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'               IMPACT ASSESSMENT
|                 WORK GROUP I
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•                 FINAL REPORT
                  JANUARY 1983
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                                        WORK GROUP  I
                                   Work Group  Co-Chairmen

                                    G.E.  Bangay,  Canada
                                 C.  Riordan, United  States
                                        February 1983
                                       IMPACT ASSESSMENT
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 '§                                       FINAL REPORT
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                               Submitted to the Coordinating Committee in
                               fulfillment of the requirements  of the
                               Memorandum of Intent on Transboundary Air
                               Pollution signed by Canada  and the United
                               States.

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TO:      Co-Chairmen
         Canada/United States
         Coordinating Committee


FROM:    Co-Chairmen
         Impact Assessment Work Group I
We are pleased to submit our final  report completing the Phase  III  activities
of the Impact Assessment Work Group I.   Although we have reached agreement
on the majority of information and  conclusions found in  the  report, there  are
a number of instances when Canadians and Americans could not reach  agreement.
These differences are confined to the aquatic section of the report (Section  3)
and has required the preparation of separate summary statements in  Section 1.
Those portions of the text which represent a lack of Canada/United  States
consensus are typed in italics.

This report completes our activities under the terms of  reference contained
in the Memorandum of Intent and as  such represents the joint efforts by
representatives of our two countries to provide information  to  the  negotiators.

                                 Sincerely yours,
G.E. Bangay                                       Courtney Riordan
Canadian Co-Chairman                              United States Co-Chairman

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                                  TABLE OF CONTENTS
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TABLE OF CONTENTS


LIST OF FIGURES
LIST OF TABLES
PREFACE
ACKNOWLEDGEMENTS
SECTION 1 SUMMARY

1 . 1 INTRODUCTION
1.2 AQUATIC ECOSYSTEM EFFECTS - Canada
AQUATIC ECOSYSTEM EFFECTS - United States
1.3 TERRESTRIAL ECOSYSTEM IMPACTS
1.3.1 Effects on Vegetation
1.3.1.1 Sulphur Dioxide
1.3.1.2 Ozone
1.3.1.3 Acidic Deposition
1.3.2 Effects on Terrestrial Wildlife
1.3.3 Effects on Soil
1.3.4 Sensitivity Assessment
1.4 HUMAN HEALTH AND VISIBILITY
1.4.1 Health
1.4.2 Visibility
1.5 MAN-MADE STRUCTURES
1.6 METHODOLOGIES FOR ESTIMATING ECONOMIC BENEFITS
OF CONTROL





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                    TABLE OF CONTENTS (continued)
1.7   NATURAL AND MATERIAL RESOURCE INVENTORY

      1.7.1  Introduction

      1.7.2  Aquatic - United States

      1.7.3  Aquatic - Canada

      1.7.4  Agriculture - United States

      1.7.5  Agriculture - Canada

      1.7.6  Forests - United States

      1.7.7  Forests - Canada

      1.7.8  Man-Made Materials - United States

      1.7.9  Man-Made Materials - Canada

1.8   LIMING

      1.8.1  Aquatic Systems

      1.8.2  Terrestrial Liming

      1.8.3  Drinking Water Supply


SECTION 2   INTRODUCTION

2.1   THE EXTENT OF RESOURCES EXPOSED TO ACIDIC DEPOSITION
      AND POTENTIAL FOR LARGE-SCALE EFFECTS

      2.1.1  Methods of Measuring Effects

      2.1.2  Hydrologic Cycle

2.2   ATMOSPHERIC INPUT, TRANSPORT AND DEPOSITION
      OF POLLUTANTS

      2.2.1  Emissions of Pollutants to the Atmosphere

      2.2.2  Atmospheric Transport of Pollutants

      2.2.3  Atmospheric Removal Processes

      2.2.4  Alteration of Precipitation Quality
ii

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TABLE OF CONTENTS (continued)


2.3 REFERENCES
SECTION 3 AQUATIC IMPACTS

3 . 1 INTRODUCTION
3.2 ELEMENT FLUXES AND GEOCHEMICAL ALTERATIONS
OF WATERSHEDS
3.2.1 Hydrogen Ion (Acid)
3.2.2 Nitrate and Ammonium Ions
3.2.3 Sulphate
3.2.4 Aluminum and Other Metals
3.3 NATURAL ORGANIC ACIDS IN SOFT WATERS
3.4 CATION AND ANION BUDGETS
3.4.1 Element Budgets at Hubbard Brook, New Hampshire
3.4.2 Element Budgets in Canada
3.4.3 Effects of Forest Manipulation or Other Land
Use Practices on Watershed Outputs
3.5 AQUATIC ECOSYSTEMS SENSITIVE TO ACIDIC DEPOSITION

3.5.1 Mapping of Watershed Sensitivity for
Eastern North America
3.5.1.1 Eastern Canada
3.5.1.2 Eastern United States
3.5.2 Aquatic - Terrestrial Relationships
3.5.3 Geochemical Changes Due to Acidic
Precipitation
3.6 ALTERATIONS OF SURFACE WATER QUALITY
3.6.1 Present Chemistry of Aquatic Systems
3.6.1.1 Saskatchewan

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                    TABLE OF CONTENTS (continued)                               •
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                                                       Number
       3.6.1.2  Ontario                                 3-59

       3.6.1.3  Quebec                                  3-65

       3.6.1.4  Atlantic Provinces                      3-68

       3.6.1.5  United States                           3-74

3.6.2  Time Trends in Surface Water Chemistry           3-74

3.6.3  Time Trends in Representative Areas              3-76              •
             3.6.3.1  Time Trends in Nova Scotia
                       and Newfoundland                       3-76

             3.6.3.2  Historical Trends in Northern
                       Wisconsin                              3-79

             3.6.3.3  Historical Trends in
                       New York State                         3-83

             3.6.3.4  pH Changes in Maine and
                       New England                            3-86
      3.6.7  pH Declines During Spring Runoff in Ontario
               and Quebec

      3.6.8  pH Depression During Flushing Events
3.7   ALTERATION OF BIOTIC COMPONENTS RECEIVING ACIDIC
      DEPOSITION                                              3-100
      3.7.1  Effects on Algae                                 3-104

      3.7.2  Effects on Aquatic Macrophytes                   3-105

      3.7.3  Effects on Zooplankton                           3-106
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             3.6.3.5  Time Trend in New Jersey                3-88

      3.6.4  Paleolimnological Evidence for Recent                              H
               Acidification and Metal Deposition             3-90              I

      3.6.5  Seasonal and Episodic pH Depression              3-92
                                                                                •
      3.6.6  Seasonal pH Depression in Northern Minnesota     3-92              •
         and Quebec                                     3-94              \|
          Depression During tiusning events                               M
         in West Virginia                               3-94              •


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                    TABLE OF CONTENTS (continued)
3.8
3.9
3.7.4  Effects on Aquatic Macroinvertebrates


3.7.5  Effects on Bacteria and Fungi


3.7.6  Effects on Amphibians


3.7.7  Effects of Low pH on Fish


3.7.8  Effects of Aluminum and Other Metals on Fish


3.7.9  Accumulation of Metals in Fish


       3.7.9.1  Mercury


       3.7.9.2  Lead


       3.7.9.3  Cadmium


       3.7.9.4  Aluminum and Manganese


3.7.10 Effects on Fisheries in Canada and the

         United States


       3.7.10.1 Adirondack Region of New York


       3.7.10.2 Ontario


       3.7.10.3 Quebec


       3.7.10.4 Nova Scotia


       3.7.10.5 Scandinavia


3.7.11 Response to Artificial Acidification


3.7.12 Effects of Acidic Deposition on Birds
         and Mammals


CONCERNS FOR IRREVERSIBLE EFFECTS


3.8.1  Loss of Genetically Unique Fish Stocks


3.8.2  Depletion of Acid Neutralizing Capacity


3.8.3  Soil Cation and Nutrient Depletion


ATMOSPHERIC SULPHATE LOADS AND THEIR RELATIONSHIP
TO AQUATIC ECOSYSTEMS
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 3-107


 3-108


 3-109


 3-112


 3-115


 3-123


 3-123


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 3-126


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              TABLE OF CONTENTS  (continued)                               "


                                                         Page             M
                                                        Number

3.9.1  The Relative Significance of  Sulphur  and                          •
         Nitrogen Deposition  to  Acidification of
         Surface Waters                                  3-148

3.9.2  Data and Methods for Associating  Deposition                       •
         Rates with Aquatic Effects                      3-151

       3.9.2.1  Empirical Observations                   3-153            |

                Saskatchewan  Shield  Lakes                3-153            ~

                Experimental  Lakes Area,  Ontario        3-154            *

                Algoma, Ontario                          3-155            M

                Muskoka - Haliburton, Ontario           3-157

                Laurentide Park, Quebec                  3-160            |

                Nova  Scotia                              3-164

                Boundary Waters  Canoe Area and                           •
                   Voyageurs  National Park,  Minnesota   3-167



                Adirondack Mountains of  New York        3-171            m

                The Hubbard Brook Ecosystem,
                  New Hampshire                          3-174

                Maine and New England                    3-177            •

                Summary of Empirical Observations       3-178            •

       3.9.2.2  Short-term or Episodic  Effects          3-181
3.9.2.3  Sensitivity Mapping and Extrapolation                    •
           •f~^t fi •§- V\ a >• A •*• .-•»«-»£•>  s\f IT o c« <- *^ i—1-»  f* ** Y^ *\ A f\       *\,~ 1 ft /i            ^"
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                   to  Other Areas of Eastern Canada      3-184

                 Terrestrial                             3-184

                    Terrain characteristics of Three
                    Specific Study Areas                 3-185

                    Results of Terrain Extrapolation     3-191

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_                           3.9.3.3   Summary                                 3-212
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                                   TABLE OF CONTENTS (continued)



                                                                             Page
                                                                            Number


                                     Aquatic                                3-192


                                        Possible Magnitude of Effects       3-197


                     3.9.3  Use of Acidification Models                     3-198


                            3.9.3.1  The "Predictor Nomograph" of
                                       Henriksen                            3-199


                            3.9.3.2  Cation Denudation Rate Model
                                     (CDR)                                   3-206
                     3.9.4  Summary of Empirical Observation and
                              Modelling                                     3-212


               3.10  CRITICAL RESEARCH TOPICS                               3-215


                     3.10.1  Element Fluxes and Geochemical Alterations
                              of Watersheds                                 3-216


                     3.10.2  Alterations of Surface Water Quality            3-216


                     3.10.3  Alteration of Biotic  Components                3-217


                     3.10.4  Irreversible Impacts                            3-218


                     3.10.5  Target Loadings and Model Validation            3-219


•                           3.10.5.1  Long-Term Data Collection
                                        and Monitoring                      3-220
               3.11   REFERENCES                                             3-222



               SECTION 4   TERRESTRIAL IMPACTS


               4.1    INTRODUCTION                                           4-1


               4.2    EFFECTS ON VEGETATION                                  4-2


                     4.2.1   Sulphur Dioxide (S02)                            4-2


                            4.2.1.1  Introduction                            4-2


                            4.2.1.2  Regional Doses of S02                  4-3

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                    TABLE OF CONTENTS (continued)
             4.2.1.3  S02 Effects to Agricultural
                        Crops

             4.2.1.4  S02 Effects to Forest Vegetation

             4.2.1.5  S02 Effects to Natural
                       Ecosystems

      4.2.2  Ozone (03)

             4.2.2.1  03 Effects to Agricultural Crops

             4.2.2.2  03 Effects to Forest Vegetation

      4.2.3  Acidic Deposition

             4.2.3.1  Acidic Deposition Effects to
                       Agricultural Crops

             4.2.3.2  Acidic Deposition Effects to
                       Forest Vegetation

      4.2.4  Pollutant Combinations

             4.2.4.1  S02 - 03 Effects

             4.2.4.2  S02 - N02 Effects

             4.2.4.3  S02 - 03~Acidic Deposition
                       Effects

4.3   EFFECTS OF ACIDIC DEPOSITION ON TERRESTRIAL
      WILDLIFE

4.4   EFFECTS ON SOIL

      4.4.1  Effects on Soil pH and Acidity

      4.4.2  Impact on Mobile Anion Availability
               and Base Leaching

      4.4.3  Influence of Soil Biota and Decomposition/
               Mineralization Activities

      4.4.4  Influences on Availability of Phosphorus

      4.4.5  Effects on Trace Element and Heavy Metal
               Mobilization and Toxicity
viii

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4-26
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TABLE OF CONTENTS (continued)


4.5 SENSITIVITY ASSESSMENT
4.5.1 Terrestrial Sensitivity Interpretations
4.5.2 Terrestrial Mapping for Eastern North America
4.5.2.1 Eastern United States
4.5.2.2 Eastern Canada
4.6 RESEARCH NEEDS
4 . 7 CONCLUSIONS
4.8 REFERENCES
SECTION 5 HEALTH AND VISIBILITY
5 . 1 HEALTH
5.1.1 Contamination of Edible Fish
5.1.2 Contamination of Drinking Water
5.1.3 Drinking Water From Cisterns
5.1.4 Recreational Activities in
Acidified Water
5.1.5 Direct Effects: Inhalation of Key
Substances Related to Long Range
Transport of Air Pollutants
5.1.6 Sensitive Areas and Populations at
Risk - Health
5.1.7 Research Needs
5.2 VISIBILITY
5.2.1 Categories and Extent of Perceived Effects
5.2.2 Evaluation of Visibility
5.2.2.1 Aesthetic Effects
5.2.2.2 Transportation Effects



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                    TABLE OF CONTENTS (continued)
5.3
5.2.3  Mechanisms and Quantitative Relationships

