  to  ice,  such as silicas and clays (McDonald 1964).
Sulfate aerosol are not activated as cloud condensation nuclei in the upper
portions of the cloud and are  not initially incorporated into the hydrometeor
water.  Sulfate pickup  comes primarily through incorporation of the dirty
cloud water in the  lower  portions of the cloud.  Surface precipitation from
this type of cloud  may  be  snow or rain.

     The Bergeron or  cold cloud is  felt to be responsible for the majority of
precipitation  falling from  layer-type clouds over the continents (Mason
1971).  The precipitation  from continuous rain or snow storms over northern
Minnesota almost  certainly  relies upon a Bergeron process for its
development.

     In the second  situation (Figure 2b) the ice-growth process is assumed to
be  ineffective in initiating precipitation.  Rain develops entirely through
warm phase mechanisms.  Gentle uplift (0.1-0.5 m/s) is implied, and long
times are available for precipitation-sized drops to develop by condensation
and coalescence.  A major fraction  of the moisture and pollutants is assumed
to be transported through the  sides of the storm.  For this second case,
sulfate aerosol flowing into the storm at the higher levels are activated in
environs saturated  with respect to  water.  The collector particles therefore
have an initial sulfate concentration when they begin their descent through
the lower portions  of the cloud.  Net sulfate pickup is equal to the sum of
the sulfate material  activated in the collector particles at their formation
altitude and the  sulfate  accumulated by accretion of the dirty cloud droplets
near cloud base.  Thus, this warm cloud is capable of removing more sulfate
than the cold  cloud.

     The third case (Figure  2c) considers precipitation development in
convective storms.  Here  strong updrafts produce large supersaturations and
large liquid water  contents  which enable combined condensation and
coalescence to produce  precipitation-sized drops faster than they can be
removed by hydrometeors falling from above.  The mass flux of moisture and
pollutants  is  assumed to be  largely through the cloud base.  In the
convective cloud  both the ice-capture mechanism of the cold cloud and the
condensation,  coalescence growth of the warm cloud are effective in removing
sulfate from the  atmosphere.   The removal potential exceeds that of either
the individual warm or  cold  clouds  primarily because those droplets that grow
into collector particles have  grown by coalescence in the lower portions of
the cloud where the cloud water contains high concentrations of sulfate.
Showery, summertime precipitation in Minnesota should exhibit removal
characteristics of  the  convective cloud; that is,  extremely high concen-
trations of sulfate should be  associated with convective showers affecting a
small (approximately 1-10% of  the total area) area at any one time.

* Hydrometeors refer to ice  or water particles large enough to fall from the
  cloud to the land surface

                                      23

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     These qualitative  results  can  be  expressed  explicitly in terms of a
washout ratio, E, defined as  the  ratio  of  sulfate  concentration in the
precipitation water  (gsulfate/8water)  C°  the  sulfate  concentration
in air below the cloud  base  (ggulfate^air^ '   Fi§ure  3  (from Scott
and Laulainen 1979)  illustrates the predicted  variation in washout ratio as a
function of precipitation rate, J,  for  the  cold  cloud (curve 3),  the warm
cloud (curve 2), and the convective cloud  (curve  1).  For  a fixed concen-
tration of airborne  sulfate  and for a  given precipitation  rate, Figure 3
predicts the lowest  sulfate  concentrations  in  precipitation originating as
snow.  Factor 2 and  3 increases are predicted  when precipitation  develops by
warm phase mechanisms in stratiform clouds.  The  greatest  sulfate concen-
trations are predicted  to occur in  precipitation  from convective  clouds.  The
convective and warm  cloud mechanisms would be  most prevalent during the
summer months whereas the ice-growth mechanism would  naturally occur during
the winter.

     If the precipitation is  in the form  of snow  or originated as snow in the
upper portions of the clouds  (curve 3), then the  surface sulfate  concen-
tration in precipitation is  roughly proportional  to J".3  over the
interval from J = 0.2 to 2.0 mm h~^.   If  the precipitation-sized  drops
develop independently of an  ice stage,  then the  surface sulfate concentration
becomes more strongly dependent upon rainfall  rate and  upon the airborne
sulfate concentration at the  inflow levels of  the  storm.   If the  precip-
itation forms without the benefit of an initial  ice-growth stage, then for
light precipitation  rates (j-0.2 mm h~^)  the sulfate  concentrations in
precipitation water  can increase by a  factor of  70 or more over the ice-
dependent predictions.  At more moderate  precipitation  rates (J<1 mm h~l)
the precipitation originating as  snow  is  predicted to have about  one-third to
one-half the sulfate concentration  of  that originating  on  water droplets.  At
heavy precipitation  rates (j>7 mm h~^), the sulfate concentration is
nearly independent of the precipitation-formation  mechanisms.

     The curve of Figure 4 provides a  clue that might help to  explain natural
seasonal variations  in  sulfate concentration detected in the northeast United
States.  Figure 4 illustrates the variability  observed  in  the  Multistate
Atmospheric Power Production Pollution  Study (MAP3S 1977)  precipitation
chemistry network.  Although  the  scatter  is considerable in these
precipitation-chemistry data, there seems  to be a  definite decline in winter
concentrations of sulfate followed  by  an  increase  during the warmer seasons.
High concentrations  in  the summer may  be  related  to removal by convective
storms, whereas winter-time  removal of  sulfate is  probably associated with
cold rain and snowstorms.  Similar  seasonal variations  in  sulfate removal are
also expected in northern Minnesota.

     In summary, both experimental  and  theoretical data are beginning to
accumulate that suggest that  sulfate deposition  is seasonally  dependent and
related to such features as  storm type, precipitation rate, and concentration
of pollutant being drawn into the storms.  Of  the  three storm  situations
discussed above, the sulfate  concentration  in  the  precipitation falling on
the BWCA should be best predicted by using the cold cloud  model,  except for
situations when the  precipitation is clearly from convective clouds.
                                     24

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                                     CL

                                     O
                                o
                                o
                                o'
                           CVJ
                             CD
25

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     The BWCA  faces  an  additional impact due to the washout of S02> which
once in the  surface  waters  is  likely to convert to SO^.  This conversion of
S02 in surface waters may or may not present problems for the environment,
depending upon its concentration and acidity.

DESCRIPTION  OF THE THREE-DIMENSIONAL DISPERSION MODEL

     The model may be characterized  as a grid-type model of atmospheric
dispersion which  numerically integrates the species continuity equation.
Chemical reaction between two  species, horizontal advection, vertical
diffusion, and wet and  dry  deposition processes are simulated.  The model
computes temporal and three-dimensional spatial concentration distributions
due to single  or  multiple point  and  area sources.  A fully  implicit finite
difference scheme is utilized  so that numerical errors are minimal.  A single
station is used  to characterize  the  meteorological conditions throughout the
grid.  Three-h,  24-h, and annual average concentrations and deposition fluxes  are
computed.

     The model formulation,  the  numerical solution procedure, and the
meteorological data  used  are described in the remainder of this section.
The modeling scheme  and treatment of meterological parameters follows that
reported by  Ragland  (1973),  and  Ragland and Dennis (1975).

Model Formulation

     Consider  first  a two-component  mixture undergoing a first-order chemical
reaction.  The pollutant  species are affected by advection of the wind,
diffusion in the  lateral  and vertical direction, and removal by dry and wet
deposition.  The  wind speed  and  diffusivity vary with height, surface
roughness, and net heat flux (Figure 5).  The plume is trapped by an elevated
inversion layer.
     If we align  the x-axes  with the wind vector and use the fact that the
diffusion term in the x-direction is small compared to transport by the wind,
then the set of equations to be  solved for two species C and S is:

             —   + u — - K —- - — (K  |-C) * -kC - W  + Q     (1)
             >\ 4-      ^-v   NT ^-\rZ   % v   v % v           r    r*
             o L      o-*t    y o y     o z   & o£           *-    *—

             —   + u — - K -^ - — (K  ~) - kC ms - W  + Q   (2)
             at    u 3x    y ayz   3z ^ z 3z'      w~    s   xs

at z = 0                       ^  |C =                           (3)
                                 z 3z     DC

                               v  -§Ji -  v  r
                               K  ^   - ~vnc,i>
                                 z 3z     DS
                                      k
for the reaction                    ^ •> S.                        (5)

The upper boundary condition is  zero species flux into the inversion layer at
z=zm.   For example,  C represents the concentration of sulfur dioxide and S
represents the concentration of  sulfate aerosol.  If,  for example, mercury is
to be simulated,  C represents  mercury and S is zero.  Equation (5) defines

                                      27

-------
                 Heat Flux
                       V
              Inversion Layer
            Diffusity
                            Chemical Rxn.
                                    so;
                           T   Wet   T
                            Deposition
Surface  Roughness
                         Dry Deposition
    Figure 5.  Schematic diagram of the parameters

          used in the grid model.
                      28

-------
the rate constant, k.  The  letter  W is  the  wet  deposition removal rate per
unit volume, Q is the mass  flow rate of emissions,  Vp is the dry deposition
velocity, and m is the molecular weight.

     The wind speed  (u) and  vertical eddy diffusivity (Kz)  are calculated
as a function of height (z)  within the  surface  layer which  extends up to
ZSL and  from the top of the  surface layer to the inversion  layer zm.
According to the scheme outlined in Table 3 the parameter L is defined as
                                    -u  pel
                                    0.16 u
and                       ..	£
                                          - 1.8

     It should be noted  that  the  geostrophic  wind (Vfe)>  the net heat flux
(H), and the surface  roughness  (ZQ)  are required inputs.  Since only the
surface wind at  10 m  is  available hourly,  the program internally computes the
geostrophic wind.

     The net heat flux  is  obtained from data  for cloud cover and cloud ceiling
height by first  computing  a radiation  index according to the scheme used for
STAR data (Turner 1964).   The radiation index is then converted by the
following procedure:
 Radiation Index         43210       -1       -2
           - min)      0.24    0.18    0.12   0.06    0     -0.03    -0.06
     The lateral diffusivity  is  an  important  parameter that is not well-
known for the time and distance  scales  of  this  study.   The available data
have led us to the assumption  that  Ky = 100 KZ .   This  accounts for gusts
that veer and back and also accounts for a certain amount of wind vector shift
with height due to the Coriolis  force.

     Changes in the wind direction  from hour  to  hour are handled by a
coordinate rotation transformation.  In this  way any arbitrary wind direction
can be simulated.

     The deposition velocities (Vp) that appear  in Eq. (3) and (4) depend
on an aerodynamic resistance  (ra). and a surface  resistance (rg),

                               V = - 1 --                  (8)
                                D
                                       ra  +  rs
The aerodynamic resistance  is  represented  by
                                  ra =  "(1)   .                      (9)
                                       29

-------
TABLE 3.  WIND AND DIFFUSIVITY PROFILES


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Vertical Wind speed
Stability distance u
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Neutral 0
-------
and hence may change hourly.  The  surface  resistance  depends  on the
particular pollutant and  surface such  as snow,  water,  vegetation,  etc.

     The reaction rate  constant  (k)  can also  vary  hourly and  is a  function of
the solar radiation index and other  pollutants  present in the plume.   In very
clean air, such as is typical of the BWCA,  the  conversion rate constant is
smaller than in urban air.  Following  the  work  of  Husar  et  al. (1978)  we have
used 2% per hour during  the day  time and 0.5% at night.

     The wet deposition  removal rate is calculated according  to the
procedures outlined in  Appendix A.   By using  Eq. (A-22)  we  have

                    Wc(rain) = 0.96  3  C J0'9,                        (10)

           Wc(snow) = 0.48 B C J0-9  (l-exp(-2m)),

and             Ws(rain  or snow) = 0.44 S  J0'625.                     (12)

The symbols C and S are  the average  sulfur  dioxide and sulfate
concentrations (pg/m-5)  and J is  the  rate of precipitation (water equivalent)  in
millimeters per hour.  From Eq. (A-15) m is given  by

                               m = 1.56 +  0.44  In  J.                  (13)

The parameter 3 depends  on the pH of the rain according  to  Figure  A-2,  which
for this study has been  simplified to  the  following equation:

                     Iog10  B = -2 + 0.75  (pH-3.9)                    (14)

for pH less than 5.1; otherwise 3 =  0.067.

     As explained in Appendix A,

                         pH = -log 10(2,000 Sw/96),                   (15)

where Sy is the sulfate  concentration  in the  cloud drops from Eq.  (A-10):

                              Sw = 0.45 S  J~°-27.                     (16)

The wet deposition fluxes are determined by multiplying  Eqs.  (10),  (11),  and
(12) by the height of the layer being  scavenged, which is given by  Eq.  (A-9).
For this study we have used a height of 2,000 m as  an  approximation to  Eq.
(A-9).

Numerical Solution of the Plume Model

     The solution of the diffusion equation with the various  terms  as
described above can only be accomplished by numerical  techniques.   Equation
(1) with boundary and initial conditions is solved  numerically by means  of  a
first-order fully implicit finite difference  technique.   This  method  is
numerically stable for any step size.  Consider a  volume of fluid with  sides
Ax> Ay» AZ located at a point i+1,  j,  k.  Properties at  the point  i,  j, k  at

                                       31

-------
the time t are known, but  in  the  i+1  plane at  time t and the i plane at the
time t + At are unknown.   Conservation  of  mass for a particular species in
an element of fluid not  adjacent  to  a boundary may be written as:
       ukc'i+i,j,k(dydz)
       (Ky)k(C'i+1J)k-C'i+ljj_1)k)(dxdZ/dy)
     = c        (dxdydz/dt)  +  UkC'.     (dydz)  + Qc                  (17)
        11-1 jj » K                  i > J > K
     Here C' denotes  the unknown  concentration at  time t + At, and C denotes
the known concentration at  time t.   At  a boundary  one or more terms on the
left hand side is zero.  A  similar  equation is written for each cell of fluid
in the i+1 plane, and  the set  of  equations  is  solved simultaneously stepping
forward along x and then stepping through t.   A similar equation is written
for species S from Eq. (2)  and  solved  along with Eq. (1).  The source
emission rate Qc is added in only one  cell  at  the  point of effective
release .

     For an individual step it  is seen  that Eq. (17) can be written as

       [A]  [C] x + AXj t or x> t + At  = u  [C] Xjt>

where  [A]  is determined as a  dispersion matrix (NUMY'NUMZ)^
            large containing only known meteorological parameters and
            step size, and

       [C]  is the concentration  vector NUMY times NUMZ long.  The right-
            hand side  contains  only known terms, and NUMY and NUMZ are
            the number of cells in the  cross-wind  and vertical directions,
            respectively.

     The set of equations (18)  is solved by factoring A such that A = LL  ,
where L is a lower triangular matrix and L" is the transpose of L.  This
may be readily done since A is  a  positive-definite,  symmetric band matrix.
The solution of the system  of  linear equations is  determined by lettering Y
L™C and computing Y by back substitution in the equations LY = D.  When Y =
is known, C may be determined  by  back  substitution in L^C = Y.

     Changes in wind  direction  were handled by means of a rotation of the
coordinate axes.  Hence two grid  systems are used:  a rotating grid in which
                                       32

-------
 the  computations  are  done  and a fixed system in which the results are stored.
 The  x and y  coordinates  of  a  grid  point  are transformed as follows:
                     XF  =  Xr cos  (6)  - Yr sin

                     YF  =  Xr sin  (6)  + Yr cos (9)

where 0 is  the  wind  direction.

     A major  difficulty in the procedure is that  the grid rectangles don't
overlap in  a  uniform way,  so the question arises  of how to apportion the
concentrations  for one  grid to  the grids for the  other system.  This difficulty
was overcome  by  subdividing a grid into  a number  of smaller grids and assigning
to each small grid the  concentration of  the larger divided by the number of
subgrids.   The  subdivision can be as fine as desired,  but more subgrids means
greater computing  time  and cost.  In this model there  are nine subgrids.  The
final concentration  is  the sum of all the smaller grids of the rotation system
which overlap it.  The  concentrations originally  calculated in the rotating
system have now  been stored in the fixed system,  so we can rotate the grid to
the new wind  direction.   Then we simply  reverse the process and subdivide the
grids in  the  fixed system,  use the above f ixed-to-rotating equations to
transform the coordinates,  arrive at the "already present" concentrations in
each larger grid in  the rotating system, and begin the model's numerical
calculations  for the next hour.   This procedure of going back and forth between
the rotating  and fixed  grid systems  for  wind-direction changes continues for as
long as there is a continuous set of meteorological data.  The errors created
by the coordinate transformation are generally less than 5%.

     For  the  model runs reported here a  box system of  13 x 17 x 6 high was
used with AX, AY = 9,655  m (6 mi)  and AZ = 50 m for the lower three boxes and
AZ = (ZM-150)/3  for  the upper three  boxes, where  ZM is the height of the
inversion layer.  The time step  used in  the model's numerical scheme was 10
min.  The meteorological  input,  as previously noted, varies every hour.  The
model can therefore  simulate on  a continuous basis and is limited only by
computer  core space  and time.

     The  required computer  core  space for a single non-reacting species was
28 K and  for  the S02/S0^  reacting species was 40  K. The computing time
per hour  of simulated time  was approximately 9.7  s for a single species and
20.1 s for  S02/S04.  The  computer used was a UNIVAC 1110, and the code for
the model is  on  file at the Madison  Academic Computing Center.

     The  parameters  in  the  model,  which  are dependent  on the  type of pollutant
to be simulated, are summarized  in Table 4,  and the values that we have used
are shown.

Meteorological Data  Used  in the  Model

     International Falls,  Minn.,  was selected as  the site for the meteoro-
logical data.  It is reasonably  close to the BWCA and  is the  nearest site with
a consistent  set of  surface and  upper air data.  International Falls is
considered  to be representative  of the BWCA.

                                       33

-------
             TABLE 4.  MODEL PARAMETERS THAT ARE  SPECIES  DEPENDENT
  Parameter
S02
          Fly ash
          Hg
Chemical reaction
 rate (%/h)

Dry deposition
 surface resistance
 (summer s/cm
 (winter s/cm)

Wet deposition
 coefficient
 (%/h)
0.5 (nighttime)
2.0 (daytime)
0.5
3.0
5.0
5.0
5.0
5.0
                         36
a
a
                        0.5
a For Hg a dry deposition velocity of 0.001 m/s was  used  rather  than
  specifying the surface resistance, which is not known.

k The washout of S02 and SO^ was handled  in a more  complex  manner  than
  the fly ash and mercury.  See text for a detailed  description  of  the
  precipitation washout formulation.
                                      34

-------
     The year 1964 was  chosen  for  the  model  runs because this was the last
year when hourly surface data  were  recorded.   After 1964 the surface data are
available only every 3  h.  The total  precipitation was about 10% greater than
average during 1964.  Upper  air  data,  which  are taken twice daily, are used to
obtain the height of the inversion  layer.  Hourly values of the inversion
height were obtained from  a  National  Climatic  Center data tape.  All other
necessary data are generated from  the  surface  observation data tape.

     The cloud cover, cloud  ceiling height,  day of the year, and time of day
are used to calculate a radiation  index,  which is used to define the net heat
flux, H, as indicated earlier.  The wind  speed at the inversion height, Ug,
is calculated from the  wind  speed  at  10 m.   In summary,  the following
meteorological data are needed as  input to  the model:

     1)  Surface wind speed
     2)  Surface wind direction
     3)  Net heat flux
     4)  Surface air temperature
     5)  Height of the  inversion
     6)  Precipitation  type  and  amount

     The Atikokan generating station  subtends  an arc of about 90° across the
BWCA.  The model was run for those  periods when the wind persisted from the
NW to NE direction for  at  least  6 h.   A duration of 6 h or more implies that
the plume will be over  the BWCA  for 3  h or more.  Forty-nine  different
periods covering 901 h, or 10.3% of the year 1964, met this criterion and
hence were used.  Only  winds from  the  NW  to  NE were considered to reduce the
amount of computing time without seriously  influencing the results in the
BWCA.

     The total precipitation during the year was 68 cm (26.63 in.) of water,
and with winds from NE-NW  sector the  total precipitation was 4.9 cm (1.92
in.) or 7.2%.  The total rain  for  the  region was 55.8 cm (21.96 in.) of
water, and the total snow was  11.9  cm  (4.67  in.) of water.  With the winds out
of the NE-NW sector, total rain  was 3.1 cm  (1.22 in.) of water or 5.5%, and
the total snow was 2.0  cm  (0.77  in.)  of water  or 16.4%.

     Although the model is run from hourly  data, it is instructive to consider
some seasonal and annual average meterological data from International Falls
(Table 5).  The wind is northerly 20%  of  the time, the annual mean wind
through the mixed layer is 7.2 m/s, the annual nighttime inversion height is
400 m, and the annual daytime  inversion height is 1,300 m.  Frequently at
night and also sometimes during  the day in winter the plume rise from a tall
stack such as Atikokan  is  in or  above  the  inversion layer and hence isolated
from the ground.

PLUME MODEL RESULTS FOR ATIKOKAN

     The model was run  for every hour  in  the year when the wind was from the
NW to NE sector causing the  Atikokan  plume to  flow over the BWCA.  Three
separate runs were made: one for sulfur dioxide and sulfates, one for
particulate matter, and one  for  mercury.  Ambient air concentrations, dry
deposition fluxes, and  wet deposition  fluxes for each cell in the region and
for each hour were computed  and  stored on tape.  Annual,  seasonal, 24-h, and
                                      35

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3-h average ground-level concentrations  were  obtained,  and frequency
distributions of 1-h, 3-h, and  24-h  averages  were  tabulated by means of a
separate tape-processor program.   The  seasonal  and annual wet and dry
deposition fluxes were obtained.   The  total mass of the particular pollutant
that is transported  out of the  region  by the  wind  during the year was also
computed.

     The ambient air concentrations  and  deposition fluxes were computed for
each grid point indicated in Figure  1.   Since only winds from the NW to NE
were used, it is appropriate to  consider a traverse across the region in the
N-S direction starting with the  grid containing the source at Atikokan.
Figures 6-10 present the model  output  as a function of  distance due south of
Atikokan for sulfur  dioxide, sulfates,  fly ash,  and mercury.

     The annual arithmetic average ambient ground-level concentrations due to
the Atikokan generating station  are  presented in Figure 6.  In the BWCA the
levels were computed to be 0.25  yg/m3  for S02>  0.025 yg/m3 for SO^,
0.01 yg/m3 for fly ash, and 4xlO~" yg/m3 for  mercury.   The 24-h average
worst-case concentrations, which  is  a  composite of the  worst-case days for each
grid point, is shown in Figure  7.   The  worst-case  day occurred on February 23
along the N-S line.  In the BWCA  the highest  24-h  concentrations were computed
to be 10 yg/m3 S02, 0.75 yg/m3  804,  0.4  yg/m3 fly  ash,  and 0.0015
yg/m3 Hg.  The 3-h worst-case concentrations, which also occurred in the BWCA
on February 23, are  shown in Figure  8.   In the  BWCA the levels were 30-35
yg/m3 S02, 1.8 yg/m3 804, 1 yg/m3  fly  ash, and  0.0004 yg/m3 Hg.

     The frequency of occurrence  of  1-h, 3-h, and  24-h  average SC>2
concentrations at a  grid point  due south of Atikokan just across the U.S.
border in the BWCA is presented  in Table 6.   The  results for the non-snow season
from April 15 to November 15, defined  here as "summer," are also shown. The
summer season experiences significantly  lower concentrations than the winter
(snow) season because the inversion  height is generally higher in the summer,
and the thermal turbulence that  disperses the plume is  greater.

     The computed levels for sulfur  dioxide and particulate matter may be
compared to the U.S. standards  for wilderness areas.  According to the Clean
Air Act Amendments of 1977 for  any class I area, the maximum allowable increase
in concentrations of sulfur dioxide  and  particulate matter over the baseline
concentration of such pollutants  shall  not exceed  the following amounts:

               Particulate matter
                  Annual geometric mean             5 yg/m3
                  24-h maximum                      10
               Sulfur dioxide
                  Annual arithmetic  mean           2 yg/m3
                  24-h maximum                      5
                  3-h maximum                       25

     The modeling results show  that  the  24-h  and  the 3-h SC>2 standards would
be exceeded a few times during  the year  during  the snow season.  The annual
average SC>2 standard would not  be  exceeded.   The particulate matter standards
may be addressed by  adding the  fly ash  and the  sulfate  concentration levels.
The results indicate that the particulate matter standards would not be
exceeded.                            ~

-------
1.4


1.0


0.6


0.2
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z  0.06
O
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UJ
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    20
    10
                 Annual SOJ (/ig/m3)
                              I   I  I   I
           Annual Fly Ash (/ig/m3)
                  Annual  Hg (/z/ng/m3)
                           BWCA^
            20   40   60   80   100   120
   DISTANCE SOUTH  FROM SOURCE, km
  Figure 6.  Computed annual average concentrations
   due south of Atikokan for S02> SCT, fly ash,
   and mercury.
                    38

-------
   20
    16
    12
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   1.25
   1.0
Z
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                          i   i  i   i
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   0.3
   0.2
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              24-hr Hg (ng/m^)
                           -BWCAH
          20   40   60  80  100   120
  DISTANCE SOUTH FROM  SOURCE, km

  Figure 7.  Computed 24-h worst-case concentrations
   due south of Atikokan for  SO , SOT1, fly ash,
   and mercury.
                   39

-------
            U.S. Class IStd.
UJ
o
z
o
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   0.8
   0.4
    0
3-hr Fly  Ash (/ig/m3)
   3-hr  Hg (ng/m3)
                                BWCA-]
          20   40   60   80   100  120

 DISTANCE SOUTH FROM SOURCE , km


 Figure 8.  Computed 3-h worst-case concentrations
   due south of Atikokan for SO , S07, fly ash,

   and mercury.
                   40

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     The deposition fluxes from the model  runs  are  shown  in  Figures  9  and 10.
These annual and seasonal values were obtained  by summing  the  hourly values.
The deposition fluxes due to the Atikokan  generating  station may  be  summarized
as follows for a location due south of the  source in  the BWCA:
S02
Winter
Summer
Annual
804
Winter
Summer
Annual
Fly ash
Winter
Summer
Annual
Mercury
Winter
Summer
Annual
Dry
deposition
0.3
0.25
0.55
Dry
deposition
0.010
0.005
0.015
Dry
deposition
4
2
6
Dry
deposition
1
0.5
1.5
Wet
deposition
0.01 kg/ha
0.02
0.03
Wet
deposition
0.01 kg/ha
0.01
0.02
Wet
deposition
6 g/ha
6
12
Wet
deposition
0.05 mg/ha
0.05
0.10
     The dry and wet deposition may be  added  to  obtain  the  total  deposition.
If we assume that the SC>2 deposition  is  converted  to  sulfate at the surface
(multiply by 1.5 for additional 02),  then  the total  sulfate deposition at
this location in the BWCA is 0.9 kg/ha-yr.  The  fly  ash total  deposition is 18
g/ha-yr, and the mercury deposition is  0.0016 g/ha-yr.   These  deposition
values are, of course, an addition to the  regional background  deposition
fluxes of 11 kg/ha-yr for sulfates (see  Table 1),  indicating an absolute
increase of about 10 percent in sulfate  loadings over present  background at
the BWCA.

     Two other comparisons  are also worth  making.  Earlier  (Section III) it
was noted that the sulfate  in the precipitation  of the  Quetico-BWCA area is
about two-thirds neutralized (7.6 kg/ha-yr) by other  atmospheric  constituents,
while 3.1 kg/ha-yr of sulfate (and a  contribution  of  nitrate)  are producing
the net depression in pH.   The projected addition  of  0.9 kg/ha-yr of sulfate

                                      42

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  0.5
   0
  2.5

   I
   0
                S02 Dry Deposition
                    (kg/hectare)
                $04 Dry Deposition
                    (g/hectare)
                      Summer
              Fly  Ash  Dry Deposition
                  (g/ hectare)
                 Hg Dry Deposition
                   (mg/hectare)
BWCAHl
         20   40   60   80   100  120

DISTANCE SOUTH FROM SOURCE ,km


Figure 9.  Computed  annual and seasonal dry deposition
 flux due  south of Atikokan for S0?, S0=, fly ash,
 and mercury.  There are only two seasons: summer
 and winter.  Summer is defined as the time when the
 snow is not on the  ground.

                    43

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0.4


0.2
O.I
 0
S02 Wet Deposition
   (kg/hectare)
                         Deposition
                     g/hectare)
             Fly Ash Wet Deposition
                 ( g/hectare)
             Hg Wet Deposition
           *   (mg/hectare)
          X,
                            BWCAH
        20  40  60  80  100  120

DISTANCE SOUTH  FROM  SOURCE,km

Figure 10.  Computed annual and seasonal wet deposition
 flux due south of Atikokan for S0?, S0=, fly ash,
 and mercury.  There are two seasons:  summer is
 rain, and winter is snow.
                  44

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(and nitrogenous  compounds)  from operation of the Atikokan generating station
at full capacity  thus  represents  a  potential  increase of 25 percent in the
unbuffered atmospheric  acidity.

     These estimates of total  acid  deposition also can be evaluated from the
viewpoint of mitigative needs.   The present  Steep Rock iron mine operations,
which release  15  to 30,000 tons  of  SC>2  annually,  may be terminated before
the Atikokan power facility  is completed.   Thus,  the present deposition rates
for sulfate could be expected  to decrease  somewhat at that time.  The Steep
Rock emissions  are about 40  percent of  those  expected from the 800-MW
generating station, but the  reduction in sulfate  deposition in the BWCA would
be less than half of this proportion of the  projected power plant increase
because doubling  the stack height of the power plant effectively transmits
twice the amount  of S02 to the BWCA compared  to the shorter stack height of
the iron sintering operations.   These data,  however, allow the contribution
of the Atikokan generating facility to  be  judged  as a percent addition to the
background acid deposition levels after the  proposed closing of iron ore
operations.  Taking half of  the  40  percent of the generating station transport
to the BWCA as  the improvement from closing  of the iron mines gives a net
decrease of 0.2 kg/ha-yr in  total sulfate  deposition and unbuffered acidity.
These considerations indicate  little change  in the projected 10 percent total
increase in sulfate loadings and 30 percent  increase in unbuffered acidity (0.9
kg deposition  in  relation to 2.9 kg/ha-yr  of  unbuffered acidity) following the
closing of the  iron mine.  Even  if  the  mine  closed, and only one-half of the
Atikokan plant  was constructed (400-MW),  the  unbuffered acid sulfate
contributed by  the new source  represents a 15 percent deterioration in
precipitation  quality.   Thus,  the absolute levels of acid loadings in the
region will significantly increase  by operating the Atikokan facility at
400-MW, even assuming  the iron ore  facility  closes.

Atmospheric Loadings in the  Quetico Area

As indicated in Figures 9 and  10,  the deposition  loadings are much higher in
the northern Quetico than in the BWCA for  the 10.3% of the time the winds are
from the NE to  NW for  a duration of more than 6 h.  The watersheds of the
Maligne River  and other rivers in the Quetico south of Atikokan drain to
international waters along the BWCA boundary.  Hence deposition from the
Atikokan plume  within  these  watersheds  must  be considered in the total
BWCA-VNP impacts  evaluation.  Model estimates of  deposition 35 km south of
Atikokan in the area of Sturgeon Lake are  as  follows:

          Annual  sulfate deposition              3.4 kg/ha-yr
          Annual  fly-ash deposition             88 g/ha-yr
          Annual  mercury deposition              4 mg/ha-yr

These results  for the  proposed Atikokan source are for only the long duration
windfield; three  to five times these values will  be the probable minimum
total deposition  at the Sturgeon Lake location.  These estimates  represent a
100% or more increase  over the current  sulfate deposition in this area,  and a
much larger increase over the  expected  background deposition following
closing of the  Steep Rock Iron mine operations.
                                       45

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VALIDATION OF THE MODEL

     In a brief study  such  as  this  it  is  not  possible  to  complete direct
validation of the model  in  the  field.  A  number  of  approaches  can be used,
however, to determine  the present  level of  confidence  appropriate for the
model.

     First of all, a version of  this model  which does  not include deposition
or chemical transformation  has been used  successfully  in  a  seven-county region
in southeastern Wisconsin.  A detailed emission  inventory was  developed by
State and local agencies.   Computed annual  average  particulate concentrations
were compared with 25 high-volume  particulate monitors,  and a  correlation
coefficient of 0.87 was  obtained.   Computed annual  average  sulfur dioxide
concentrations were validated with  six monitoring stations, and a correlation
coefficient of 0.78 was  obtained (Southeastern Wisconsin  Regional Planning
Commission 1978).  The modeling  work is being used  to  develop  the Wisconsin
Implementation Plan as required  by  the U.S. Clean Air  Act.

     The validity of the model  depends in part on the  value of the parameters
selected for the execution  of the model.  The key parameters which are
dependent on the particular pollutant  species to be modeled were summarized in
Table 4.  These values were selected from experimental values  in the
literature and are felt  to  be known within  a  factor of 2  except for the values
for mercury, which are probably  known only  to a  factor of 10.   In addition, the
surface roughness and  the horizontal eddy diffusivity  are important parameters.
One surface roughness must  be selected for  the entire  region,  and the selected
value of 1 m represents  typically  wooded  terrain.  The horizontal eddy
diffusivity is not well  known for  this scale  model,  and more research is needed
on this parameter (see Liu  and Durran  1977).   The model  used a value of 100
times the vertical diffusivity.

     A sensitivity analysis was  performed on  the key parameters in the model.
A worst-case day was selected,  and  the model  was run for  24 h.  The sensitivity
of the ground-level concentration  of S02  to a factor of  2 change in each of
the key parameters was determined  as shown  in Figure 11.  The  most sensitive
parameter was the height of the  inversion.  This parameter  was measured at
International Falls and  hence  is well known.   The horizontal eddy
diffusivity was the next most  sensitive parameter:   a  doubling decreased the
S02 concentration by 10-15%.  The  other three parameters  —the chemical
reaction rate, the surface  resistance, and  the surface roughness— when
doubled, changed the concentration  by  less  than  10%.

     The accuracy of the input  data is another factor  that  influences the
validity of the results.  Assumptions have  been  made on  the type of coal used
and the reliability of the  electrostatic  precipitator.   The meteorological
data— the wind speed, wind direction, solar  intensity,  inversion height, and
precipitation amount and type —will all  influence  the resultant output.
Nevertheless, it is felt that  the  input data  are rather  well known.

     When any complex model is  used, the  results should  be  compared with those
from other models, and especially  from less complex models. Examination
                                       46

-------
ro
 E
\
 o>
o

!5
LU
O

O
o
   27
   25
   23
    21
    19
    17
    15
LU  13


LU
O
CC
CVJ

 OJ
O
V)
                            Slack  Height
                                       2RS
                                       2ZR
                                       Base Case
                                       2RR

                                       2EDDY
      EDDY = Horizontal Eddy Diffusivity
      -  RR = Chemical Reaction Rate
      -  RS = Surface Resistance

        ZM = Height of Inversion Layer

    I I-  ZR = Surface Roughness
        i   i  i   i
                            j	i
                               -BW.CA-
       10   30  50   70   90   110   130

    DISTANCE DUE  SOUTH  OF ATIKOKAN ,km

Figure 11.  Results of. the sensitivity tests of the grid
  model showing the influence on SO  concentration for
  a worst-case day.
                       47

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of the similarities and differences between  different  modeling results can
yield confidence in the final results.  Modeling  results  from a simple box
model approach, from Gaussian plume concepts,  and from the  EPA CRSTER model
are summarized in Appendix B.  These results  lend support  to  the findings of
the numerical grid model.

SUMMARY DISCUSSION OF THE ATIKOKAN MODELING  RESULTS

     A time-dependent plume model that  includes transport,  diffusion coupled
chemical transformation, and wet and dry  deposition  has been  developed and
applied to Atikokan.  A grid was set up that  included  Atikokan,  Quetico
Provincial Park, and the Boundary Waters  Canoe Area.   The  model was run hour
by hour for an entire year for those hours when the  wind was  from the NW to
NE.  Separate model runs were made for  sulfur dioxide  and  sulfates, fly ash,
and mercury.  The sensitivity of key model parameters  was  analyzed, and the
validity of the results was examined.

     The following conclusions are drawn  from the modeling  effort with respect
to the Atikokan plume on the BWCA:

     1.  The 3-h and 24-h worst-case sulfur  dioxide  concentrations exceed
         the U.S. allowable incremental standards of 25 and 5 yg/rn^,
         respectively, for protection of  a Class  I wilderness area.  The
         frequency with which these values are exceeded is  low,  however.  The
         annual average S02 concentration was 0.25 yg/nH,  which is eight
         times less than the U.S. standard.

     2.  The increase in particulate matter  is not expected to approach the
         U.S. allowable incremental standards for a  Class  I wilderness area.
         The annual particulate  (fly ash  plus sulfate) concentration was 0.03
         yg/m-% and the worst-case 24-h concentration  was  1.1 yg/nH.
         The particulate matter  contains  twice as much sulfate as fly ash.

     3.  The total potential sulfate deposition was  0.9-1.4 kg/ha-yr in the
         BWCA, which is significant compared  to the  existing  regional
         background deposition of 11 kg/ha-yr.

     4.  The total deposition of fly ash  was  0.018 kg/ha-yr for the BWCA.

     5.  Annual mercury ambient  air concentrations were 4  x 10~^ g/m »
         and the total deposition flux  was 1.6 x  10~^  g/ha-yr for the
         BWCA.
                                       48

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                                   SECTION 4

               POTENTIAL EFFECTS OF  COAL-COMBUSTION EMISSIONS
                    ON THE  TERRESTRIAL  BIOTA OF THE BWCA
INTRODUCTION AND GOALS

     The expanse of  relatively  pristine  terrestrial ecosystems in Minnesota's
Boundary Waters Canoe Area Wilderness  is  a  major reason for its recognition as
a unique recreational resource  in  the  United  States.   The flora and fauna
growing in the BWCA  have not  previously  been  subjected to elevated
concentrations of  toxic  air  emissions  or  the  deposition of chemically
transformed products of  these emissions  (Section 3).   However, the emissions
inventory presented  earlier  indicates  a  gradual  increase in toxicant
concentrations and deposition over  previous very low levels (Section 3).  A
careful assessment of the consequences of continued increases for terrestrial
species in these ecosystems  now seems  warranted.

     In this section we  will:

     1)  Characterize the components of  terrestrial ecosystems in the BWCA
         that could  be affected by  elevated concentrations or increased
         deposition, as  a consequence  of  coal-burning emissions;

     2)  summarize the research results  available for evaluating  the
         responses of sensitive species  to  changes in air, water, and soil
         characteristics, and the  overall sensitivity of the ecosystems to
         these changes;  and

     3)  define potential effects  on plants,  animals, and ecosystems where
         sufficient  information is  available  to  cause concern, but is
         insufficient to quantify  the  magnitude  or timing of responses.

     Sensitivities of the regional  biota  to the  emissions and deposition
products from coal-fired generating facilities have been reviewed in several
previous forms (N. R. Glass  1978).  Because of measurable differences in
terrain, meteorology, vegetation density, rainfall, and soil moisture from one
location to the next within  the BWCA,  absolute comparisons are not possible for
short- or long-term  biological  responses  at specific  sites.  Thus, responses to
air pollutants and dry fall  that hold  for several locations  already studied
must be used to evaluate potential  impacts  on other, locations, such as the
BWCA.

     Under relatively extreme emission loads, many effects on ecosystems such
as the BWCA are well documented.   Some responses  are  evident on a short-term
(less than a decade) time scale, and others are  apparent on a long-term
(decades) time scale.  Studies  of other  influences on the vegetation of the

                                     49

-------
BWCA, particularly the effects  of  intermittent  fire  in  the  past,  require the
use of time scales of hundreds  of  years.  Although the  studies  presented here
focus on relatively  immediate,  often  subtle  impacts  on  species,  it  is
apparent that these  impacts also should be viewed  in  a  time  frame  of 100 or
200 yr if their ultimate  effect upon  the  entire  ecosystem is to be  assessed
fully.

BIOLOGICAL AND TEMPORAL CHARACTERISTICS OF THE  BOUNDARY WATERS  CANOE AREA

     Approximately 70,000 ha  (172,000 acres)  of  the  total 439,000  ha
(1,085,000 acres) of the  BWCA are  taken up by lakes  and streams over 4 ha (10
acres) in size.  Some 215,000 ha (532,000 acres) support  remnants  of the
natural ecosystems of Minnesota's  Laurentian  shield  country, virgin areas
with the flora and fauna  nearly intact.   These  virgin areas  are those which
have never been directly  altered by human activities  such as logging,
clearing, tree planting,  farming,  mining, road  building,  etc.   Almost all
these areas, however, have been burned in the past 400  yr,  and  many virgin
forests are postfire successional  communities less than 110  yr  old
(Heinselman 1973) .   It is these virgin areas  of  natural vegetation  patterns
upon which this discussion will focus.

     Part of the Superior Upland Physiographic  Region,  the  BWCA's  landscape
has a generally slight but locally rugged relief left by  preglacial erosion.
Elevations above sea level range from 341 m  (1,119 ft)  at Crane Lake to 680 m
(2,232 ft) in the Misquah Hills (Ohmann and Ream 1971); local differences in
elevation range from 30 to 150 m (Heinselman  1973).   Most of the  relief of
this area, glaciated repeatedly during the Pleistocene  and  deglaciated some
16,000 yr ago, is related to  the contours of  its exclusively pre-Cambrian
bedrock:  metamorphosed sedimentary rock  leading to  quartzite,  metagraywacke,
and slate.  In contiguous Quetico  Provincial  Park  (Ontario)  the bedrock types
are principally associated with a  granite batholith  exposed  as  part of the
Laurentian Shield.

     A network of more than 1,000  interconnected lakes  and  streams  occupies
the bedrock troughs  and basins  of  the BWCA, some lying  in granite  (Saganaga
Lake and Lac La Croix) and some in ancient greenstones  and  slates  (Knife
Lake).  The landforms are determined by the configurations  of the  bedrock:
slates typically form long, narrow, steep ridges,  and granites  the  low,
irregular round-topped hills  (Ohmann and Ream 1971).

     Deposition was  offset by glacial scouring,  which left  bedrock  exposed on
many ridgetops, cliffs, and lakeshores, and a thin covering  of  till,  outwash,
and lacustrine deposits varying considerably  within  short distances.   Glacial
boulders are common within the  soils derived  from  this  sandy and gravelly
loam glacial deposition.

Plant Community Type_s

     The plant communities of the  virgin  upland  forests have been  quantita-
tively described by  Ohmann and  Ream (1971).   Even  after 60  yr of  fire control
the jack pine (Pinus banksiana) communities remain the  most  common  of the
virgin upland forest, followed  closely by the broadleaf group,  which is

                                     50

-------
largely dominated by  aspen  (Populus  tremuloides)  and paper birch (jetula
papyrifera) (Table  7).  White  pine  (Pinus strobus)  and red pine (J\ resinosa)
communities made up 10% of  the 106 virgin stands  randomly sampled by Ohmann
and Ream (1971).  The distribution of  the vegetation types in the BWCA area
is shown in Figure  12.

     Transitional between  the  Great  Lakes-St.  Lawrence and boreal forest
regions, biotic communities  in the area have an abundance of boreal trees:
jack pine, black and  white  spruce  (Picea mariana, J^. glauca), balsam fir
(Abies balsamea), tamarack  (Larix  laricina),northern white cedar (Thuja
occidentalis),and  paper birch.  The two pines characteristic of the Great
Lakes forest, eastern white  pine and red pine, are  also plentiful (Heinselman
1973).  Citing Dean's preliminary  1971  study of the area wetland communities,
Heinselman (1973) indicates  that they  are closely  related to the glacial Lake
Agassiz peatland communities,  a region  some 160 km (100 miles) to the west.

     Of the 12 community types described by Ohmann  and Ream (1971), only the
lichen community type is nonforest.   Characterized  by the lack of many woody
plants and by the importance of  lichens and mosses, this type comprises
slightly less than  5.7% of  the stands  in their random sample of 106 sites.
Ohmann and Ream grouped lichens  other  than the reindeer mosses, and mosses
other than the feather mosses, Dicranum, and the  hairycap moss.  Together
they make up 40% of the ground cover within the community.  Another 30% of
the ground surface  is bare  rock.   The  reindeer mosses (actually lichens) are
also important in this essentially two-layered community.

     Lichens  and mosses are  also an  important  component of the ground cover
in four other communities designated by Ohmann and  Ream:  jack pine (fir),
19% of the ground cover; red pine, 26%; black spruce-jack pine, 59%; and
budworm-disturbed balsam fir,  46%, including herbs.  As computed by Ohmann
and Ream, these communities  make up  32% of the upland virgin vegetation area
in the BWCA.  They  view the  lichen community as an  early stage of succession
after some major disturbance,  such as  fire, as primary succession on rock
outcrop.

     In the BWCA today tree  lichens  are found  largely on the lower limbs of
old fir and spruce  and on dead balsam  fir killed by the spruce budworm.
Ground lichens are  most abundant on  open bedrock  ridges and upper slopes,
which become well covered by lichens 60-100 yr after fire (Heinselman 1973).

     Stands including the white  and  red pine community types are slightly
older than those in most of  the other communities  and make up 9.5% of total
stands sampled by Ohmann and Ream  in 1971 (5.7% white pine;  3.8% red pine).
As described by these researchers  the white pine community is really a two-
layer forest:  an upper canopy of  large, old white  pines with scattered red
pines, and a lower  layer of  balsam fir  trees and saplings.  The attractive-
ness of the red pine  community stems from the  presence of open stands of old,
majestic red and white pines that  survived fires along the lakeshore and are
prominent along the ridgetops  forming  the skyline.   The understory is short
on saplings and seedlings, and shrubs and lichens  characteristic of dry
conditions are dominant.
                                       51

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   TABLE 7.  VIRGIN UPLAND COMMUNITIES IN THE BWCA AND  THE  IMPORTANCE  OF
                  STANDS, TYPES, SPECIES, AND FAMILIES3

Stands
Community
type
Lichen
Jack pine (oak)
Jack pine (fir)
Jack pine-black spruce
Black spruce-jack pine
Aspen-birch
Maple-aspen-birch
White pine
Red pine
Budworm-disturbed balsam fir
Fir-birch
White cedar
Numb er
6
11
7
7
10
13
15
6
4
10
8
9
Percentage
of total
5.7
10.4
6.6
6.6
9.4
12.3
14.2
5.7
3.8
9.4
7.5
8.5
Number of
species
32
81
95
83
75
112
104
80
67
102
86
85
Number of
families
19
25
30
26
23 -
30
34
23
25
31
30
28

aAdapted from Ohmann, L. F., and R. R. Ream  (1971).
                                     52

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53

-------
     The mammals and birds of the area  are  also  representative  of  a transi-
tion between the Great Lakes and boreal forest ecotones.   The moose (Alces
alces), Canada lynx (Lynx canadensis),  fisher  (Martes pennati),  pine  marten
(Martes americana), snowshoe hare (Lypus americana),spruce  grouse
(Canachites canadensis), Canada jay (Perisoneus  canadensis),  and  (formerly)
the woodland caribou (Rangifer caribou)are all  species with  boreal
affinities.  The northern white-tailed  deer (Odocoileus virginianus)  and
bobcat (Lynx rufus) are species more  typical of  the Great  Lakes  forests.  The
eastern timber wolf (Canis lupus), red  squirrel  (Tamiasciurus hudsonicus),
red fox (Vulpes fulvaT^beaver (Castor  canadensisT]otter  (Lutra canadensis),
mink (Mustella vison), black bear (Ursus americanus), ruffed  grouse (Bonasa
umbellus),bald eagle (Haliaeetus leucocephalus),  etc., are  all  species more
typical of the Great Lakes forests.   Most of the native animals  and birds
also have habitat requirements that correspond with niches  in various  post-
fire successional stages (Heinselman  1973).

Long-Term Stability of the BWCA Landscape

     Ohmann and Ream (1971) conclude  from their  studies that  the  structure
and composition of each stand in today's virgin  forests are more closely
related to the length of time since the last fire,  and probably  to  the
character of the fire and the age of  composition of the former  stand,  than  to
all of the other environmental factors  studied,  such as soils,  aspect, slope,
or elevation.

     The stand origin and fire year maps developed  by Heinselman  (1973)
indicate that from 1595 to 1973 nearly  all  of  the  one-million-acre  virgin
forest study area burned at least once, 1910 being  the last  year  of major
burns.  At least 44% of the million-acre virgin  study area was  involved  in
the drought year burns of 1893 and 1894.  Many even-aged  stands  also  date
from a similar drought-fire sequence  220 yr ago  in  1755-59.   Those  large
upland ridges and ridge complexes distant from or  west of  natural  firebreaks
were the areas most frequently or intensely burned.  Such  areas  are today often
dominated by jack pine, black spruce, birch, and other sprout hardwoods.  White
pine, red pine, white spruce, northern  white cedar, black  ash,  elm, and  fir are
relatively more abundant on those sites burned least frequently  or  intensely:
swamps, valleys, ravines, the lower slopes  of high  ridges,  islands, and  the
east, north, northwest, or southeast  sides  of  large lakes  or  streams.  Very
fire-sensitive northern white cedar has retreated  to the  lakeshores where  it
forms a typical narrow fringe (Heinselman 1973).

     Heinselman (1973) cites Ayres' 1899 observation that  by  1855,  because  of
its long history of fire, only 20% of the region supported  the  mature  pines
desired for lumber.  Thus, Heinselman indicates, just a small  fraction of  the
BWCA was affected by the early logging, and the  young stands,  recent  burns,
and scattered areas of older forest that covered three-fourths  of  the  region
were little touched.  As of 1973, he  notes, the  net land  area  undisturbed by
cutting exceeded 167,950 ha (415,000  acres), most within  the  lands  set aside
for national forest between 1902 and  1913.  The  Anderson  bill,  recently
passed by the U.S. Congress, eliminates logging  as  a management  alternative
from the entire BWCA.
                                      54

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     As  indicated by H. E.  Wright  Jr.  (1974),  the same 370 years covered by
Heinselman1s tree-ring/fire  studies  in the  BWCA represent only a portion of
the total  lifespan  of  the  forest.  Although humans may have modified the
natural  frequency of fire during  those years,  pollen curves and charcoal
profiles from  the sediment  of  Lake of  the  Clouds (in the heart of the BWCA)
show that major  fires  occurred about every 80  yr for the last 1,000 yr.

     What H. E.  Wright Jr.  (1974)  has  called the "time factor in landscape
evolution" must  be  applied  to  environmental influences other than fire
control.   If we  look ahead  50,  100,  or 200  yr  to how succession in the
absence  of a natural constituent,  fire,  may significantly change the BWCA
forest communities, then  it  is equally appropriate to consider a similar time
frame for  assessing what  effects  rising  levels of pollutant deposition may
eventually have  on  these  same  communities.   Such a long-range view provides
an important perspective  on  the possible significance of relatively
immediate, if  subtle,  effects  now manifested in individual indicator species
in other ecosystems, where  effects of  exposure to increased doses of S(>2,
NOX, TSP, H2SC>4, HF, and Hg  are already  known.

     The vegetation resource that  presently covers the BWCA was initiated 300
to 100 yr  ago.   Today's land managers  and  policy decision-makers are stewards
of whatever the  landscape of this  area is  to be 200 years from now.

BIOTIC RESPONSES TO COAL-FIRED POWER-PLANT  EMISSIONS

     The following  considerations  have been summarized from various  current
research projects on the  impact of coal-fired  generating stations and from
the literature on the  BWCA  ecosystem components and their response to known
levels and durations of exposure  to  point-source pollutants from coal-fired
power plants.

     Various types  of  terrestrial  ecological effects may be anticipated from
exposure to generating station emissions and associated deposition (Figure
13).  Direct effects may be  anticipated  from both dry and wet deposition of
air pollutants on ecosystem  components (see Section III).  In addition to
direct effects,  a number of  indirect effects may be manifested through
changes  in ecosystem processes, such as  bioaccumulation of toxic compounds,
alterations in mineralization  or  rates of  nutrient flow,  and changes in
host-parasite relationships.

     The discussion that  follows  considers  such major emission products
(residuals) from the viewpoint of  the  plant, animal,  and  soil components of
the terrestrial  ecosystem on which they  could  have important potential
effects.  The material presented  reflects data or information already
available.  New  data needs  are  identified by the inadequacy or lack of
results  from long-term, low-level  exposures.   The emission residuals
considered are those for which  sufficient  information is  available to
anticipate some effect on an ecosystem component at some  concentration,  and
for which the air-quality modeling work  has provided estimated concentrations
and loadings in  the BWCA.
                                      55

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Residuals of Concern

so2—

     Sulfur dioxide and  the  effects  of  exposure  to it  have been studied more
than any other pollutant  (Benedict et al.  1971,  Guderian 1977,  Rennie and
Halstead 1977).  A wide  variety  of organisms  are sensitive to damage from
exposure to elevated S02  concentrations (Tibbitts et  al.  1977,  Electric
Power Research Institute  1976, Van Haut and Stratman  1970).   Many organisms
also exhibit synergistic  reactions to combinations of  S02 with other
coal-fired power plant emissions such as  03 or NOX (Dochinger et al.
1970, Kress and Skelly 1977, Houston 1974).

     Numerous extensive  reviews  of SC>2  and its effects are available
(Braunstein et al. 1977,  N.  R. Glass 1978).   A reading of these and other
references in relation to the  principal vegetation types  reviewed supports
focusing on responses of  pines,  lichens,  and  soils in  the BWCA.

NOX N02—

     Forest soil and insects are generally less  sensitive to N02 than
to other major pollutants (National  Academy of Sciences  1977).   Although
organisms are more sensitive to  N02  than  to the  other  nitrous oxides,
the usual measurement combines the forms  as NOX, and  levels  necessary to
affect susceptible members of  the terrestrial ecosystem  (vegetation) are much
greater than for sulfur  dioxide  and  photochemical oxidants (MacLean 1975).
Estimates of the economic impact of  air pollutants on  vegetation have not
included NOX by itself;  rather it has been combined with  ozone and
peroxyacetyl nitrate (PAN).  However, emissions  of NOX have  been increasing
substantially throughout  the United  States and Canada,  and the synergistic
effects on plants from low concentrations  of  N02 and  sulfur  dioxide
(found in experimental exposures) and of  NOX  in  the production of
photochemical smog and acid  precipitation  pose the greatest  threat (N.  R.
Glass 1978) .

Ozone—

     Photochemical oxidants, ozone (03),  and, to a lesser extent, peroxy-
acetyl nitrates are the most damaging air  pollutants affecting agriculture
and forestry in the United States (Jacobson 1977). Peroxyacetyl nitrate is
more phytotoxic than 03,  but the ambient  concentration of PAN is much lower
than 63 in most areas of  the United  States (Taylor 1969).  In the northern
Minnesota area it may be  almost  negligible.   Formation of ozone in the
atmosphere has a complex  dependence  on  the amounts of  precursors (nitrogen
dioxide and hydrocarbons), meteorological  conditions,  and time  of day
(National Academy of Sciences 1977), but  moderately high  levels are being
observed in northern Minnesota given the  area's  relative  isolation from the
usual ozone sources (Table 1).   Photochemical oxidants,  including ozone, have
been problems in southern California for more than 30  years.   The severity of
losses to agricultural crops, exclusive of forests and ornamental plantings,
had reached more than $55 million by the  1970's  (Millecan 1976).
                                      57

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Trace elements—

     Trace elements have been defined  as  those  elements  present  in the crust
of the earth at less than 0.1% or  100,000  ppm.  More  than 63  of  them are
found in coal.  Some are more concentrated than others  in coal,  and there is
considerable variation in trace-element concentration from different coal
sources.  Most trace elements (including  arsenic,  beryllium,  chromium,
copper, lead, selenium) appear to  occur at  mean concentrations  less than
7,000 ppm, notable exceptions being boron,  zinc,  and  titanium (Ruch et al.
1974, Zubovic 1975).  These trace  components, however,  are concentrated on
the surface of the fly ash particles and  are highly reactive  (G.  E. Glass 1978)
Of the macro elements in coal (e.g., aluminum,  calcium,  iron,  silicon,
sulfur, and sometimes titanium) only sulfur is  the element of concern here.
Sulfur oxides represent the major  pollutants of gaseous  emissions and are
mentioned here because of the known ability of  some metallic  trace elements
to catalyze the further oxidation  of sulfur oxides into  more  toxic substances
capable of greater respiratory damage  than sulfur  dioxide alone  (Amdur and
Underbill 1970) or to interact and form metallic  sulfates.  Excessive
deposition of trace elements upon  a balanced ecosystem  can cause  problems
because of the high toxicity of many trace  elements and  the potential for
bioaccumulation.

Acidic fallout (acid rain)—

     Although acidic fallout has long  been studied by European  researchers
(Oden 1968), the phenomenon received only  cursory  attention by Canadian and
United States scientists until the early 1970"s.   Since  the beginning of the
decade, however, scientists of both these  North American countries have
expanded their interest in the long-term effects  of acidic precipitation and
the precursors of this phenomenpn.  Canadian scientists  have  shown that
acidic precipitation is a serious  problem  in both  terrestrial and aquatic
ecosystems of eastern Canada (Summers  and  Whelpdale 1976,  Beamish 1976,
Stokes and Hutchinson 1976).

     In the United States a report to  the  Secretary of  the Department of
Health, Education, and Welfare by  a special scientific  advisory  committee
considered the long-term consequences  of the United States National Energy
Plan (NEP).  This committee concluded  that  one  of  the most  serious
environmental consequences of the  expanded  use  of  coal-fired  power plants
will be increased acidic precipitation throughout  the areas where the power
plants are located (U.S. Federal Register  1978).   Although this  advisory
committee supported the conversion from oil to  a  coal-based energy economy
(NEP), they concluded that all converted and new  facilities should install
the best available abatement technology to  reduce  to  a minimum the precursors
of acidic precipitation.

     Contributors reviewing the literature  and  current  research  for this
report reached the consensus that, for the  BWCA,  the  principal ecosystem
components or organisms to be emphasized regarding the  effects of acid rain
were pines, lichens, insects, and  amphibians (direct  effects)  and soils
(indirect effects).
                                     58

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Conifers (Pines)  and Aspen

Effects of SC>2 on pines —

     The effect  of  the gaseous  emissions of large coal-fired power plants
initially becomes  evident  in  the  responses of the most sensitive of the
species in any ecosystem.   In the BWCA these sensitive species are lichens,
conifers of  the  genus Pinus,  and  trembling aspen.  The three dominant species
of Pinus in  the  BWCA are P_.  strobus, j>.  resinosa, and jP. banksiana.  Of these
three species eastern white  pine  is  the  most sensitive to S(>2.  Red pine
and jack pine are considered  about equally sensitive to SC^j but not as
sensitive as eastern white  pine.   Trembling aspen is a dominant species over
20% of the BWCA  (Table 7,  Figure  12)  and is recognized by Driesinger and
McGovern (1970)  as  a very  sensitive  species.

     The major manifestations of  pollution damage in these three species of
pine are foliar  tip necrosis, mottling chlorosis, basal necrosis of the
needle tissues beneath the  fascicular  sheaths,  and premature needle casting.
The premature loss  of needles from the second-,  third-, and fourth-year
internodes causes  a reduction in  annual  growth  as well as the loss of normal
health and vigor, which in  turn predisposes these species to more severe
effects of other  abiotic (drought, frost,  nutrient deficiencies) and biotic
(insect infestations, root-attaching  fungi) causal agents (Carlson 1978).

     Several studies document the development of visible injury symptoms on
eastern white pine  by low  level chamber  fumigations.  Costonis (1970)
reported tissue  damage on  new needles  of eastern white pine after a single
1-h treatment with  5 pphm  SC>2 •  Houston  (1974)  observed necrosis in
elongating needles  of eastern white  pine after  6 h of fumigation with 2.5
pphm S02•  In a  field study  in  the Sudbury, Ontario, region Linzon (1971a)
observed damage  to  eastern white  pine  at a 7-yr  fumigation average of 0.8
pphm, a level of  S02 commensurate with the background levels already being
recorded in  areas of Ontario  near Atikokan (Table 1).

     After field  observations Costonis (1972) reported that 6 pphm of S02
caused acute injury to the new  needles of  eastern white pine after A h of
exposure.  Ozone  measurements in  the  field did  not exceed 4 pphm.
Preliminary  laboratory tests  conducted before these field studies indicated
that sensitive white pines developed necrotic lesions after S02 exposure of
3 pphm for 1 h;  if  fumigation was continued for  3 h, severe necrosis on
current needles  occurred.  Laboratory  tests also revealed that 03
fumigations of 15 pphm for 4  h  produced  equivalent injuries.