5.2.4  Sensitive Areas and Populations

5.2.5  Data Needs/Research Requirements

REFERENCES
SECTION 6  EFFECTS ON MAN-MADE STRUCTURES

6.1   INTRODUCTION

6.2   OVERVIEW

6.3   MECHANISMS AND ASSESSMENT OF EFFECTS

      6.3.1  Factors Influencing Deposition

      6.3.2  Effects of Sulphur Dioxide Pollutant/
               Material Interactions

             6.3.2.1  Zinc

             6.3.2.2  Steels

             6.3.2.3  Copper and Copper Alloys

             6.3.2.4  Aluminum

             6.3.2.5  Paints

             6.3.2.6  Elastomers

             6.3.2.7  Masonry

      6.3.3  Effect of Nitrogen Dioxide and  Ozone
               Pollutant/Material  Interactions

             6.3.3.1  Metals

             6.3.3.2  Masonry

             6.3.3.3  Paints

             6.3.3.4  Elastomers
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5-34
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6-7
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6-10
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6-11
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TABLE OF CONTENTS (continued)


6.3.4 Effect of Ammonia Pollutant /Material
Interactions
6.3.5 Effect of Particulate Pollutant /Material
Interactions
6.4 IMPLICATIONS OF TRENDS AND EPISODICITY
6.5 DISTRIBUTION OF MATERIALS AT RISK
6.6 DATA NEEDS AND RESEARCH REQUIREMENTS
6.7 METHODOLOGIES
6.8 ASSESSMENT OF ECONOMIC DAMAGE
6.9 REFERENCES

SECTION 7 THE FEASIBILITY OF ESTIMATING THE ECONOMIC
BENEFITS OF CONTROLLING THE TRANSBOUNDARY
MOVEMENT OF AIR POLLUTANTS
7.1 INTRODUCTION
7.1.1 Purpose
7.1.2 Background
7.1.3 Emission-Benefit Relationship
7.1.4 Efficiency and Equity Considerations
7.2 BENEFITS: CONCEPTUAL APPROACHES
7.2.1 Primary Benefits
7.2.1.1 Market Approach
7.2.1.2 Imputed Market Approach
7.2.1.3 Nonmarket Approach
7.2.2 Secondary Benefits





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                    TABLE OF CONTENTS (continued)                              •


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7.3   BENEFIT ESTIMATION TECHNIQUES                          7-14              I

      7.3.1  Aquatic                                         7-14

             7.3.1.1  Recreational Fishery                   7-14              I

             7.3.1.2  Commercial Fishery                     7-19              m

             7.3.1.3  Aquatic Ecosystem                      7-19

      7.3.2  Terrestrial                                     7-20              I

             7.3.2.1  Agriculture                            7-20

             7.3.2.2  Forestry                               7-20              •

             7.3.3.3  Ecosystem                              7-20              M

      7.3.3  Water Supply                                    7-21              *

      7.3.4  Effects on Buildings and Structures             7-21              •

      7.3.5  Human Health                                    7-22

             7.3.5.1  Mortality                              7-22              |

             7.3.5.2  Morbidity                              7-23              g

      7.3.6  Visibility                                      7-24              *

      7.3.7  Summary                                         7-26              I

7.4   QUALIFICATIONS, CONCLUSIONS AND RECOMMENDATIONS        7-26

      7.4.1  Qualifications                                  7-26              |

             7.4.1.1  Dose-Response Relationship             7-28

             7.4.1.2  Inclusion of All Values                7-28
                        Nothing Feature                       7-28

      7.4.2  Conclusions and Recommendations                  7-30

7.5   REFERENCES                                              7-32

      APPENDIX - REVIEW OF RELEVANT  ECONOMIC  CONCEPTS         7-34
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             7.4.1.3  Irreversibilities and the All  or                         •
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TABLE OF CONTENTS (continued)


SECTION 8 NATURAL MATERIAL RESOURCES INVENTORY
8.1 INTRODUCTION
8.2 AQUATIC ECOSYSTEM
8.2.1 U.S. Aquatic Resources
8.2.2 Canadian Aquatic Resources
8.3 AGRICULTURAL RESOURCES
8.3.1 U.S. Agricultural Resources
8.3.2 Canadian Agricultural Resources
8.4 FOREST RESOURCES
8.4.1 U.S. Forest Resources
8.4.2 Canadian Forest Resources
8.5 MAN-MADE STRUCTURES
8.5.1 U.S. Historic Inventory
8.5.2 Canadian Historic Inventory
8.6 REFERENCES
APPENDIX-TABLES
SECTION 9 LIMING

9 . 1 INTRODUCTION
9.2 AQUATIC
9.2.1 Liming as a Mitigative Measure
9.2.2 Liming Programs
9.2.2.1 Sweden
9.2.2.2 Norway
9.2.2.3 United States

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9.3
9.4

9.5

9.6
                    TABLE OF CONTENTS (continued)
       9.2.2.4  Ontario, Canada

9.2.3  Economic Aspects of Lake Liming

       9.2.3.1  Costs in Sweden

       9.2.3.2  Costs in Norway

       9.2.3.3  Costs in New York State

       9.2.3.4  Costs in Canada

9.2.4  Technical Evaluations Necessary in
         Liming Programs

TERRESTRIAL LIMING

9.3.1  The Application of Lime to Agricultural Soils

9.3.2  Economics of Agricultural Liming

9.3.3  Forest Liming

9.3.4  Terrestrial Liming Summary

DRINKING WATER SUPPLY

COSTS OF CORROSION CONTROL

REFERENCES
xiv

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               2-4        Precipitation amount-weighted mean annual         2-14
                          pH in North America.
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                                         LIST OF FIGURES

              Figure                                                        Page
              Number                                                       Number
               2-1        Regions of North America containing lakes         2-3
                          sensitive to acidification by acidic
                          deposition based on bedrock geology.

               2-2        Wind patterns for North America based on          2-10
               a + b      surface stream-lines for January and July.

               2-3        Seasonal precipitation patterns for North         2-11
               a + b      America.
               2-5a       Precipitation amount-weighted mean H+             2-15
                          concentration.

               2-5b       Precipitation amount-weighted mean H+             2-16
                          deposition.
               2-6a       Precipitation amount-weighted mean SO"          2-19
                          concentration.
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               2-8a       Precipitation amount-weighted mean N03~           2-23
•                        concentration.
               2-8b       Precipitation amount-weighted mean N03~           2-24
•                        deposition.
               2-9        Percent of normal precipitation in North          2-26
                          America in 1980.
               2-6b       Precipitation amount-weighted mean SO"          2-20
                          deposition.

               2-1 a.       Precipitation amount-weighted mean NH4+           2-21
                          concentration.

               2-7b       Precipitation amount-weighted mean NH4+           2-22
                          deposition.
               3-1        Relationship between pH and the relative          3-5
                          proportions of inorganic carbon species.

               3-2        Simplified nitrogen cycle showing chemical        3-8
                          changes caused by plant and soil processes.

               3-3        Simplified sulphur cycle showing chemical         3-10
                          changes caused by plant and soil processes.

               3-4        Aqueous aluminum in equilibrium with gibbsite.    3-13

-------
                       LIST OF FIGURES  (continued)
Figure
Number
 3-5


 3-6


 3-7



 3-8


 3-9



 3-10



 3-11



 3-12


 3-13

 3-14



 3-15


 3-16



 3-17


 3-18
Relationship of observed stream concentrations
of aluminum to the pH of surface water.

Schematic representation of the hydrogen ion
cycle .

Percent of ionic composition of precipitation
for the Hubbard Brook Experimental Forest
during 1964 to 1977.

Hydrogen ion budget for Hubbard Brook
Experimental Forest.

Potential of soils and bedrock to reduce the
acidity of incoming atmospheric deposition
for eastern Canada.

Potential of soils and bedrock to reduce the
acidity of incoming atmospheric deposition
for eastern United States.

Total concentration of calcium plus magnesium
with respect to alkalinity for lakes in
Canada.
for
[Ca2+ + Mg2+ - alkalinity] vs.
lakes in Canada.

Hydrographic Regions of Quebec.
Sulphate versus  [calcium + magnesium -
alkalinity] for  lakes on the Precambrian
Shield in Quebec.

Mean and range of  sulphate concentrations
in Canadian lakes.

Mean and range of  basin specific  yield  of
excess sulphate  compared with  atmospheric
excess sulphate  deposition in  precipitation.

Areal distribution of sulphate concentrations
in Quebec lakes,  summer 1980.

Relationship  between alkalinity and calcium
+ magnesium for  northern Saskatchewan  lakes.
xvi
Page
Number

3-14

3-18
3-20

3-23

See map
folio

See map
folio
3-48
3-49
3-51
3-52

3-53

3-56

3-57

3-60



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Figure
Number

3-19

3-20
3-21
3-22
3-23
3-24

3-25

3-26

3-27

3-28
3-29
3-30

3-31
3-32


                                                          XVI1
           LIST OF FIGURES (continued)
Distribution of lakes sampled in Ontario
Ministry of the Environment  1981 and  1982
surveys .

Mean summer epilimnetic alkalinity,
mean summer epilimnetic pH and minimum surface
water pH in spring for 16 lakes in Muskoka-
Haliburton (1976-1980).

Minimum pH values of 57 headwater streams  in
Muskoka-Haliburton, 1976-80.

Calcite saturation indices for 181 lakes in
southern Quebec, summer 1980.

pH Values for Quebec lakes,  summer 1980.

            values for Quebec lakes,  summer
1980.

Distribution of calcite saturation  index
values for New Brunswick, Prince Edward Island
and Nova Scotia.

Distribution of calcite saturation  index
values for Newfoundland.

Distribution of calcite saturation  index
values for Labrador.

Distribution of surface water alkalinities  for
the United States.

Surface water alkalinity of New England states .

Annual changes in median pH and mean
discharge-weighted excess SO^" for
the St. Mary's and Medway Rivers, Nova Scotia,
and the Isle aux Morts and Rocky Rivers,
Newfoundland.

Geographic distribution of pH levels measured
in Adirondack lakes higher than 610 metres
elevation, June 24-27, 1975.

Frequency distribution of pH and fish
population status for 40 high elevation lakes
surveyed in the 1930s and again in  1975.
                                                   Page
                                                 Number
3-62
3-63
3-64


3-66


3-67

3-70


3-71



3-72


3-73


See map
folio

3-75

3-80
3-84
3-85

-------
                       LIST OF FIGURES  (continued)
Figure
Number
 3-33
 3-34
 3-35
 3-36
 3-37
 3-38
 3-39
 3-40
 3-41
 3-42
 3-43
 3-44
 3-45
New Jersey stream pH, 1958-1979, Oyster Creek
and McDonalds Branch.

Profiles of the lead concentration in  four
sediment cores from Jerry Lake, Muskoka-
Haliburton.

Discharge, hydrogen ion load per unit  area,
pH, and depth of precipitation for each day
that: a precipitation event occurred  for Harp
Lake No. 4.

Hydrogen ion content of streams draining Red
Chalk Lake watersheds No.3 and No.4  (Muskoka-
Haliburton).

Mean daily pH for the Shavers Fork River at
Bemis, West Virginia and precipitation event
pH and accumulation Arborvale, West  Virginia.

Relative number of taxa of the major taxonomic
groups as a function of pH.

Generalized response of aquatic organisms  to
low pH.

Age composition of yellow perch (Perca
flavescens) captured in Patten Lake, Ontario,
pH 4.1.

Changes in the age composition of the  white
sucker (Catostomus commersoni) in George Lake,
Ontario.

Percent survival of brook trout fry  plotted  as
a  function of time in treatment waters at  pH
level 5.2.

Brook trout survival (arcsin transformation)
as a function of total aluminum concentration
at each pH level.

Mercury concentrations in yearling yellow
perch vs. epilimnetic pH for selected  lakes
in Ontario.

Age composition of the white sucker  population
of three lakes in the Muskoka-Haliburton
Region of Ontario.
xviii
Page
Number

3-89
3-93

3-97

3-98
3-101
3-102
3-103
3-116
3-117

3-119

3-120

3-124
3-131


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                                                                   xix


                       LIST OF FIGURES (continued)


Figure                                                         Page
Number                                                        Number
 3-46       Atlantic salmon angling data since  1936            3-134
            normalized for comparison between high and
            low pH rivers.


 3-47       Angling records for six Nova Scotia Atlantic       3-136
            coast rivers with mean annual pHs   5.0.


 3-48       Atlantic salmon rivers of the Maritimes            3-137
            divided into 4 pH categories based  on
            significance to salmon reproduction.


 3-49       Distribution of alkalinity values for lakes        3-195
            in six regions of Ontario.


 3-50       Cumulative distribution of alkalinity              3-196
            values for lakes in five  regions of Ontario.


 3-51       Nomograph to predict the pH of  lakes given the     3-201
            sum of nonmarine calcium  and magnesium
            concentrations (or nonmarine calcium
            concentration only) and the nonmarine sulphate
            concentrations in lake water (or the weighted-
            average hydrogen ion concentration  in
            precipitation).


 3-52       The model plot-pH predicted for consideration     3-207
            of the sum of cations and sulphate.


 3-53       Cation Denudation Rate Model applied to  rivers     3-209
            of Nova Scotia and Newfoundland.


 3-54       Relation of excess sulphate and cation             3-210
            concentration for pH 5.3 and 5.8 for basin
            runoff of 30, 50 and 100 cm/yr.


 4-1        Sulphur dioxide emissions in eastern North         4-4
            America.


 4-2        Geographic distribution of monthly  arithmetic     4-5
            means for S02.


 4-3        Conceptual model of factors involved in  air        4-9
            pollution effects (dose-response) on vegetation.


 4-4        Regression of yield response vs. transformed       4-13
            dose for controlled exposures using field
            chambers.