     Houston and Dochinger  (1977)  reported a decrease both in the number of
seeds produced per  cone and  in  the percentage of pollen germination in white
pines in a low level S02~polluted area.  Effects on red pines included
decreases in cone  length, seed  weight, percentage seed germination,
percentage pollen germination,  and pollen  tube  length.  None of the trees
displayed foliar  injury patterns,  indicating that low levels of air
pollutants may be  affecting  the reproductive tissues of pines at
concentrations lower than those required to produce visible injury.  In the
vicinity of  a copper smelter  at White  Pine, Mich., low level S02 exposure

                                     59

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has caused no plainly visible vegetation  damage,  but  ring  widths  of balsam
fir and white spruce suggest that growth  has  been substantially reduced in
trees downwind  from the  smelter  (Kotar  1978) .

     Driesinger and McGovern (1970)  found  trembling aspen  to  be the most
sensitive forest species to air  pollution  in  the  Sudbury,  Ontario,  area.
Visual injury to foliage was caused  by  S02 concentrations  of  26 pphm for
4 h.  Pollen-tube elongation is  inhibited  at  S02  concentrations greater
than 30 pphm for 4 h (Karnosky and Stairs  1974).

     The U.S. Environmental Protection  Agency  (Davis  and Wilhour  1976)
attempted to classify the  susceptibility  of various woody  plants  to SC>2 and
photochemical oxidants based on  foliar  injury,  growth  loss, etc.   They
observed that eastern white pine near the  Sudbury, Ontario, region (S02
source) has a poorer regenerative capacity to  repeated S02 exposures than
various hardwoods (aspen,  birch).  They also  documented  that  red  pine was
very sensitive  to S02 emissions.

Effects of NOX  on pines—

     Skelly et  al. (1972)  carried out field observations of eastern white
pines exposed to S02 and NOX.  The most severely  affected  trees were in
areas where the highest  readings were 8.5  pphm NOX (l-h  average)  and 69
pphm S02 (2-h average).  They also found  that  oxides  of  nitrogen  at
moderate concentrations  acting alone or in combination with low S02
concentrations  caused acute to chronic  damage  in  eastern white  pine. Young
seedlings were  extremely susceptible to NOX fumigations.   Van Haut and
Strattman (1967) observed  damage to  plants exposed to  250  pphm  NOX for  4-8
h.

Effects of ozone on pines  and aspen—

     In chamber studies conducted by the  EPA,  eastern  white pine  was
classified in the intermediate sensitivity range  to 0-j and red  pine in  the
tolerant range.  Davis and Wood  (1972)  used chamber experiments to determine
the relative susceptibility of 18 conifers to  ozone.   They found  jack pine to
be the most susceptible, damaged by 4 h of 25  pphm 0^•  Eastern white pine
was also very sensitive, damaged by 8 h of 25  pphm 0-j, but red  pine was
resistant (no injury manifestation)  at  these  fumigation  levels.

     In a field study in West Virginia, Berry and Ripperton  (1963) observed
damage to eastern white  pines 48 h after  a l-h fumigation  of  5  pphm 03.
The damage observed was considered a "light attack" of emergence  tipburn, but
severe symptoms were noticed following  ambient 03 exposures of  6.5 pphm for
a total of 4 h during a 48-h period.  Using chamber experiments,  they
determined 03 was the causal agent of the  injury  observed  in  the  field.
(The damaged area was remote from any major sources of air pollutants.)
Ozone levels higher than these have  already been  observed  in  the  BWCA (Table
1).

     Botkin et  al. (1971)  observed that fumigations of 03  (50 pphm for  4 h
and 80 pphm for 3 h) suppressed  photosynthesis of eastern  white pines.

                                     60

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Further  studies  carried  out  by Botkin et al.  in 1972 determined that
photosynthetic depression occurs before visible 63 damage becomes apparent.
In a chamber experiment  on 5-yr-old eastern white pine they determined that
50 pphm  fumigations  of 63 for 4 h was the threshold level for photo-
synthetic  suppression  (Botkin et al.  1972).

     Treshow and  Stewart (1973) found visible injury to trembling aspen at 15
pphm 03  for 2 h.   Since  this was the  lowest concentration tested, it does
not establish the injury threshold, but does  indicate that trembling aspen is
among  the  most sensitive species tested.

Effects  of SC>2 and 63  in combination  on pines—

     Eastern white pine  is generally  considered to be more susceptible than
other  pines to a  pollutant mix.  Several studies support the finding that
greater  than additive  responses occur when eastern white pine is exposed to
both S02 and 03  (jaeger  and  Banfield  1970, Berry 1971, Banfield 1972,
Costonis 1973, Houston and Stairs 1973, Houston 1974) (Table 8).  Menser and
Heggestad  (1966)  support the findings that "tolerable levels of a single
pollutant  can damage plants  (in general) when in association with another at
an equally low level."   These studies, however, are mainly chamber studies
and deal only with SC>2 and 63.   They  do not account for other pollutants
and environmental stresses that occur in the  field.

     Berry (1971)  conducted  chamber studies to determine the relative sensi-
tivities of red  pine,  jack pine, and  eastern  white pine seedlings to 03 and
SC>2 fumigations.   The  3-, 5-, and 7-wk-old seedlings were exposed to 2-h
fumigations of 25 pphm 03, 50 pphm 63, 25 pphm 862, or 50 pphm SC>2.
Jack pine  was the most sensitive to both SC>2  and 63, but there was no
significant difference in the sensitivities of the age groups of any of the
trees.  At 50 pphm 03  red pine  was less tolerant than eastern white pine.
Fumigations with  SC>2 at  25 pphm, however, were more injurious to eastern
white  pine than  to red pine.   Red pine injury was detected at 25 pphm 03
for 2  h, but at 50 pphm  63,  87% of the 468 seedlings observed were injured
(banding,  flecking,  tip  necrosis).   Injury symptoms were detected from 24 to
48 h after fumigation.

     Jaeger and Banfield (1970) studied responses of eastern white pine to
prolonged  exposures  to 63,  SC^j and a mixture of both pollutants.  When
eastern white pine was exposed  to 50  pphm of  03 and 50 pphm SC>2 for 10
days,  profuse necrotic spotting occurred on new and 1-yr-old needles.  The
most significant  finding was  that at  the above fumigation levels, with
increasingly humid environments,  severe necrotic spotting occurred after 3
days.  That is, the  synergistic effect was much more severe with high
humidity.  Banfield  (1972) observed necrotic  spotting and tipburn of eastern
white  pine when exposed  to 10 pphm 03 and 0.5 pphm SC>2 for 1-12 days in a
chamber fumigation study.

     Dochinger et  al. (1970)  observed injury  to eastern white pines  when they
were exposed to 10 pphm  03 for  10-20  days and 10 pphm SC>2 for 10-20  days.
When exposed to 10 pphm  of both 03  and SC>2 for the same time intervals,
injury to  the pines quadrupled.

                                       61

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Effects of  trace  elements  on  pines—

     Accurate  assessment  of  trace-element  impact  cannot be known without a
thorough characterization  of  endogenous  levels  of soil trace elements and the
processes ongoing within  soil.   Trace  element  input from weathering differs
from that of fossil  fuel  combustion and,  in some  cases, may exceed that from
fossil fuels.  Trace-element  input  is  attentuated by distance from the
pollutant point source  and by filtering  action  of the surrounding canopy.
Since more  than 80%  of  the BWCA is  forested (about 75% of this in coniferous
stands), most  trace-element  emissions  may  affect  the tree canopy directly.
Very little  is known concerning the effects of  most trace elements applied
directly to  foliage.

     Fluoride  is  known  to  be  directly  phytotoxic, but very little work has
been done on the  susceptibility of  either  eastern white pine or red pine to
ambient concentrations  of  fluoride  pollutants.   In 1970 the EPA carried out
field studies  on  fluoride-affected vegetation  in  Glacier National Park,
Montana, the closest  boundary of which is  15 miles northeast of a large
aluminum reduction facility  (U.S. EPA  1973). They observed that tip necrosis
due to fluorides  was  clearly  visible on  older  needles of sensitive western
white pine  growing in areas deep within  the interior of Glacier National
Park.  Western white  pine  (Pinus monticola) was classified by EPA in 1976 as
being "less  sensitive"  to  airborne pollutants  than eastern white pine (Pinus
strobus).   In  another report  (Gordon 1974), the EPA observed tissue necrosis
on western white  pine occurring at  fluoride levels only two or three times
higher than  background  fluoride levels in  healthy trees.

     Linzon  (1971b)  carried out studies  during  the 1969 growing season in the
Cornwall area  of  Ontario  near three fluoride-emitting industries.  Early in
the growing  season the  current  1969 needles on  eastern white pine had not
emerged, but the  1968 foliage displayed  severe  brown terminal necrosis and
many needles were  prematurely lacking.  Later  the 1969 needles displayed
severe orange-red  terminal necrosis.   Studies  carried out in the summer of
1977 in the  same  area of Ontario by the  University of Montana documented
severe visible injury to  both eastern  white pine  and red pine despite
considerably lower fluoride concentrations  in the needles than determined by
Linzon in 1971 (Miles 1978).

     Solberg and Adams  (1956)  state that,  in general, fumigation of
vegetation with HF or S02 may produce  temporary decreases in photosynthesis
in the absence of visible  injury.  They  found that histological responses to
S02 and HF were indistinguishable in ponderosa  pine and apricot leaves.

Impacts of acidic precipitation on coniferous forests—

     Effects on growth  of  fully mature coniferous species have been difficult
to document with methods currently available.   Several studies have failed  to
identify significant  effects  (Abrahamsen et al. 1977, Tamm et al. 1977),
whereas other studies provide  suggestive circumstantial evidence that acidic
precipitation has  adversely affected growth of  trees in coniferous forests
(Jonsson and Sundberg 1972, Jonsson 1977).   Long-term growth effects are
exceedingly difficult to demonstrate because their cause may be confounded  by
interaction with numerous variables.   In addition,  even if the long-term
                                     63

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effects on growth are very  significant,  significant  changes  in growth do not
usually occur within the timespan of typical  research  projects.

     The quickest and most  severe impact of  acidic precipitation on soils is
likely to occur in the 1-2-cm horizon.  Deeply  rooted  plants  (e.g.,  trees)
are not likely to be directly affected very  much  by  changes  in this horizon,
but plants rooting in this  zone  (understory  vegetation and germinating plants
of all types) may be affected considerably (Mayer and  Ulrich  1977).   Effects
on understory vegetation may be very important  because at certain stages of
succession a greater weight of chemical elements  circulates  through the
understory than through the trees.  This relationship  has been demonstrated
in old spruce and pine forests in the U.S.S.R.  (Ovington 1962).

     Perpetuation of a coniferous forest depends  upon  the continued
reproductive success of the conifers.  Spruce  (Picea abies)  germination has a
broad optimum around pH 4.8 and  is adversely  affected  at soil  pH of 4.0 or
lower.  Spruce seedling establishment has a  narrow optimum at  pH 4.9 and is
quite sensitive to pH levels lower than this  (Abrahamsen et  al.  1977).  In  a
20-wk study of the effects  of acid rain on growth of white pine  (Pinus
strobus) seedlings, best growth was found in  seedlings exposed to rain of the
lowest pH (pH 2.3) (Wood and Bormann 1977).   This increased  growth was
presumed to be caused by the increased nitrogen impact from  the  acid rain.
Apparently, once seedlings  are established,  they  are relatively  tolerant of
acidic soil.  Considerable mineral leaching  occurred throughout  the 20-wk
experiment.  Availability of basic cations would  probably have become limiting
to growth had the experiment been carried out over an  extended period.

     Impacts of acidic precipitation were also  reported at the First
International Symposium on Acid Precipitation and the  Forest  Ecosystem
(Dochinger and Seliga 1976) when European, Canadian, and United  States
scientists presented the data obtained on both  continents during the last 20
yr.

Summary of effects on pines—

     Based on the above literature evidence  and the  projected  ambient air
levels of total suspended particulates (TSP),  SC^, NOX, and  trace elements,
it is possible but unlikely that short-term, visible damage will be incurred by
the pines in the BWCA.  Acid rain damage to  plant tissues seems  possible in
view of results suggesting  that  the pH of rain  under worst conditions may
become as low as 3.5-4.3, although the projected  frequency of  these rains is
not immediately available (Section 3).  Literature reports indicate that this
range of pH could alter growth and reproductive success of conifers.

     The long-term implications  of small, subinjurious effects on processes
such as photosynthesis rates, radial growth,  nutrient  uptake,  germination
success, and lifespan could be substantial.   Whether the effect  would be
strong enough to affect community structure  or  the rate of secondary
succession is open to debate.  In view of recent  data  which  indicate that
impacts may occur at residual levels lower than previously reported (Gordon
et al. 1978, Kotar 1978), the possibility of  long-term effects must be
seriously considered.  Signficant new research  programs focused  on the most

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sensitive  species  and  on  subinjurious  effects  must be carried out if these
problems are to be resolved.

Lichens and Bryophytes  (Sphagnum)

Effects of SC>2 on  lichens—

     The adverse effects  of  gaseous  SC>2  °n lichens are well documented in
field and  laboratory observations.   The  laboratory observations have
generally  been made at  S02 levels  of above 50  pphm and will not be
elaborated on here.  The  field  observations have  tended to concentrate on
mapping lichen communities around  pollution sources,  documenting the
disappearance of lichen species  as one approaches the pollution source
(LeBlanc and Rao 1975).  This  approach seems to be accurate in determining
zones of air quality in urban  and  industrial areas where there has been a
pollution  source for a  long  period of  time (e.g., Sudbury, Ontario;  LeBlanc
et al. 1972), where environmental  conditions are  such that no interruptions
in adequate indicator  lichen cover would be expected.  The approach  is also
useful where one is close enough to  the  source that short-term acute effects
can be easily observed  (Clay Boswell plant, Cohasset, Minn.;  Coffin  1978).

     LeBlanc and Rao (1973)  indicate that  lichens in  the Sudbury, Ontario,
area were  not injured  if  ambient S02 concentration for the 6-month growing
season was less than 0.2 pphm;  growing season  average concentrations of 0.6-3
pphm were  adequate to  produce  chronic  injury.   Average growing season
concentrations above 3 pphm produced acute injury.  Background levels in the
BWCA have  reached  10 pg/m3,  or  0.37  pphm (Table 1).

     Significant decreases in  respiration  rates of lichen samples occurred in
100-200 days at median S02 concentrations  of 1.8  pphm in southeastern
Montana (Eversman  1978), a level that  could be approached in  the BWCA given
projected  effects  from Atikokan  (Section 3).  Thalli  of yellow-green lichens
(Parmelia  chlorochroa, Usnea hirta)  bleached to a yellower color within 100
days, and  the percentage of normally plasmolyzed-^ cells increased from a
baseline of 5-8% to 25-30% in  30 days  (Eversman 1978).  Usnea hirta  is an
epiphyte on trunks and branches  of ponderosa pine in  southeastern Montana.
It also grows in the BWCA (Hale  1969).   This type of  lichen (fruticose)  is
particularly sensitive to air  pollutants.   Parmelia chlorochroa lives on bare
soil between grass clumps and  shrubs in  the grasslands.  This foliose lichen
intergrades with western  forms  of P. taractica, and is found  on exposed rocks
in the BWCA (Hale  1969).          ~

     At median S02 values above 2 pphm in  southeastern Montana, bleaching
and plasmolysis occurred faster, and P.  chlorochroa and U. hirta exhibited
symptoms of acute  damage.  Within 33 days  of S02  exposure at  median  concen-
trations greater than 3.3 pphm, plasmolysis of algal  cells approached 100%,
and the respiration rate of these  lichens  dropped significantly below that of
controls (Eversman 1978).  Selected  indicator  species in Minnesota,  such as
•^Plasmolysis is the shrinking of  the  cytoplasm  away from the  wall  of a
 living cell due to water loss by exosmosis.
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E-' caPerat:a  and U_-  subfloridana,  could  be  expected  to show effects of SC>2
at median concentrations of  less  than 2 pphm.

     Recent  studies  of  lichens  in the vicinity  of  the Columbia generating
station  in Wisconsin  (S. Wolf,  personal communication,  1979)  have shown more
subtle responses.   Here, maximum  1-h  SC>2 exposures  at only 3-5 pphm occur
once or  twice a month.  Two  of  four species  studied  (Parmelia caperata and P.
bolliana) showed  significant  increases  in  the number of plasmolysed cells at
the "high" impact sites (1-h  exposures  at  3-5 pphm  once or twice a month)
compared with samples from more remote  sites.   In  another part of the study,
these results have  been related to small changes  in  the abundance of these
and other lichen  species during a 4-yr  field study  of lichen  species
composition  in a  zone around  the  power  plant impacted by the  1-h exposures at
3-5 pphm.  A number  of  secondary  effects,  including  nitrogen  fixation (see
later section) are  influenced by  the composition of  lichens in conifer
forests, and species  changes  over a period of a decade  or more could be
significant  for forest growth.

Effects  of 03 on  lichens—

     The very few studies that  have been made on  the effects  of Og on
lichens  indicate  that at concentrations of about 25  pphm and  below, 03 has
stimulatory  effects.  A study by  Anderson  (1963) cited  in Rosentreter and
Ahmadjian (1977)  concluded that 0^ may  have  induced  production of young
reproductive structures in Cladonia coniocraea,  a  common ground species.
They also cited a study by Sernander-du-Rietz (1957), that suggested
lightning storms  stimulate fruiting of  lichens.

     Rosentreter  and Ahmadjian  (1977) found  that 63  concentrations of 10,
30, 50,  and  80 pphm  for 1 wk  did  not appreciably change the chlorophyll a_
content  of the algae, the thallus color, or  morphology  of the reproductive
structures of C.  arbuscula.   Chlorophylls  a  and  b_  increased slightly at 10
pphm.  Rosentreter  and Ahmadjian  (1977) agreed  with  Anderson  and Sernander-
du-Rietz that 03 may  induce  lichen fruiting. Lichens may thus respond
physiologically to  levels of  63 already reached  on  occasion in the BWCA
(Section 3,  Table 1).  Nash  and Sigal (1979), however,  documented significant
reduction in gross  photosynthesis in Parmelia sulcata and Hypogymnia
enteromorpha when these lichens were fumigated with  0.5 and 0.8 ppm ozone.

     Unpublished  field data  (Sigal, personal communication, 1978) from the
San Bernadino Mountains in California show a marked  reduction in percentage
cover of Letharia vulpina and Nypogymnia enteromorpha on conifers in areas
subjected to oxidants (03 and PAN), compared with  those on control sites.

Effects  of trace  elements on  lichens—

     Work involving  lichens  has not usually  dealt  with  any potential or
possible effects of  trace elements.  One Michigan  study conducted near Lake
Superior established  an inverse relationship between lichen cover on tree
bark and the presence of chloride precipitate found  in  snow (Brown 1977).
Lichen cover varied  from 85%  at 0.001 g/cm H20  of  chloride precipitate to
0% at 0.012  g/cm 1^0 chloride.  Among the  lichens  eliminated  at the higher

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concentrations  of  chloride  precipitate were P.  caperata, J>. exasperatula, and
Physcia millegrana,  all  present  in the BWCA flora (Hale 1969,  Wetmore,
personal communication,  1978) .

Effects of total suspended  particulates on lichens—

     Relatively little  information is  currently available regarding
potential or possible effects  of TSP on lichens.   In his study of snow as an
accumulator of  air pollutants,  Brown (1977) recorded an inverse relationship
between lichen  cover on  tree bark and  the amount  of total particulate matter
present in the  snow.  At 0.045  g/cm t^O of total  solid particulate, lichen
cover was 85%;  at  0.23 g/cm 1^0 it was 0%.  He  did not determine, however,
if this decrease was due to the levels of TSP or  to those of SC>2 and
chloride also measured.

Impacts of acidic  precipitation on lichens—

     Lichens are sensitive  first to the ambient SC>2 concentration, then to
the pH of stem-flow water (Robitaille  et al. 1977).  The gaseous SC>2 and
particulate SO^ are adsorbed onto moist bark surfaces, as well as onto
lichen surfaces, a process  that  decreases pH.

     Lotschert  and Kohm  (1977)  compared ambient S(>2 concentrations with
bark sulfur content  and  pH  of  deciduous trees (which have a higher natural pH
than conifers)  in  Frankfurt.   Where the SC>2 concentration was  less than 2.8
pphm (0.09 rng/m^),  the bark pH was greater than 3.5 and the "greatest
number" of lichens occurred.   As SC>2 concentration increased to 3.9 pphm
(0.10-0.11 mg/m-'),  bark  pH  dropped to  3.1-3.2,  and the lichens disappeared.

     The buffering capacities  of both  bark and  lichens decrease with acidic
precipitation according  to  Robitaille  et al. (1977).  From this 1977 study
these researchers  concluded that stem-flow pH determined bark  pH, thus the
proportions of  sulfurous acid  (^SOg)  and the very toxic HSO-j,
which in turn determine  the presence or absence of sensitive lichen species.
Of the derivatives S02 forms with water, HSO^ is  the most toxic to
lichens (Puckett et  al.  1973,  Robitaille et al. 1977).  In addition, when the
HS05 dissociates to H+ and  S03=, the ratio of S03= to HSO^
(which is 1:1 at pH 7) increases by a  factor of 10 for each decrease of one
unit in pH (i.e.,  10:1 at pH 6,  100:1  at pH 4)  (Turk and Wirth 1975).

     The mapping studies of Gilbert (1970) showed that bark pH and lichen
cover decrease  as  SC>2 increases  and that lichens  only survive  on highly
buffered substrates  (e.g.,  limestone and calcareous soil).  Conifer trees,
the habitat of  many epiphytic  lichens  in northern Minnesota, probably have
bark pH of less than 5.00 (Gough 1975).   Thus lichens on conifer trees have
very little pH  "maneuvering space" and could be expected to be adversely
affected by increasing ambient  SC>2 and resulting  acid precipitation
conditions before  lichens on deciduous trees and  calcareous substrates.

     Denison et al.  (1977)  reported less nitrogen fixation by  Lobaria
pulmonaria at pH 2  than  at  pH  4, 6,  or 8.   As acid rain increases in Pacific
                                      67

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northwest forests,  they  expect  the  nitrogen-fixing  activities on L.
pulmonaria and similar _L. oregana to decrease.

Impacts of acidic precipitation  on  Sphagnum—

     Although much  is known of  the  distribution  of  swamp  and bog organisms in
relation to natural  pH gradients, there  is currently no  complete study of the
effects of acid deposition upon  wetland  ecosystems  (Gorham 1978).

     Gorham (1978) has observed  completely "dead" peat bogs in the vicinity
of Sudbury, Ontario, where both  acid and heavy metal pollution are extreme.
Apparently, a progressive decline in both biotic diversity and productivity
occurs with increasing saturation of the peat exchange complexes by hydrogen
ions.  Direct and secondary effects upon invertebrate and vertebrate animals
may be anticipated,  but  are essentially  unknown  as  are effects upon bacteria
and fungi—which must be presumed vital  to the breakdown  of organic detritus
and the recycling of limiting nutrient elements  such as nitrogen,  phosphorus,
etc. (Gorham 1978) .

     Ferguson et al. (1978) state that the disappearance  of Sphagnum species
from the bog vegetation  of the  southern  Pennines in Great Britain is
correlated with the  Industrial Revolution of  the past 200 yr.  Peat profiles
of the southern Pennines show that  Sphagnum species were  once a much larger
component of the blanket bog vegetation  than  they are now.

     The laboratory  studies (artificial  acid  rain,  immersion, fumigation)
reported by Ferguson et  al. (1978)  suggest that  the growth of a number of
Sphagnum species is  sensitive to sulfur  pollutants  (HSO^, SO^,
802) within the range of concentrations  found in Great Britain today.   The
species differ in their  response to the  pollutants; 0.5 mM HSC>3
eventually proved lethal to the  most sensitive species, but reduced the
growth rate of the most  resistant,  S. recurvum,  by  only 35%.

     Ferguson et al. (1978) also note that in 1973  Tallis determined _S_.
recurvum to be a recent  dominant in the  mire  communities  of north Cheshire.
The only Sphagnum to exist in considerable quantities in  the southern
Pennines today, it  is confined  to flush  areas.   The ability of j^.  recurvum to
withstand relatively high concentrations of the  sulfur pollutants  may
contribute to its ability to survive and achieve dominance.

Summary of effects on lichens and Sphagnum—

     Lichens are among the most  sensitive organisms to air pollution.   Though
response thresholds  for  SC>2 exposure have not been  established for most
species, available  information  suggests  that  effects are  not to be expected
at median S02 concentrations below 0.2 pphm.  Lichens appear to be tolerant
of short-term exposure to relatively high ozone  concentrations (up to  80
pphm).  Lichens on  the trunks of conifers are probably those most  susceptible
to direct effects of acid rain  and  SC^ because their substatum may have an
inherently low pH and be poorly  buffered.
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     Sphagnum has been shown to be  sensitive  to  lowered  pH due  to  acidic
rainfall near industrial areas.  Thresholds for  effects  have  not been
established.

     Concentrations of those toxic  emissions  from Atikokan known  to affect
lichens and Sphagnum are not expected  to  affect  lichen populations  in any
substantial manner quantitatively or  qualitatively.   Some  worst-case rainfall
events in the BWCA may have low enough  pH to  have some effect on  some
species.  Effects (if they occur) will  be subtle and  insidious.

Arthropods (insects)

Effects of SC>2 °n insects—

     The effects of air pollutants  on  insects and plants are  complex.  The
effects of environmental contaminants  on  insect-plant  interfaces may be
reciprocal, acting on the insect through  the  plant  or  on the  plant  through
the insect.  Air pollutants reported  to have  significant effects on
entomological systems include  sulfur  and  nitrous oxides, ozone, hydrocarbons,
fluorocarbons, smog, dusts, acid mists, major and trace  elements,  and
radionuclides.

     Air contaminants accumulate in the tissues  of  insects by ingestion,
respiration, or penetration through the cuticle. These  substances  may act
directly on an insect, be passed through  food webs  to  the  insect,  or
indirectly affect the insect through  alterations in food and  habitat
resources.  Toxic substances may be transferred  through  food  chains to higher
trophic levels and accumulate  in the  insect predators  and  parasites.  Pollin-
ators, particularly social insects  such as bees, appear  to be especially
susceptible to poisoning from  the zootoxins they accumulate during  their
foraging activities.

     Known effects of air pollutants  on insects  include  death of  sensitive
species, proliferation of pest insects  in forests and  croplands,  loss of
parasitic and predacious insects, loss  of saprophagous  insects,  and loss of
pollinators.  Other effects include temporary or permanent changes  in
behavior, reduced hatchability and  fecundity, teratologies, and genetic
alterations such as chromosome disjunction.   No  one has  attempted  to
establish the thresholds of dose responses.   Reported  relationships between
pollutant concentrations and changes  in insect systems  represent,  for the
most part, historical incidents and not a reliable  threshold  of response.
The response  threshold probably occurs  at lower  concentrations  than reported.

     Investigations of S02 effects  by Bromenshenk (1979, 1978b)  and
Bromenshenk and Gordon (1978)  at the  EPA  Zonal Air  Pollution  Delivery System
(ZAPS) in southeastern Montana have demonstrated significant  reductions in
decomposer beetles, particularly Canthon  laevis, on the  fumigated  plots of ZAPS
sites I and II.  Data from 15  cm, the lowest  fumigation  level measured,
indicated that the levels at which  these  beetles first  responded  did not exceed
2.1-2.6 pphm  average  for 30 days.   Because S0£ concentrations decreased
closer to the ground, this level probably was higher  than  that  to  which the
beetles were  responding.  The  decreased abundance  (sometimes  termed

                                      69

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activity abundance) occurred  on  the  lowest  SC>2  treatment  plots at both ZAPS
I and II during 1976 and 1977.   Beetle  captures  demonstrated  a significant
inverse linear regression with  increasing SC>2 expressed as  the reciprocal of
the sulfation concentrations.

     Similarly, Leetham et  al.  (1979) noted  population  reductions with
increasing S(>2 concentrations for  the coleopteran  families  Curculionidae
and Carabidae (predators),  the  lepidopteran  family Pyralidae  (larvae), and
adult grasshoppers (Acrididae).  Also population reductions were observed in
the high-treatment plots at both the ZAPS areas  for tardigrades and rotifers
in the soil.

     Hillmann (1972) studied  insect  populations  near a  615-MW coal-burning
power-generating station in Clearfield  County,  Pennsylvania,  which emitted
172 metric tons (190 tons)  of S02/day.   (Atikokan  emissions are projected
to range from 83 to 192 metric  tons  (92-212  tons)  of S02/day.)  One site
was located 1,219 m (4,000  ft)  from  the  power plant,  the  other 23.5 km (14.7
miles) from the power  plant.  Significantly  greater numbers of Aphididae and
significantly lower numbers of  parasitic Hymenoptera (wasps)  and social
Apidae (bees) were captured at  the site  nearest  to the  power  plant.  Since
aphid numbers in the area exposed  to greater amounts of S(>2 increased
concurrently with parasitic wasp decline, Hillmann concluded  that SC>2 may
have induced host-parasite  imbalance.

     Freitag et al. (1973)  conducted a  field investigation  on ground beetle
populations near a Kraft paper mill  in  Ontario,  Canada,  and found that a
drastic reduction in the number  of carabid  fauna paralleled increasing
fallout of sodium sulfate (^2804) .

Effects of 03 on insects—

     The work on the effects  of  03 on insect systems that has been done to
date has been carried  out under  03 levels higher than would be encountered
in the BWCA-Quetico area.

Effects of NOX on insects—

     As with 03, very  little  seems to be known  about the  effects of oxides
of nitrogen on insect  systems.   The  work that has  been  done has involved
higher levels than would 1  experienced  in  the  BWCA-Quetico area.

Effects of trace elements on  insects—

     Studies have shown that  a  large number  of  trace elements can move
through insect systems, often accumulating  in insects at  the  higher trophic
levels.  Many of these elements  are  toxic to insects at relatively low
concentrations, and many are  toxic to insects at levels lower than those that
affect mammals.

     The most extensive trace-element work has  been carried out on substances
harmful to honeybees.  This work has been reviewed by Lillie  (1972),
Debackere (1972), Toshkov et  al. (1974), and Steche (1975).  Because of their

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extensive foraging  activities,  bees  contact,  gather,  and consume these
materials.  Bees also are magnifiers  of  noxious  substances  in their environs.
Pesticide studies  indicate  that  pollinators  smaller than honeybees may be
more susceptible to toxicosis because they  receive  a  proportionally larger
dose relative to body size  (Johansen  1972).

     A few studies have particular relevance  to  problems associated with
emissions from coal-fired power  plants.   Svoboda (1962)  found that about 500
bee colonies were destroyed within a  6-km radius of a power plant that
released arsenic into the air.

     Hillmann (1972) found  that  social pollinators  and parasites (which are
similar in terms of trophic relations to predators) were most severely
affected by power-plant emissions.  He recorded  a significant decrease in
social insects such as bumblebees and predatory  wasps near  a 615-MW power
plant in Pennsylvania when  compared with populations  at  a site 23.5 km (14.7
miles) away.  Hillman correlated declines in  insect abundance with 863
levels, but did not analyze for  trace elements.   Many trace elements are more
toxic to bees than  sulfur dioxide (see review by Debackere  (1972)).

     Dewey (1972) found relatively high  fluoride levels  in  the 1,005 preda-
tory insects collected near an  aluminum  smelter  which reportedly emitted
between 1,134 and 2,837 kg/day  (2,500 and 7,600  Ib/day)  of  fluoride.  Four
major groups of insects were collected within a  half  mile of the plant:
tissues of pollinators contained 5,800-58,500 pphm  fluoride; predators
610-17,000 pphm; foliage  feeders 2,130-25,500 pphm; cambial feeders 850-5,250
pphm.  Levels in the control groups,  taken  at least 80 km (50 miles) away,
ranged from 350 to  1,650 pphm.

     Bromenshenk (1976, 1978a,  b, 1979)  reported that preoperational and
postoperational studies of honeybees  taken  from  commercial  apiaries near two
350-MW power plants in southeastern Montana  showed  significant increases in
the levels of fluorides in or on the  tissues  of  adult worker honeybees.
After 1 yr of operation, during which neither plant had  been in continuous
operation and both had operated  at one-third  to  one-half capacity,  fluorides
increased by as much as twofold  in bees  taken from  apiaries downwind and as
far as 15 km away from the plants.  There were no increases in fluoride
levels in bee tissues upwind from the power  plant.

     Other elements from coal combustion also affect  insect populations.
Before to the development of synthetic organic insecticides, several
inorganic chemicals were widely used  for insect  control. These included
compounds of arsenic, fluoride, mercury  selenium,  antimony, boron,  and
thallium (O'Brien 1967).  The first six,  and  possibly all seven,  are released
by combustion of coal in electric power  generating  stations.  The mercury
content of the coal, emission rates of Hg, deposition fluxes,  and background
levels in fish from lakes of the BWCA have been  characterized elsewhere in
this report (Table 2, Figures 7, 8, 9, 10).   Based  on concentrations in
Saskatchewan lignite coal (Appendix C),  the  ratios  of some  other toxic
elements to mercury in coal are 268-430  for  fluoride, 21-34 for arsenic,
0.59-3.0 for cadmium, and 2.5-4.0 for selenium.   Taking  into account the
concentration in precipitator fly ash, and assuming that these materials are

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emitted in ways similar to mercury,  estimated  emissions  as  a ratio to mercury
are 233-399 for fluoride, 14-28 for  arsenic, 0.42-2.4  for  cadmium,  and
1.3-3.2 for selenium.

     Fluoride and arsenic are  likely to  be  released  in quantities much
greater than mercury, and they are of particular  concern with regard to
long-term, low-level exposures, since many  compounds of  fluoride and arsenic
act most effecively through slow release by weathering and  rapid release in
the gut (O'Brien 1967).  In addition, honeybees  and  presumably other
pollinators are magnifiers of  arsenic and fluoride  in  their environs
(Bromenshenk 1979).  According to Debackere  (1972)  danger  to bees from
arsenic poisoning is greatest  when:   (1) the wind has  blown in the same
direction for extended periods, (2)  precipitation has  been  low or infrequent,
(3) in spring when blossoms are few  and  foraging  is  intense,  and (4) after a
heavy dew, fog, or mist.  Whereas arsenic poisoning  often  causes sudden
die-off for a few days, fluoride poisoning  usually  occurs  as  death over a
long period (Lillie 1972, Debackere  1972).  Both  fluoride  and arsenic
compounds may be stored in food supplies resulting  in  even  longer exposure
periods (Bromenshenk 1978a),  and severe  bee kills near industrial sources of
arsenic and fluoride are well  documented (Lillie  1972, Debackere 1972).

     In a later section on aquatic ecosystems  (Section 5)  concern is
expressed that:  (1) mercury has been found to occur in  fish at levels in
excess of FDA standards, (2) the sources of mercury  are  unknown, and (3)
emissions from the Atikokan power plant  may increase these  levels.  Whatever
the source, where mercury is  found,  elevated levels  of other injurious trace
elements are also likely to be found.  In view of the  high  toxicity of
arsenic and fluoride to insects, and because large  quantities of these
materials (in comparison to mercury)  are to be emitted by  the Atikokan power
plant, more information is needed about  the background levels of these
substances in the BWCA and in  the insects,  vegetation, and  soil of the
region.  With these background data  the  significance for entomological
systems of the worst-case concentrations and depositions could be evaluated.

Summary of effects on  insects—

     Although responses to threshold exposures to pollutants have not been
established, a number of insect groups with strong  sensory  systems,
particularly saphrophagous and predacious beetles,  social  bees (pollinators),
and parasitic wasps, have been shown to  be  reduced  in  abundance at very low
concentrations of air  pollutants, apparently because of pollutant avoidance
or disorientation, or both.   Several plant-feeding  insect  groups increase
rapidly when the activity of  parasite or predator-control  insects is reduced,
or the vigor of host-plant species is reduced, both  of which have been shown
to occur  from gaseous  air emissions. If physiological stress is demonstrated
by the host coniferous trees  in the  BWCA, concurrent alterations in
entomological systems will occur.  The available  literature suggests that
disturbances in the population dynamics  of  phytophagous forest insects may
occur at  levels below  those manifesting  visible  injury to  pines.  Direct
injury to the vegetation of the BWCA by  exposures to pollutants from the
Atikokan  power plant,  and from other regional  sources  if incurred, could be
intensified by insect  interactions.

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Amphibians

     In the United States  50%  of  the  frog  and toad species breed in temporary
pools formed annually by accumulated  rain  and melted snow.  One-third of the
species of salamanders  in  the  United  States  that  are aquatic before
metamorphosing into terrestrial adults  also  breed in temporary ponds.  Such
ponds are more fragile  than  lakes  or  streams because their acidic
precipitation input has little contact  with  soil  buffer systems and is not
diluted by mixing with  standing water (Pough 1976).

     A study of embryonic  mortality of  spotted salamanders (Ambystoma
maculatum) (Pough 1976) showed less than 1%  egg mortality in pools near
neutrality, but more than  60%  in  low  pH (less than 6)  ponds, with an abrupt
transition in mortality below  pH  6.   Furthermore, field results were
reproducible in the laboratory, where effects of  both  predation and
temperature were eliminated.

     Other studies of anurans  include one  in which the breeding sites of most
anurans in or near the New Jersey  Pine  Barrens were  limited to grassy ponds
and gravel pits resulting  from the normally  lower pH (3.6-5.2) of sphagnous
pools (Gosner and Black 1957). Prestt  et  al. (1974) postulate that
acidification of anuran breeding  sites  may be contributing to the recent
decline in British frog populations.   Pough  (1976)  reiterates the earlier
observations of several authors that  the significance  of any widespread failure
of salamander reproduction will have  far-reaching consequences.  Salamanders in
temporary ponds are an  important  predator  on dipteran  larvae (flies) and an
important energy source for higher trophic levels in an ecosystem (as are other
anurans such as frogs).  Pough also notes  that these ponds are major breeding
sites for many invertebrates as well.   Changes in these ponds could therefore
limit the breeding of numerous species, while allowing pest species to
flourish.

     Some changes in the acidity  of standing pools in  the BWCA may occur
because of acidic snowmelt and acidic  precipitation.  If this change occurs
in the spring, salamander  reproduction  may be affected.

Soils

     The configuration of  granites, slates,  and argilites and ultrabasic
bedrocks in the BWCA have  determined  the local patterns of soils and
land forms.  Glacial scouring also  has  exposed the bedrock on many ridges and
left only a shallow varying cover  of  till  on the  slopes and ravines.
Although locally some soils are deep,  large  areas of thin rocky soils are
derived from sandy glacial deposits.   These  soils are  among the most
sensitive in the Superior  National Forest  area (Heinselman 1977).

Bedrock geology—

     Bedrock in the Voyageur's National Park and  the Boundary Waters Canoe
Area shows a wide variation in rock types.   All bedrock found in the two
parks is part of the Precambrian  (>600 m.y.)  Canadian  Shield and is covered
by varying depths of glacial till, outwash,  and lacustrine material deposited
during the Wisconsin stage of  glaciation.  Bedrock in  the VNP is part of a
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high grade metamorphic terrain, with  schists, gneisses, migmatites,  and
granites as major rock types; minor feldspathic quartzite  and metaconglom-
erate are also present.  Metamorphic  grade  increases  to the  south  and  east.
Rock types present in the VNP include 50% (of park area) metagraywacke and
biotite schist, 20% schist-rich migmatite with 25-75% paleosome  (a migmatite
is a rock that has been raised to temperatures and pressures high  enough  to
cause partial melting; paleosome is that portion  of rock which does  not
melt), 12% granite, 10% granite-rich migmatite, 4% mixed metavolcanic  rocks,
2% leucogranite, 1% feldspathic quartzite/metaconglomerate,  1% quartz-
feldspar gneiss.

     The BWCA contains rocks generally representative of a much  lower
metamorphic grade terrain than that seen in  the VNP as well  as a much wider
variety of rock types.  The western portion  of the BWCA, that occurring west
of R8W-R9W (91°25'W) boundary and north of Highway 18 (47°58'N)  consists
dominantly of rocks of the Vermilion Massif, a series of granitic  intrusives
ranging from diorite to granite.  Related rocks include granite-rich
migmatite, amphibolite-migmatite and biotite schists.  The migmatites  found
in the VNP represent the northern contact zone of the Vermilion Massif with
surrounding country rock (Southwick 1972).   On the eastern edge  of this
portion are rocks of the Newton Lake Formation, a series of mafic  to
intermediate metavolcanic flows and tuffaceous sediments (Sims 1972),  rocks
of the Knife Lake Group, which include slate-graywacke, conglomerate,
arkose-graywacke, agglomerate, and andesite  porphyry  (McLimans 1972),  and
rocks of the Ely Greenstone, a series of dominantly basaltic and diabasic
metavolcanic flows (Sims and Viswanathan 1972).

     The central portion of the BWCA, that  area between R8W  to R11W  (91°25'W
to 91°40'W) and R1W (90°31'W), below  the Gunflint Trail, contains  a  wide
variety of rock types.  This area is dominated by rocks of the Duluth  Gabbro
Complex, a series of mafic  intrusions ranging  from gabbroic  to troctolitic to
anorthositic.  Within, and  surrounded by, the Duluth  Complex are rocks of the
North Shore volcanic group, a series  of lava flows dominantly basaltic but
with appreciable amounts of felsic and intermediate flows.

     The remainder of the area, that  north  of  the Duluth Gabbro  Complex
contact, is underlain by a variety of rock  types.  The majority  of the Knife
Lake Group occurs in the western half as do  minor amounts  of Ely Greenstone
and rocks of the Giants Range Batholith, a  series of  tonalitic (quartz
diorite) to granitic intrusions (Sims and Viswanathan 1972).  The  Saganaga
Batholith, dominantly tonalitic in composition, is present east  of the Knife
Lake Group.  Minor amounts  of metabasalt, metaandesite and metadiabase
(minor) are also present to the south and southwest of the Saganaga
Batholith.  Part of the Gunflint Iron Formation occurs along the Duluth
Gabbro Complex Contact.  In addition  to the  forementioned  rock formations,
small granitic to andesitic intrusives are  present, and are  generally
associated with the Knife Lake Group.

     The eastern portion of the BWCA, that  between R2W (91°31'W),  above  the
Gunflint Trail (47°54'N), and R2E (90°15'W), is dominated  by the Rove  Formation
(graywackes and argillites) and the Logan Sills,  a series  of diabasic  dikes  and


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sills which  intrude  the  Rove  Formation.   To the south a lesser amount of Duluth
Gabbro  is present.   By visual  estimate,  the area covered by each rock type (for
the entire BWCA)  is:

     Duluth  Complex                40
     Vermilion Massif              30
     Knife Lake Group               8
     Saganaga Batholith             5
     Granite-rich magmatite         5
     Logan Sills                    3
     Rove Format ion                 2
     North Shore Volcanic  Group     2
     Newton  Lake  Formation         2
     Giants  Range Batholith         2
     Ely Greenstone                 1

Distribution of poorly buffered  soils—

     A  number of  soil  surveys  have been  carried out on parts of the BWCA, but
the survey by Prettyman  (1978) of  the  Kawishiwi area of Minnesota covered an
area central to the  BWCA and  included  the soil-type boundaries on printed
aerial  photographs.  Lakes and streams associated with the deeper soils in
the BWCA seem less  likely  to  show  effects from acid rainfall within the
immediate future.

     The report by Prettyman  describes 22 soil-mapping units in the Kawishiwi
area.   These units are grouped into roughly 12 soil types, half loosely
defined (e.g., "peat and muck" and "poorly drained loamy soils").  The
principal soil types covering a  large  acreage  are the following:

             Barto                          Gravelly coarse sandy loam
             Conic                          Gravelly sandy loam
             Insula                         Gravelly sandy loam
             Mesaba                         Gravelly sandy loam
             Quetico Rock  Complex           Loam

     Of these five types the Mesaba and  Conic  soils are described as usually
deep soils,  51-102 cm  (20-40  in.)  to bedrock,  whereas the Barto and Insula
soils are 13-51 cm (5-20 in.) deep.  The Quetico Rock Complex has soils that
range from 10 to 20  cm (4  to 8 in.)  deep,  and  although its texture is given
as "loam," this texture  refers to  the  portion  of the soil that is not coarse
fragments and small  rocks.  Thus,  if the capacity of the soil to withstand
additions of hydrogen  ions can be  measured by  a combination of soil texture
and total soil depth (within  the specified mineralogy of the Canadian Shield
bedrock types), then we  can define a soil  grouping within the Kawishiwi area
by combining the three shallow soils,  Barto,  Insula, and Quetico, despite the
fact that some differences in texture  and  geological origin can be
recognized.

     Chemical data on  these shallow soils  are  quite limited.  Results of a
number of analyses for the Barto soils have been provided, however,  by
personal communication from Dr. Prettyman.  These results indicate the
following cation exchange  capacity (CEC)  and  percentage base saturation:
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                                              CEC
        Soil                               (meg/lOOg)          Base
        series       Horizon      pH       average        saturation  (%)
        Barto          B 21      4.8        24.21             18.63
                       B 22      5.2        21.95             16.58
                       B 3       5.7        13.78             10.39

The data here contrast with similar analyses  for Mesaba  soils.   The  latter have
37% base saturation in the parent material horizon  (compared  with  10%  for  Barto
soils).  The higher base saturation in the upper horizons  of  Barto  soils (18%)
probably reflects the increased organic matter and  clay  content  and  the
different type of exchange sites present  there.

Effects of Acidic Precipitation on Soils  —

     The absence of a large soil volume for geological weathering  greatly
influences the potential for small watersheds to withstand  changes  in  the
rate of addition of hydrogen and sulfate  ions from  the atmosphere.   These
pollutants are likely to enter the soil environment primarily through
precipitation, stem flow (precipitation draining along the  trunks  and  stems
of vegetation), and throughfall (precipitation filtering through the forest
canopy).  Pollutants transported long range will probably  enter  forest
systems primarily through precipitation.  Effluents from local  sources may
also contribute to this regional precipitation loading.  In addition,
quantities of local pollution will be dry deposited on vegetation.   The
fraction of this material which is not biologically assimilated  will be
subject to leaching by precipitation and  will enter the  soil  as  stem flow or
throughfall.  Stem flow and throughfall may be considerably enriched in
pollutants compared to precipitation carrying only  the regional  atmospheric
load (Abrahamsen et al. 1977).

     The most significant soil-mediated effects may result  from  the  fact that
rainfall bearing pollutant loads initiated as 862 or NOX has  depressed
pH.

Effects of Acid Precipitation on Geochemical  Weathering—

     Since the pH of water in contact with minerals has  a.  marked effect  on
weathering products that result during the breakdown of  mineral, changes in
the pH of precipitation also have effects on  the products  and rate  of
weathering.  Through hydrolysis specific  cations can be  removed  from the
mineral, allowing a more rapid change of  crystal structure.   Jenny (1950)
showed H+ replacing Na+, K+, or Csr+ in the crystal structure or
bonding with an 0 to form an OH" group.   The  H+ ion is very important
because its size allows easy penetration  into the mineral,  and  its  high
charge-to-radius ratio has a marked disrupting influence on the  crystal's
charge balance (Loughnan 1969).
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     Birkeland  (1974)  determined  a series of mobilities for various ions and
found:

     Ca2+ > Na1 + > Mg2+ >  K1+  > Si4+ >  Fe3+ > A13+.

Under the normal pH  produced by background levels of carbonic acid (112003),
values for Fe   and  A13+ are generally  so low as to be negligible.
Situations do occur, however,  where  the pH of soil solutions is such as to
allow Al to become soluble.  In well-drained northern soils containing
abundant organic matter a  pH of < 4  is  possible.  The compound A^C^ may
become mobile and migrate  to a less  acidic area and be precipitated (Loughnan
1969).

     Where precipitation exceeds  evaporation and soils are very permeable,
several pH dependent responses are observed:

     1)  Most of the Na+,  K+,  Ca2+,  and Mg2+ is leached.

     2)  A10   and Si0 are released.
         a.  If  soils  are  neutral  to alkaline with low Csr+ and Mg  ,
             SiC>2 may  leave  in solution as does Na+ and K+.

         b.  If  moderately acidic  (4.5-6.5),  Si02 and Al2C>3 are
             immobile  with the development of clay or a fine-grained mixture
             of  gibbsite  (AHOH^)  and quartz (Si02).

         c.  If  highly acidic  and  rich in humic or other organic material,
             Al2C>3 and Fe2C>3 may be removed in solution (Moore and
             Maynard 1929)  (Figure 14).

     Since background  levels of H+ in these major soils are traceable to
the carbonic acid in water,  as well as the humic reactions, additions of
H+ from nitric and sulfuric  acid in precipitation can dominate the
inorganic reactions.   The  separation of A13+  and Fe3+ may also be
seen in soils  that show  some  evidence of podzolization, a process where Fe ,
Al, and  organic material  are  leached from an eluvial (exit) horizon to an
elovial (into) horizon below.   Recent work suggests that Fe and Al are
carried as part  of a metallo-organic chelating complex, of which fulvic acids
are thought to be the  common chelating compounds for a number of soils.
Fulvic acids are produced  in the A or 0 horizons and chelate with A13+
and Fe3+ ions or with  A13+ and Fe3+ hydroxy ions.  Because these
compounds are  water soluble they  can be carried downward with percolating
water.  At some  depth  in  soils the complexes  are destroyed and the metals
deposited, but if the  percolating  water reaches a soil or bedrock channel,
the metals can be carried  with the organics to a stream or lake.  Van
Schuylenborgh (1965) suggested that the organic portion of the molecule may
be destroyed by  microbial  action,  with release of the cation.

     Work by Schnitzer (1971)  clarified the fulvic acid-metal complex
transfer.  Under constant  pH the complexes became more insoluble as metal
                                     77

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                       78

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 ions were  added  to  the  fulvic  acid solution; 1:1 molar Fe^+-Al^+-
 fulvic acid  complexes were  completely soluble while 6:1 complexes were water
 insoluble.   Even 2:1 complexes showed decreasing solubility.

     Thus  transfer  of Al^+  and Fe^+ could be envisioned as follows.
 Fulvic acid  is formed in  the A or 0 horizon and, being water soluble, is
 transported  downward by percolating waters, constantly picking up Fe-*
 and Al   .  As more  metallic ions  are picked up, the complex becomes
 insoluble  and can be precipitated in the B horizon if it has not reached a
 bedrock  surface  or  stream channel.  Schnitzer (1971) showed that up to 56 g
 of iron  or 27 g  of  aluminum can be dissolved and kept in a solution by 670 g
 of fulvic  acid.   These  values  are equivalent to 84 mg of iron or 40 mg of
 aluminum per gram of fulvic acid.

     Recent  experiments indicate  that increased acidity of precipitation,
 through  additions of dilute nitric and sulfuric acid, also can affect these
 and other  reactions  in  the  soils.  Availability of nitrogen, decreased soil
 respiration  and  increased leaching of nutrient ions from the soil have been
 reported (Abrahamsen et al. 1977).  Since acid rainfall adversely affects
 many other components of  the soil-plant-water relationship, it has not yet
 been possible to demonstrate clearly the nature of causal relationships in
 the field.   It is possible  that acid damage to shallow,  poorly buffered soils
 might  initially  be  partly offset  by the nutritional benefits gained from
 nitrogen compounds  commonly occurring in the acid rain.   Changes detected to
 date in  soil processes  are  too small to affect plant growth, but the studies
 have been  in areas  of deeper soils than in the BWCA.  In addition, the
 enhanced acidification  of soils produces a continuous loss of essential
 cations  and  eventually  the  addition of nitrogen is of no advantage if other
 nutrients  are not available.

     The H+  additions associated  with the projected increase in SO^
 deposition of 0.9-1.4 kg/ha-yr over the apparent presettlement depositon of
 4-5 kg/ha-yr (Section 3)  appear to be an increase of consequence for element
 transformation and mobilization on the poorly buffered soils in this region.
 Elements mobilized  in this  fashion may be taken up by plants,  may reach
 streams  via  the  shallow groundwater,  but most often will be carried to
 deep,  slow-moving groundwater  surfaces.  Here, these elements may remain in
 their more toxic  forms  for  extended periods and, in this sense an
 irreversible effect  is  produced.

 Nutrient Cycling

 Soil-mediated effects of  acidity  on vegetation—

     Although the relationships between soil acidity and vegetation growth,
metabolism,  and  reproduction are  receiving increasing attention, many areas
of uncertainty remain.  The following discussion will focus on available
 information  concerning  soil-mediated effects on:  (1) decomposition of
 organic matter;  (2) effects of cation losses and mobilized toxic elements on
 growth of  coniferous species;  and (3) reproduction of coniferous species.
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     Any potential reduction  in  a  soil's  cation exchange capacity and
essential nutrients, such as  discussed  in  the  previous  section,  will affect
the growth of the trees  it  supports.  In  general,  forest plants  obtain the
nutrients necessary for metabolism  and  growth  primarily from soil.
Atmospheric sources are either indirect (mediated  by soil)  or secondary in
importance.  Therefore, the potential for  reduced  availability of these
nutrients in forest soils is  of  concern.

     In an unmanaged forest near its climax  successional state important
macro- and micronutrients tend to be conserved in  the  soil-plant system.
Most remain within the cycle  of  organic production,  decomposition,  and
mineralization  followed by  reincorporation into living  material.  Leaching
losses in ground water are minimal  (Frink  and  Voigt  1977) .   Nutrient cycles
are not closed, however.  Precipitation and  nitrogen fixation are important
sources of nutrients to the forest  (Ovington 1962),  and additional  supplies
of nutrients are made available  by  weathering  of soil  particles.  These
inputs are countered by some  ground-water  leaching.   Potential effects on
plant-soil interactions may result  from effects on inputs  and outputs to
nutrient cycles as well as  soil-mediated  changes in  rate within  the cycles.

     Since Al^  is highly toxic  to  plants,  the mobilization of this element by
additions of H+ to the soil medium  can have  important  detrimental effects on
nutrient utilization and growth.  Although Al^+ toxicity is well known for crop
plants, it is only now being  investigated  for  the  common tree species (McCormick
and Steiner 1978) .

Sulfur and nitrogen cycles—

     The capacity of a forest to utilize  additional  sulfur  is often closely
related to the nitrogen cycle.   The two nutrients  usually  are utilized in a
fixed ratio.  If nitrogen is  abundant,  the system  may  be sulfur  limited and
have a considerable capacity  to  absorb  anthropogenic sulfate.  Such inputs of
sulfates might well stimulate increased growth.  In  such cases ttjSO^ in
rainfall might not increase soil acidity  or  degrade  the nutrient pool.
However, mature timber stands are more  likely  to be  nitrogen limited than
sulfur limited.  If the capacity of these  systems  to utilize anthropogenic
sulfur inputs is exceeded,  deleterious  effects of  I^SO^ on  the
ecosystem's nutrient pool are possible.

     As in the  sulfur cycle,  overall production and  consumption  of H+ ions
in the nitrogen cycle are balanced.  Loss  of soil  bases and acidification are
still possible, however.  When mineralization  occurs followed by oxidation of
ammonium ion to nitrate, H+ ions formed will replace basic  cations.  These
basic cations are then subject to  leaching in  association with nitrate ions
as water passes through  the soil profile  if  conditions  allow any buildup of
nitrate ion (e.g., if the system is other  than nitrate  limited)  (Reuss
1977).
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     Most natural  ecosystems  tend to maintain low nitrate levels because
nitrates formed  are  rapidly taken up by the vegetation.  In nitrogen-limited
forests anthropogenic' nitrates  may stimulate plant growth.  This would
prevent increased  soil  acidity  due to processes within the nitrogen cycle and
also accelerate  sulfate uptake  reducing the potential for acidification due
to processes  in  the  sulfur cycle.

     Acid rain  is  postulated  to decrease decomposition rates through adverse
effects on microbial  activity (Oden 1976,  N. R. Glass 1978).  Apparently soil
pH values below  3.5  are required before effects on decomposition of pine
needles can be seen  (Abrahamsen et al.  1977).  Negative effects of soil
acidification in pine  forests on microbial activity have been shown, but the
effect on decomposition was unclear (Tamm et al. 1977).

     The direct  effects of pollutants on ground beetles cited earlier can
have a marked effect  on rates within the nutrient cycle.  Benefits of
decomposer beetles  include the  return of nitrogen and inorganic phosphate,
the reduction of surface runoff,  burial and mechanical breakdown of organic
materials, decreasing  wastage of organic materials, increased surface storage
of nutrients, reduced  loss of nutrients in runoff,  and increased infiltration
and storage of moisture in the  soil.  In addition,  these arthropods serve as
food for other insects  and higher animals,  aid in the dispersal of soil
microflora and microfauna, and  may compete with less desirable (from a human
viewpoint) insects  such as hornflies for organic material resources (Ritcher
1958, Macqueen 1975, McKinney and Morley 1975).  In forest systems as much as
90% of the net primary  production does  not  pass through herbivore food chains
but is deposited on  the soil  as litter  and is acted on by complexes of
animals, fungi,  and  bacteria  (Kurcheva  1960,  Edwards and Heath 1963, Cross ley
1970, Whittaker  1975,  and others).  Examples of resource partitioning by
saprophagous  arthropods are numerous,  and  their role in resource partitioning
and their use as indicators of  environmental quality has been reviewed by
Cornaby (1975, 1978).   He comments that they may have an exploitable role in
the deactivation of  noxious materials and  decomposition of slowly degrading
materials.  Also, he points out  that they  may be very important as regulators
of the rate of release  of nutrients and as  detectors of subcritical levels of
pollutants in soils.

     Specialists in  the field of soil-litter arthropods seem to agree that
these insects are susceptible to harm from pollutants and that they may
affect important functional components  of  ecosystems.  From a theoretical
study Harte and  Levy  (1975) and Dudzek  et  al. (1975) concluded that damage to
decomposers or nutrient pools is  a potential source of instability to the
entire ecosystem.

Influence of affected  lichens on nitrogen  inputs in forests—

     The potential reduction  in  nitrogen-fixing lichens or in their rate of
nitrogen fixation would have  most  effect in highly  nitrogen-deficient soils,
such as those in the BWCA.
                                       81

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     Although most  lichens  contain  only  green algae,  several genera contain
only nitrogen-fixing blue-green  algae  or blue-green  algae in addition to
their green  algae.  Lpbaria pulmonaria (on  Thuja occidentalis and sandy rocks
in northern  Minnesota), many Peltigera and  Nephroma  species (on soils,  duff,
and moss), and Sterocaulon  paschale (on  soil) contain blue-green and green
algae.  Leptogium and  Collema species  (on soil  and rock)  contain only blue-
green algae.  The percentage of  cover  of these  lichens and their contri-
butions to the nitrogen regime of Minnesota forests  is not presently known.

     Forman  and Dowden (1977)  manipulated laboratory  figures (Scott 1956,
Millbank and Kershaw 1969,  Henriksson  and Simu  1971)  for  amounts of fixed
nitrogen and determined that three  Peltigera species  (P.  canina, P.
rufescens, and _P_. praetextata) would  fix a  total of 0/05-0.6 g N Tm2 lichen
cover)"  day"-*- in a spruce-fir forest  in Colorado.

     Denison et al. (1977)  investigated  the current  status of ^ fixation
in western Washington  forests  and the  potential  effects of acid rain on this
process.  It is thought that even the  low concentrations  of S02 now found
in this area have a deleterious  effect  on N2 fixation by  restricting the
distribution of the ephiphytic ^-fixing lichen, Lobaria  pulmonaria.  This
species, also present  in the BWCA,  is  found in  the Pacific Northwest forests
only where the mean annual  SC>2 concentration is  less  than 5 yg/m^ (0.175
pphm), a figure lower  than  some  background  levels already recorded in the
BWCA (Section 3, Table 1).   Lobaria pulmonaria  fixes  100  times more nitrogen
than does litter and 10,000  times more nitrogen  than  soil organisms in  these
acid forests.  The  sensitivities of Peltigera species are not known.