-------
                                                                    XX
                       LIST OF FIGURES  (continued)

Figure                                                         Page
Number                                                        Number
           of mercury in ecosystems.
           visibilities for North America.

           a   1950-54                                        5-17
           b   1960-64                                        5-18
           c   1970-74                                        5-19
           d   1976-80                                        5-20
7-4        Change  in  demand due  to  visibility  improvement.    7-25
                                                                               I
4-5        Effects on base cation loss, soil acidification    4-69
           and Al^+ solubilization  for nonsulphate-
           adsorbing soils.                                                    B

4-6        Effects on base cation loss, soil acidification    4-72
           and Al+ solubilization  for  sulphate-                               •
           adsorbing soils.                                                    •

4-7        Soil characteristics of  eastern United             See  map           ^
           States.                                            folio             •

5-1        Varying effects of lake  pH on  the  distribution     5-4
                                                                                I
5-2        Mercury in yearling yellow  perch  and               5-5
           epilimnetic pH relationships.                                       M


5-3        Seasonal and spatial distribution of  long-
           term trends in extinction weighted  airport                          •
                                                                                I

                                                                                I
5-4        Median 1974-76 visibilities  (miles)  and            5-22
           visibility isopleths  for  suburban/nonurban
           airports.                                                           •

5-5        Visual range as a  function of  fine mass  con-       5-33
           centration.                                                         •

5-6        Summertime fine particle  levels  for  non-          5-35
           urban sites.                                                        _

7-1        Conceptual relationship between  emissions  and      7-5
           economic effects.

7-2        Variation in effects  due  to  different  emission-   7-5              •
           deposition relationships.

7-3        Change in demand due  to water  quality              7-16             •
           improvement.
                                                                                I

                                                                                I

                                                                                I

-------
                                                                                xxi
I
                                     LIST OF FIGURES (continued)
•            Figure                                                        Page
              Number                                                       Number

               7-5        Measure of consumer surplus.                      7-35
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               7-6         Change in consumer surplus.                       7-35

               7-7         Change in demand due to visibility improvement.   7-38

               7-8         Compensating and equivalent surplus.              7-38

               7-9         Producer's surplus.                               7-39

               7-10       Change in producer's surplus due to change        7-39
                          in supply.

               7-11       Hypothetical change in producer's surplus         7-41
                          due to reduction in LRTAP deposition.

               8-la       Annual sulphate deposition regime for             8-3
                          eastern United States.

               8-lb       Annual sulphate deposition regime for             8-4
                          eastern Canada.

               8-2         Conceptual scheme for identifying resources       8-5
                          potentially at risk.
               18-3        Forest regions in eastern Canada and acidic        8-26
                          deposition.

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                                                                 xxiii

                           LIST OF TABLES


Table                                                          Page
Numb e r                                                        Number



 2-1        Current emissions in the U.S. and Canada.          2-6


 2-2        Air emmissions from a typical 1000 MW  coal         2-7
            fired system plant.


 2-3        Summary of global sources,  annual emmission,       2-8
            background concentration, major  sinks,  and
            residence time of atmospheric gaseous
            pollutants.


 2-4        Concentrations in bulk deposition and  total        2-18
            bulk deposition of four ions at  four calibrated
            watershed studies.


 2-5        Conversion factors for concentration               2-25
            and deposition units.


 3-1        The retention of nitrate, ammonium ion and  total   3-9
            nitrogen by forested watersheds.


 3-2        Annual budgets of bulk precipitation inputs        3-22
            and stream-water outputs of dissolved  substances
            for undisturbed watersheds  of the Hubbard-Brook
            Experiment Forest.


 3-3        Description of watersheds in Canada utilized       3-25

            for mass balance studies.


 3-4        Net export of major ions for calibrated           3-26
            watersheds in Canada.


 3-5        Summary of total cation release, hydrogen  ion     3-28

            production, and the cation  release ratio for
            three manipulated watershed studies.


 3-6        Terrestrial factors and associated criteria        3-31
            for determining the potential of terrestrial
            ecosystems to reduce the acidity of atmospheric
            deposition.


 3-7        Terrestrial factors and associated data bases     3-31
            utilized for the interpretation  of the potential
            to reduce acidity of atmospheric deposition.


 3-8        Terrestrial characteristics of areas having        3-36
            high, moderate and low potential to reduce
            acidity for eastern Canada.

-------
                     LIST OF TABLES (continued)
Table
Number
 3-9



 3-10


 3-11


 3-12



 3-13


 3-14


 3-15



 3-16

 3-17


 3-18


 3-19



 3-20


 3-21

 3-22



 3-23
Characteristics of map classes for  the  eastern
United States as to the potential to  reduce
acidity of acidic deposition.

Formal names, locations, lake data  sources and
the laboratories that analyzed data.

Regional water chemistry survey  results  for
surface water pH distribution.

Summary of the percentage of lakes  and  streams
in each alkalinity class by county  or district
for Ontario.
Some statistics on the ratios  of
for waters of Quebec.
Mean concentrations of  ions  in  the water  of
four Nova Scotia rivers.

Apparent changes in summer pH values  in lakes
in Nova Scotia and southern  New Brunswick during
the period 1940-79.

pH of streams in Muskoka-Haliburton,  Ontario.

Monthly discharge hydrogen ion  loads  and
percent of annual total.

Spring/summer comparison  of  average
parameter values.

Susceptibility of breeding habitat  to pH
depression for amphibians whose range overlaps
areas receiving acidic  deposition.

Approximate  pH at which fish in the  LaCloche
Mountain Lakes stopped  reproduction.

Metals residues in yearling  yellow  perch.

Distribution and frequency of  occurrence  of
fish species collected  during  surveys of
Adirondacks  Lakes.

Summary of biological  effects  observed.
xxiv

Page
Number
3-43
3-54
3-58
3-61
3-69
3-78
3-82
3-95
3-96
3-99

3-110

3-114

3-125
3-128
3-140


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Table
Number
3-24
3-25
3-26
3-27

3-28

3-29

3-30

3-31
3-32
3-33
4- la
4-lb
4-2


                                                       XXV
         LIST OF TABLES (continued)
Avian and mammalian species most likely  to be
influenced by a reduction in food resources
due to acidic deposition.

Mean and range of pH values for 21 headwater
streams.

Periodic pH depressions observed in  streams
and lakes with different sulphate loadings
and corresponding biological effects.

Coverage of terrain types in eastern Canada
interpreted for their potential to reduce
acidity.

Summary of terrain types and potential to
reduce acidity for all of eastern Canada.

Terrain characteristics of watersheds
containing the detailed study areas  of
eastern Canada.

Average annual or spring total inflection
point alkalinities for nine lakes in the
Muskoka-Haliburton watershed study area.

Distribution of 141 lake alkalinities,
grouped by sensitivity classes, in various
terrain types.

Calculation of wet sulphate loadings consistent
with pH 5.3 or greater in lakes with initial
calcium concentrations of 50 yeq/L or greater.

Acidification sensitivity of surface waters
related to sulphate loading for two  pH
objectives and three runoff values.

Summary of crop effects from S02 exposure
in field closed chambers.

Summary of crop effects from S02 exposure
in field zonal air pollution systems.

Sulphur dioxide concentration causing visible
injury to various sensitivity grouping of
vegetation.
                                                   Page
                                                 Number
3-145



3-150


3-183



3-186



3-187


3-190



3-193



3-194



3-205



3-211



4-10


4-11


4-15

-------
                     LIST OF TABLES (continued)

Table
Number


 4-3        Summary of studies reporting  results  of  SC>2
            exposures under laboratory  conditions for
            various tree species.

 4-4        Effects of long-term controlled  ozone
            exposures on growth, yield  and foliar injury
            to selected plants.

 4-5        The number in 1980 and 1981 that ozone
            concentrations exceeded the USEPA standard of
            0.12 ppm along the U.S./Canada border.

 4-6        Summary of growing season:  daylight  ozone
            trends in rural locations in  southern Ontario,
            1976-81.

 4-7        Summary of growing season:  daylight  ozone
            trends in urban locations in  eastern  Canada,
            1976-80.

 4-8        Repesentative tolerance limits to simulated
            acid precipitation.

 4-9        Effects of mixtures of S02  and 03 on  plants.

 4-10       Acidity related reactions influencing
            availability of several elements.

 4-11       Terrestrial factors and associated criteria
            limits to assess  forest productivity
            sensitivity.

 4-12       The sensitivity of various  soil  categories  to
            acidic deposition.

 4-13       Theoretical sensitivities of  terrestrial
            ecosystems to acidic deposition  effects.

 4-14       Terrestrial factors  and associated data bases
            utilized for terrain characteristics  mapping
            in eastern Canada and  the eastern United States.

 4-15       Soil chemical classes  and areas  dominated by
            histosols in the  eastern United  States.

 4-16       Terrain characteristics of  eastern Canada
            summarized by soil  category.
xx vi

Page
Number
4-17
4-27

4-33

4-34

4-35
4-41
4-47
4-55
4-65

4-66

4-68
4-76

4-77

4-79


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                                                                xxv ii
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             Table                                                          Page
             Number                                                       Number
5-1        Canadian and United States drinking  water          5-9
           guidelines for toxic metals.

5-2        Current health related ambient  air quality        5-11
           standards.

5-3        Summary of qualitative evidence for                5-24
           visibility related values.

5-4        Summary results of iterative  bidding              5-26
           visibility studies.

6-1        Experimental regression  coefficients with          6-8
           estimated standard deviations for small  zinc
           and galvanized steel specimens.

6-2        Examples of material loss  in  one year.             6-12

7-1        Activity categories.                               7-7

7-2        Summary of methods.                                7-27

7-3        Summary of physical science data needed            7-29
           for benefit evaluation.

8-1        Summary of eastern U.S.  surface water area.        8-8

8-2        Surface water area with  low and moderate          8-9
           potential to reduce acidity.
              18-3        Summary of surface water area in eastern           8-11
                         Canada.
8-4        Ranking of U.S. crops  by  1978 value  of             8-14
           production.

8-5        1978 yield of six crops in 38 states by           8-15
           deposition regime.

8-6        Select U.S. agricultural  crops  by  state           8-16
           receiving greater than 40 kg/ha.yr
           sulphate deposition.

8-7        Ranking of crops in eastern  Canada by 1980         8-18
           value of production.

8-8a       Value and percentage of total 1980 yield           8-19
           of each crop in eastern Canada  by
           deposition regime.

-------
                     LIST OF TABLES (continued)
Table
Number
 8-8b


 8-9


 8-10

 8-11


 8-12


 8-13


 8-14

 8-15
1980 yield of major crops in eastern Canada
by deposition regime.

Value of major crops by province receiving 40
kg/ha. yr sulphate deposition.

U.S. hardwood and softwood volume and growth.

U.S. forest volume by state receiving greater
than 40 kg/ha. yr sulphate deposition.

Hardwood, softwood and mixed wood annual
growth in eastern Canada by deposition regime.

Annual forest growth by province receiving
greater than 20 kg/ha. yr sulphate deposition.
U.S. historic sites by ambient
Canadian historic inventory by province and
deposition.
APPENDIX TABLES
SECTION 8
 8-1
 8-2
 8-3
 8-4
 3-5
 8-6
 8-7
U.S. aquatic resources by state and
sensitivity category  10-20 kg/ha.yr
sulphate deposition.

U.S. aquatic resources by state and
sensitivity category  20-40 kg/ha.yr
sulphate deposition.

U.S. aquatic resources by state and  acid
sensitivity category  for greater than
40 kg/ha.yr sulphate  deposition.

U.S. agriculture resources in areas  receiving
10-20 kg/ha.yr of  sulphate deposition.

Agriculture resources in areas receiving
20-40 kg/ha.yr of  sulphate deposition.

U.S. agriculture resources in areas  receiving
more than 40 kg/ha.yr sulphate deposition.

U.S. agricultural  resources - state  totals
for six crops.
xxviii

Page
Number
8-20
8-20
8-23
8-24

8-27
8-28
8-31
8-33

8-37

8-38
8-40
8-41
8-42
8-44
8-45

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Table
Number
8-8
8-9
8-10
8-11
8-12
8-13

8-14

8-15
9-1
9-2






                                                     XXIX
         LIST OF TABLES (continued)
U.S. forest resources in areas receiving
20-40 kg/ha.yr sulphate deposition - volume.

U.S. forest resources in areas receiving
20-40 kg/ha.yr sulphate deposition - growth.

U.S. forest resources in areas receiving
greater than 40 kg/ha.yr sulphate deposition-
volume .

U.S. forest resources in areas receiving
greater than 40 kg/ha.yr sulphate deposition -
growth.

1980 Canadian agricultural production by  crop
and province for deposition zone 10-20
kg/ha.yr.

1980 Canadian agricultural production by  crop
and province for deposition zone 20-40
kg/ha.yr.

1980 Canadian agricultural production by  crop
and province for deposition zone >40 kg/ha.yr.

Sulphate deposition for forest resources  by
province.

Cost of corrosion control by lime addition as
a function of plant size.

Example of cost calculation for feeding lime
at a 5 MGD plant.
                                                  Page
                                                 Number
8-47


8-49


8-51



8-52



8-53



8-54



8-57


8-58


9-13


9-14

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                                                                  XXXI
PREFACE

In August, 1980, the Governments of Canada and  the United  States
signed a Memorandum of Intent concerning  transboundary  air pollution.
This action was taken in response  to concern  for  actual and potential
damage resulting from the long-range transport  of air pollutants
between countries and in recognition of the already  serious problem
of acidic deposition.

Each country has demonstrated concern  for the causing of damage  to
the other's environment by transboundary movement of its pollutants.
This concern is rooted in international agreements,  such as the  1909
Boundary Waters Treaty, the Great  Lakes Water Quality Agreement,  and
the 1979 E.C.C. Convention on Long-Range Transboundary  Air Pollution,
all of which both Canada and the United States  have  signed.

The Memorandum noted that both countries hae  set  a priority on
developing a scientific understanding  of long-range  transport  of  air
pollutants and resulting environmental effects, and  on  developing and
implementing policies and technologies to combat  such effects.