     The rate of fixation of L.  pulmonaria  is about three times that of L.
oregana (Denison et al. 1977), the  major N£ fixer of  old  growth and
coniferous forests  in  the Pacific Northwest.  After exposure to l^SO^ of
pH 4 or less, L. oregana fixes less N2 •

     Kallio  and Varheenmaa  (1974) exposed Stereocaulon paschale and Nephroma
articum to the air  of  Turku.  Finland,  where maximum SC>2 values in 1969  were
5.36 pphm S02 (153  yg  SO^/m^) with  NO^ and  sulfates.   Nitrogen
fixation decreased  to  10-20%  of  controls.   They  suggest that the SC>2
combined with water on  the  lichen structures  containing the blue-green  algae
decreases the pH of the medium sufficiently to  interfere  with the metabolism
of the blue-green algae.

Influence of Affected  Trees  on Insect  Populations

     Three authors  have reviewed interactions among air pollutants,  plants,
and insects  (Heagle 1973, Hay  1975, Ciesla  1975).  Heagle notes "a common
finding is that trees  injured and weakened  by pollutants  are more likely to
be atacked by insects  that  normally require weakened  trees for successful
reproduction."  Ciesla  (1975) concludes  that  photochemical oxidant injury  to
ponderosa pines in  the  San  Bernardino  Mountains  predisposed the trees to bark
beetle attack.  The understanding of the physiological mechanisms involved
needs to be determined  for  other combinations of pollutants, trees,  and
insects.
                                     82

-------
     Pest  insects do  not  always  proliferate in areas subjected to air-pollu-
tion stress.  In some  instances  declines  in pest-insect populations have been
observed.  The difference  in  response  appears to be a result of interactions
of many variables.  One variable seems  to  be feeding habit.   Several lines of
evidence indicate that stress  from pollutants such as S0£ and natural
occurrences such as drought may  reduce  the tannin content of leaves (Feeny
and Bostock 1968, oak  leaves)  and needles, which results in more free or
unbound protein foliage.   Thus the foliage becomes more nutritious and a
"better" diet for foliage-feeding insects  (G. Orians, University of
Washington, personal  communication,  1978).

     Our understanding of  the  effects  of  air pollutants on tree-insect
relations  depends almost entirely on geographical historical surveys of trees
severely damaged by pollutants,  insects,  or combinations of the two.  No
attempts have been made to determine dose-response thresholds.  In most
cases patterns of insect  outbreak relative to a pollution source, deviations
from normal outbreak  patterns, or the  appearance of insects  in outbreaks that
rarely reach epidemic  levels  have been  described (Ciesla 1975).  Carlson et
al. (1974a) used stepwise  multiple regression analyses and demonstrated that
foliar fluoride content was  significantly  related to damage caused by
complexes  of foliage-feeding  insects.   Some of the observed insect-tree
pollution  interactions are summarized  in Table 9.

     In an attempt to  identify research problems considered critical for an
acceptable understanding of  the  interactions of air pollution and wood
vegetation, Bromenshenk and Carlson  (1975) concluded, "There can be no doubt
that air contaminants  are  harmful to insect pollinators, although the exact
processes  are not understood.  Many  forest trees and shrubs  would not produce
seeds or reproduce themselves without  insect pollinators...".  Changes in the
population dynamics of forest pest insects may result from a predispositon of
the host to insect attack, as described earlier.

Bioaccumulation

     Many  trace elements are  accumulated and concentrated through food-chain
processes.  Organisms at higher  trophic levels often have higher tissue
concentrations than do their  prey.   Potentially toxic compounds from the
Atikokan generating facility may become accessible and toxic to various
organisms  through this process of biological magnification.   The processes by
which this could occur are discussed below.

Trace-element availability from  soils  and  plant uptake—

     Factors affecting trace-element availability include pH,  organic matter
content, soil drainage, soil-microorganism content,  cation exchange capacity
(CEC),  and anion content.  Plant-root components may also affect nutrient
uptake by  releasing organic compounds  into the surrounding soil, modifying
the soil environment,  and  thereby modifying trace-element uptake (Tiffin
1977).
                                      83

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     Soils already high  in various  trace  elements  may be  more vulnerable to
additional trace-element load, although in depleted  or nutrient-poor soils
various trace elements (e.g., Mo, B,  Zn)  may  improve the  nutrient  composi-
tion.  In recent studies of the environmental  impact of trace elements added
to soils as a result of  coal  combustion (Vaughan et  al. 1975, Dvorak et al.
1977, Dvorak and Pentecost 1977), predictions  of particulate  deposition for
areas proximate to the power-plant  model  amounted  to less than 10% of the
total endogenous content of trace elements.   Each  affected site must be
examined individually, however, since  these models assumed worldwide soil
concentrations of trace  elements and  the  variability factor among  various
soils may be as much as  several hundred.

     The rates and processes  involving trace  elements are complex, and
factors controlling trace-element uptake  in plants are not yet very well
understood.  Once absorbed into the root  system, however,  trace elements may
be translocated to shoots which herbivorous animals  may consume.  Plants as
well as animals vary in  their sensitivity to  trace-element accumulation, and
different plant and animal organs respond differently with respect to trace-
element uptake.  Obviously, the elements  that  are  taken up in large
quantities and stored  in organs preferred by  certain wildlife forms
constitute a hazard to each trophic level in  which this occurs.  Furthermore,
the rate of vegetation turnover from  grazing  wildlife will modify  the rate at
which material stored  in shoots is  recycled to the soil.

     The bioaccumulation potential  in  various  food chains requires much more
study in terrestrial animals.  Food habits change  seasonally, and  seasonal
movements may take animals out of the  path of the  area of particulate
fallout, unless winds mix the pollutant path  over  a  large area.  This fallout
may be exacerbated by  secondary pollutant sources  from outlying areas, such
as is expected for the BWCA from the  industrial north as  well as areas on
either side of the Mississippi River,  extending down to the Gulf of Mexico.

     Incremental deposition of trace  elements  from the Atikokan facility onto
the BWCA is estimated  to be comparatively small.   The increase in deposition
of Hg predicted in Section 3  is being  further  investigated.

Impact of trace elements on terrestrial vertebrates—

     The penetration of  trace elements into animal systems largely occurs by
inhalation and ingestion (in  food or  water).   Cutaneous absorption becomes
more critical in aquatic vertebrates,  especially amphibians (such  as
salamanders and frogs) and fish (which can absorb  certain elements through
their gills).  Virtually no information is available on the long-term effect
of low-dosage intake of  various trace  elements upon  wildlife species,
information essential  to an understanding of  the long-term or cumulative
effects, or both, of trace-element  accumulation.

     Dewey's (1972) investigations  show that  fluorides may build up in
insects of the higher  trophic levels,  and he  expressed concern that fluoride
accumulated by insects could  affect insectivores up  the food chain.  Gordon
et al. (1978) are attempting  to determine that portion of the diet of deer
                                      88

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mice which constitutes  a  fluoride  source  for  mice with excessive fluoride in
their femurs.  Their data  indicate  that  insects  represent  a considerable
percentage of the diet.

     Kovacevic and Da'non  (1952,  1959)  analyzed  stomachs of 136 species (34
families) of birds in Yugoslavia and  found  beetles representing 31 species
(17 families).  Numerous  other  studies both in  Europe and  the United States
attest to the importance  of  insects  as a  food resource to  birds.  Thiele
(1977) provides a review  of  the  predators of  a  specific family of insects
—the carabids.  He lists  hedgehogs,  shrews,  moles,  bats,  rodents, mice, and
birds (including owls and  other  birds  of  prey).

     The population of  timber wolves  (Canis lupus) in northern Minnesota is
the largest of the continental 48  states.  Because of their size wolves do
not appear to be immediately vulnerable  to  trace-element discharge,  unless it
exceeds processing limits  of soils  and plant  systems.  The prey animals that
are herbivores will constitute the  interface  between trace elements  in plants
and in wolves.

     The eastern pine marten (Martes  americana  americana)  is a fur-bearing
carnivore of considerable  economic value  in past  years.  Since the principal
regular food  item for the  marten is  the  small mammal (such as the red-backed
vole Clethrionomys gapperi in the  BWCA),  the  greatest impact of trace
elements upon marten populations is  likely  to be  exerted  through small-mammal
populations.  Voles may be affected by selected  roots with high storage
levels of trace elements  or  through  water supply  (this may be obtained in
food).

     The bald eagle (Haliaeetus  leucocephalus)  and osprey  (Pandion haliaetus
cardinensis) rely upon  fish  for  food  items  although  other  vertebrates appear
to be eaten as well.  Ospreys have  been  known to  take several species of
small mammals, other birds,  reptiles,  and frogs,  as  well  as occasional
crustaceans, sea snails,  and beetles.  The  bald  eagle diet in north-central
Minnesota consists of 90%  fish,  8% birds,  and 2%  mammals and invertebrates
(Dunstan and Harper 1975) .  Obviously,  trace-element effects on raptors are
best considered in view of their fish  diet.   Scientists have determined that
Hg levels in fish are already high  in  some  lakes  in  northeastern Minnesota
(see Sections 5 and Appendix D).

     Many other changes in major or  key  ecosystem processes, other than those
discussed, probably occur.  Because of the  lack of information on the effect
of pollutants on insect populations,  food chains, and on  the composition of
the ecosystems of the BWCA,  it is  premature to  predict the potential economic
or ecological damage, or  both.

     Too many unknown factors make  reliable statements impossible concerning
the effects of the Atikokan  facility  on  trace-element fluxes through food
chains.  Lakes already high  in Hg may  experience  additional loads if acid
rain causes the release of existing  sediment-bound Hg. Top carnivores and
fish consumers, such as raptors  and  aquatic mammals, are  likely to accumulate
additional Hg, but the pace of bioaccumulation may vary considerably within
The BWCA.  The low rates  of  trace-element deposition within the BWCA from

                                      89

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Atikokan imply negligible  short-term  effects,   but  possible  long-term
consequences.

APPLICATION OF RESEARCH FINDINGS TO THE  BOUNDARY  WATERS  CANOE AREA

     The impacts of air pollutants on  terrestrial ecosystems  and  their compo-
nents can be grouped  into  four major  categories:  1)  acute  direct  effects on
ecosystem components; 2) acute indirect  effects on  components and  complete
ecosystems; 3) chronic direct effects  on ecosystem  components;  and 4)
chronic indirect effects on components and  ecosystems.   Each  of these types
of impacts may have significance to the  continued functioning of  a given
ecosystem.  To date the majority of data collected  relate only to  the acute
direct effects.  In some cases, however,  acute  indirect  and  chronic effects
may be more important to the overall  ecosystem  than the  acute direct  effects
because the former relate  to factors  such as  forest productivity,  community
diversity, and ecosystem stability.

     The severe limitations on data applicable  to acute  indirect  and  chronic
effects indicate a limit in the "state of the art"  rather than an  absence of
effects.  These limitations have several causes:  lack of long-term baseline
studies; lack of instruments that can measure very  low levels of  air
pollutants; and, perhaps most important,  limitations  in  techniques that can
first measure the subtle changes occurring  in ecosystems due  to low levels of
pollution and then relate  these changes  to  those  levels  of  pollution.

     Although data on direct and indirect effects from chronic low-level air
pollution are limited, basic ecological  principles  indicate  the potential for
significant effects on the terrestrial ecosystems.   These effects  must be
extrapolated from studies  of short-term  effects,  and  the limits and the
sensitivity of such extrapolations must  be  taken  into account.   Through their
influence on the generation of oxidants,  acid particulates,  and acid
precipitation, the indirect effects of emissions  contribute  to regional
loading and are likely to  be the most  serious effects for the Quetico-BWCA
area.

     In air-pollution impact studies  a few  characteristics  remain  fairly
consistent regardless of the differences between  two  or  more  physical and
biological areas:

     1)  Coniferous and lichen species within a polluted area are  almost
         invariably the first plants  to  manifest  symptoms of  injury,  usually
         because of toxic  gases; and

     2)  Plant species growing along  ridge  tops or  on any moderately  elevated
         area will accumulate greater effects from  the phytotoxic  gases than
         the same species  growing  in  the valleys, or  riparian areas.

     The following statements of projected  significance  of  air^pollutants for
the terrestrial ecosystems of the BWCA are  a  synthesis of the research and
literature previously cited and, when possible, anticipate  explicit responses
from applicable findings.
                                     90

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 Significance  for  Pines

     The most  sensitive native higher plant species for which information  is
 available  is  the  eastern white pine,  a prominent canopy tree.  This species
 is  known to have  been lost  entirely from large areas subjected to frequent
 exposures  of  high SC>2 levels.   It can persist for many years, however, with
 moderate levels of damage each year.   In this situation growth is slowed,  the
 trees  are  less  resistant to insect outbreak, and longevity is reduced.

     Red pine  and jack  pine,  the other two most dominant pine species in the
 BWCA,  may  be  less sensitive to SC>2 than eastern white pine.  As such, at
 increased  SC>2  levels,  these species would be expected to exhibit a lesser
 degree of  both visible  and  nonvisible effects than eastern white pine.

     In general,  most  acid  rain damage to plant tissues will occur over a
 long period of  time (many growing seasons) and, therefore, will be difficult
 to  evaluate.   The earliest  manifestation of acid damage in conifer needle
 tissues will  probably be the  cessation of meristem activity in the basal
 areas, causing  the needles  to  be dwarfed and, in later stages, to abort and
 be  cast prematurely from the branch (Northern Cheyenne Tribe 1976).  Although
 slightly acidic rain in an  area may not cause dwarfing during early needle
 development,  damage of  the  basal tissues may occur 1-3 yr later.

     If the ambient concentrations of total solid part iculates,  SC>2,  63,
 and trace  elements attributable to Atikokan are no higher than projected,  it
 is  unlikely that  short-term, visible  damage will occur.  Several recent
 studies suggest,  however, that growth and reproductive rates may be affected
 at  lower ambient  pollution  levels than those necessary to cause visible
 injury, levels commensurate with S(>2  background levels already being
 recorded near Atikokan  (Section 3,  Table 1).  The usual time for planning  and
 developing the  forest cover of a State forest,  private property, or
 recreational  area is  seldom less than 50-100 yr.  More often it  is as much as
 200 years.  White pine  ordinarily live 350-400  yr.  Plant scientists and
 recreational  area managers  have,  therefore,  had to take a long-term view of
 their  resource and look at  its development over tens of decades.  Over these
 periods, even small  effects on the growth rates or lifespan of the dominant
 species can have  major  consequences for the regional vegetation.

 Significance  for  Lichens

     Direct, visible  effects on lichens are not anticipated in the BWCA
within 5 yr after  the projected pollution levels attributable to the  Atikokan
 facility occur.   The  thresholds arid time-requirement for subtle  effects on
 species composition  are not well established, but effects could  be
 significant in a  decade or  two.  As more pollution sources begin operation
near the BWCA a complex interaction of potential lichen species
 substitutions, changes  in nitrogen balances, and other effects may begin.
 Since  the nitrogen-fixing species (Lobaria pulmonaria,  many Peltigera spp.,
Nephroma, Collema,  Leptogium,  and Stereocaulon  paschale) are present  in the
Minnesota coniferous  forests,  detrimental effects on these components of the
 forest ecosystem
                                      91

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could lead to a significant  loss  to  the  nitrogen  balance.   Although the
ultimate consequences are not expected to be  great,  their  degree  cannot be
reliably predicted at this time.

Significance for Insects

     The thresholds for air-pollution  impacts  on  plant-insect  relationships
are unknown.  Effects at the concentrations for the  BWCA have  not been
documented.  If effects occur they will  probably  be  manifested as:

     1)  Injury to pollination systems dependent  upon  or benefited  by insect
         pollination  (primarily by native pollinators).  Compiled lists of
         plants benefited by or dependent upon  insect  pollination for seed
         production,  or utilized  by  insects as  food  resources  are lengthy;

     2)  Changes in the pest-insect  populations of conifer and hardwood
         forests;

     3)  Alteration in litter-soil subsystems  resulting  from harm to
         saprophagous and predacious insects;

     4)  Mobilization of zootoxins through  insect  food chains  to  small
         mammals and  birds;  and

     5)  Changes in key ecosystem processes or  components  that cannot be
         identified in advance because of lack  of  information  on  the
         functioning  of insect populations  in  the  BWCA.

Potential for the Bioaccumulation of Toxic Materials

     The high density of forest vegetation  in  the  BWCA potentially could
absorb and render unavailable much of  the toxic material deposited  from
aerial fallout.  Trace elements could  be expected  to increase  slightly in the
trees themselves (needles, seeds, bark,  etc.)  from direct  dry  deposition or
from secondary storage.  Under the impact of  acid  rain the forest soils would
have lower cation exchange and organic matter  content. Hence, the  effect of
trace elements would  be amplified by making the elements more  available
(because of low pH) and by accumulating  in  small  herbivores and fish.

     Several fish species (e.g.,  bullhead,  suckers,  pike)  form much of the
diet of osprey and eagle.  Experimental  work  is needed to  determine element
sensitivity and rates of bioaccumulation in these  top  carnivores  of the
terrestrial system.   Scientists have determined that mercury levels in fish
are already high in some lakes of northeastern  Minnesota.   Input  from the
Atikokan plant itself may help shift the balance  further toward harmful
levels of ingestion by raptors.

     The BWCA also lies within the upper Mississippi flyway for migrating
birds.  Incremental pollution damage to  the BWCA  ecosystem may harm not only
indigenous biota, but also affect migrants  that pass through the  area to
                                     92

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feed.  Many waterfowl  are  sediment  filter-feeders,  taking both invertebrates
and algae.  These detrital materials  may  contain  moderate levels  of trace
elements  in low pH systems,  injurious to  various  birds.

Significance for Nutrient  Cycles

     Generalizations about the  potential  effects  of acid rain on  soils and
soil-plant interactions must be interpreted  carefully because the BWCA is a
mosaic of diverse environments.   Soils  in the  BWCA  are already acid (pH 4 to
pH 5.7 at various depths).   In many  areas there  is  a 5-10-cm (2-4-in.) humus
layer with pH about 4,  low cation exchange  capacity (10-30 meq/100 g), and
high buffering capacity.  For even  sensitive soils,  however, further
acidification by air pollutants whenever  they  are 15 cm (6 in.)  or more deep
will be a slow process.  Probably considerable time will elapse  before growth
effects can be recognized.   Sulfur  and  nitrogen  entering the system in
precipitation could be  a small nutrient source for  the system.

     Effects will be first noticeable on  shallow  soils or bare bedrock
systems.  U.S. Forest  Service studies have  indicated that because thin, rocky
soils are widespread,the BWCA lands  are the  least productive and  most
sensitive in the Superior National Forest (Heinselman 1977).  Even small
additions of acidity to these systems could  have  relatively short-term,
irreversible effects.

Lake and Watershed Chemistry in Relation  to  BWCA  Soils

     By using the over-printed, six-photo maps provided  in the Kawishiwi Area
Soil Report described  earlier (Prettyman  1978), mapping  of an area central to
the BWCA was carried out on  all portions  in  which the potentially sensitive
soil types (shallow coarse soils  overylying  igneous bedrock) predominate.
This mapping is summarized on an  index  sheet (Figure 15).  An example of the
pattern among the soils and  the distribution of  lakes is shown in a copy of
mapsheet number 1 (Figure  16).

Potentially sensitive headwater lakes—

     Within the areas of shallow  soils  it is possible to recognize additional
criteria to define individual lakes most  likely to  show  changes  in lake
chemistry due to changes in  rainfall  chemistry.   These criteria would include
the following:

     1)   No stream or  spring inlets  (i.e., headwater lakes);
     2)   Hard rock basins permitting  no leakage except to the lake;
     3)   Shallow, coarse, or negligible soils  throughout the watershed;
     4)   The absence of any  significant adjacent  wetland or peat; and
     5)   The watershed  in which the  adjacent land area is of about the same
         or less than twice  the area  of the  lake.

     In the course of mapping Kawishiwi area soils  into  a "sensitive" group,
16 small lakes were identified within the mapping area,  each apparently
                                      93

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meeting most of the above  criteria.  This  assessment  has  been based on the
experience of the author in studies of  the  soils  and  vegetation in the
Kawishiwi and BWCA areas,  combined with  interpretation of the soil mapping
and evidence of drainage channels and wetlands  from the aerial photographs.
Field inspection of these  and 200-300 other small lakes in this area may
reveal that some of the 16 lakes  identified as  "susceptible" may fail to meet
the above criteria fully,  and that other  small  sensitive  lakes have been
missed.  These 16 lakes, however, appear  to be  among  the  most likely
candidates for chemical and biological  change  if  such changes are to be found
in the BWCA.  It is urgent that observations of chemical  characteristics be
made on these lakes at the earliest possible date.   The lake locations and
characteristics are summarized  in Table  10.
                                       96

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                                   SECTION  5

    IMPACTS OF ACIDIFICATION ON AQUATIC ECOSYSTEMS  OF  THE  BOUNDARY WATERS
             CANOE AREA (BWCA) AND  VOYAGEURS  NATIONAL  PARK (VNP)
INTRODUCTION

     Deposition of acid  from  the  atmosphere,  with  consequent  severe effects
upon aquatic ecosystems, is by now a well-known  phenomenon  (Braekke 1976,
Dochinger and Seliga 1976).   Both sulfuric  and nitric  acids  are  involved,  and
hydrochloric acid may be a much more local  source  (Gorham 1976) .   Many other
toxins are deposited in  addition  to acids,  including heavy  metals, a variety
of hydrocarbons, and nutrients such as nitrogen, potassium,  calcium,  and
probably phosphorus (Gorham 1976, 1978, Lunde  et al. 1976,  Wright  and
Hendriksen 1978).

     These pollutants may exert a wide range  of  effects  upon  organisms and
ecosystems, particularly oligotrophic (or nutrient-poor)  ecosystems.   Both
synergistic and antagonistic  interactions are  very likely.  Although  these
have had little investigation it  is known that metal toxicity may  increase
with increasing acidity.  The acid may also have indirect  effects  upon the
toxicity of other ecosystem components (e.g.,  soil-derived metals, such as
aluminum and several trace metals) and upon the  availability  of  nutrients
through weathering and biological activity  (e.g.,  N, P,  K,  Ca,  etc.)  (Glass
1977).

     The impact of increased  acid loading and  nutrients  is  determined by the
vulnerability of aquatic ecosystems.  Geologic,  physical,  and chemical
characteristics of the aquatic environment  are important  variables in
determining the level of vulnerability.  Biotic  effects  range from acute
toxicity and impairment  or failure of reproduction within  species  to  lowered
production and biotic diversity.

     This section is a discussion of the impact  of acidification  on aquatic
ecosystems of temperate  North America and Europe and the  application  of these
findings to the BWCA-VNP receptors.  Comprehensive data  on  all  aquatic organ-
isms present in the BWCA-VNP  are  lacking, but  the  information discussed can
be related to the BWCA-VNP by utilizing data  collected  in  similar  adjacent
areas.  The Minnesota Copper-Nickel Study Area (MCNSA)  (a 5,515-km^ area of
northeastern Minnesota south  of the BWCA, including Ely, Minn.)  and the
Experimental Lakes Area  (ELA) of Ontario are  located adjacent to  and  150 km
from, respectively, the  BWCA-VNP.  Because of  the  similar  terrestrial and
geological character of  the areas, species  present in  both  of these study
areas can be considered  to be generally representative of  the species present
in the BWCA-VNP.  Therefore,  lists of aquatic  organisms  found in  the  MCNSA
are included in Appendix D (Gerhart et al.  1978, Johnson  et  al.  1978, Piragis
et al. 1978).  Specific  information about the  aquatic  organisms  in the ELA

                                     98

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can be found  in Hamilton  (1971),  Patalas  (1971),  Sakamoto (1971),  Schindler
and Holmgren  (1971),  Schindler  and  Noven  (1971),  Stockner (1971)  and Stockner
and Armstrong  (1971).   Information  on  the chemistry and fishes of 109 ELA
lakes can be  found  in Armstrong and Schindler  (1971),  Beamish et  al. (1976),
Brunskill et  al.  (1971),  Cleugh and Hauser (1971) and  Schindler (1971).

CHARACTERISTICS OF  LAKES  VULNERABLE TO ACIDIFICATION

     Lakes  in  eastern Canada  and  the northeastern United States are generally
very sensitive  to acidification.  Calcareous bedrock,  overburden,  and soil
are scarce  in  these regions,  so that surface waters are poorly buffered
(Figure 17).   Lakes of  this type  in the Adirondack Mountains of New York
state and Scandinavia have been severely  damaged  by anthropogenic S02
sources several hundred kilometers  away (Johannessen et al.  1977,  Hendrey et
al. 1976, Overrein  1977).  Similar  sources exist  within a few hundred
kilometers  of  lakes in  the southern Precambrian Shield areas of North
America, and  it is  likely that  the  most vulnerable waters are already
affected.   It  therefore seems  important to identify physical and  chemical
characteristics of  these  most  sensitive waters  so that they  can be closely
examined and monitored  for symptoms of increasing acidity or other changes.

Physical Factors  in the Characterization  of Vulnerable Lakes

     For any given  geological  substrate,  lakes  with the smallest  ratio of
drainage area  to  lake volume  may  have  the poorest buffering  because of the
small area  of  substrate available for  neutralization by weathering.  Lakes at
higher elevations are often affected first because more precipitation usually
falls in such  areas,  resulting  in greater deposition.   Such  lakes  also are
likely to be headwaters,  or at  least high in the  order of lakes in a chain,
and likely  to  have  less calcareous  material in  their drainages.  Greater
volume (depth)  allows greater  capacity for diluting acid inputs.   Few exact
studies of  the  efficiency of  acidification exist  because of  the difficulty of
quantifying acid  inputs and outputs in affected areas.

     The location of Atikokan  is  of special significance since a  large
portion of  the  area, within a  100-km radius, is in the Rainy Lake watershed
(Figure 18).   The rivers  within the 38,100-km^  watershed flow toward the
U.S./Canadian  border  lakes.   Streams and  lakes  east of the Laurentian Divide
flow toward Lake  Superior.  Lakes to the  west  of  the divide  drain into the
western edge of Rainy Lake where  the water flows  at an annual average rate of
280,000 1/s through the dam at  International Falls, Minn,  before  it starts a
northwest course  through  Lake of  the Woods, Lake  Winnipeg, and into Hudson
Bay.

     The entire Quetico Provincial  Park and Voyageurs  National Park are
within the  Rainy Lake basin.  Most  of  the BWCA  is included,  except for the
eastern section, which  is  part  of the  Lake Superior watershed (Figure 19,
Figure 20).  Of a park  total of 88,800 ha,  several thousand  of the 34,700
ha of recreational  water  in the VNP were  created  by dams,  leaving  54,080 ha
of land.  The  park  has 31 named lakes  and 422 unnamed  swampy ponds larger
than 2 ha.  The BWCA has  a surface  area of 439,093 ha  patterned by 1,493
lakes greater  than  2 ha,  and over 480  km  of major fishing  and boating rivers
in addition to  numerous streams and creeks.
                                     99

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      600
Miles
                                                        Rainy Lake
                                                           Basin
    Figure 17.   Regions of North America containing
      lakes that are  sensitive to acidification by
      acid precipitation, based on bedrock geology.
      Calcareous overburden will modify this picture
      somewhat.   (From Galloway and Cowling 1978).
                           100

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Chemical Characteristics and Responses  of Vulnerable  Lakes

     Alkalinity, or the capacity of a solution  to  neutralize  acid,  is  the
characteristic  that reflects the sensitivity  of lake  water  to pH change
resulting from  strong acid input.

     Any ion that enters into  chemical  reaction with  strong acid,  signifi-
cantly above the endpoint pH,  can  contribute  to titrated  alkalinity.

Alkalinity =  [Cations] -  [Anions]                 ~
Alkalinity = 2[Ca2+] + 2[Mg2+] + [Na+]  +  [K+] - 2[S0~] - [N03-]  -  [Cl~].    (19)
For the most part, alkalinity  is  produced by  anions  or  molecular species of
weak acids that are not fully  dissociated above  a  pH of 4.5.   In most
natural water the alkalinity is practically all  produced by  dissolved
carbonate and bicarbonate ions.   A definition expressing alkalinity in terms
of the "changeable" ions present  is  given in Eq. (20)  (Deffeyes  1965):
Alkalinity = [HC03~] +
                                             x ~
with [x] giving the sum of the equivalents of noncarbonate weak  acid  species
(e.g., organic acids,  silicate,  ammonia) where  applicable.   In humic  lakes
of low total alkalinity, organic acid  anions  (carboxylates)  may  make  up the
major fraction of the  alkalinity (Beck et  al . 1974).   Equilibrium pH  levels
in these brown-water lakes will be  lower than in  purely  bicarbonate-buffered
waters because of the  lower pKa values (4-5)  of  the  carboxylic acids,
compared to carbonic acid (pKa 6.3).   This also means  that for comparable
levels of total alkalinity, a given  level  of  strong  acid input will  produce a
lower pH in humic water than in pure bicarbonate  water.   The change  in
hydrogen ion concentration per unit  change in alkalinity (A[H+]/A
Alkalinity) is thus determined by the  total concentrations and species of
weak acid present.

     Under any system  of reporting  titrated alkalinity now  in use the effect
of all the anions that may react when  a strong  acid  is added are lumped
together and reported  as an equivalent amount or  a single substance  or in
terms of postulated ions (e.g., CaCC>3  mg/liter  or HC03~  eq/liter).

     Irrespective of differences in  the content  of weak  acids and their
influence on relative  pH change, the distinguishing  feature  of all  lakes
potentially sensitive  to acidification is  low total  alkalinity.   For  lakes
situtated in regions of hard bedrock resistant  to weathering, low alkalinity
is imparted by low concentrations of base-forming cations.   Throughout large
areas of the Precambrian Shield, carbonates are  undetectably low in  lake
watersheds.  In other  areas calcareous drift deposited by receding glaciers,
lacustrine clays (for  example, in the  Lake Agassiz basin), or marine
sediments help to buffer lakes, rendering  them  less  vulnerable to
acidification.  The most vulnerable  lakes  in  granite (noncalcareous)  regions
have conductivities as  low as 10-20 ymhos  cm    and alkalinities  of 10-20
yeq/liter.  Some BWCA-VNP lakes are  as low as this in  neutralizing capacity,
and many approach these levels.  The percentage  distribution of  85 BWCA-VNP
lakes based on the water alkalinity  observed  in  November 1978 is shown in
Figure 21 (Glass et al., unpublished data, 1979;  see also Appendix D) .
                                     104

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Atmospheric Acidification of BWCA-VNP Lakes

     Several lines of evidence  suggest  that  some  lakes  in  the  BWCA are at or
near the threshold of serious acidification,  severe  enough to  initiate
species depletion and lowered productivity.

     1)  The mean annual pH of  precipitation  in  several  areas  on the
Laurentian Shield of eastern North America,  both  adjacent  to  and far from the
BWCA,  is often at or below 4.8  (Table 11).   This  value  is  the  minimum mean
annual pH level observed to be  without  major  biotic  consequences (so far) in
southern Scandinavia (Wright and Gjessing  1976).   The  pH of precipitation in
these Laurentian Shield areas seems  likely to have declined since the
mid-19501 s, when it may well have been  above  5.6  (cf.  Likens  1976).   At the
present time it is frequently observed  to  fall (in separate precipitation
events) below pH 4.5.  A mean annual precipitation pH  of less  than 4.5 (only
twice the hydrogen ion concentration at pH 4.8)  is associated  with severe
damage to the aquatic biota in  both  southern  Scandinavia (Wright and Gjessing
1976) and the Adirondack Mountains of New York (Schofield  1976a) and has led
lake pH in many instances to fall well  below  5 from  initial levels well above
6.

     2)  Many lakes in the BWCA-VNP  are somewhat  acid  (pH  6.1-6.3) and low in
alkalinity «100 y equiv/liter) (Figure 22).  They also  exhibit  calcite
saturation indices (CSl) (Conroy et  al. 1974, Kramer 1976)  high  enough to
suggest great susceptibility to damage  by  acid loading  (Table  12).  Moreover,
these are not the most acid lakes in the BWCA.  R. F.  Wright  (1974)  has
reported one lake with a mean pH of  5.7, and  it  is likely  that other lakes of
the more than 2,000 have even lower  values.

     3)  Sulfate loadings to northern Minnesota  from historic  background and
distant urban-industrial sources now amount  to an average  of  about 11
kg/ha-yr ranging from 4 to 14 kg/ha-yr  (Table 1).  Such  loadings appear to
have reached a level that is extremely  critical  for  lake acidification.
Dickson (1978) has shown that,  in southern Sweden, sulfate  loadings  of as
little as 5 kg/ha-yr appear to  lower the pH of some  lakes  below  their initial
levels of about 6.5 (sensitive  lakes with  low neutralization  capacity in
their surroundings) or 7.0 (less sensitive lakes  with  greater  neutralization
capacity).  In the more sensitive lakes, as  sulfate  loading enters the range
of 10-20 kg/ha-yr, pH declines  very  sharply  from  above  6 to nearly 5 (Figure
23).  Further sulfate loading produces  a much slower decline  in  lake pH,
about 60 kg/ha-yr being required to  lower  it  to  slightly above 4.

     Any additional sulfate loading  from the  Atikokan  power plant, e.g.,
0.9-1.4 kg/ha-yr to some BWCA lakes  and 3.4-5.1 kg/ha-yr to some Quetico
lakes, is likely to tip the balance  further  toward the  point  of  severe
acidification effects upon aquatic ecosystems, such  as  have been observed in
southern Scandinavia, the La Cloche  Mountains of  northwest  Ontario,  and the
Adirondack Mountains of New York.  In these  locations,  however,  the  most
severe acidification — to levels of pH near  4 — has  required loadings of
about 60 kg/ha-yr.  It may be noted  that the  strong  acid loadings observed in
southern Scandinavia, the La Cloche  Mountains, and the  Adirondacks have
resulted in very rapid declines of lake pH.   The  rate  of acidification has

                                     106

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    TABLE 12.  CALCITE SATURATION  INDICES (CSl) FOR  85
                    BWCA-VNP LAKES3

Percentage
of lakes
10.6

18.8
34.1
29.4
7.1
CSI
index"
<1

1-2
2-3
3-4
4-5
CSI
classification
Terrain is most stable and
not susceptible to change
Possibly susceptible to change
Probably susceptible to change
Susceptible to change
Highly susceptible to change

aCalculated according to Conroy et al. (1974) and
 Kramer (1976).

bCSI = p(Ca2+) + p(Alk) - p(H+) + pk, where p(x) =
 -log^Q (x), pk = +2, (Ca2+) is given as mol/liter  ,
 and (Alk) and (H+) are given as eq/liter.
                         109

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                          O    -
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-------
ranged between -0.02  and  -0.06  pH units/yr in southern Scandinavia, where
original  lake pH values ranged  from 6.2 to 7.3,  and between -0.05 and -0.10
units/yr  in  eastern North America,  where the original lake pH ranged from 5.0
to 6.7 (Wright and Gjessing 1976).   Such rapid declines are not expected in
the BWCA  unless acid  loadings  increase considerably above present levels.
Slower declines in lake pH may  be occurring even with present loadings,
however,  and cannot be viewed  with  equanimity.

     An experimental  example  illustrates the great sensitivity of lakes with
low alkalinity.  In 1976  and  1977 a total of 1.14 eq/liter of H+ were added
to the surface of  an  ELA  lake  (#223)  as H2SC>4 (Schindler et al. 1979).
The bicarbonate content of the  lake was reduced  from an original value of 86
eq/liter  to  10 eq/liter.   Since the original pH of  precipitation was 4.95,
this acidification regime is  equivalent to changing the pH of precipitation
to 4.2 for a period of 10 years (Schindler, personal communication, 1978).
Lake 223  is  not one of the most vulnerable lakes in the region.  Its
bicarbonate  value  is  slightly  above the mean.  Other lakes in the area have
alkalinities as low as 8% of  that of lake 223.  Depending on pH levels, such
lakes may be seriously affected by  precipitation that has been acidified to
even a few tenths  of  a pH unit  more acid than normal.  The effect of acid
addition  on  the pH of water from selected BWCA-VNP lakes and the influence of
the alkalinity and CSI of the water are shown in Figure 24.  Note the large
differences  in acid required  to reach pH 5, a value critical for most fish
reproduction.

     In addition to the shifts  in major ion composition that constitute
acidification, significant changes  in certain trace metals and organic
fractions of acidified lakes have been observed.  Increased concentrations of
aluminum, manganese,  zinc,  copper,  and nickel have been reported in lake
water from acidified  regions  (Dickson 1975, Schofield 1976b, Wright and
Gjessing  1976, Dillon et  al. 1977).  These increased metal concentrations may
be due in part to  increased atmospheric loading  (Ni, Cu) associated with
specific  pollutant sources,  and to  increased leaching from soils or lake
sediment  (Al, Mn,  Zn).  Schofield (1977) determined that 0.25-1.0 ppm
aluminum  leached from soil by snowmelt water at  pH 4.4-5.9 was a major factor
in causing severe  gill damage  and death among larval brook trout, a fish
species found in the  BWCA as well as  the Adirondacks.  Mobility of these
metals is also enhanced at low  pH levels.  Increased transparency reported in
some acidified lakes  (Dickson 1975, Schofield 1976a) may be due to
precipitation of humic and fulvic acids at low pH and high aluminum
concentrations (Dickson 1977).

     Marked  temporal  and  spatial  variations in strong acid and metal
concentrations have been  observed' in  lakes and streams  as a result of snow-
melt (Johannessen et  al.  1977,  Schofield 1977, Siegel 1979).  During the
initial phase of melting,  acids stored in the snowpack  are leached out  by
water percolating down through  the  snowpack.   Strong acids are thus concen-
trated in the early fractions of  meltwater leaving the  snowpack.   Passage of
this acid meltwater through  ice-covered lakes, at low levels of discharge,
results in the temporary  formation  of a shallow  (usually <1 m) ,  but highly
acid layer of surface water under the ice.  This phenomenon has even been
observed  in moderately well-buffered  lakes in the Adirondack region

                                      111

-------
       4.0r
       4.9
                                                                  "Alkalinity as ppm CaCQj
                                                                  *LoKe number
                                                                  eCalcl«* Saturation Index
                900
                        KJOO    1900    XXX)    2900    3000    3900   4000
                         Mteroequivotonts [rf] added per liter of lake water
                                                                           4500
                                                                                  9000
       4.0 r
       4.9
                                                                   Alkalinity as ppm CoCOj
                                                                  *Lokt number
                                                                  cCalcltt Saturation Index
                900
                       1000     1500   2000    2500    3000    3900    4000

                         Microequivalents [H*l added per liter of lake water
                                                                           4900
                                                                                  5300
Figure  24.   Effect of acid addition on  the  PH of water  from  selected
   BWCA-VNP lakes.
                                              112

-------
(Schofield 1976b) .   Sensitivity  of  lakes  to this  short-term, but intense,
form of acidification  is  thus  governed  more by the physical process of acid
concentration  from  the  snowpack  and  transport  of  meltwater under ice cover
than by alkalinity  of  the  lake water alone.  The  degree and time of meltwater
in contact with  soil's  in  the  drainage system will also significantly affect
acid and metal levels  in  the  runoff.  Table 13 shows snow-meltwater quality
from samples collected  in  the  BWCA-VNP  in March 1978.   First meltwater
contains concentrations of  acids  two to three  times the mean values for the
samples.  Measured  snow loadings  for 1977-78 are  given in Appendix D.

     The concentrations of  most  trace elements in the  surface waters of the
BWCA-VNP are generally  low  (Poldoski and  Glass 1975, Glass et al.,
unpublished data, 1979).  Because of the  low concentrations of most
components, increased  concentrations will result  in greater percentages of
toxic metals present in biologically active forms (Poldoski and Glass 1975,
Glass 1977).

     Another concern related  to  acidification  in  northern Minnesota is the
recent (1976) discovery of  elevated  mercury residues in fish in several BWCA
lakes (Minnesota Department of Natural  Resources  1978) .  Mean Hg levels in
fish from two large  lakes,  Basswood  and Sand Point, exceeded the 1978 FDA
action level of 0.5  ppm.  Figure  25  and Tables 7-9 in  Appendix D provide data
on the mercury levels  in  fish  from lakes  from  the BWCA-VNP region.  These
fish are from lakes  that  previously  would not  have been considered endangered
by acidification.   No  specific source for the  mercury  contamination has yet
been identified.  Two hypothesized  sources are fallout from regional
atmospheric concentrations  of  fossil-fuel combustion products or mobilization
of mercury from bedrock geological sources, or both.

     Regardless of  its  source, the Hg problem  in  the BWCA is likely to be
aggravated in several ways  by  increased combustion-product deposition.  The
direct addition of more mercury  is one  such way (see previous discussion).
Lower pH may increase  the mobility of mercury  from sediments and rocks.
Studying the relation of  acidification  to mercury accumulation in  fish in
Sweden, Jernelov et  al. (1976) and others (Brouzes et  al. 1977) have found
that the formation  of methylmercury,  the  form  of  mercury most rapidly
accumulated in tissues, is  enhanced  at  pH levels  below 6.  In addition, fish
are thought to take up methylmercury more rapidly at low pH.  The  net effect
of reduced pH on accumulation  is  well illustrated by Figure 26 in  which Hg
residues in brook trout from Adirondack lakes  are compared (Schofield,
personal communication, 1978) .  Trout from acid drainage lakes had mean
tissue concentrations that were three times higher than those of trout from
limed, seepage, and bog lakes.

IMPACTS UPON AQUATIC COMMUNITIES

     The most obvious biological  effects  of acidification occur to fish
populations.  Less conspicuous, but  no  less severe damage also occurs to
other organisms ranging from  frogs to microbes.   In fact, acidification
affects organisms at all trophic  levels in fresh  waters.  The number of
species is reduced,  biomass is altered, and major processes are interrupted.


                                      113

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TABLE 13.  SNOW-MELTWATER ENRICHMENT BY DISSOLVED COMPONENTS -  CONCENTRATIONS
    AND PERCENTAGE OF TOTAL MASS FOUND IN MELTED SNOW AS A FUNCTION  OF  THE
           PERCENTAGE MELTED (AVERAGE OF THREE SITES IN BWCA-VNP)

Percentage [H+]
snow-melt pH %
10
20
30
40
50
60
70
80
90
100
4.26
4.25
4.30
4.46
4.63
4.71
4.76
4.80
4.82
4.86
(18)
(19)
(17)
(11)
(7)
(6)
(5)
(6)
(5)
(5)
[NH4 + ]
mg/1 %
0.15
0.19
0.16
0.11
0.08
0.08
0.07
0.07
0.07
0.07
(14)
(18)
(15)
(11)
(8)
(8)
(7)
(7)
(7)
(7)
[504]
mg/1 %
1.8
1.9
1.7
1.0
0.5
0.4
0.3
0.3
0.3
0.2
(21)
(23)
(21)
(12)
(6)
(4)
(4)
(4)
(3)
(2)
[NO^]
mg/1 %
2.3 (18)
2.4 (19)
2.3 (17)
1.5 (11)
l.Q (8)
0.8 (7)
0.8 (6)
0.6 (5)
0.7 (5)
0.6 (5)
[cr]
mg/1 %
0.15
0.16
0.15
0.11
0.11
0.08
0.09
0.08
0.09
0.07
(14)
(15)
(14)
(10)
(10)
(7)
(8)
(7)
(8)
(6)
[F-]
mg/1 %
0.02
0.02
0.02
0.02
0.01
0.01
0.01
0.01
0.01
0.01
(14)
(14)
(14)
(14)
(7)
(7)
(7)
(7)
(7)
(7)
                                    114

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    Mercury Concentration  (m g /1)
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  of walleye and northern pike  taken  from  selected BWCA-VNP area lakes.
  (Data from Minnesota Department of  Natural Resources 1978.)
                                         115

-------
   1.00
  0.50
E
Q.
Q.
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O
k.
0>
  0.05
         Acid  drainage  lakes
               O  O °O O   O
                 O
                 Limed,  seepage  8  bog  lakes
20
                                   30
                             Length (cm)
40
      Figure 26.  Regressions of log mercury concentration
       against total length for brook trout sampled from
       acid drainage lakes and limed, seepage, and bog
       lakes in the Adironacks.  (©, adjusted mean
       mercury concentrations from the two classes, for
       convariance analysis). (After Schofield, personnal
       communication, 1978).
                            116

-------
     Although the  literature  concerning  effects  of acid mine drainage (AMD)
on freshwater ecosystems  is extensive,  it  is  not  directly applicable to the
acid-precipitation  problem.   Often the  uncontaminated waters of coal mining
areas have higher  alkalinity  and  hardness  than the very soft waters acidified
by acid precipitation.  Acid  mine drainage water  usually has a heavy load of
iron and other heavy metals and  frequently depresses  the oxygen concentration
of receiving waters.  High  turbidity and the  presence of chemical floe are
also common and greatly alter aquatic habitats.   These factors make it very
difficult to extrapolate  observations  from AMD situations to those in the
Laurentian Shield,  for example.   The evidence used in this report is taken
primarily from literature pertaining to  acid  precipitation,  although some
reference to AMD literature is made  where  relevant.

     The variety of species of plants  and  invertebrate animals occurring in
fresh waters is enormous, and the kinds  of organisms  present differ markedly
from one locale to  another  even  though  water  chemistry may be similar.  It is
at best difficult  and probably futile  to try  to  interpret ecosystem damage at
lower trophic levels by comparing lists  of species.   On the  other hand,
changes in major processes  such  as primary and secondary production and
decomposition can  be broadly  described  and compared.   Effects of stress on
the major functional guilds may  be compared from  place to place.  Finally, a
few groups of organisms seem  to  be remarkably insensitive to strong mineral
acidity and are common to many acid  environments,  whereas some other groups
are clearly intolerant of pH  levels  below  6.0 to  5.5.

Effects on Microbiota

     The production of fish and  other  animal  life  in  a lake  is ultimately
dependent upon the  availability  of organic food  resources, primarily plant
materials.  The sources of  organic materials  may  be  divided  into two major
categories:  autochthonous, originating  by primary production in the lake,
and allochthonous,  transported into  the  lake  by  inflowing water, airborne
litter, or dissolved in rain.  The relative importance of each of these
sources varies greatly from lake  to  lake.   One principal route for both
autochthonous and  allochthonous  organic  matter into  the trophic system of a
lake is via the detritus  (organic particulate matter).

     Bacterial consumption  and mineralization of  organic matter, both parti-
culate (POM) and dissolved  (DOM),  allows a cycling of carbon which dominates
the structure and  the functioning of the system  and  provides what Wetzel
(1975) has called  a fundamental  stability  to  the  system.  In the deep, open
water of the pelagic zone, where  phytoplankton production normally provides a
substantial portion of the  nonrefractory organic  matter, bacteria rapidly
assimilate dissolved labile organic  substances (DOM)  derived from photo-
synthesis and convert them  into  bacterial  biomass  (Hellebust 1974,  Fogg
1977).  Only a small portion  of  the  DOM  refractory material  is likely to
survive longer than 24 h  (Saunders and Storch 1971).   The bacterial
mineralization rate of POM  appears to be rather  slow, a few  percent per day
(Wiebe and Smith 1977, Cole and Likens 1979), so  that this new biomass is
actually available  to other trophic  levels.  Not  only do the bacteria
conserve the energy stored  in labile DOM,  which  otherwise would be lost from
the system, but they also convert  (at a  slower rate)  some of the refractory

                                      117

-------
DOM into a usable  form.  Fungal  and  bacterial  communities render other POM
into forms that are useful  for detritivores  (Boling  et  al.  1975).   The
significance of these  activities  to  ecosystem  energetics can be better
appreciated when one considered  that  on  the  order  of 90% of the organic
carbon in the water column  is DOM and  that  detrital  POM is  many times larger
than the total living  carbon biomass.

     There are other sources of  detritus  in  the  pelagic zone.   In  some lakes,
particularly small or  shallow lakes,  macrophytes  and benthic algae are
important sources  of autochthonous organic  carbon.   Material from  these
plants may contribute  significantly  to detritus  in  the  pelagic  zone.   In
deciduous forest lakes,  leaf litter  falling  or blown onto the  surface has
been found to be 200-500 g  dry leaves  per meter  of wooded shore line  (Jordan
and Likens 1975, Gasith  and Hasler 1976).   This  forest  litter  plus that which
is added by stream inputs contributes  to both  DOM (after leaching) and POM.

     Water-column  detritus  generated  from all  of  these  sources  has three
possible fates.  It can be  transformed biologically,  it can sink to the
sediments where it accumulates or is  transformed  biologically,  or  both, or it
is lost from the system by  outflow.   In  the  first  two cases, microbial
activity plays a key role in removing  detritus.

     The inhibition of microbial  decomposition can have profound effects
throughout an aquatic  ecosystem.  Detritus  removal,  conservation of energy,
nutrient recycling, primary production,  detritivore  production, and thus
production at higher trophic levels  can  all  be affected by  changes in
microbial activity.

     Several investigations have  indicated  that  microbial decomposition is
greatly inhibited  in waters affected  by  acid precipitation. An abnormal
accumulation of coarse organic detritus  has  been  observed on the bottoms of
six Swedish lakes where  the pH decreased by  1.4-1.7  units in the past three
to four decades (Grahn et al. 1974).   Bacterial  activity apparently
decreased, and in  some of the lakes  the  sediment  surfaces over  large  areas
were made up of dense  felts of fungus  hyphae.  In  one of the lakes, Gardsjon,
85% of the bottom  in the 0-2-m depth  zone was  covered with  a thick felt of
fungus.  Lime treatment  caused a  rapid decomposition of the organic litter as
well as great reductions of the  fungal felt  (Andersson  et al.  1974),
indicating that an inhibition of  bacterial  activities had taken place at low
pH.  Similar neutralizations of  acidified lakes  in Canada resulted in a
significant increase in  aerobic  heterotrophic  bacteria  in the  water column
(Scheider et al. 1975).  Results  from  field  and  laboratory  experiments with
litterbags in Norway (Hendrey et  al.  1976)  also  indicate reduced weight loss
of leaves in acidic waters.  Dissolved organic carbon (DOC) in  the inflowing
water was found to contribute ca. 50%  of  allochthonous  inputs  and  8%  of all
organic carbon in Mirror Lake, while  fine particulate organic  carbon  (FPOC)
was negligible (Jordan and  Likens 1975).  The  extent to which  this DOC input
is converted to bacterial biomass or  otherwise enters into  the  energetics of
a lake is not known.   Observations of  abnormal accumulations of organic
debris have also been  made  in AMD waters  in  South Africa (Harrison 1958) and
West Virginia (DeCosta, personal  communication,  1978).
                                      118

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      In  laboratory  experiments  Bick and Drews (1973) found that the decompo-
sition rate of  peptone  by microbiota decreased with pH and that the oxidation
of  ammonia ceased below pH  5.   Bacterial cell counts and the species number
of  ciliates also decreased.   Numerous other studies indicate that the
microbial decomposition of  organic  materials is markedly reduced at pH levels
commonly encountered  in lakes  affected by acid precipitation (Hendrey et al.
1976).

      Accumulations  of organic  debris and extensive mats of benthic algae, as
observed in the Swedish lakes  (Grahn et al. 1974), both seal off the mineral
sediments from  interactions  with  the overlying water and hold organically
bound nutrients that  would  otherwise have become available if normal
decomposition had occurred.   The  reduction in nutrient availability can be
expected to have a  negative  feedback effect on the organisms, further
inhibiting their activities.  The reduction of nutrient supplies to the water
column from the sediments,  because  of the physical covering and from reduced
mineralization  of organic materials in the water itself, will lead to reduced
phytoplankton productivity.   These  ideas have been formulated into the
hypothesis of "self-accelerating  oligotrophication" by Grahn et al. (1974).
Qualitative observations support  this hypothesis,  but  quantitative evaluation
is  lacking.

      Reduction  of microdecomposer activities may have  a direct effect upon
the invertebrates.  Although  certain benthic invertebrates appear to feed
directly on the allochthonous detritus material, it seems that "conditioned"
(colonized by microorganisms) material is preferred, and that the nutritional
value of the detritus is highly increased by conditioning (Boling et al.
1975).  Bacteria may  also be  a  food source to be removed by the filtering
apparatus of organisms  such  as  the  Calanoida.  An inhibition of the
microbiota or a reduction in microbial decomposition processes would
therefore have  a direct  impact  on the lakes'  animal communities.

      Because of the low temperature and lack of nutrients in the BWCA-VNP
waters for in-lake  energy fixation, the terrestrial production of energy in
the form of plant detritus  is very  important  for supplying energy to the food
chain as well as transferring nutrients to the aquatic production system.
When  the decomposition  and  transformation of the detritus is reduced or
eliminated by acidification,  then less energy is available for ultimate fish
production.  Since  the  waters of  the BWCA-VNP are  generally infertile and
support relatively  low  concentrations of fish,  the resultant decrease in the
fish  crops would be expected  to decrease to levels even lower than those at
the present time.

Effects on Benthic  Plants

      In waters  affected by  acid precipitation major changes occur within
plant communities.  Most of  the available data are qualitative and descrip-
tive although some  experimentation  has been done.   Intact lake-sediment
cores, which included the rooted  macrophyte Lobelia dortmanna,  were incubated
at four pH levels (4.0, 4.5, 5.5, 6.0) at Tovdal in southern Norway.   The
growth and productivity of  the  plant (C>2 production) were reduced by 75% at
pH 4 compared to the  control  (pH  4.3-5.5),  and  the period of flowering was
delayed 10 days at  the  low pH (Laake 1976).
                                      119

-------
     In five lakes of the Swedish west  coast,  a  region  severely affected by
acid precipitation, Grahn (1977) reports  that  in  the  past  three to five
decades the macrophyte communities dominated by  Sphagnum have  expanded.  In
the sheltered and shaded locality Lake  Orvattnet,  in  the 0-2-m depth zone,
the bottom area covered by Sphagnum  increased  from 8% to 63% between 1967 and
1974.  In the 4-6-m depth zone, the  increase was  from 4% to 30%.   At the same
time, pH in Orvattnet decreased 0.8  units  to approximately 4.8.  Similar
growths of Sphagnum occur in other Swedish  lakes,  in  Norwegian lakes,  and in
AMD water as well (Harrison 1958, Harrison  and Agnew  1962, Hagstrom 1977).
At the pH of these acid waters, essentially all  of the  available  inorganic
carbon is in the form of C02 or 112^3.  Conditions are  more  favorable
for Sphagnum, an acidophile which is not  able  to  utilize HCO^j  as  do
many other aquatic plants.  The moss appears to  simply  outgrow the flowering
plants under acid conditions.

     In developing their hypothesis  on  oligotrophication,  Grahn et al.  (1974)
have stressed two biologically important  consequences of this  Sphagnum
expansion.  First, Sphagnum has an ion-exchange  capacity which results  in the
withdrawal of base ions such as Ca from solution,  thus  reducing their avail-
ability to other organisms.  Secondly,  dense growths  of Sphagnum  form a
distinct biotype that is unsuitable  for many members  of the bottom fauna.

     Under some acid conditions, unusual  accumulations  of  both epiphytic and
epilithic algae may occur.  In the Swedish  lakes  Grahn  et  al.  (1974) report
that Mougeotia and Batrachospermum become  important components of the
benthos.  In Lake Oggevatn (pH 4.6),  a  clear-water lake in southern Norway,
not only is Sphagnum beginning to replace Lobelia dortmanna  and Isoetes
lacustris, but these macrophytes have been  observed to  be  festooned with
filamentous algae.

     Heavy growths of filamentous algae and mosses occur not only in
acidified lakes, but have also been  reported in  streams in Norway affected  by
acidification.  In experiments in artificial stream channels using water and
the naturally seeded algae from an acidified brook (pH  4.3-5.5),  increasing
the acidity to pH 4 by addition of sulfuric acid  led  to an increased
accumulation of algae compared to an unmodified  control (Hendrey  1976).  The
flora was dominated by Binuclearia tatrana, Mougeotia sp., Eunotia lunaris,
Tabellaria flocculosa, and Dinobryon sp.,  each accounting  for  at  least 20%  of
the flora at one time or another.  The  rate of radioactive carbon uptake per
unit of chlorophyll in the channels, measured  on  two  occasions, was lower in
the acid channel by approximately 30%,  suggesting greater  algal biomass
accumulation at low pH despite lower productivity.

     Several factors may contribute  to  these unusual  accumulations of certain
algae.  The intolerance of various species  to  low pH  or consequent chemical
changes (Moss 1973) will allow just  a few algal  species to utilize the
nutrients available in these predominantly  oligotrophic waters.  Many species
of invertebrates are absent at low pH,  and  removal of algae  by grazing is
probably diminished.  Microbial decomposition  is  inhibited,  as was previously
noted, which also reduces the removal  of  algal mass.

     In the BWCA-VNP, reduction in growth  and  production of  benthic plants
will probably not be important since the  lakes most  likely to  be  acidified
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are the same lakes  that have  few,  if  any,  aquatic plants.   If indeed the two
were to co-exist, then decreases  in benthic  plants  could reduce juvenile fish
recruitment for  those  species  which utilize  macrophyte beds for nursery
areas.  The biomass of benthic  plants  usually enters  the detrital food chain
and reductions in this energy  source  could reduce fish standing crops.  If
filamentous algae were to be established  during  acidification,  the visual
aesthetics of pristine lake  shorelines could be  reduced.

Effects on Phytoplankton

     There is no consistency  among various investigations  as to which
phytoplankton taxa  are likely  to  be dominant under  conditions of
acidification.   The Pyrrophyta  may be  more common (e.g., species of
Peridinium and Gymnodinium)  than  others  in lakes near pH 4.0.  With
decreasing pH in the range 6.0-4.0, many  species of the Chlorophyta are
eliminated, although a few tolerant forms  are found in the acid range.  In
their survey of  155 Swedish west  coast lakes, Aimer et al. (1974) found that
blue-green algae became less  important with  decreasing pH, but  Kwiatkowski
and Roff (1976)  found  the opposite to  be  true in lakes of  the Sudbury,
Ontario, region.

     Conspicuous decreases occur, however, in phytoplankton species number,
species diversity,  biomass,  and production per unit volume (mg/nH) with
decreasing pH.  Lake clarity and  the  compensation depth increase with lake
acidification, so that primary  production (mg/m2),  although lower in acid
than non-acid lakes, is not  as  severely depressed as  is production per unit
volume  (Johnson  et  al. 1970, Aimer et  al.  1974,  Hendrey and Wright 1976,
Kwiatkowski and Roff 1976).  The  low  phytoplankton  biomass «1  mg/liter has
been correlated  with the concentration of available phosphorus, which
generally decreases with lower  lake pH (Aimer et al.  1974).  Low availability
of inorganic carbon has also been suggested  as a factor limiting primary
production in acidic lakes (King  1970, Johnson et al.  1970).

     In the BWCA-VNP,  if production is decreased, the energy available for
food-chain transfer is reduced,  and an effect on total fish production would
be expected.  If the grazing  zooplankton  are reduced  before the phytoplankton
are affected, the fish population will respond to the zooplankton while the
algal populations will not be  utilized, possibly removing  nutrients from the
production system without being recycled.

Effects on Invertebrates

     Zooplankton analyzed from  net samples collected  from  84 lakes in Sweden
showed that acidification caused  the  elimination of many species and led to
simplification of zooplankton  communities  (Aimer et al. 1974).   Crustacean
zooplankton were sampled in 57  lakes  during  a Norwegian lake survey in 1974
(Hendrey and Wright 1976), and  the number of species  decreased  with pH.  The
distributions and associations  of crustacean zooplankton in 47  lakes of a
region of Ontario affected by  acid precipitation were strongly  related to pH
and to the number of fish species present  in the lakes. However, fish and
zooplankton were each  correlated  with  the  same limnological variables,
especially pH (Sprules 1975a,  1975b) .  Zooplankton  communities  become less

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complex with fewer species present  as  acidity  increases.   Food  supply,
feeding habits, and grazing of zooplankton will  probably  be  altered  following
acidification, as a consequence of  decreased biomass  and  species  composition
of planktonic algae and bacteria.   Parsons (1968)  reported that  in  streams
continuously polluted by AMD the  number  of zooplankton  species  was  small
compared to the numbers of individuals;  greater  numbers were found  in less
polluted conditions downstream.

     Surveys at many sites receiving acid precipitation  in Norway,  Sweden,
and North America (Andersson et al. 1974, Conroy et al. 1975, Hendrey and
Wright 1976, Borgstr^m et al. 1976) have  shown  that waters affected  by acid
precipitation have fewer species  of benthic invertebrates  than  localities
that are less acid.  In 832 lakes J. Okland (1969) found  no  snails  at pH
values below 5.2; snails were rare  in  the pH range 5.2-5.8 and  occurred  less
frequently in the pH range 5.8-6.6  than  in more  neutral or alkaline  waters.
The amphipod Gammarus lacustris,  an important element  in  the diet of trout  in
Norwegian lakes where it occurs,  is not  found  in lakes with  pH  less  than 6.0
(K. A. Okland 1969).  Experimental  investigations have shown that the adults
of this species cannot tolerate 24-48  h  of exposure to pH 5.0  (Borgstr^m
and Hendrey 1976).