To achieve the first steps of this overall objective, the  memorandum
established a plan of action for the period October, 1980  to January,
1982, during which time five documents are to be  prepared  by the
following work groups:

     1.   Impact assessment
     2.   Atmospheric modelling of pollutant  movements
     3A.  Strategies development and implementation
     3B.  Emissions, cost and engineering assessment
     4.   Legal, institutional arrangements and drafting
          (preparation of the actual document to  be  signed).

General terms of reference that apply  to all  work groups were
established, together with detailed terms dealing with  each work
group.

General Terms of Reference (as per MOI)

1.   The Work Groups shall function under the general direction and
     policy guidance of a United States/Canada  Coordinating Committee
     co-chaired by the Department  of External Affairs and  the
     Department of State.

2.   The Work Groups shall provide reports assembling and  analyzing
     information and identifying measures as  outlined below, which
     will provide the basis of proposals for  inclusion  in  a
     transboundary air pollution agreement.   These reports shall  be
     provided by January, 1982, and shall be  based on available
     information.

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xxxii
                                                                               I
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3.   Within 1 month of the establishment of the Work  Groups,  they               •
     shall submit to the United States/Canada Coordinating  Committee            •
     a work plan to accomplish the specific tasks outlined  below.
     Additionally, each Work Group shall submit an  interim  report  by
     January 15, 1981.

4.   During the course of negotiations, and under the  general                   am
     direction and policy of the Coordinating Committee,  the  Work               •
     Groups shall assist the Coordinating Committee as  required.

5.   Nothing in the foregoing shall preclude subsequent alterations             •
     of the tasks of the Work Groups or the establishment of                    •
     additional Work Groups, as may be agreed upon  by  the
     Governments.                                                               •

Specific Terms of Reference;  Impact Assessment Work  Croup

The Group will provide information on the current and  projected                 •
impacts of air pollutants on sensitive receptor areas,  and  prepare
proposals for the 'Research, Modelling and Monitoring1  elements  of an
agreement.                                                                      •

In carrying out this work, the Group will do the following.

     1.   Identify and assess physical and biological  consequences             •
          possibly related to transboundary air pollution.

     2.   Determine the present status of physical  and  biological               •
          indicators which characterize the ecoloigcal  stablity  of             •
          each sensitive area identified.

     3.   Review available data bases to establish  historic adverse             |
          environmental impacts more accurately.

     4.   Determine the current adverse environmental  impact  within             •
          identified sensitive areas (e.g., annual, seasonal,
          episodic).                                                            _

     5.   Determine the release of residues potentially related  to             •
          transboundary air pollution, including possible episodic
          release from snowpack melt in sensitive areas.                        •

     6.   Assess the years remaining before significant ecological
          changes are sustained within identified sensitive areas.             _

     7.   Propose reductions in the air pollutant deposition                    *
          rates (e.g., annual, seasonal, episodic)  which  would be
          necessary to protect identified sensitive areas.                      fl
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                                                                  XXX111
     8.   Prepare proposals  for  the  "Research,  Modelling and
          Monitoring" elements of  an agreement.


A time frame was established which called  for  preparation of the
report of Work Group 1 in  three  phases.  The Phase  1 report, an
interim working paper dealing primarily with acidic deposition,  was
completed in February, 1981.  The  Phase 2  report, which represented a
considerable improvement in  the  information base  that was available
for the Phase 1 report as  well as  receiving more  thorough peer
review, became available in  October,  1981.  This  Phase 3 report, the
final report of Work Group 1, contains not only a further refinement
and expansion of the data  base used  in the Phase  2  report, but also a
brief treatment of several additional air  pollutants.  The Phase 3
report has received fairly extensive  peer  review  from governmental,
university, and industrial reviewers  and together with Phase 3
reports from all other work groups will undergo formal peer  review
under the auspices of the United States/Canada  Coordinating
Committee.

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                                                                     xxxiv
Chairmen:
Vice Chairmen:
        WORK GROUP-1 MEMBERS


G.E. Bangay, Environment Canada
  C. Riordan (1982-83), U.S. Environmental Protection
     Agency
C.I. Harris (1981-82), B.R. Flamm (1980-81), U.S.
     Department of Agriculture


  D. Jeffs (1981-83), G. VanVolkenburg (1980-81),
     Ontario Ministry of the Environment
N.R. Glass, U.S. Environmental Protection Agency
     (1980-82)
R.J. Pickering, U.S. Department of the Interior
Work Group Structure:


     Subgroup


Aquatic



Terrestrial



Man-Made Structures


Health & Visibility



Economic Benefits



Canadian Members:
        Canada - Leader
        T. Brydges
        P. Rennie (1981-83)
        C. Sullivan (1980-81)


        H. Martin


        R. Paolini (1981-83)
        G. Becking (1980-81)


        A. Castel
U.S.A. - Leader


R. Wilhour (1981-83)
G. Glass (1980-81)


J. Corliss (1981-83)
C. Harris (1980-81)


D. Flinn


J. Bachmann



R. Luken
       W. Ayre, New Brunswick Department  of Environment
       G. Beggs, Ontario Ministry  of Natural Resources
       J. Cooley, Fisheries  and Oceans  Canada
       F. Elder, Environment Canada
       K. Fischer, Environment Canada
       R. Halstead, Agriculture Canada
       S. Linzon, Ontario Ministry of  the Environment
       L. Metras, Environment Canada (1980-81)
       H. St. Martin,  Environment  Quebec
       H. Sandhu, Alberta Department of Environment
       W. Shilts, Energy, Mines, and Resources
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                                                                XXXV
United States Members:

       R. Adams, University of Wyoming (1981-83)
       J. Baker, North Carolina State University (1982-83)
       J. Bain, U.S. Environmental Protection Agency (1981-83)
       J. Barse, U.S. Department of Agriculture (1981-83)
       R. Beadle, U.S.  Department of Energy
       D. Bennett, U.S. Environmental Protection Agency (1981-83)
       J. Blanchard, U.S. Department of State (1980-82)
       D. Brakke, University of Western Washington (1982-83)
       P. Brezonik, University of Minnesota (1982-83)
       R. Buckman, U.S. Department of Agriculture
       F. Burmann, U.S. Environmental Protection Agency (1980-81)
       D. Burmaster, Council on Environmental Quality (1980-81)
       J. Carter, U.S.  Department of the Interior (1981-83)
       R. Church, North Carolina State University (1982-83)
       S. Cramer, U.S.  Department of the Interior
       C. Cronan, University of Maine
       C. Daniel, Council on Environmental Quality (1981-83)
       M. Davis, U.S. Environmental Protection Agency (1981-82)
       L. Dochinger, U.S. Department of Agriculture
       G. Foley, U.S. Environmental Protection Agency
       J. Fulkerson, U.S. Department of Agriculture (1981-83)
       W. Heck, U.S. Department of Agriculture
       M. Heit, U.S. Department of Energy (1981-83)
       R. Herrmann, U.S. Department of the Interior
       J. Jacobson, Boyce Thompson Institute
       D. Johnson, Oak Ridge National Laboratory
       R. Kane, U.S. Department of Energy
       R. Livingston, U.S. Environmental Protection Agency (1981-83)
       H. Marguiles, U.S. Department of Health and Human Services
          (1980-81)
       W. McFee, Purdue University
       J. Miller, National Oceanic and Atmospheric Administration
          (1980-81)
       S. Norton, University of Maine (1982-83)
       B. Ostro, U.S. Environmental Protection Agency (1981-83)
       R. Phillips, U.S. Department of Energy (1980-82)
       T. Pierce, U.S.  Environmental Protection Agency (1980-81)
       R. Porter, U.S.  Department of State
       D. Raynal, State University of New York (1981-83)
       K. Schreiber, U.S. Department of the Interior (1982-83)
       S. Sherwood, U.S. Department of the Interior (1981-83)
       D. Shriner, Oak Ridge National Laboratory
       J. Spence, U.S.  Environmental Protection Agency (1981-83)
       W. Warnick, U.S. Department of Energy (1981-83)
       S. Wilson, U.S.  Environmental Protection Agency (1981-83)
       T. Wilson, U.S.  Department of State (1982-83)
       T. Williams, U.S. Department of Energy (1982-83)

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                                                                xxxvi
Liaison:
       M. Beaulieu, Department of External Affairs - Canada
       M. Levine, U.S. Environmental Protection Agency (1982-83)
       P. Smith, U.S. Department of Agriculture
       D. Weber, U.S. Environmental Protection Agency (1980-82)
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                                                               xxxvii
                          ACKNOWLEDGEMENTS

The Work Group wishes to acknowledge the assistance in the  form  of
technical consultation or peer review of the following individuals
and organizations during the several phases of this study.  The
enthusiasm and dedication of this assistance were  fundamental  to  the
successful completion of this report.  Inclusion in the following
list should not be taken to indicate endorsement of the report by the
named individual or organization:  F. Adams (Auburn University),
A. Anders (University of Wisconsin), N. Baer (New  York University),
D. Bjonback (Environment Canada), D. Carter (U.S.  Department of  the
Interior), R. Coote (Agriculture Canada), D. Cowell (Environment
Canada), E. Cowling (North Carolina State University), T. Crocker
(University of Wyoming), S. Dean (Air Products & Chemicals
Incorporated), D. Dixon (Wordcom Centres Ltd.), D. Dodge  (Ontario
Ministry of Natural Resources), J. Donnan (Ontario Ministry of the
Environment), C. Driscoll (Syracuse University), H. Eisler
(Stelco Incorporated), B. Forster (University of Guelph), N. Foster
(Environment Canada), G. Gilbert (Environment Canada), W. Gizyn
(Ontario Ministry of the Environment), C. Griffith (Ontario Ministry
of the Environment), M. Griffith (Ontario Ministry of the
Environment), W. Hart (Environment Canada), A. Harfenist  (Environment
Canada), R. Harter (University of New Hamphsire),  F. Haynie (U.S.
Environmental Protection Agency), H. Hirvonen (Environment  Canada),
B. Hosier (Environment Canada), H. Hultberg (Swedish Water  & Air
Pollution Research Institute), T. Hutchinson (University  of Toronto),
M. Hutton (Environment Canada), C. Jackson (University of Georgia),
M. Kelly (Tennessee Valley Authority), J. Kelso (Fisheries  and Oceans
Canada), J. Kerekes (Environment Canada), J. Knetsch (Simon Eraser
University), A. Lefohn (ASL & Associates), R. Linthurst (North
Carolina State University), R. Livingston (U.S. Environmental
Protection Agency), 0. Loucks (Institute of Ecology), A.  Lucas
(Environment Canada), C. Lucyk (Ontario Ministry of the Environment),
J. MacLean (Ontario Ministry of Natural Resources), R. McLean  (Domtar
Limited), S. Milburn (Environment Canada), H. Miller (U.S.  Department
of the Interior), K. Mills (Fisheries and Oceans Canada), K. Minns
(Fisheries and Oceans Canada), R. Morris (U.S. Department of Energy),
I. Morrison (Environment Canada), J. Nicholson (Environment Canada),
D. O'Guinn (Northrop Services, Inc.), R. Olson (Oak Ridge National
Laboratory), C. Olver (Ontario Ministry of Natural Resources),
J. Pagel (Ontario Ministry of the Environment), M. Parker (Wordcom
Centres Ltd.), R. Pearson (Ontario Ministry of the Environment),
D. Rambo (Northrop Services, Inc.), E. Rhea (Reynolds Metals
Company), C. Rubec (Environment Canada), C. Russell (Resources for
the Future), R. Saunders (Fisheries and Oceans Canada), D.  Schindler
(Fisheries and Oceans Canada), C. Schofield (Cornell University),
P. Sereda (National Research Council - Canada), K. Shea (U.S.
Department of Agriculture), S. Singh (Agriculture  Canada),  J.  Skelly
(Pennsylvania State University), J. Smith (Ontario Ministry of the
Environment), W.  Smithies (Ontario Ministry of the Environment),
C. Taylor (University of California - Riverside),  M. Thompson
(Environment Canada), D. Thornton (University of Minnesota), G.  Voigt

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                                                              xxxviii
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(Yale Universty), D. Wark (Environment Canada), W. Watt (Fisheries             •
and Oceans Canada), M. Weaver (Heritage Canada), E. Winkler                    ™
(University of Notre Dame), N. Yan (Ontario Ministry of the
Environment), M. Young (Ontario Ministry of the Environment).                  H




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SECTION I



SUMMARY

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                                                                  1-1
                               SECTION 1
                                SUMMARY
1.1   INTRODUCTION


Wet and dry deposition  of  acidic  substances  and  other pollutants are
currently being observed over most  of  eastern  North  America.   The
Impact Assessment Work  Group was  charged with  identifying and making
an assessment of the key physical and  biological consequences
possibly related to these  transboundary air  pollutants.


During the Work Group's assessment  of  these  effects  it  has been
necessary to conduct the work along strictly disciplinary lines.
Thus the presentation of our findings  follows  a  sectoral  approach
(i.e., aquatic, terrestrial).  While this  approach has  been useful
for organizing and presenting our findings,  it has also  limited our
consideration of the interactions which exist  among  these sectors.
These effects do not occur in isolation.


The following sections  summarize  findings  of the Work Group with
respect to impacts on aquatic and terrestrial  sectors of  the
biosphere, health and visibility, and  man-made structures.  There are
also summary statements with regard to methodologies for  estimates of
economic benefits of controls, natural and material  resource
inventory, and liming.
1.2   AQUATIC ECOSYSTEM EFFECTS - CANADA


The potential effects from the deposition  of acid  and  associated ions
and compounds (sulphur dioxide, sulphate,  nitrate,  ammonia,  and
others) on water quality, and on the aquatic ecosystem,  appear to be
more fully quantified and understood than  for  terrestrial  ecosystems.
Data have been drawn from a number of study areas  in eastern North
America including Labrador, Newfoundland,  Nova Scotia, New Brunswick,
the southern part of the Canadian Shield in Quebec, and  Ontario.
Primary study areas in the U.S. are found  in New Hampshire and
southern Maine, Adirondack Park in New York, the Boundary  Waters
Canoe Area of Minnesota, and numerous lakes in north-central
Wisconsin.