     In the River Duddon in England, pH  is the  overriding factor  that
prevents permanent colonization by  a number of  species of  benthic inverte-
brates, primarily herbivores, of  the upper acidified  reaches of  the  river
(Sutcliffe and Carrick 1973).  In the  more acid  tributaries  (pH <5.7) the
fauna consisted of an impoverished  plecopteran  community.  Ephemeroptera,
Trichoptera, Ancylus (Gastropoda),  and Gammarus  (Amphipoda)  were  absent. The
epiphytic algal flora was reduced (in  contrast  to  increases  noted in Norway),
and litter decomposition was retarded.   The food supply of the herbivores was
apparently decreased, and this may  have  played  a role  in  the simplification
of the benthic fauna.  Quantitative data concerning the effects of  low pH on
the benthic fauna are also available for  some acid Norwegian lakes  (Hendrey
et al. 1976), where notably low standing crops have been  observed.

     Many studies of invertebrate communities  in streams  receiving AMD have
been conducted.  Comparisons are  usually made between  affected  and unaffected
zones or tributaries, and experimental acidification  has  been performed
(Herricks and Cairns 1974).  The  numbers of species,  species diversity,  and
biomass are usually greatly reduced.   Generally, in AMD waters  Chironomidae
(midges) and Sialis (alderfly) are  the most tolerant  macroinvertebrates. The
order Trichoptera has more tolerant species than does  Ephemeroptera  (may-
flies) (Harrison 1958, Harrison and Agnew 1962,  Dinsmore  1968,  Parsons 1968,
1977, Dills and Rogers 1974, Wojcik and  Butler  1977).

     This order of tolerance is essentially the  same  as that in waters
acidified by acid precipitation.  However, the Hemiptera,  Notonectidae (back-
swimmer), Corixidae (waterboatman), and  Gerridae (water strider)  are often
abundant in acidified soft waters at pH  as low  as 4.0.  This pattern of
distribution may, in part, be due to lack of fish predation,  as well as  the
partial adaptation of these invertebrates to terrestrial  living.

     Benthic plant communities in lakes may be  greatly altered  as a  conse-
quence of lake or stream acidification (as discussed  above). Under  these
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conditions, benthic  invertebrate  populations may be affected by starvation,
evacuation, or  extinction  due  to  the  loss  of preferred habitat.  Chironomids
(Oliver  1971) and  other  benthic  invertebrates (Cummins 1973) present in many
of the poorly buffered northeastern  lakes  have diverse feeding habits
and habitats.   These  invertebrates,  in many situations, will be affected by
altered  decomposition cycles  and  variations in available foods caused by
increased  acidification.

     The tolerance  of aquatic  invertebrates to low pH varies over their life
cycles,  and the emergence  of  adult  insects seems to be a period particularly
sensitive  to  lower  pH levels.  Bell  (1971) and Moss (1973), in similar
studies with Trichoptera and  Ephemeroptera, found emergence patterns to be
affected at pH  levels that  were higher than the 30-day survival limits.  Many
species  of aquatic  insects  emerge early in the spring, even through cracks in
the ice  and snow cover.  Because  of  the contamination of spring meltwaters by
atmospheric pollutants,  including heavy metals (Hagen and Langeland 1973,
Hultberg 1977,  Johannessen  et  al. 1977, Henriksen and Wright 1976), the early
emergers must,  in many cases,  be  exposed to the least desirable water
conditions .

     Changes  in invertebrate  communities will influence other components of
the food chains.  Benthic  invertebrates assist with the essential function of
removing dead organic material.   In  litterbag experiments the effects of
invertebrates on leaf decomposition were much more evident at higher pH than
at low pH  (Hendry et al. 1976).   A reduction of grazing by benthic
invertebrates may also contribute to  the accumulation of attached algae in
acidified  lakes and  streams.

     A short reach  of Norris  Brook,  a tributary to Hubbard Brook in New
Hampshire, was  acidified to pH 4  in  the spring and summer of 1977 to evaluate
the effects of  acidification  on a stream ecosystem.  Excessive accumulations
of algae occurred, bacterial biomass  and heterotrophic activity per unit of
organic matter  were  reduced,  and  both invertebrate diversity and biomass
decreased  (Hall and Likens, unpublished data, 1979).

     In unstressed  lake ecosystems  a  continuous emergence of different  insect
species tends to be available  to  predators from spring to autumn.   In acid-
stressed ecosystems  the variety of  prey is reduced, and periods may be
expected to occur in which  the amount  of prey available to fish,  waterfowl,
songbirds, and  other predators is diminished.

     In the BWCA-VNP the zooplankton  and benthos are  the algal grazers  and
detritivores that transfer  energy from vegetable to animal biomass.  Factors
adversely affecting these organisms will adversely affect the transfer  of
energy through  the  food chains and ultimately affect  the fish product.

Effect on Vertebrates-Fish

     The loss of fish species  with  increasing acidity has been well
documented in Scandinavia and  in  North  America.   In Sweden,  Hultberg and
Stenson (1970)  collected all of the  fish in two lakes acidified by acid
precipitation.  At a pH of  4.8 one lake  contained a single yellow perch and
seven eels; the other lake  at  pH  4.6  contained 26 northern pike and 19  eels
                                      123

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and had lost its former perch population.  Jensen  and  Snekvik  (1972)  recorded
the elimination of salmon and trout populations  from many  rivers  and  lakes in
southern Norway.  In Canada Beamish and Harvey (1972)  described  the loss of
eight species of fish from a lake as the pH  fell from  6.8  to 4.4.   Beamish et
al. (1975) recorded the loss of  fish from  another  lake undergoing
acidification,  and Harvey (1975) reviewed  the effects  of acidification  on the
fish populations in a group of 68 lakes.

     The tolerance of fishes to  low pH has been  studied under  laboratory
conditions for half a century.   This effort  has  been directed  at  recording
the death of fishes in relation  to hydrogen  ion  concentration  and  duration of
exposure (Douderoff and Katz 1950, Lloyd and Jordan 1964,  European Inland
Fisheries Advisory Commission 1969, Rooney 1973).  The results of  these works
are statements of criteria or pH tolerance of various  fish species.

     In the natural environment  fishes may be exposed  to adverse  levels of
acidity throughout their life.   Thus pH will act to control  their  survival or
well-being at the most critical  stage or time in their life history.
Accumulation of acidic snow gives rise to  spring runoff of acid  water which
coincides with the time of spawning of many  fish species.   Headwater  lakes
undergo more rapid acidification than those  lower  in the watershed, as  a
function of flushing rate and buffering capacity of the drainage  basin.
Thus, fish tend to be lost first from headwater  lakes.

     One of the effects commonly observed  in populations of  acid-stressed
fishes is a failure to reproduce successfully, often manifest  by  an absence
of young fish (Hultberg and Stenson 1970,  Beamish  and  Harvey 1972,  Ryan and
Harvey 1977).  The cause of this reproductive failure  varies from  species to
species.  In one population of white suckers, females  failed to  reach
spawning condition (Beamish and  Harvey 1972); physiologically  these fish did
not show the normal pattern in protein-bound serum calcium (Beamish et  al.
1975).  Lockhart and Lutz (1977) have also proposed disruption of  Ca
metabolism as an explanation for losses of fish  from acid  lakes.   Another
mechanism of action is the disruption of spawning  behavior (Conroy et al.
1974).

     In some species spawning is successful, but recruitment  into  year  class
0 is lacking, indicating lesser  tolerance  of eggs  and  larvae (Milbrink  and
Johansson 1975) or greater susceptibility  of young or  small  fish  such as
Robinson et al. (1976) found for brook trout.  Two recent  laboratory  chronic
exposures (Menendez 1976, Smith  1977) have demonstrated a  reduction in the
hatchability of brook trout embryos at pH  6.0 and  lower.   Both investigators
commented that continual exposure to pH values below 6.5 would be  highly
detrimental.  Trojnar (1977a) observed reduced hatchability of brook  trout
embryos at pH 5.6.  In a study of lake trout in  the acidified  lake number 223
of the ELA, L.  Kennedy (personal communication,  1978)  found  that  egg  weights
were  lower and survival was drastically reduced at a  pH of 5.75.   The
absence of a previous year class indicated that  similar effects  might have
occurred when the pH was 6.0.  These data  indicate that the lake trout, one
of the most sought after and valuable fish species in  the  BWCA-VNP, is  highly
vulnerable to the effects of acidification.
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     Other species  found  in  the  BWCA area are also very sensitive to low pH.
Mount (1973) observed a reduction  in embryo  production and hatchability at pH
5.9 in fathead minnows.   A  pH  of 5.6 was  marginal for vital life functions.
A reduction  in the  development of  white  suckers  to the swim-up (early larval)
stage occurred at pH  5.3  and  lower (Trojnar  1977b) .   Embryo production,
embryo fertility, and fry growth were impaired at pH 6.0 and lower among
flagfish (Jordanella  floridae),  a  species not found  in the BWCA (Craig and
Baski 1977).  Generally speaking,  several fish species have been found to be
sensitive to pH levels around  6.0  or a little above.

     Laboratory-determined  effects appear to agree closely with field obser-
vations made in the LaCloche Mountain lakes  area near Sudbury, Ontario.  The
pH values at which  various  species disappeared from  lakes are shown in Table
14 (Beamish  1976) .

     Acute physiological  effects of acid  have also been investigated.  It is
known that brook  trout suffer  malfunction of sodium  regulation and lose
excessive amounts of  this ion  to the water (Packer and Dunson 1970).  These
authors suggest (1972) that  anoxia may be the primary cause of death in
fishes exposed to very low  pH.   Leivestad and Muniz  (1976) also observed an
inability of acid-stressed  fish  to regulate  plasma sodium and chloride
levels.  Mudge et al. (1977) found evidence  of an inhibition of RNA synthesis
and presumably of steroidogenesis  in interrenal  tissue.

     Whatever the mechanism  of action of  the acid stress, serious changes in
the population structure  can result.  Beamish and Harvey (1972) noted the
complete absence  of one age  class  (5-year-old fish)  in a population of white
suckers, probably resulting  from an acid  pulse 5 yr  earlier.  In another
population of white suckers, older animals were  lost in response to gradual
acidification, and  maximum  age declined  from 16  yr to 7 yr (Beamish et al.
1975).  Spinal deformity  resulting from  disintegration of several vertebrae
in adult fish was also observed.

     The more common  effect  of acidification is  to reduce the population to a
small number of older individuals.  This  change  has  been observed in
Scandinavia  (Hultberg and Stenson  1970)  and  in a group of acid-stressed lakes
in Canada (Ryan and Harvey  1977).   In some species the growth rate of
survivors increased,  presumably  in response  to reduced competition for food.

     These changes  in the form of  populations precedes their extinction.
There is a long and increasing list of water bodies  from which some or all
fish populations have been  lost  because  of low pH.  Major rivers in southern
Norway have  reduced populations  of trout  and salmon, and large kills have
been recorded in association with  acid precipitation (Jensen and Snekvik
1972).  Schofield (1975,  1976a)  described the acidification and loss of
fishes from  a large group of lakes in the Adirondack Mountains.  Lakes at pH
4.5-5 yielded no  fish in  response  to survey  netting.  In the LaCloche
Mountains of Ontario a study of  67 lakes  yielded 28  that had lost the
majority of  their fish; many of  these lakes  had  supported good sport
fisheries until relatively recently (Beamish 1976).   Many of the remaining
lakes showed reduced numbers of  fishes,  perhaps  influenced by changes in
other populations of organisms (see section  on effects on invertebrates).

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  TABLE 14.  APPROXIMATE pH AT WHICH FISH IN THE LACLOCHE
      MOUNTAIN LAKES, ONTARIO, STOPPED REPRODUCTION3
     pH
         Species
   Family
6.0+-5.5
5.5-5.2
5.2-4.7
4.7-4.5
Smallmouth bass
  Micropterus dolomieui

Walleye
  Stizostedion vitreum

Burbot
  Lota lota

Lake trout
  Salvelinus namaycush

Troutperch
  Percopsis omiscomaycus

Brown bullhead
  Ictalurus nebulosus

White sucker
  Catostomus commersoni

Rock bass
  Ambloplites rupestris

Lake herring
  Coregonus artedii

Yellow perch
  Perca flavescens

Lake chub
  Couesius plumbeus
Centrarchidae


Percidae


Gadidae


Salmonidae


Percopsidae


Ictaluridae


Catostomidae


Centrarchidae


Salmonidae


Percidae


Cyprinidae
aAfter Beamish (1976).
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     Most likely  the  early  effects  of acidification of BWCA-VNP lakes will be
a decrease in  fish production,  and  very quickly 'direct effects on the fish
community will be apparent.   Loss  of production followed by loss of desirable
species and complete  elimination of fish would be expected in the sensitive
lakes in the BWCA-VNP.  Little  or  no effect  is expected for nonsensitive
lakes and watersheds.

Effects on Other  Vertebrates

     Vertebrate animals other than  fishes have received scant attention.
Birds and mammals that feed on  fish are faced with a reduction or loss of
food supply.   In  the  LaCloche Mountain lakes, for example, loons continued to
nest on and attempted to  fish in lakes that  had lost much or all of their
fish life.

     Amphibians are especially  prone to acidification of shallow surface
waters.  Pough (1976)  has described effects  of acid precipitation on spotted
salamanders (Ambystoma jeffersonianum and A. maculatum), which breed in
temporary rain pools.  Below  pH 5  and 7,  respectively, these species suffered
high mortality during hatching  in  laboratory tests.  This mortality was
associated with distinctive embryonic malformations.  The development of
salamander eggs in five ponds near  Ithaca,  New York, ranging from pH 4.5 to
7.0 was observed.  An abrupt  transition from low to high mortality occurred
below pH 6.  Although a synergistic effect  of several stresses may have been
possible, the  studies  suggested that pH was  the critical variable.  Pough
(1976) cites studies  which  indicate a decline in British frog populations.

     Hagstrbm  (1977)  has  investigated frog  populations in Tranevatten,  a lake
acidified by acid precipitation, near Gothenburg, Sweden.  The lake pH has
declined to 4.0-4.5,  and  all  fish have been  eliminated.  The frog species
Rana temporaria is being  eliminated as well.  Currently, only adults 8-10
years old are  found.   Many  eggs were observed in 1974, but few were found in
1977.  The few larva  observed in 1977 subsequently died.  A toad species,
Bufo bufo, is also being  eliminated from this lake.

     Frogs and salamanders  are  important  predators on invertebrates in lakes
and puddles or pools,  including mosquitoes  and other pests.  In turn, they
are themselves important  prey for higher trophic levels in an ecosystem
(Pough 1976).

SUMMARY

     Acid precipitation,  by causing increased acidity in lakes, streams,
pools, and puddles, can cause slight to severe alteration in communities of
aquatic organisms.  The effects are similar  to those observed in waters
receiving acid mine drainage, but the toxicology and chemistry are not  as
greatly complicated by the  presence of high  concentrations of heavy metals,
chemical floes, turbidity, etc.  Bacterial decomposition is reduced, and
fungi dominate saprotrophic communities.   Organic debris accumulates and
nutrient salts are taken  up by  plants tolerant of low pH (mosses,  filamentous
algae) and by fungi.   Thick mats of these organisms and organic debris  may
develop which inhibit  sediment-to-water nutrient exchange.  Phytoplankton

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species diversity and production  are  reduced,  although  biomass  accumulations
may be high due to reduced grazing.   Zooplankton  and  benthic  invertebrate
species diversity and biomass are  reduced.  Ultimately  the  remaining benthic
fauna consists of tubificids and  Chironomus (midge)  larvae  in the  sediments.
Some tolerant species of  stoneflies and mayflies  persist,  as  does  the
alderfly.  Air-breathing  insects  (water boatman,  backswimmer, water strider)
may become abundant.  Fish populations are reduced  or eliminated;  some of the
most sought-after species (brook  trout, walleye,  smallmouth bass)  are the
most sensitive and therefore are  among the first  to  be  affected.   Toxicity or
elevated tissue concentrations of  metals may result  either  from direct
deposition or increased mobilization, or both.  Amphibian  species  may be
eliminated.  Finally, either the  populations or the  activities  of  terrestrial
vertebrates utilizing aquatic organisms for food  (or  recreation)  are likely
to be altered.

     Acidification of the BWCA-VNP will affect  the  fish communities in some
of the lakes, either by reducing  populations,  changing  species  composition,
or directly eliminating fish from the lakes.   As  the  acid  load  increases or
continues, more lakes will fall in the affected category.   Although the small
headwater lakes in poorly buffered watersheds  are the most  likely  candidates
for impact, the importance of these lakes in the  total  recreational picture
is unknown.  However, as more lakes are eventually  affected,  the  general
objectives of wilderness management for the BWCA-VNP  will be  violated.
Operation of the Atikokan generating  facility  will  add  about  10%  to the total
sulfate deposition on the area and increase the acid  content  by 25 to 30%.
These quantities should be judged  in  relation  to  the  shortening of the time
period within the above effects are expected to be  observed.
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                                 APPENDIX A

              WET REMOVAL RATES FOR  S02 GAS AND  804 AEROSOL

     In most models describing pollutant transport, transformation,  and
removal one typically finds an equation of the form

                                        c                           
-------
where w  is  the vertical wind  speed  and  Vf  (positive)  is  the fall  speed of
precipitation particles.  Application of Eq.  (A-3)  for  the  description of  wet
removal  implies  that  pollutant  is  carried  to  and  from the volume  of  interest
only by  the wind and  falling  precipitation.   Assuming that  boundary- layer  flow
in  the atmosphere  is  nondivergent  and rearranging Eq. (A-3) in terms of a  sub-
stantial derivative results in  a form analogous  to  Eq.  (A-l),

                    dn
                    dt

Integration over height,  z, provides  the desired  expression for describing the
wet removal of pollutants from  the  atmosphere;

                            (yf>. - (yf >.„                           (A.6)
                      dn =   - >
                     dt
                                   z -
where n represents  the vertical  average  over  a  column  extending  from zo
to z.  Therefore  instead of  finding  that  pollutant  removal  is  directly
proportional  to the  pollutant  concentration as  in Eq.  (A-l), we  find that
removal is actually  determined by  the vertical  flux divergence of  pollutant  in
the  column under  consideration.  The rate of  mass (concentration)  removal  is  a
consequence of the mass flux of  pollutant into  the  top  of a volume minus  the
mass flux of  pollutant out  the bottom.

     For wet  removal  the mass  flux of pollutant  past a  particular  level  can  be
represented by the precipitation rate, j,  multiplied by the pollutant
concentration of  the  precipitation water,  C,  where  j has  the units of  a  water
flux and C has units  of mass of  pollutant per mass  of water.   Thus,  the  flux
divergence can be represented by

                           (JC)Z  -  (JC)Z
                     dn                 o
                    dt
                               z ~  zo                                     (A-7)

     A major difficulty in describing  the wet removal of pollutants  is
determination of the vertical  extent of  the region  being scavenged.  Modelers
often wish to determine pollutant  removal for a  layer of fixed  thickness and
generally apply Eq. (A-l) to a surface  layer of  air.  However,  unless  the
surface layer encompasses the  entire vertical extent of the region being
cleansed by precipitation, such an approach will produce only a crude
approximation to the true removal.  As Eq. (A-7) illustrates, both the  flux
into and out of the surface layer  must be considered.  Without  the assistance
of detailed vertical profiles of precipitation rates and pollutant
concentration, the flux into the top of  a surface layer will be indeterminate.
Currently detailed vertical profiles of  precipitation and pollutant
concentration are unavailable.  Thus we  find our first restriction to apply Eq.
(A-7) or Eq, (A-l); the layer under consideration must extend to heights where
the wet, downward flux of pollutant is near zero.
                                     155

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WET REMOVAL OF SULFATE AEROSOL

     Figure A-l represents  the simplest  case  for wet  removal.   Sulfate aerosol
removal is considered, and  the removal model  described by  Scott  (1978)  is
employed.  Briefly, the model assumes that  in the  portion  of  the figure above
cloud base, cloud droplets  are nucleated on sulfate condensation nuclei.   Large
collector particles (snowflakes) then enter the box from above  and,  as they
descend, grow to larger sizes primarily by accretion  of the cloud droplets.
The process envisioned here is one of precipitation development  in a cold  cloud
by the Bergeron process.  The sweeping out of  a dirty layer of  cloud water
above the cloud base by relatively pure  collector  particles  is  the major  removal
mechanism.  The region of the cloud where precipitation growth  is primarily by
accretion of cloud droplets is designated as  the rimtng zone.   Since the  snow-
flakes are assumed to be relatively sulfate free when they enter the riming
zone, the wet, downward pollutant flux at the top  of  riming zone is  zero.

     The thickness of the riming zone can be  estimated from the  fall speed of a
typical collector particle  and from the  time  required for  the  particles to grow
to raindrop sizes.  By utilizing the work of  Kessler  (1969),  the fall speed of
the median volume drop can  be expressed  in  terms of the precipitation rate as

                        vf  = 3.89 jO.105 (m/s)f                          (A-8)

where here, J represents the precipitation  rate in mm h~ . In  continuous
rainfalls, precipitation rates generally average between 0.5 and 1.0 mm
h~l.  For such rainfall rates the median volume drop  diameter  is roughly
between 0.7 and 1.0 mm.  Millimeter-sized ice particles can be  produced by
riming in 5-13 min in mixed phase clouds with water concentrations near 1  g
m~3 (Hindman and Johnson 1972, Scott 1976).   Therefore, a  time  of 9  min is
felt to be an appropriate estimate for the  time collector  particles  remain in
the riming zone while growing to precipitation sizes.

     Taking the height of the riming zone to  be defined by collector particle
velocity [Eq. (A-8)], and multiplying by the  time  of  collector-particle growth
in the riming zone gives the riming zone thickness, Az, as

                          Az = 2100 J0.105  (m).                          (A-9)

Thus, the thickness of the  riming zone is generally near 2,000 m and weakly
depends upon precipitation  rate.

     The distance from the  ground to cloud  base in a  precipitating cloud  is
typically small compared to 2,000 m.  Therefore, Az can be considered to
represent the distance from the ground to the top  of  the riming  zone.  Since
Z-ZQ % Az, the flux divergence over the  entire column extending  from the
ground to the top of the riming zone can then be evaluated by  computing only
the pollutant flux at the surface.

     The concentration of sulfate in the precipitation water  reaching the
surface can be described in terms of the sulfate concentration  of the air  being
drawn into the cloud base.  Fitting curve 3 of Figure 2 in Scott (1978) with a
least square curve for 0.13
-------
CLOUD BASE
   GROUND
                                                      RIMING ZONE
  Figure A-l.  The volume considered for sulfate removal.  The
    symbols represent:  *,  ice particles;  0, liquid drops; o,
    cloud droplets; -»-, the direction of the sulfate flux at
    the upper  and lower boundaries of the volume.
                                157

-------
CT
   io-2
   10-3
         3.0    3.5
4.0
4.5
5.0
5.5
6.0
6.5
                                   PH
  Figure A-2.   Curves of  C  /xe  as  a  function  of  pH.   The labels
                          2&                  •     /  / -^ \
     for the curves  represent  S02 air concentrations  (yg/m ).

     The units of  C   and x  are  grams of  dissolved S02 per gram

     of water and  grams of air-borne  SC>2  per cubic meter of air,

     respectively.
                                 158

-------
of sulfate  (grams of  sulfate  per  gram of  water)  as

                      C =  0.46 xg(SO^)j~°-27,                       (A-10)
where Xg(SO^) is  the  clear  air  concentration of sulfate (grams of sulfate
per m-* of air) being  drawn  into  the  cloud at cloud base.  Generally, the
subcloud air is well  mixed,  and  the  sulfate  concentration should be fairly
uniform between the ground  and  cloud base.   Therefore we approximate xg with
the surface-air concentration of  sulfate.

     If we combine Eq.  (A-7), (A-9),  and  (A-10),  the wet removal rate for
sulfate can be expressed as

                  dx(SOp    = _  o 92 x  (S07)J°-625
                  -        0.22 xg^S04;j     ,                (A-ll)
                    dt
where X(SO;jj) represents the  average  SO^ aerosol concentration (grams of
sulfate per m-* of air)  in the layer  extending from the ground to the top of
the riming zone.

REMOVAL OF S02 BY SNOW

     Much of the  preceding  material  can be used to describe the wet removal of
S02 •  For the simplest  case, that of S02  scavenging  by snow,  a direct
analogy follows.  Here  we assume  that the bulk of  S02 picked  up by frozen
collector particles occurs  as these  particles capture cloud droplets in the
riming zone.  The dissolved  S02  in these  cloud droplets is assumed to be in
equilibrium with  the  environment,  which,  if  the S02  air concentration
decreases monotonically with height,  implies that  the droplets at the upper
portions of the riming  zone  will  contain  less S02  than those  droplets near
cloud base.  As the snowflakes collect cloud droplets,  the droplets will freeze
rapidly and will  have no opportunity to adjust to  new equilibrium values as
they are carried  to lower levels  in  the cloud.

     Since the wet, downward flux of  S02  through  the upper boundary of  the
riming zone is negligible,  the S02 removal rate by snow is determined by
evaluating the pollutant flux at  the  ground.  Written in terms of flux
divergence over the riming  zone,  the  wet  S02 removal rate is  given by

                      dX(S02)
                        dt
                                         = - JjC
                               snow           2

                                         = 0.48 J°-9C,              (A-12)

where C represents  the dissolved  S02  concentration in  the snowflakes arriving
at the ground.

     From Scott (1978) the  final  concentration of  pollutant in a collector
particle passing through the riming zone is  given  by

                        C = C[l -  exp(-2m)],                       (A-13)

                                     159

-------
where C is the vertical average  of  the  SC>2 water  concentration in the
riming zone and m is  the vertical average of  the  cloud  water concentration.
Then, taking C to equal the arithmetic  average  of  the  equilibrium
concentration at the  ground, Cg, and  at  the  top of  the  riming zone,  and
setting the upper level concentration equal  to  zero  results  in
               dX(S02)
                  dt
                          snow
                                  -  0.24  CeJ°-9(l-exp(-2m)).
                                   (A-14)
Furthermore, Scott (1978) has  presented  an  expression  relating precipitation
rate to cloud water concentration:
                      m = 1.56  +  0.44   In J.
                                    (A-15)
Equation (A-15) was intended to generalize all  precipitation  events.   However,
no liquid water needs  to be present  in  snow  clouds.   Caution  should be
exercised when applying it to snowfalls,  particularly when  precipitation rates
are very light.

     Values of Cg can  be obtained  from  Figure A-2 which  presents  equlibrium
concentrations or SC>2  as a function  of  pH and SC>2 air concentration.   The
curves of Figure A-2 result from the  simultaneous solution  of  three equilibrium
equations describing the dissociation of  SC>2 in water (e.g.,  see  Appendix A,
Easter and Hobbs 1974).

REMOVAL OF S02 BY RAIN

     To extend these concepts to S02  removal by rain  scavenging,  consider the
features illustrated in Figure A-3.   Again the  riming zone  is  represented by
the distance  (Z-ZQ), and the freezing level  height  is designated  by (zf
zo).  For this model,  snowflakes,  as  before, are assumed to accrete cloud
droplets containing dissolved S02  and then to melt  to raindrops  after falling
through the freezing level.  In applying  the flux divergence  concept, the
vertical fluxes in and out of each of the two boxes  in Figure  A-3 must be
considered.   In the upper box the  only  change in S02  concentration results
from a downward flux through the freezing level. As  in  the purely snow case,
the amount removed is
                    dX(S02)
                      dt
                  C(zf)
                             ice
             (z-Zf )
                                                                   (A-16)
where both the precipitation rate and  the  862  concentration in the snow are
evaluated at the freezing  level.  Below  the  freezing  level  the removal due to
ran  s
        dX(S02)
           dt
                liquid
j(zf) C(zf) - j(z0) C(z0)

        (zf-z0)
                                                                   (A-17)
                                      160

-------
FREEZING
  LEVEL
 GROUND
          2km
          1km
               T
                         S02
        Figure A-3.  The volume considered for wet SO
          removal by snow and rain.   The ground is at
          ZQ and the top of the riming zone is at z.  The
          freezing level is at Zf.  The air concentration
          of SO- is assumed to decrease with height.
                             161

-------
where j(zo) and C(ZQ) are  ground values.   Below the  freezing level the SOo
concentration in the drops  is assumed  to  be  determined  solely by establishing
an equilibrium concentration between  the  dissolved and  airborne SOo.

     To derive a removal rate that  is  analogous  to the  previous removal rates
and applied over the entire region  being  scavenged (the top of the riming
zone to the ground) a weighted average over  both  boxes  is  performed:
dX(S02)
  dt
         rain
(z-zf)
dX(S02)
dt
-f- (-7 -
' . (zf
ice
(z-z
dX(SOj
7 \ z ,
V dt
liquid .
0>
                                                                     (18)
Substituting Eq. (A-16) and  (A-17)  into Eq.  (A-18)  results  in the desired
expression for SC>2 removal by  rain:
                           dX(S02)
                              dt
          0.9r
= - 0.48 J   cc
                                                                     (A-19)
                                      rain
Comparison between Eq. (A-14) and Eq.  (A-19)  illustrates  that  the rain
removal rate of S(>2 can  exceed  the  snow  removal  rate  by a factor of two or
more at equivalent precipitation rates.   In  particular,  as  the cloud water
concentration goes to zero,  the wet  removal  of  SC>2 by the snow riming
mechanism postulated above becomes negligible.

     For both Eq. (A-14) and  (A-19)  the  ground-level  concentration of
dissolved  SC>2 is related through the  curves  of  Figure A-2  to  the ground
level SC>2 air concentration, X(S02).   That  is,
                              Cg =  3 X(S02),
                      (A-20)
Thus, the expressions describing wet  removal  of  S(>2  and  804  [Eq.  (A-ll),
(A-14), and (A-19)] can be generalized  to
                           dx
                           —= - K XeJa.
                           dt       *
                       (A-21)
Notice that Eq. (A-21) is not an  exact  first-order  expression,  as  was assumed
a priori in Eq. (A-l).  The average wet  removal  of  S02  and  SO^  for a layer
depends not on the average pollutant concentration  in  the  layer, but upon the
surface-level concentration in  the layer.   If  the surface-level concentration,
Xg, can be expressed  in terms of  a layer average, then  the  first-order
relationship of Eq. (A-l) wij.1  result.   For  example,  suppose  the surface-level
concentrations of S02 and SO^ decrease  linearly  to  zero at  the  top of the
riming zone.  Then Xg = 2X and
                                     162

-------
                    dX(S04)                  Q.625
                         ^  _=  -  0.44  X(S04)J
                       dt
dX(S02)
  dt
-0.48 g X(S04)J°-9 (l-exp(-2m))
(A-22)
        snow
             dX(S02)
               dt
           -0.96 3 X(S02)J°'9%
                     rain
Another common situation  is  to  assume  a Gaussain  profile  for  a plume.   Then

            Xg = X  Az/  [1.25 az erf(Az/(1.41az))]s                 (A-23)

               = YX .

Substitution of Eq. (A-23)  into Eq.  (A-ll),  and  (A-19)  gives

                              BY =  - 0.22 Y  X(S04)J   0-625,
                       dt
   dX(S02)
      dt
            snow

        dX(S02)
           dt
      - 0.24  3Y X(S02) J°'9 (l-exp(2m)),
         = - 0.48 BY X(S02) J°-9
                                                                    (A-24)
                 rain
WET FLUX OF SULFUR AND PRECIPITATION  pH

     After procedures for computing removal  rates  of  S02  and  S04  by
precipitation have been developed, calculations  to  determine  sulfur degostion
and rainwater acidity follow directly.   In  fact,  the  flux of  S02  or S04  is
obtained by multiplying Eq. (A-21) by  the region  being  scavenged,  Az,  which  is
defined by Eq. (A-9).  As for pH,  the  major  portion of  acidity found in
rainwater can be attributed to the incorporation  of sulfate (Granat 1977).
Indeed, as Figure A-4 illustrates, a  good approximation to rainwater pH  results
from assuming two hydrogen ions for every sulfate  ion (Dana 1978).   The  figure
presents precipitation chemistry data  collected  from  the  MAP3S precipitation
chemistry network and suggests that during the summer months  when  nitrate
concentrations in precipitation water  are the  lowest, the two hydrogen to one
sulfate ion is regularly observed.  During the winter months  when  nitrates play
a greater role in determining rainfall acidity,  there is  an excess  of  hydrogen
ions;   the molar ratio of hydrogen to  sulfate  is  then_greater than 2.  Still,
at pH values less than 4.3, the assumption of  [H]/[S04]  = 2 is quite good.
Thus,  determination of the sulfate concentration  in precipitation  water  should
provide accurate estimates of rainfall pH.
                                      163

-------
  1000
   100
o>
o
E
   10
                                                              I  I  I I  I
10
                                                100
                                     pmoles/4
1000
          Figure A-4(a).  Observed relationships  between the
            ion concentrations of H and  SOr  for summer 1977.
            The solid line represents  two  hydrogen moles for
            every sulfate mole;  the circles  represent data
            points.
                                   164

-------
  1000
g>
O
E
                                                                     1000
       Figure A-4(b).  Observed  relationships  between the  ion
         concentrations of H and SOf  for winter  1977-78.   The
         solid line  represents two hydrogen moles  for every
         sulfate mole; the circles represent data  points.
                                  165

-------
REFERENCES

Dana, M. T.  1978.  Seasonal trends of S(>2, SO^, Ntfy and NC>3  in
     precipitation.  MAP3S Precipitation Chemistry Network.   Presented  at  the
     MAP3S Precipitation Chemistry Network Meeting, May  11-12, 1978,  Ithaca,
     N.Y.

Easter, R. C., and P. V. Hobbs.  1974.  The formation of sulfates  and  the
     enhancement of cloud condensation nuclei in clouds.  J.  Atmos. Sci. 31:
     1586-1594.

Granat, L.  1977.  Sulfate in precipitation as observed by  the European
     Atmospheric Chemistry Network.  Presented at the International Symposium
     on Sulfur in the Atmosphere, September 7-14, 1977, Dubrovnik, Yugoslavia.

Hindman, E. E., II, and D. B. Johnson.  1972.  Numerical simulation of  ice
     particle growth in a cloud of supercooled water droplets.  J. Atmos.  Sci.
     29:1313-1321.

Kessler, E.  1969.  On the distribution and continuity of water,  substance  in
     atmospheric circulation.  Meteor. Monogr. 10(32):1-84.

MAP3S Precipitation Chemistry Network. 1977.  First periodic  summary  report.
     Battelle, Pacific Northwest Laboratories, Richland, Wash.  In press.

Scott, B. C.  1976.  A theoretical study of the evolution of  mixed phase
     cumulus clouds.  Ph.D. Thesis.  Univ. Washington, Seattle, Wash.  209  p.

Scott, B. C.  1978.  Parameterization of sulfate removal by precipitation.  J.
     Appl. Meteor. In press.
                                      166

-------
                                  APPENDIX B

          SIMPLE MODEL CALCULATIONS  OF  EMISSIONS APPLIED TO ATIKOKAN

     Annual averages, 3-h,  and  24-h  worst-case concentrations and deposition
fluxes may be estimated by  using  simplified models.   These calculations
provide a comparison with  the more  complicated grid  model.

ANNUAL AVERAGE CONCENTRATIONS

     The single box model  approach  is used.  Since all possible
meteorological conditions  occur in a year we may consider that the plume is
uniformly mixed in a cylindrical  box.   Assume that the wind blows with equal
frequency in all directions.  From conservation of mass,
or
                               Q =  2 TV  x  L  U  C

                                       Q _  .
                               c  =
                                     2 IT x LU
Let C be the annual ambient  air  concentration  (yg/m-*)  at  distance x (m)
from the source Q (g/s).  Let U  be  the  average  annual  wind  speed (m/s)
through the average mixed layer  of  height  L(m).   Let  us  now divide this
result by 2 to account for the time when  the plume  is  in  stable air and
hence not dispersing to  the  ground.   The  equation to  be  evaluated ^'s then
                                C  =
                                    4ir  x LU
Holtzworth (1972) gives the mean  annual  day  time  value  of L at  International
Falls as 1,300 m and the mean  annual  wind U  as  7.2 m/s.   We choose x = 80 km
as the distance from Atikokan  to  the  center  of  the BWCA.   For the indicated
emission rates
       Species
              ,  Q, the annual average concentrations,  C,  are  as  follows:

                         Q(f)       c(£f)    C(ppb)
S02
804
PM
Hg
NOX as N02
2,230
335a
328
0.0290
1,320
0.24
0.04
0.04
3 x 1(T6
0.14
0.09
0.01
	
0.001
0.005
       a Assumed 2%/h conversion  of  S02  to  804  plus
         2% conversion in the stack.
                                     167

-------
     The EPA CRSTER model, which runs a Gaussian plume  calculation  for  every
hour of the year, gave an annual average S02 concentration  at 80 km due south
of 0,25 Mg/ra  (Goklany, personal communication, 1978).

THREE-HOUR WORST-CASE CONCENTRATIONS

     Assume that the plume is fully trapped and calculate the plume centerline
concentration for neutral stability at 80 km downwind.  The Gaussian plume
result is
                            C =
                                 /2ira  LU
                                     y
Because of plume meandering an average concentration across  the  plume  is  more
appropriate than the centerline value.  The width of the  plume  is  taken  as
4.3 a  and the result is

                                     0.4 Q  .
                                  /2rra y LU

For neutral stability  Oy = 0.13 x 0.903, and assuming  x  =  80 km,  u = 5 m/s,
and L = 500 m, we have

                                    Q(g/s)
                              ~     106.5

     In order for this to represent a 3-h average concentration  the  wind  would
have to blow steadily in one direction for 7 h since  the  travel  to the  receptor
is about 4 h.  Hence, this is an upper limit to  the real  situation.  The
results of this 3-h calculation are as follows:
Species
S02
SO^
PM
Hg
NOX as N02
QV CV^j; C(ppb)
2,230
335
328
0.0290
1,320
21
3
3
0.0003
12
8
1
	
4 x
6



10-5

     The EPA CRSTER model calculated the highest 3-h  concentration  of  S02  at
80 km south-southeast as 20
TWENTY-FOUR-HOUR WORST-CASE CONCENTRATIONS

     The 24-h case cannot be calculated without having  actual meteorological
data because conditions do not persist in the atmosphere  for 24 h.  The  EPA
CRSTER model calculated the highest 24-h S02 concentration 80 km  south of
Atikokan as 5 ug/m^.  Taking this  in relation to  the  emissions we have the
following 24-h worst-case concentrations:
                                     168

-------
Species Qxs' 1^3' u(ppb)
S02
SOr
PM
Hg
NOX as N02
2,230
335
328
0.0290
1,320
5
1
1
0.00006
3
2
0.2
	
7 x 10"
1.6
ANNUAL AVERAGE DRY DEPOSITION

     The annual average dry  deposition  flux  may  be  estimated  by multiplying an
effective depositive velocity, Vp,  by  the  annual  average  concentration:
or
                   FDRY = C VD  (vg/™  per  second),
                      F    =  315 C VD  (kg/ha-yr).
                       DRY

This assumes that the ambient air concentration  is  not  significantly  decreased
because of dry deposition upwind of  the  receptor  point  in  question.   Hence the
calculation is an upper  limit.  The  annual average  dry  deposition  fluxes  are  as
follows :
Species
S02
so?
PM
Hg
NOX as N02
VD(cm/s)
1
0.1
0.1
0.1
0.5
FDRY(kg//ha~yr)
0.75
0.014
0.014
1 x 10~6
0.22
WET DEPOSITION FLUXES

     For typical rainfall rates of  1 mm/h  continuous  rainfalls,  the  procedure
outlined in Appendix A yields a concentration of  1.8  mg/liter  for  the  sulfate
in precipitation if we assume an average sulfate  concentration of  3  pg/m   in
the air.  By assuming two hydrogen moles for every  sulfate mole,  the sulfate
concentration converts to a rainfall pH of 4.4, and 3 =  0.0237.  The removal
rate for 21 pg/m3 of S02 is

                    Wq0  = 0.24 (pg/m3 per hour),

and for 3 pg/m3 of SO^ is

                     WOA= = 1«0 (pg/m-5 per hour).
                                      169

-------
If we use a height of  1,300 m  for  the mixed  layer,  the  deposition rate due to
rain is
                        F
-------
Deposition
(kg/ha-yr)
Rain
Snow
Dry

S02
0.02
0.02
0.75

804
0.10
0.06
0.01

PM
0.01
0.01
0.01

Hg
3 x 10~8
3 x 10~8
1 x 10~6
                                                               ,-6
        Total                0.79     0.17       0.03      1  x 10
     The deposition rates for SO^ are probably  an  upper  limit  because  up-wind
removal between Atikokan and the BWCA due  to wet and  dry  deposition  would
decrease the concentrations used in  the  calculation.  The wet  deposition of
SC>2 might be increased since the pH of the rain would be  less  and  therefore
the scavenging coefficient would be greater.
REFERENCES

Holtzworth, G. C,  1972.  Mixing heights, wind speeds, and  potential  for
     urban air pollution throughout the contiguous United States.  U.S.
     EPA, AP-1-1, January.
                                     171

-------
                                 APPENDIX C

  REPRESENTATIVE ANALYSIS OF COAL AND FLY ASH FOR MAJOR AND TRACE COMPONENTS:
                       SOUTHERN SASKATCHEWAN LIGNITE3

Component
Aluminum (%)
Antimony (ppm)
Arsenic (ppm)
Ash (%)
Barium (%)
Beryllium (ppm)
Bismuth (ppm)
Boron (ppm)
Bromine (ppm)
Cadmium (ppm)
Calcium (%)
Cerium (ppm)
Cesium (ppm)
Chlorine (ppm)
Chromium (ppm)
Cobalt (ppm)
Copper (ppm)
Fluorine (ppm)
Gallium (ppm)
Gold (ppm)
Hafnium (ppm)
Heat content (BTU)
Holmium (ppm)
Iron (%)
Lead (ppm)
Coal
1.7
1.1
6.8
22
0.05
<0.14
9
37
2.7
<0.6
1.8
-
-
-
25
9
46
86
-
-
-
8,600
-
0.6
<29
Ash
9.4
2.1
19
-
0.50
3
-
400
2.0
1.8
8.1
112
3
460
60
9
43
94
1,090
0.005
12
-
6
2.2
30
Component
Lithium (ppm)
Magnesium (%)
Manganese (ppm)
Mercury (ppm)
Molybdenum (ppm)
Nickel (ppm)
Phosphorus (%)
Potassium (%)
Rubidium (ppm)
Silicon (%)
Selenium (ppm)
Silver (ppm)
Sodium (%)
Strontium (%)
Sulfur (%)
Tantalum (ppm)
Tellurium (ppm)
Tha 1 1 ium ( ppm)
Thorium (ppm)
Titanium (%)
Tungsten (ppm)
Uranium (ppm)
Vanadium (ppm)
Zinc (ppm)
Zirconium (ppm)
Coal
9
0.45
180
0.3
9
37
0.15
0.4
-
4
0.8
-
0.2
0.02
0.8
-
-
<0.5
-
0.05
-
8
20
40
80
Ash
-
2.5
400
-
20
39
-
-
40
-
<3
0.4
2
0.2
0.48
1.7
90
-
14
-
2.5
11
70
20
240

aG. E. Glass, unpublished data, 1979.
                                     172

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                                 APPENDIX D

 DATA PERTINENT TO THE AQUATIC ECOSYSTEMS OF THE BOUNDARY WATERS  CANOE AREA

Table D-l.  Fishes Known to be Present  in the BWCA  and Border Lakes  of
            Minnesota

Table D-2.  Lake Benthic Invertebrates  Collected from Five Large  Lakes  in
            Superior National Forest  in  1976

Table D-3.  Zooplankton Collected  from Five Large Lakes  in Superior  National
            Forest in 1976 and 1977

Table D-4.  Phytoplankton Collected  from Five Large Lakes in Superior
            National Forest during the  fall and summer of 1976  and  1977

Table D-5.  BWCA-VNP Water Quality -  November 1978:  Field + Descriptive Data
            (lakes within and near the BWCA and VNP sampled 11/6, 7, 8, 9,/78
            and 11/15, 16/78)

Table D-6.  Summary of Snow Data from the BWCA Region for the Period November
            1977 - March 1978:  Bulk  Concentrations in Melted Snow  and
            Calculated Loadings

Table D-7.  Mercury Concentrations in Fish from Selected Northern Minnesota
            Lakes

Table D-8.  Relative Sizes (inches)  and  Mercury Content  (ppm) of  Walleye from
            12 Northern Minnesota Waters, 1977

Table D-9. Relative Sizes (inches) and Mercury Content (ppm) of Pike from  14
           Northern Minnesota Waters, 1977
Figure D-l. Distribution of Lake Surface Areas  for BWCA  and VNP  Fall  1978
            sampling.
                                     173

-------










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-------
   TABLE D-2.  LAKE BENTHIC INVERTEBRATES COLLECTED FROM FIVE LARGE LAKES3
                    IN SUPERIOR NATIONAL FOREST  IN 1976b
PLECOPTERA
     Capniidae
     Acroneuria lycorias
     Perlinella drymo

EPHEMEROPTERA
     Isonychia sp.
     Siphlonuridae
     Siphlonurus sp.
     Siphlonurus marshalli
     Heptageniidae
     Arthroplea bipunctata
     Stenacron sp.
     Stenacron candidum
     Stenacron interpunctaturn
     Stenacron minnetonka
     Stenonema sp.
     Stenonemn tripunctatum
     Siphloplecton interlineatum
     Bactidae
     Callibactis sp.
     Clocon sp.
     Leptophlebiidae
     Leptophlebia sp.
     Ephemerella sp.
     Ephemerella versimilis
     Ephemerella temporalis
     Caenis sp.
     Ephemera simulans
     Hexagenia sp.
     Hexagenia limbata

ODONATA
     Coenagrionidae
     Enallagma sp.
     Comphidae
     Dromogomphus spinosus
     Hagenius brevistylus
     Acshnidae
     Acshna sp.
     Basiaeschna Janata
     Boycria sp.
     Boycria vinosa
     Didymops transversa
     Macromia sp.

(continued)
ODONTA (continued)
     Macromia illinoiensis
     Somatochlora williamsoni
     Notonecta sp.
     Ranatra sp.
     Belostroma sp.
     Lethocerus sp.
     Corixidae

TRICHOPTERA
     Nyctiophylax moestus
     Polycentropus c^_nereuj[
     Polycentropus interrupta
     Hydroptillidae
     Agraylea sp.
     Hydroptila sp.
     Ochrotrichia sp.
     Agrypnia improba
     Banksiola crotchi
     Phrygabea cinerea
     Ptilostomis sp.
     Limnephilidae
     Gramotaulis sp.
     Nemotaulius hostilis
     Pycnopsyche guttifer
     Agarodes distinctum
     Mo1anna sp.
     Mo1anna blenda
     Molanne tryphena
     Helicopysche borealis
     Ceraclea sp.
     Ceraclea neffi
     Ceraclea resurgens
     Triaenodes injusta
     Triaenodes tarda

MEGALOPTERA
     Chauloideg rastricornis
     Sialis sp.

COLEOPTERA
     Haliplus sp.
     Dytiscidae
     Cyrinidae
     Dineutus sp.
                                     175

-------
Table D-2.  (continued)
COLEOPTERA (continued)
     Cyrinus sp.
     Hydrophilidae
     Ectopria nervosa
     Dubiraphia sp.
     Macronychus glabratus
     Donacia sp.

DIPTERA
     Tabenidae
     Aedes sp.
     Chironomidae
     Clinotanypus sp.
     Conchapelopia sp.
     Dicrotendipes sp.
     Endochironomus sp.
     Eukiefferriella sp.
     Glyptotendipes sp.
     Larsia sp.
     Palpomyia group
     Polypedilum sp.
     Procladius sp.
     Stenochironomus sp.
     Xenochironomus sp.
     Chironomidae pupae

DECAPODA

CRUSTACEA
     Crangonyx sp.
     Hyalella azteca
NEMATODA

TURBELLARIA

HIRUDINEA

OLIGOCHAETA

GASTROPODA
     of. Amnicola limosa
     Carpeloma decisum
     Ferrissia sp.
     Cyraulus sp.
     Hellsoma anceps
     H. carpanulata
     jl. corpulentum
     ji. trivolvis
     Helisomi sp.
     Physa gyrina
     Sphaerium strintinum
     Stagnicola sp.

PELECYPODS
     Sphaeriidae
OTHER
     Lepidoptera
aBirch, Colby, Gabbro, Seven Beaver, and White Iron Lakes.

^Collections made by  the Minnesota Copper-Nickel Study Group  (MCNSG)
 (Johnson et al.. 1978).
                                      176

-------
    TABLE D-3.   ZOOPLANKTON  COLLECTED  FROM  FIVE  LARGE LAKES3 IN SUPERIOR
                      NATIONAL  FOREST  IN  1976  AND 1977b
 ROTIFERA
     Keratella cochlearis
     Polyarthra vulgar Is
     Synchaeta sp.
     Conch ilus sp.
     Kellicott La  congispina
     Tr ichocera cylindrica
     Kell icott la  bostoniens is
     Collocheca sp.
     Tr ichocera s im i1is
     Fil inia long iseta
     Keratella quadrata
     Ploesoma  truncatum
     Pompholyx sulcata
     Tr ichocera porcellus
     Hexachra  sp.
     Ploesoma  lent iculare
     Lecane sp.
     Trichocera mult icr inis
     Asplanchna sp.
     Lophochavis  salpine
     Trichocera weberi
     Brachionus sp.
     Lophocharis  sp.
     Tr ichocera clongata
     Trichocera longiseta
     Ascomorpha sp.
     Enthlanis d ilatata
     Hexarthra mira
     Ploesoma hudsoni
     Tescudinella patina
     Trichocera  sp.
     Tr ichotria  tetraet is
     Ascomorpha  oval is
     ^. saltans
     Bdelloid sp.
     Brach ionus  quadr identatus
     Cephalodella intuda
     Euchlanxs sp.
     Keritella h iemalIs
     JK. paludosa
     K. serrulata
     1C. taurocephala
     Kotholca acuminata
     Notholca sp.
     Rotaria peturia
     Synchaeta stylata
CLADOCERA
     Bos imina long irostris
     Daphnia galeata mendotae
     Holopedium gibberum
     Daphnia retrocurva
     D iaphanosoroa sp.
     Chydorus sphaericus
     Ceriodaphnia lacustr is
     Daphnia pulex
     Leptodora kindti i
     Daphnia shodleri
     Alona c trcumf irobr iata
     Ceriodaphn ia quadrangula
     Alona guttata
     Cer iodaphnia sp.
     Chydorus b icornutus
     Daphnia catauba
     Daphnia long iremis
     13. parvula
     V. sp.

COPEPODA
     Tropocyclops pras inus
          (Cyclopoida)
     Cyclops b icuspidatus thomas i
          (Cyclopoida)
     Diaptomus oregonens is
          (Calanoida)
     Epischura lacustris
          (Calanoida)
     Cyclops vernal is
          (Cyclopoida)
     Mesocyclops edax
          (Cyclopoida)
     Diaptomus minutus
          (Calanoida)
     Ergas ilis chautaquaens is
          (Cyclopoida)
     Macrocyclops alb idus
          (Cyclopoida)
     Eucyclops agilis
          (Cyclopoida)
     Orthocyclops modestus
          (Cyclopoida)
     Diaptomus sic il is
          (Calanoida)
aBirch, Colby, Gabbro, Seven Beaver, and White Iron Lakes.

^Collect ions made by the Minnesota Copper-Nickel Study Group  (MCNSG)
 (Piragis et al. 1978).
                                   177

-------
   TABLE D-4.  PHYTOPLANKTON COLLECTED FROM FIVE LARGE LAKES3 IN SUPERIOR
        NATIONAL FOREST DURING THE FALL AND SUMMER OF 1976 AND 1977b
BACILLARIOPHYTA
     Asterionella formosa
     Cyclotella bodanica
     Fragilaria crotonensis
     Melosira ambigua
     Melosira distans
     Nitzschia sp.
     Tabellaria fenestrata

CHLOROPHYTA
     Ankistrodesmus falcatus
       including varieties
       aricularis & mirabili^
     Botryococcus Braunii
     Oocystis sp.
CYANOPHYTA
     Agmenellum quadruplicatum
       (MerismopedJ^a glauca)_
     Aphanocapsa delicatissima
     Cpelosphaerium Kuetzingianum

 CHRYSOPHYTA
     Dinobryon bavaricum
     _Dinqbrypn divergens
     Dinobryon sertularia var.
       protuberans

 CRYPTOPHYTA
     Cryptononas erosa

 PYRRHOPHYTA
     Ceratim hirundinella
aBirch, Colby, Gabbro,  Seven Beaver, and White Iron Lakes.

^Collections made by the Minnesota Copper-Nickel Study Group (MCNSG)
 (Gerhart et al. 1978).
                                      178

-------


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-------
 TABLE D-7.  MERCURY CONCENTRATIONS  IN FISH FROM  SELECTED NORTHERN MINNESOTA LAKES3

Lake
Vermilion

Trout



Pelican


Basswood

Sand Point

Namakan

Kabetogama

Burntside



White Iron



Fall



Gunf lint

Colby


Greenwood


Gabbro


Pike River
Number
of
Species fish
Walleye
Northern pike
Walleye
Northern pike
Lake trout
Smallmouth bass
Walleye
Northern pike
Smallmouth bass
Walleye
Northern pike
Walleye
Northern pike
Walleye
Northern pike
Walleye
Northern pike
Walleye
Northern pike
Lake trout
Smallmouth bass
Walleye
Northern pike
White suckers
Yellow perch
Walleye
Northern pike
White suckers
Yellow perch
Walleye
Northern pike
Northern pike
White suckers
Yellow perch
Northern pike
White suckers
Yellow perch
Northern pike
White suckers
Yellow perch
Walleye
30
22
25
5
15
5
6
25
5
28
25
8
7
10
4
26
10
6
34
4
9
26
25
20
25
24
25
24
24
24
18
20
21
25
25
25
25
21
25
25
6
Range,
length
(inches)
12.4
17.6
14.0
20.0
15.0
11.3
9.5
10.8
13.1
12.5
15.5
11.8
19.2
11.5
15.5
9.4
15.8
11.2
19.5
21.0
9.0
11.0
15.2
12.8
5.2
9.3
14.0
8.8
5.2
10.0
14.0
6.7
13.1
5.3
14.9
8.5
5.4
17.6
8.8
5.7
14.2
- 23.0
- 33.0
- 21.4
- 30.0
- 24.8
- 14.8
- 25.9
- 28.2
- 15.4
- 29.0
- 25.5
- 21.0
- 24.5
- 17.5
- 23.3
- 21.3
- 30.5
- 24.0
- 32.0
- 28.0
- 18.0
- 21.5
- 23.7
- 20.0
- 10.6
- 18.8
- 40.7
- 22.1
- 11.3
- 26.0
- 28.0
- 21.0
- 19.6
- 8.6
- 27.7
- 18.8
- 10.9
- 34.5
- 22.0
- 9.6
- 29.0
Expected size
(inches) at the
Range, 0.5 ppm
ppm Hg threshold
0.09 -
0.10 -
0.20 -
0.25 -
0.11 -
0.28 -
0.10 -
0.13 -
0.13 -
0.24 -
0.23 -
0.25 -
0.21 -
0.13 -
0.09 -
0.03 -
0.09 -
0.18 -
0.19 -
0.37 -
0.27 -
0.26 -
0.21 -
0.03 -
0.10 -
0.21 -
0.15 -
0.04 -
0.09 -
0.21 -
0.12 -
0.09 -
0.09 -
0.15 -
0.31 -
0.07 -
0.08 -
0.22 -
0.03 -
0.08 -
0.46 -
0.73
0.47
0.95
0.98
0.50
0.42
0.87
0.69
0.36
1.95
0.86
2.67
0.83
0.58
0.28
0.40
0.24
0.95
1.01
0.76
0.65
0.78
0.58
0.27
0.68
0.53
1.29
0.35
0.50
1.23
0.56
0.80
0.62
0.53
0.75
0.56
0.68
0.95
0.20
0.88
1.50
25
N/Ab
18
24


20
30

15
21
13
22
>30
N/A
>30

17
28


15
24


25
23


16
29
18 (est.)


19 (est.)


22 (est.)




a Data from:  Minnesota Department of Natural Resources.  1978.  Mercury levels
  in eleven northeastern lakes, 1977.  Spec. Publ., Ecol. Serv. Sect, (mimeo).  34 p.

k N/A " not applicable.
                                         183

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-------
                                          TECHNICAL REPORT DATA
                                 (Please read Instructions on the reverse before completing)
1. REPORT NO.
  EPA-600/3-80-044
                                   2.
                                                                       3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
   Impacts of  Airborne Pollutants  on Wilderness Areas
   Along  the Minaesota-Ontario Border
                                        5. REPORT DATE
                                          May 1980  issuing date
                                        6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
   Gary E.  Glass
   Orie L.  Loucks
                                                                       8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS

   SAME AS BELOW
                                                                       10. PROGRAM ELEMENT NO.
                                                                       11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
  Environmental Research  Laboratory -  Duluth, MN
  Office  of Research  and  Development
  U.S.  Environmental  Protection Agency
  Duluth,  Minnesota 55804
                                                                       13. TYPE OF REPORT AND PERIOD COVERED
                                         14. SPONSORING AGENCY CODE

                                             EPA/600/03
15. SUPPLEMENTARY NOTES
16. ABSTRACT
      The goal of  this study  was to examine previously  unanswered  questions  concerning potential effects of the
  proposed Atikokan, Ontario power plant  on ecosystems in the Boundary Waters Canoe Area Wilderness (BWCA) and
  Voyageurs National Park (VNF) of Minnesota by using the most relevant data  and analytical methods.   The principal
  steps were to focus on:  (1) the ultimate deposition of emissions from the  plant (rather than only  on pollutant
  concentrations),  (2) the use of a time-varying grid model with provision for atmospheric transformations, and (3) a
  detailed review of all available data from the region  on atmospheric deposition of pollutants, water quality, and
  effects.  The results are considered in relation to a  review of responses by terrestrial and aquatic organisms to
  changes in the chemistry of  this environment.
      The sensitive aquatic and terrestrial receptors in the BWCA-VNP region are described quantitatively, and this
  information is assessed in terms of what is currently  known about the Impacts of atmospheric pollutants.  Specific
  conclusions based on factual information, probable consequences,  and possible impacts of the proposed coal-fired
  power generating station at  Atikokan are presented.
      The study supports, in  part, the conclusions reached previously concerning the predicted air concentrations of
  sulfur dioxide, but differs  significantly with the conclusions concerning the significance of future impacts.  When
  the  total emissions from the proposed power plant are  considered, the increased loadings of sulfuric and nitric
  acids, fly ash, and mercury  as an addition over and above other regional sources will, with high probability, have
  significant consequences for the sensitive receptors in the BWCA-VNP region, especially for the future of sport
  fisheries and other aquatic  resources.
17.
                                      KEY WORDS AND DOCUMENT ANALYSIS
                     DESCRIPTORS
                                                       b.lDENTIFIERS/OPEN ENDED TERMS
                                                         c.  COSATI Field/Group
 Air  pollution
 Water pollution
 Acid rain
 Investigations
 Documentation
 Modeling
Wilderness  areas
Park areas
Plumes
Power Plants
Northern Minnesota
BWCA,
Boundary Waters Canoe
Area Wilderness
Atikokan (Ontario)
Power Plant
1313    06F
06.T, 06P, 06S
08L08F
18. DISTRIBUTION STATEMEN1

  RELEASE  TO PUBLIC
                         19. SECURITY CLASS (ThisReport)
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                                21. NO. OF PAGES

                                      199
                                                       20. SECURITY CLASS (Thispage)
                                                           UNCLASSIFIED
                                                                                        22. PRICE
EPA Form 2220-1 (Rev. 4-77)    PREVIOUS  EDITION is OBSOLETE
                                                      187
                                          (,US GOVERNMENT PRINTING OFFICE 1980-657-146/5663

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