The findings and conclusions of the Work Group with respect  to
acidification effects are contained in the following statements:


     Sulphuric acid has been identified as the dominant  compound
     contributing to the long-term surface water acidification
     process.  Nitric acid contributes to  the acidity  of precipi-
     tation, but is less important in eastern North America  than
     sulphuric acid in long-term acidification of  surface  waters.
     Nitric acid contributes to pH depression of surface waters
     during periods of snowmelt and heavy  rain runoff  in some areas.

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                                                                  1-2
Observed Historical Changes

     Sediments from lakes in Maine, Vermont, and New Hampshire
                                                                         I
                                                                         I
     Studies of lakes in eastern North America have provided  evidence
     that atmospheric deposition accounts for sulphate levels in
     excess of those expected from natural processes.  In  the absence         •
     of effects from mine drainage and industrial waste water,  the            •
     symptoms of acidification (e.g., pH depressions of surface
     waters and loss of fish populations), have been observed only  in         _
     lakes and rivers where the accompanying elevated concentrations          I
     of surface water sulphate (and nitrate in some cases)  indicate          *
     atmospheric deposition of these ions.  Land use changes, such  as
     fires, logging, and housing developments have taken place  in             I
     many areas with sensitive (low alkalinity) surface waters, but          •
     the symptoms of acidification have not been observed  unless
     there is an accompanying increase in surface water sulphate              •
     concentrations.  Nitrate concentrations also increase  in some            I
     areas, especially during snowmelt.

     In eastern Canada, the surface waters which have elevated  excess         •
     sulphate occur in areas which have high atmospheric deposition          ^
     of sulphate.  All of the surface waters sampled in northeastern
     North America that have experienced loss of alkalinity also have
     elevated excess sulphate concentrations.  In areas with  less
     acidic deposition, loss of alkalinity in surface waters  has not
     been observed.  In Quebec, sulphate concentrations in  surface            •
     waters decrease towards the east and north in parallel with              •
     deposition patterns.  Sulphate concentrations are equal  to or
     greater than the bicarbonate concentration in lakes in the              _
     southwest part of the Province.  This indicates that  the surface         I
     water chemistry has been altered by atmospheric sulphur                  •
     deposition.
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indicate increased atmospheric acidic deposition has affected             I
terrestrial and aquatic ecosystems as measured by changes  in
metal concentrations and diatom populations.  It has been
inferred from the sediment record that the rate of acidification          •
of aquatic ecosystems has increased since the late 1800s as               •
measured by declines in metals (zinc, copper, iron, calcium,
magnesium and manganese) in the sediments.  Conditions  of  low  pH
maintain metals in the water column, where they can be  flushed
out of the system before being deposited in the sediments.
Diatom data are less complete, but they also indicate a                  M
statistically significant pH decline since the early 1900s.               I

In this report numerous historical chemistry records have  been
examined for waters not influenced by local urban or industrial           •
discharges.  Reviews have been conducted for 2 rivers in                  B
Newfoundland and 6 in Nova Scotia; 7 lakes in Nova Scotia  and  3
in New Brunswick; 40 lakes in Adirondack Park, New York; 250              •
lakes in New England; 2 streams in New Jersey Pine Barrens; and           |
275 lakes in Wisconsin.  Historical records which are available

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                                                                  1-3
     from areas of soils and bedrock with  a low potential  to  reduce
     acidity exposed to acidic deposition, show an  increase in
     sulphate and corresponding decrease in alkalinity  and pH.  Areas
     of similar lithology and land use practices, but not  receiving
     significant acidic deposition do not  show similar  losses of
     alkalinity.

     Lakes in the Adirondack Mountain range have some of the  lowest
     alkalinity values and are located in  watersheds with  a low
     potential to reduce acidity.  They are located in  the eastern
     U.S. in a zone receiving high acidic  deposition (26-40 kg/ha.yr
     of sulphate in precipitation 1978-81).   Historical data  on fish
     and pH are available for 40 high elevation Adirondack lakes.   In
     the 1930s, only 8% of these lakes had pH less  than 5.0;  10% had
     no fish whereas in the 1970s, 48% had pH less  than 5.0 and 52%
     had no fish.  In some cases, entire fish communities  consisting
     of brook trout, lake trout, white sucker,  brown trout, and
     several cyprinid species apparently have been  eliminated over
     the 40-year period.  The New York Department of Environmental
     Conservation has concluded that at least 180 former brook trout
     ponds are acidic and no longer support brook trout.   The
     relative contribution of natural and  anthropogenic sources to
     acidification of these lakes is not known.

     In New England, deposition of wet sulphate has been measured  to
     be 17-40 kg/ha.yr.  A study of 95 lakes  for which  there  are
     historical pH data from the 1930s to  the 1960s has indicated
     that 36% either had the same pH or higher while 64% now  have
     lower pHs.  For 56 lakes, a comparison of historical  alkalin-
     ities to modern values indicated that 30% of the lakes had
     increased and 70% had decreased in alkalinity.  Over  the period
     of record, measured alkalinity values have decreased  by  an
     average of 100 yeg/L.  The lakes were small to medium size
     oligotrophic to mesotrophic with moderately to very transparent
     water, low to moderate concentrations of humic solute, low
     alkalinity and conductance and with moderately disturbed to
     pristine watersheds.  For four rivers in Nova  Scotia  data from
     1980-81 showed a decrease in bicarbonate,  ah increase in
     sulphate and hydrogen ion concentrations when  compared to
     1954-55 data.

Short-Term pH Depressions

     While the rate of change of water quality of lakes (i.e., the
     time required for a lake to become acidified)  is one  of  the
     least well-defined aspects of the acidification process,  there
     is evidence that current acid loadings are damaging to fish
     populations and other biota due to short-term  pH depressions
     following snowmelt and storm runoff.  Both sulphate and  nitrate
     are associated with short-term changes in water chemistry but in
     the majority of surveyed cases sulphate  appears to be the larger
     contributor to the total acidity.

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                                                            1-4
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Short-term pH depressions, and elevated concentrations of
metals, particularly aluminum, have been observed during periods
of high infiltration or runoff.  Metal accumulation in surface           •
waters (Al, Mn, Fe, Zn, Cd, Cu, Pb, and Ni), first noted in              |
streams and lakes of Scandinavia, also has been reported from
such places as Hubbard Brook, the Adirondacks, and the Great             _
Smoky Mountains of the U.S., and the southern Precambrian Shield         I
area of Ontario, Canada.  Artificial acidification of a lake in          ™
the Experimental Lakes Area of Ontario has also shown rapid
mobilization of metals from lake sediments to the water column.
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Data for 57 headwater streams in Muskoka-Haliburton show that
65% experience minimum pH values less than 5.5 and 26% have              m
minimum pH values less than 4.5.  Some inlet streams were                •
observed to have pH values below 4.0 during spring snowmelt.

Data from intensive studies of 16 lakes in the Muskoka-                  I
Haliburton area of Ontario currently receiving about 23-29               •
kg/ha.yr sulphate in precipitation have shown that lakes which
have summer alkalinity values up to about 40 yeg/L, experience           •
pH depressions to values below about 5.5 during snowmelt.  In            |
Ontario and OueJbec there are about 1.5 million lakes on the
Precambrian Shield.  In Ontario, of the 2,260 lakes sampled on           im
the Precambrian Shield, 19% have alkalinities below 40 yeg/L.            I
In the Shield area of Quebec, a 1981 survey of 162 lakes
indicated 37% were extremely sensitive to acidification (CSI
greater than 5.0), while 15% had summer pH values less than 5.0          I
(alkalinity less than 0).

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     A very large number of surface waters are being affected  by
     acidic deposition, even though the total number of lakes  and
     rivers in eastern North America which are known to have been
     acidified (alkalinity less than 0) by atmospheric acidic                 «
     deposition is a relatively small percentage of the total  aquatic         I
     resource.                                                                ^

Biological Effects                                                            •

     Detailed studies of watersheds have been carried out  in
     sensitive regions of North America and Scandinavia under  a range         •
     of sulphate deposition rates.  The results of the studies               |
     conducted in North America are described below.

     Observed changes in aquatic life have been both correlated with          •
     measured changes in the pH of water and compared for  waters of           *
     different pH values.  Differences have been documented in
     species composition and dominance and size of plankton                   B
     communities in lakes of varying pH.  Study results show that  the         |
     number of species is lower in low pH lakes compared to lakes  of
     higher pH.  These alterations may have important implications           m
     for organisms higher in the food chain.  Individual lakes often          •
     experience several symptoms of acidification at the same  time.
     For example, in Ontario, Plastic Lake inlet streams have  low  pH
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                                                             1-5
and high aluminum concentrations during spring  runoff  and
extensive growth of filamentous green algae, and fish  kills  have
been observed in Plastic Lake.

For those regions currently  receiving loadings  of  sulphate  in
precipitation of less than 17 kg/ha.yr (Wisconsin, Minnesota and
northwestern Ontario), there have been no  observed detrimental
chemical or biological effects.

For regions currently receiving between 20 and  30  kg/ha.yr
sulphate in precipitation there is evidence of  chemical
alteration and acidification.  In Nova Scotia rivers which
currently have pH less than  5 there have been salmon population
reductions as documented by  40 years of catch records.  Fish
stocks have remained viable  in adjacent rivers  with pH values
presently greater than 5.  Water chemistry records (1954-55  to
1980-81) have indicated a decline in pH to values  presently  less
than 5 for other rivers in the same area.  In Maine there is
evidence of pH declines over time and loss of alkalinity from
surface waters.  In Muskoka-Haliburton there is historical
evidence of loss of alkalinity for one study lake  and  there  is
documentation of pH depressions in all study lakes and streams
with low alkalinity.  Fish kills were observed  in  the  shore  zone
of a study lake during spring melt.  In the Algoma region there
are elevated sulphate and aluminum levels  in some  headwater
lakes.

For regions currently experiencing loading greater than
30 kg/ha.yr there are documented long-term chemical and/or
biological effects and short-term chemical effects in  sensitive
(low alkalinity) surface waters.

In the Adirondack Mountains  of New York, comparison of data  from
the 1930s with recent surveys has shown that some  more lakes
have been acidified.  Fish populations have been lost  from  180
lakes.  Elevated aluminum concentrations in surface waters have
been associated with low pH  and survival of stocked trout is
reduced by the aluminum.

In the Hubbard Brook study area in New Hampshire where the
influx of chemicals is limited principally to precipitation  and
dry deposition there are pH  depressions in streams during
snowmelt of 1 to 2 units.  Elevated levels of aluminum were
observed in headwater streams.

Many species of frogs, toads and salamanders breed in  temporary
pools formed by the mixture  of spring rains and snowmelt.  Such
pools are subjected to pH depression.  Embryonic deformities and
mortalities in the yellow spotted salamander which breeds in
temporary meltwater pools have been observed in New York State
where the acidity of the meltwater pools was 1.5 pH units lower
than that of nearby permanent ponds.  Population densities  of

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                                                                  1-6
     the bullfrog and woodfrog were  reduced  in  acidic  streams and
     ponds in Ontario*
Target Loadings

     Sulphate  in  precipitation has  been used as a surrogate for total
     acid loading.   Sulphate  in precipitation can be reliably
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     A lake acidification experiment  in northwestern Ontario  clearly
     shows that alterations to aquatic food chains begin at pH values
     slightly below 6.0.  The remarkable agreement between  these            «
     whole-lake experiments and observational  studies  in Scandinavia        I
     and eastern North America provides strong evidence that  the
     observed declines in fisheries are caused by acidification and
     not by other ecological stresses.                                       I

Extent of Effects

     The terrestrial mapping analysis for  eastern Canada supported by       •
     surface water chemistry has demonstrated  that the watersheds
     of sensitive (low alkalinity) aquatic ecosystems  where effects         _
     have teen observed have a low potential to reduce acidity and          •
     are representative, in terms of  soil  and  geological
     characteristics, of much larger  areas of  eastern  Canada.

     Similarly, using related but different criteria,  maps  have been        •
     developed which characterize considerable areas of the
     northeastern United States as having  low  potential to  reduce           m
     acidity.  Therefore, there is reason  to expect  that there are          •
     sensitive surface waters in these other areas which would
     experience similar effects if subjected to deposition  rates            _
     comparable to those in the study areas.   However, quantification       •
     of the number of lakes and rivers susceptible to  acidification         ~
     in both countries will require validation of the  terrestrial
     mapping methodologies and increased information on the chemistry       I
     of lakes and streams.                                                   I

     The present empirical evidence covers a broad spectrum of              m
     physical and climatological conditions across northeastern North       I
     America and therefore provides a reasonable basis on which to
     make judgements on potential loading  effect relationships.
     However the data do have some deficiencies. More data on              •
     historical trends of deposition  and associated chemical  and            •
     biological characteristics would improve  our understanding of
     long-term rates and effects of acidification.  In addition, a          •
     better understanding of all the  mechanisms involved  in the             |
     acidification process will enhance our ability  to estimate
     loading/response relationships precisely.  Therefore any               •
     estimates of loading/response relationships should be                   •
     strengthened in the light of new scientific information  as it
     becomes available.
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     measured.  Jt  is  recognized  that  dry  deposition of sulphate and
     sulphur dioxide,  and  the wet  and  dry  deposition of nitrogen
     oxides, nitric acid,  particulate  nitrate  and ammonia,  as well as
     other compounds also  contribute to  acidic deposition.   Based on
     documented effects, wet and  dry deposition of sulphur  compounds
     dominate in long-term acidification.

     Sulphur deposition also predominates  in the majority of cases
     surveyed involving short-term pH  depressions and associated
     effects.  Insufficient data  are available to relate nitrate
     deposition to short-term water quality effects.   Therefore, we
     are unable to determine a  nitrate dose-response relationship.

     The models, which are based  on theory, that have been
     considered, permit a  quantification of the target loadings in
     terms of geochemical  basin sensitivity.   Although these models
     require further validation,  the derived loading estimates are
     generally supportive  of the  empirical observations for the study
     areas discussed above.

     Based on the results  of the  empirical studies,  interpretation of
     long-term water quality data, studies of  sediment cores and
     models that have  been reviewed, we  conclude that acidic
     deposition has caused long-term and short-term  acidification of
     sensitive (low alkalinity) surface  waters in Canada and the U.S.
     The Work Group concludes on  the basis of  our understanding of
     the acidification process  that reductions from  present levels of
     total sulphur deposition in  some  areas would reduce further
     damage to sensitive (low alkalinity)  surface waters and would
     lead to eventual  recovery  of  those  waters that  have already been
     altered chemically or biologically.   Loss of genetic stock would
     not be reversible.

     The Canadian members  of the  Work  Group propose  that present
     deposition of sulphate in  precipitation be reduced to  less than
     20 kg/ha.yr in order  to protect all but the most sensitive
     aquatic ecosystems in Canada.  In those areas where there is a
     high potential to reduce acidity  and  surface alkalinity is
     generally greater than 200 \ieq/L, the Canadian  members recognize
     that a higher loading rate is acceptable.

     As loading reductions take place  and  additional  information is
     gathered on precipitation, surface  water  chemistry and watershed
     response, it may  be possible  to refine regional  loading
     requirements.
1.2   AQUATIC ECOSYSTEM EFFECTS - UNITED  STATES

Acidic deposition has been reported  in  the literature  as  a  cause of
both long-term and short-term episodic  depressions  in  pH  and  loss in
alkalinity in some lakes and streams  in the U.S.  and Canada.

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Elevated concentrations of toxic elements, such  as  aluminum,  and
biological effects including losses  in fish populations  have  been
reported to accompany some of  these  pH depressions.   In  most  of the           •
reported cases, clear relationships  were not established between               |
acidic deposition and observed effects.  Conclusions  are based  on an
understanding of the acidification process although mechanisms  which          ^
control this process are often not completely  understood.                      •

The following summary statements are observations reported  to be
occurring in areas receiving acidic  deposition.                                I

     Both sulphuric and nitric acid  contribute to the acidity of
     precipitation.  It appears, however,  that sulphuric acid                IB
     contributes more to long-term acidification of surface waters            I
     than does nitric acid.  Nitric  acid can contribute  to  pH
     depression of surface waters during periods of snowmelt  and               _
     heavy rain runoff in some areas.  Studies of lakes  in  eastern            •
     North America indicate that atmospheric deposition  accounts  for          ™
     sulphate levels in some waters  in excess  of those expected from
     natural processes.  Lake study  areas  are  located in Labrador,            I
     Newfoundland, Nova Scotia, New  Brunswick, the  southern part  of           |
     the Canadian Shield in Quebec,  and in eight regions of Ontario.
     Primary study areas in the U.S. are found in New Hampshire and           •
     southern Maine, Adirondack Park in New York, the Boundary  Waters         •
     Canoe Area of Minnesota,  and numerous lakes in north-central
     Wisconsin.

     There is evidence of long-term  reductions of pH  and alkalinity           •
     and other water quality changes for some  low alkalinity  surface
     waters.  The rate of change of  pH and alkalinity in lakes  is one         H
     of the least well defined aspects of  the  acidification process.          |
     However, there is evidence of short-term  pH depressions  in some
     waters following high runoff from snowmelt  and storm activity.          M
     Both sulphate and nitrate are associated  with  short-term changes         I
     in water chemistry but, in the  majority of  surveyed cases,
     sulphate appears to be the larger contributor  to total acidity.

     Short-term pH depressions and elevated concentrations  of metals,        •
     particularly aluminum, iron, zinc, and manganese have  been
     observed during periods of high runoff.   Metal mobilization  from        •
     some watersheds, first noted in streams and lakes of                     |
     Scandinavia, also has been reported from  such  places as  Hubbard
     Brook, the Adirondacks, and the Great Smokey Mountains of  the           •
     U.S., and Sudbury, Muskoka, and Plastic Lake in  Ontario, Canada.        •
     Artificial acidification  of a lake in the Experimental Lakes
     Area of Ontario has shown mobilization of metals from  lake
     sediments to the water column.                                           I

     Sediments from lakes in Maine,  Vermont, and New  Hampshire
     suggest increased acidity  in aquatic  ecosystems. It has been            •
     inferred from declines in metals  (zinc, copper,  iron,  calcium,           |
     magnesium and manganese)  in the sediments that the  acidity of
     the water increased since the late 1800s.   Low pH maintains               _
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                                                                  1-9
     metals  in the water  column,  where  they  can be  flushed out of the
     system  before being  deposited  in the  sediments.   Diatom data are
     less complete, but they  also indicate a pH decline since the
     early 1900s.

There are few historical  records  of chemistry of low  alkalinity
waters not influenced by  local  urban or industrial  discharges (i.e.,
6 rivers in  Nova Scotia;  7 lakes  in Nova Scotia and 3 in New
Brunswick; 40 lakes in Adirondack Park,  New  York; 250 lakes in New
England; 2 streams in the New Jersey Pine  Barrens;  270 lakes in
Wisconsin).  The above locations  are exposed to various levels of
acidic deposition.  Some  surface  waters in these areas have shown a
decrease in  alkalinity and/or pH.   In Wisconsin,  however,  most lakes
surveyed had increased in alkalinity and pH.

The total number of lakes and rivers in eastern North America that
are thought  to have been  acidified  by acidic deposition is a very
small percentage of the total aquatic resource.   In the absence of
effects from mine drainage and  industrial  waste water, the symptoms
of acidification (e.g., long-term pH declines and/or  short-term pH
depressions  of surface waters with  loss of fish populations) have
been observed only in clearwater  lakes  and streams  with accompanying
elevated concentrations of sulphate and/or nitrate.  Natural
acidification processes do occur  but their effects  appear greatest in
coloured surface waters.  Land  use  changes,  such as fires, logging,
and housing  developments, have  taken place in many  areas with low
alkalinity surface waters.  However, the symptoms of  acidification
have not been observed in clearwater lakes and streams except in
areas receiving high levels of  acidic deposition.

Lakes in the Adirondack Mountain  range  exhibit some of the lowest
alkalinity values found in the  eastern  United States  and are located
in a zone presently receiving high  acidic  deposition  (30-40 kg/ha.yr
of sulphate  in precipitation).  In  this area, 52% of  the 214 high
elevation lakes sampled in 1975 had pH  values less  than 5.0.   Seven
percent had  pH values between 5.0 and 6.0.   The New York Department
of Environmental Conservation has concluded  that  at least  180 former
brook trout  ponds are acidic  and  no longer support  brook trout.  The
factors causing these population  extinctions  have not been
demonstrated.

New England  currently receives  wet  sulphate  deposition loadings of
17-40 kg/ha.yr.  A study  of 95  relatively  small  low alkalinity lakes
in New England for which  historical  data were available showed that
64% had decreased in pH.  However,  accompanying historical  deposition
data are not available.   A comparison of present  alkalinity values
with historical values for 56 lakes indicated that  70% had decreased
in alkalinity.  Two other studies have  indicated  pH declines in some
lakes surveyed in Maine.  The relative  contributions  of natural and
anthropogenic sources to  acidification  of  these lakes is not known.

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Data from intensive studies of 17 lakes  in  the Muskoka-Haliburton
area of Ontario currently receiving about 20-30 kg/ha.yr  sulphate in
precipitation have shown that some lakes with summer  alkalinity                •
values up to about 40 yeg/L experience pH depressions to  values  below         •
5.5 during snowmelt.  One inlet stream was  observed to  have  pH values
as low as 4.1 during spring snowmelt.  Other inlet streams had pH             _
depressions but pH did not drop as low.  Of 2,624 lakes surveyed in           •
Ontario, 50% had alkalinity of less than 200 yeg/L, a value  that may
be regarded as the upper limit for potential effects  of acidic
deposition; 13% of the lakes sampled  in  the province  had  alkalinities         I
below 40 yeg/L.  While these lakes may be representative  of  the  areas         m
sampled, they may not be representative  of  lakes located  elsewhere in
the Shield.  In another survey of 199 lakes of the Precambrian Shield         4H
of Quebec 7.5% had alkalinity of approximately 50 yeg/L or less.              M
There are about 1.5 million lakes on  the Precambrian  Shield  in the
provinces of Ontario and Quebec; but  it  is  not possible at present            _
to extrapolate results of the surveys to the total population of              •
lakes.                                                                         ™

Observed changes in aquatic life have both  been correlated with                I
measured changes in the pH of water and  inferred by comparisons  of            |
waters of different pH values.  Differences have been documented in
species composition and dominance and size  of plankton  communities in         mt
lakes of varying pH.  Study results show that the number  of  species           •
is lower in low pH lakes compared to  lakes  of higher  pH.  These
differences may have important implications for organisms higher in
the food chain, but studies to date have not been done  that  might             •
establish this connection.                                                     •

Many species of frogs, toads and salamanders breed in temporary  pools         Ij
formed by the mixture of spring rains and snowmelt and  subject to pH          |
depression.  Embryonic deformities and mortalities in the yellow
spotted salamander, which breeds in temporary meltwater pools, have           «
been observed in New York State where the acidity of  the  meltwater            I
pools was 1.5 pH units lower than that of nearby permanent ponds.
Population densities of the bullfrog  and woodfrog were lower in
acidic streams and ponds than in those of higher pH sampled  in                •
Ontario.  These data are very limited and therefore the extent of the         ™
problem is unknown.

Atlantic salmon populations have disappeared from nine rivers in Nova         |
Scotia but remain in rivers in the same  area having higher pH due to
greater alkalinity.  Decreases in alkalinity and  the  pH of water over         «
time have been observed in some low pH rivers in Nova Scotia.                 •
However, historical chemical data do  not exist for the period of
major decline in angling success nor  do  they exist for rivers in
which fish declined.                                                           •

Detailed studies of watersheds and clusters of lakes  have been
carried out in regions of North America  and Scandinavia containing
low alkalinity lakes and streams  under a range of sulphate  deposition
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                                                                  1-11
rates.  The results  of  those  studies  conducted in North America are
summarized below.

There have been no reported chemical  or biological effects for
regions currently receiving loadings  of sulphate in precipitation at
rates less than about 20 kg/ha.yr.

Evidence of chemical change exists for  some  waters in regions
currently estimated  or  measured  to be receiving between about 20-30
kg/ha.yr sulphate in precipitation.   In Nova Scotia rivers, 40 years
of historical records document reductions  in angling success for
Atlantic salmon in nine rivers of low pH.  Records over later periods
for other nearby rivers document decreases in alkalinity and pH.  In
Maine there is evidence of pH declines  over  time and loss of
alkalinity from some surface  waters.  In Muskoka-Haliburton
historical evidence  documents loss of alkalinity for one lake and pH
depressions in a number of lakes and  streams.   Fish confined to the
inlet of one lake died during spring  melt.   In the Algoma region
there are elevated sulphate and  aluminum levels in some headwater
lakes.

Long-term chemical and/or biological  effects and short-term chemical
effects have been observed in some low  alkalinity surface waters
experiencing loadings greater than about 30  kg/ha.yr.  In Quebec,
sulphate concentrations in surface waters  decrease towards the east
and north in parallel with the deposition  pattern of sulphate.
Sulphate concentrations are equal to  or greater than the bicarbonate
concentration in some lakes in the southwest part of the province.
In the Adirondack Mountains of New York comparison of data from the
1930s with recent surveys has shown that more lakes are now in low pH
categories.  The relative contribution  of  natural and anthropogenic
sources to acidification of these lakes is not known.  The New York
Department of Environmental Conservation has concluded that at least
180 former brook trout ponds  are acidic and  no longer support brook
trout, although a direct association  with  acidic deposition has not
been established.  In the Hubbard Brook study area in New Hampshire
there are pH depressions in some streams during snowmelt of 1 to 2
units.

In the watershed studies summarized above, sulphate in precipitation
was used as a surrogate for total acid  loading.   Sulphate in
precipitation can be reliably measured.  It  is recognized that dry
deposition of sulphate and sulphur dioxide,  and the wet and dry
deposition of nitrogen oxides, nitric acid,  particulate nitrate and
ammonia, as well as  other compounds,  also  contribute to acidic
deposition.  The use of a single substance as  a surrogate for acidic
loadings adds unknown error owing to  site-to-site variability in:  (1)
composition of deposition, and (2) ability of  watersheds to
neutralize incoming  acidity.  Wet and dry  deposition of sulphur
compounds appeared to predominate in  long-term acidification.

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Insufficient data are available  to  related  nitrate deposition to
short-term water quality effects.   Therefore,  we  are unable to
develop nitrate loading/response relationships.                                 •

The terrestrial mapping analysis for  eastern Canada has  demonstrated
that the watersheds in which  some surface waters  have been observed            «
to experience effects are representative, in terms of soil  and                 •
geological characteristics, of larger areas of eastern Canada.  The
level of variability within terrain classes is not known.

An alkalinity map of the U.S. shows the  location  of regions where the          m
mean alkalinity of most of the sampled surface waters is less than
200 yeg/L.  There is reason to believe that some  of these low                  •
alkalinity surface waters could  experience  effects similar to those            <|0
noted in detailed study sites receiving  similar total acidic
deposition loadings.  However, quantification  of  the number of lakes           M
and rivers in both countries  susceptible to acidification at specific          •
loading rates would require validation of mapping methodologies and
increased information on loading rates and  the chemistry of lakes and
streams.  The present empirical  evidence covers a broad  spectrum of            •
physical and climatological conditions across  northeastern North               V
America and therefore provides a basis on which to make  only
qualitative judgements regarding relationships between acidic loading          m
rates and effects.                                                              •

Based on the results of the empirical studies, interpretation of               _
long-term water quality data  and studies of sediment cores that have           •
been reviewed, we conclude that  acidic deposition has caused long-             ™
and short-term acidification  of  some  low alkalinity surface waters in
Canada and the U.S.  Based on our understanding of the acidification           H
process the Work Group concludes that reductions  from present levels           |
of total sulphur deposition would reduce further  chemical and
biological alterations to low alkalinity surface  waters  currently              «
experiencing effects and would lead to eventual recovery of those              m
waters that have been altered by deposition.

The U.S. members conclude that reductions in pH,  loss of alkalinity,           •
and associated biological changes have occurred in areas receiving             *
acidic deposition, but cause  and effects relationships have often not
been clearly established.  The relative  contributions of acidic                M
inputs from the atmosphere, land use  changes,  and natural terrestrial          |
processes are not known.  The key terrestrial  processes  which provide
acidity to the aquatic systems and/or ameliorate  atmospheric acidic            M
inputs are neither known or quantified.  The key  chemical and                  •
biological processes which interact in aquatic ecosystems to
determine the chemical environment  are not  known  or quantified.
Based on this status of the scientific knowledge, the U.S. (fork Group          •
concludes that it is not now  possible to derive quantitative                   B
loading/effects relationships.
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1.3   TERRESTRIAL ECOSYSTEM  IMPACTS
The effects of transboundary  air  pollution  on  terrestrial ecosystems
have been reviewed on  the  basis  of  direct  effects on vegetation,
effects on soils, and  effects on  wildlife.
1.3.1   Effects on Vegetation

Three main pollutants  are  of concern  with regard to vegetation
effects.  These pollutants are  sulphur  dioxide,  ozone,  and acidic
deposition.  Ozone and acidic deposition  occur  at concentrations
above background  levels  at long  distances from  emission sources.
Sulphur dioxide is more  of a concern  to vegetation in proximity to
point sources of  emissions than  at  long distances, where dispersion
effects can reduce atmospheric  levels to  those  of background.
1.3.1.1   Sulphur Dioxide

Near point sources,  the  adverse  effects  of  sulphur dioxide on
vegetation can be both visible and  subtle  (without development of
visible foliar injury).  Visible  effects can  be  associated with both
doses of high concentrations  of  sulphur  dioxide  over short periods of
time and low concentrations over  extended  periods.  However,  in a few
specific cases, atmospheric sulphur dioxide deposition may have
beneficial effects on agricultural  vegetation grown on borderline or
sulphur deficient soils.

Visible effects of sulphur dioxide  have  occurred on pine forests in
Canada subjected to  average growing season  concentrations of  sulphur
dioxide of 0.017 ppm.  Visible injury  to the  perennial foliage of
coniferous trees results in premature  needle  drop, reduced radial and
volume growth and early  death of  trees.  Reduced growth and yield of
crops without the development of  visible injury  have also been found
in certain field experiments.

Annual doses of sulphur  dioxide  of  0.02  ppm have been associated with
habitat modifications in grasslands and  the elimination of certain
sensitive species of lichens  near point  sources.  Lichens may be
markedly affected by sulphur  dioxide and are  considered as bioaccumu-
lators of very low level sulphur  dioxide exposures.  Direct effects
including visible injury, effects on reproductive capacity and
species mortality have been encountered  in  the field at concentra-
tions of sulphur dioxide as low  as  0.006 -  0.03  ppm annual average.

Despite such documented  evidence  of instances of direct effects,
obviously not all, but probably most exposures to sulphur dioxide on
a regional scale are below levels producing phytotoxic reactions.
However, long-term,  low-dose  studies have  demonstrated direct effects
on lichen communities and indirect  effects  on several plant species.

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                                                                  1-14
1.3.1.2   Ozone
1.3.2   Effects on Terrestrial  Wildlife
Soils vary widely with  respect  to  their properties, support different
vegetation communities,  are  subjected to different cultural
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Ozone is the most important  long-range  transported pollutant with
respect to vegetation effects.  Air  masses  carry ozone and its
precursors over long distances and can  affect  crops and forests in
rural areas remote from  sources.  As a  specific  example, ozone                  •
related crop injuries in southern Ontario have been reported                    •
associated with high ozone levels in air masses  moving across Lake
Erie.  In the U.S., experimentally derived  crop  yield  losses ranging
from 2 to 56% (crop dependent) were  equated with seasonal 7 hr/day              •
mean ozone concentrations of  0.06 -  0.07 ppm.  Yield losses in the              9
various crops were as follows:  kidney  bean 2%,  soybean 10%, peanut
14-17%, and lettuce 53-56%.   Although direct effects of ozone have              •
been documented on forest growth, an estimate  of loss  is difficult to           •
calculate because of the limitations stated in the main report.


1.3.1.3   Acidic Deposition

Acidic deposition in the form of simulated  rain  has been demonstrated           •
to induce a variety of direct and indirect  effects on plants grown              •!
under greenhouse or semicontrolled conditions.  Foliar injury, growth
reductions, and growth stimulations  have been  found under these                 m
growing conditions following  treatment  with simulated  acidic precipi-           I
tation.  However, visible foliar injury has not  been documented in
the field for vegetation exposed to  ambient levels of  acidic                    —
precipitation.  The potential effects of acidic  deposition on forest            •
growth have been difficult to assess because of  the complicating                -
influence of other environmental and climatic  factors.  To date,
there have been too few  studies to establish a clear relationship on            •
the interactions of acidic deposition/sulphur  dioxide/ozone to reach            H
a definitive conclusion  on effects.
                                                                                I
Direct effects of acidic  deposition  on  terrestrial wildlife have not           •
been reported and are not  considered likely.   Nevertheless, in some            •
instances, indirect effects have  been suggested  through three
possible mechanisms:                                                            (•

     1)  contamination  by heavy metals  mobilized by acidity;
     2)  reduction in nutritional value of  browse or food source;              •
         and                                                                    I
     3)  loss of browse species or impairment of habitats.

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1.3.3   Effects on Soil                                                        •
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practices, are situated  in  different  climatic  zones,  and are exposed
to a broad spectrum of acid loadings.   The following  effects of
acidic deposition probably  occur  and  in some  cases  are supported by
observation, although  the number  of  field situations  where investi-
gators have been able  to attribute acidity to  precipitation or to
compare present with former soil  pH value is  small.

On soils derived from  calcareous  parent materials,  the effects of
acidic deposition will lead to  only  insignificant increases in lime
requirement, except in situations near  strong  point emitters.  Heavy
metal deposition from  these same  point  source  emitters may also cause
soil toxicities.

On acid soils, the absence  of clear  effects upon tree growth from
radial-increment measurements covering  several decades suggests there
will be no short-term  effects attributable to  acidic  deposition.

From the few field situations where  earlier investigations permit a
comparison over a reasonable time-frame, there is evidence that less
acutely acid soils increase in  acidity  and lose bases at a faster
than normal weathering rate. For acutely acid soils, pH may show
only minor changes, while over  the same period moderate to
appreciably larger amounts  of soil aluminum are mobilized.  These
depend upon whether the  forest  cover  is deciduous (e.g., beech) or
coniferous (e.g., spruce).

From one comprehensive field investigation, it has  been suggested
that the additional amounts of  aluminum brought into  solution kill
feeding roots and permit the invasion of fungi causing tree
"dieback", but it is not known  whether  this phenomenon would occur on
other sites and soils.   What appears well established from a variety
of hydrological, limnological and catchment studies is that acidic
deposition can lead to the  release of additional amounts of soluble
aluminum, thus disturbing previous aluminum/calcium ratios in soils,
sediments and streamwaters. An eventual reduction  in base status and
fertility is suggested.

The sulphate component of acidic  deposition appears to be adsorbed by
soils containing active  aluminum  and  iron oxides, but where these are
absent or present in limited amounts, sulphate functions as a
balancing anion, leading to the leaching loss  of bases and other
cations.

The fate of the nitrate  component depends upon wet  precipitation/
snowmelt characteristics.   Nitrate,  reaching  the surface organic
horizons of acid forest  soils is  held there for assimilation by tree
roots during the growing season.  There are, however, forested catch-
ments in the northeast where nitrate  is passed to water bodies.

The lack of appropriate  experimental approaches from  which the
effects of acidic deposition on soil might be  assessed and safe
deposition ceilings estimated,  has caused scientists  to exploit

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                                                                  1-16
1.3.4   Sensitivity Assessment
1.4   HUMAN HEALTH AND VISIBILITY
1.4.1   Health
                                                                                1
                                                                                I
indirect or special situations.  These  include working  near  strong
point sources, studying soils treated with  acidifying  fertilizers,
and designing lysimetric experiments incorporating  simulated acid              ft
rains.  From such approaches, a variety of  soil  effects have been              I
demonstrated, usually of an undesirable  nature,  but  at  the present
time the problem remains of quantifying the dose-response  reactions            ._
in the field situations.                                                        •
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Regions which may be sensitive  to  acidic  deposition have  one or more
components (i.e., forests, aquatic  life,  soil,  or  water)  susceptible           JB
to degradation under the  influence  of  acidic  deposition.   Relative             m
sensitivity of these components  is  reflected  in the rate  at  which an
ecosystem component degrades under  a particular acidic deposition
loading.  Different underlying  criteria have  to be used to represent           •
sensitivity for the different ecosystem components, such  as  rate of            ™
tree growth, characterization of the soil-base  status,  or water
alkalinity.  Because so little  is  known about the  acidic  deposition
dose-response relationships, the underlying criteria are  often
imprecise.  Therefore, relative  sensitivity can only be approximately
represented or mapped, and then  perhaps for only a few species,                •
ecosystems or theoretical effects.                                              •

Attention is focused on the sensitivity of soils and bedrock because
results from studies which address  vegetation and  ecosystem  effects            •
are limited and not well  understood at this time.   In the approach             ™
used, the emphasis has been to map  a combination of potentially
important soil attributes as a  best available indicator of relative
sensitivity.  Soil attributes incorporated include texture,  depth to
carbonate, pH and cation  exchange  capacity, as  well as glacial and
bedrock features.  Incompleteness  of survey data for certain                   _
important properties (e.g., sulphate adsorption capacity, internal             •
proton production, and the role  of  dry deposition) precludes their
use in identifying detailed sensitivities of  land  or aquatic
resources.  As far as possible,  the eastern parts  of the  United                •
States and Canada are mapped using  a similar  conceptual framework              •
which indicates the general extent  of  areas of  different  possible
sensitivities to the effects of  acidic deposition.  The significance           •
of these categories will  increase  as more effects  are documented.              <•



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Available information gives little  cause  for  concern over direct
health effects from acidic deposition. The potential indirect health          mt
effects associated with transboundary  air pollution discussed are:             •
(1) contamination of the  food chain with  metallic  substances,


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especially mercury; (2)  leaching  of watersheds  and corrosion of
storage and distribution systems,  leading  to  elevated levels of toxic
metals; and (3) health implications of  recreational activities in
impacted waters.

The principal conclusions  of  the  report  are as  follows:

     Acidification of lakes is a  concern because  it may  be related to
     increased mercury contamination  of  the food  chain,  thus
     increasing the health risks  associated with  high levels of
     consumption of contaminated  organisms.   A  correlation exists
     between low pH in lakes  and  higher  mercury concentrations in
     some species of fish, although the  mechanism for this accumu-
     lation is not presently  known.   In  addition  to the  effects
     produced by acidic  deposition, the  increased input  of anthropo-
     genic sources (air  or water  effluents) of  mercury and other
     heavy metals may further complicate the  issue and lead to health
     problems when affected fish  are  consumed by  humans  in large
     amounts.

     Acidic deposition may liberate metals  in some groundwaters,
     surface drinking water supply systems  and  cisterns.   However,
     groundwater may also  be  acidic due  to  increased partial pressure
     of C02 at depths of  a few metres or more.  This should not be
     confused with acidity due to  atmospheric deposition.   Elevated
     metal concentrations  in  acidified  drinking water supplies have
     been found.  Lead levels in  tap  water  from cisterns  were much
     higher than those found  in the source  water;  about  16% of the
     households sampled  in one western  Pennsylvanian county had tap
     water levels in excess of the United  States  drinking water
     standards.  Surface  drinking  water  supplies  which are not
     treated (i.e., small  communities or individual water supplies)
     are susceptible.  No  adverse  health effects  resulting from
     consumption of such water have been reported.  Concern has been
     expressed that recreational  activities in  acidified  waters, such
     as swimming, may prove to cause  eye irritation.  To  date, no
     compelling evidence  has  been  forthcoming that indicates that
     humans are being adversely affected by these waters  in their
     current state.

     With respect to the  direct inhalation  of transported air
     pollutants for which  standards exist  (i.e.,  particulate matter,
     photochemical oxidants,  sulphur  oxides,  and  nitrogen oxides), no
     adverse human health  effects  are anticipated, providing the
     ambient air quality standards are  not  exceeded (see  Table 5-2).
     However, in regions where transboundary  air  pollution
     contributes to the  violation  of  the standard, health related
     problems cannot be  ruled out.

     Although some concern has been expressed over the effects of
     acid sulphates on mortality/morbidity, the available  data appear
     insufficient to single out this  species  as the sole  pollutant of

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                                                                  1-18
     concern in the sulphur-particulate  complex.   As  with the gaseous
     pollutants, the long-range  transport  of  particulate matter
     should only be viewed as a  concern  when  violation of the ambient
     air quality standards occur.
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1.4.2   Visibility                                                              I

Effects of transboundary air pollution  on visibility are related to
fine particle air quality and  only  indirectly to acidic deposition.            •
The major precursors of acid deposition that  can significantly affect          •
visibility are sulphuric acid  and various ammonium sulphate aerosols.
These form a large fraction of  the  fine particle loadings that                 •
dominate visibility impairment  from anthropogenic sources.   Available          V
data do not suggest that nitrates (predominantly in the vapour phase)
play a significant role in impairment of  visibility, but visible               _
brown plumes from NC>2 have been reported  at  a distance of 100 km               •
from a few isolated point sources.                                              ^

From available information on  background  and  incremental fine                  fl
particle loadings and relative  humidity,  estimates of visibility               •
impacts (reduction in visual range  and  contrast, discolouration from
haze or plumes) can be made.   Analysis  of airport data indicate a              •
substantial decline in regional summertime visibility in the eastern           •
U.S. and portions of southern  and eastern Canada between 1950 and
1975, with stable or small improving trends  since that time.  These            —
changes may be associated with  changes  in the level and distribution           •
patterns of sulphur oxide emissions.                                           ™

Areas such as those found in western North America, are the most               •
sensitive to visibility degradation. Usually,  good visibility is              f|
valued most highly in natural  settings  such  as  parks and wilderness
areas.  Any area, however, with normal  viewing  distances of a mile or          M
more may be affected by episodic regional haze  carrying acid                   •
precursor substances.  Studies  of the value  of  visibility and public
perception indicate that the public cares about visibility and is
willing to pay for maintaining or improving  it.  Accurate economic             •
assessments are not, however,  available for  eastern North America.             •


1.5  MAN-MADE STRUCTURES                                                        '|

Certain airborne chemicals can accelerate deterioration of materials.          «
There is evidence that materials in urban areas of Europe and North            I
America have suffered and are  suffering from exposure to these                 '
pollutants.  Materials at risk include  statuary and structures of
cultural value as well as commonly  used construction materials.  In            •
the present discussion, exterior surfaces are the focus of interest.           m

It is reasonable to assume that acidic  deposition due to long-range            •
transport and transformation of air pollutants  contributes somewhat            •
to material effects.  Current  understanding  of  material decay
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                                                                  1-19
processes leads to the tentative conclusion  that  local  sources of
corrosive pollution mask the  effects  resulting  from long-range
transport of acidic deposition.

The principal findings of  the Work Group  are:

     The majority of sensitive materials  tend to  be located in
     urban/suburban areas.  However,  materials  at risk  cannot be
     assumed to be proportional to population density.

     Relationships between concentration  of  corrosive gases and
     damage are better documented than  relationships between acidic
     precipitation or particulates and  deterioration.

     The main groups of materials which are  damaged by  outdoor air
     pollutants are:  metals, coatings  and masonry.  The pollutants
     are delivered to the  surfaces in wet and dry form.

     It is generally accepted that 862  is the primary species
     causing damage to materials.  The  importance of nitrogen
     compounds is closely  related to  its  particular species and may
     increase with the predicted increases in NOX emissions
     relative to S02 emissions.

     Chemical degradation  processes include  deterioration of
     calcareous building materials by the removal of calcium
     carbonate through conversion to  calcium sulphate and the removal
     of protective corrosion  products on  metals,  particularly zinc
     and copper.

     Mechanical deterioration of masonry  occurs when calcium sulphate
     enters the porous material and causes internal rupturing due to
     the pressure of crystallization  or hydration.

     Regional field studies,  chamber  tests and  atmospheric corrosion
     sites have indicated  the nature  and  extent of  accelerated
     corrosion associated with metal-pollutant  interactions.
     Dose-response relations  have been  determined for SC>2 and
     low-carbon steel and  zinc.  In some  areas  of eastern North
     America, urban centres have experienced extensive  and
     significant deterioration of zinc  coverings.

     Common materials of construction at  risk include,  limestone,
     carbon steel and galvanized steel  sheet.   Carbon steels must be
     coated in order to provide useful  service  life and, thus the
     coating becomes the material at  risk.

     Dose-response relations have been  determined for sulphur dioxide
     and ozone for some paints and coatings.  In  some urban centres,
     ozone can have a significant impact  on  the durability of
     elastomers.

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                                                                  1-20
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     For porous materials such as masonry,  the  long-term accumulation
     of pollutants is a major concern  especially for  deterioration
     associated with sulphate.                                                 •

     Materials at risk and some active  corrosion agents  have  been
     identified in numerous field and  laboratory tests.   Confidence
     in dose-response relationships  is  weakened in some  cases because         •
     of incomplete monitoring of air quality  and meteorological               ™
     parameters in field tests.
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1.6   METHODOLOGIES FOR ESTIMATING  ECONOMIC  BENEFITS OF CONTROL

Traditionally, the decision-making  process has  required an                    fl
appreciation of the costs and benefits  associated  with following a
prescribed set of actions.  Basic to  this process  has  been the
transformation of the implications  of these  actions, (i.e.,                   •
converting changes in crop yield and  fish catches,  into comparable            w
units of measurement).  Monetary units  are widely  accepted as
providing comparable weighting units  for individual variables.  In            4
order to provide the Canada/United  States Coordinating Committee with         f
guidance in this important area, the Work Group has undertaken a
review of the methodologies available for assessing the economic              «
benefits of controlling long-range  transport  of air pollution.                •

The following are the conclusions of  the Work Group:

     A number of methodologies have been reviewed  but  presently the           •
     basic conclusion of  this effort  is that  application of available
     approaches for conducting a benefit/cost analysis must either            •
     omit real but intangible benefits  or include  a wide uncertainty          B
     range.  Despite these real limitations,  these methodologies can
     provide a useful estimate of benefits for  some sectors.                  —

     There are several techniques which can  be  applied to determine           *
     the primary economic benefits  associated with a particular
     receptor category recognizing  that option  and legacy values are          II
     not captured.  However, the lack of data on dose-response                •
     relationships limits the application of  most  of these techniques
     at this time.  For some sectors, differences  in producers'               •
     income may provide benefit estimates even  in  the  absence of              •
     explicit dose-response data.

     The value of the secondary benefits can be estimated for                 •
     specific economic sectors and  regions,  to  derive  a partial               *
     estimate of the impacts in various geographical areas.

     It is evident that more economic research  is  required.  Economic         '|
     techniques have yet  to be rigorously  tested in some sectors,
     such as historical value, and  are  limited  in  their treatment of          •
     option and legacy values, and  in dealing with the issues of              •
     property rights.
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     The initial design of  future research efforts  to  document  the
     effects of acidic deposition should  reflect  the data  require-
     ments for an economic  benefit estimate.   Interdisciplinary
     cooperation at  the design  stage  is the  best  way to  ensure
     results which are amenable to economic  analysis.
1.7   NATURAL AND MATERIAL RESOURCE  INVENTORY
1.7.1   Introduction

A natural and material resource  inventory  is  a  necessary  component  of
an assessment of the benefits of emission  reductions.   Consequently,
the Work Group attempted  to compile  an  inventory  for  aquatic,
terrestrial and man-made  resources.

In all cases, the sectoral  inventories  are incomplete  and  sometimes
lacking in sufficient detail.  For example, not only does  the  aquatic
inventory not include an  accurate  accounting  of lakes  and  streams
with their associated alkalinity, but it also does not  include a
consideration of the population  size  and diversity of  aquatic
organisms depending on the maintenance  of  a stable aquatic  environ-
ment.  Similarly the terrestrial inventory has  been  limited to only a
consideration of hardwoods and softwoods because  a comprehensive
inventory at the species  level is  presently lacking.

The inventory has been established on the  basis of sulphate depo-
sition regimes coincident with the location of  terrestrial  features
such as soils and bedrock which have  a  limited  capacity to  reduce  the
impact of acidic deposition on aquatic  regimes.   In  no  cases were
there sufficient data to  indicate which particular resources are
being damaged by acidic deposition.   Thus,  this inventory  is a
categorization of resources potentially at risk,  rather than a list
of resources now adversely  affected  by  acidic deposition.   The
completion of this inventory has served to underline the considerable
weakness which exists in  our ability  to adequately quantify the
extent of the resource at risk.
1.7.2   Aquatic - United States

Approximately 36,000 km^ of  the eastern U.S.  surface  water  area
(25%) is located in areas of low and moderate potential  to  reduce
acidity (high and moderate sensitivity) and of  deposition greater
than 20 kg/ha.yr sulphate in precipitation.   Only  24% are located  in
areas with a high potential  to reduce  acidity (low sensitivity)  and
of deposition greater than 20 kg/ha.yr sulphate  in precipitation.
The actual surface water area would be more restricted  if data  had
been available on surface water chemistry  (i.e., alkalinity).
Additional refinements on the inventory should  include  data on  this

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                                                                  1-22
variable as well as more accurate measurements  of  surface  water
area.
1.7.3   Aquatic - Canada
1.7.4   Agriculture - United  States
1.7.5   Agriculture - Canada
 1.7.7   Forests -  Canada
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Approximately 52,000 km2 of  surface  water  area  is  estimated  to be             •
at risk in areas with deposition  exceeding 20 kg/ha.yr.   Of  this              9
total, about 54% (28,000 km2) is  located in areas  with a low
potential to reduce acidity  (high sensitivity).  The  inventory could          •
be improved by better data availability on actual  surface areas of             |
waters and kilometres of rivers and  streams.  Moreover,  actual data
on aquatic alkalinity and aquatic biota will be  required to  define             ^
more accurately the extent of the resource at risk.                            •
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Major crops in the eastern U.S.  (corn,  soybeans,  hay,  wheat,  tobacco
and potatoes) are grown under varying  sulphate  deposition regimes.            ••
Soybeans and tobacco are the only  ones, however,  with  approximately          •
20% of their yield grown under  sulphate deposition greater than 40
kg/ha.yr.  For the other crops,  less than  10% of  their total  yield  is        _
grown under sulphate deposition greater than 40 kg/ha.yr.                    •
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Many of Canada's most valuable  crops  are  grown  in areas of  high
deposition.  These  include  both grains  and  vegetables.   Importantly,           •
for 6 of the 12 crop types  included in  the  inventory, more  than 50%           •
of their individual total yields is grown in  areas where sulphate
deposition exceeds  40 kg/ha.yr.   Only 4%  or less  of each crop is              —
grown in areas experiencing annual  deposition levels of 10-20                 •
kg/ha.yr sulphate in precipitation.                                            ™


1.7.6   Forests - United States                                               I

The annual forest growth in those states  east of  the 100° meridian in         m
1977 was 476 million m3.  Approximately 10% of  this combined                  •
hardwood and softwood growth  occurs under sulphate deposition regimes
greater than 40 kg/ha.yr.   Over 75% of  the  growth occurs under
sulphate deposition regimes between 20-40 kg/ha.yr.                           •
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Canadian  forest  growth  occurs  in a slightly different pattern than in
the U.S.   Of  the  total  annual  yield of  150 million m3,  about 10% of           •
the hardwood  growth  is  located in the highest  deposition area,  but            •
only  1% of the softwood growth and 8% of  the mixed growth.
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Approximately 64% of  the hardwood  and  70% of  the mixed growth occurs
in the area of moderate deposition,  but  only  28% of the softwood
growth.
1.7.8   Man-Made Materials  -  United  States


There is no adequate U.S. inventory  of  renewable or cultural
resources.  Past efforts  to create an inventory of  renewable
resources have combined per capita material  estimates and census data
on population distribution.  These per  capita estimates have been
shown to be very site  specific  and are  not an adequate basis for
creating a national inventory.   The  only inventory  prepared by the
Work Group is one on historic resources exposed to  various levels of
ambient sulphur dioxide.
1.7.9   Man-Made Materials  -  Canada


As in the case in the U.S., Canada has  no  adequate  inventory of
renewable materials  or  cultural  resources.   The historic resources
inventory includes historical  landmarks, buildings  and monuments and
parks.  The inventory presented  here  indicates  the  numbers of each of
these which are located  in  2  categories of  deposition: greater than
40 kg/ha.yr and under 40 kg/ha.yr.  Geographically,  these resources
are located in the area  around Quebec City,  one of  the earliest towns
in Canada, and in southwestern Ontario  (Windsor-Sarnia).
1.8   LIMING


Mitigation of the effects  of  acidic  deposition by adding neutralizing
agents to the receptors has been  an  obvious  action to  be considered.
Limestone is most often used  although  other  chemicals  have been
tried.  The term "liming"  has  often  been  used  to  describe such
treatments and in this section will  be  used  to describe artificial
neutralization experiments regardless  of  the chemical  or chemicals
actually used.


Extensive work has been carried out  on  aquatic systems affected by
acidic deposition.  However,  the  application of lime products to
aquatic resources will not address the  potential  for damage to
forests or buildings and structures.
1.8.1   Aquatic Systems


Liming will not eliminate all problems  associated  with acidification
of surface waters but may be necessary  on  a  limited  basis as a
means of temporarily mitigating  the  loss of  important  aquatic
ecosystem components.  However,  it  cannot  be used  in all situations.

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1.8.2   Terrestrial Liming
1.8.3   Drinking Water Supply

Liming techniques have been  effectively  applied  to  the treatment of
low pH municipal supplies.   The  per  capita  costs  range from $0.18 to
$0.57.
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Further, its long-term viability and impact on  fish  populations  needs         |
additional study.

The following observations support  this  overall  conclusion:                    •

     Liming can only treat certain  aquatic situations,  mostly lakes,
     and must be repeated periodically.   It is  not  practical to                fl
     locate and treat small temporary meltwater  pools  because of              m
     their large number and widespread occurrences.   These pools,
     however, are an important habitat for amphibians  and  dependent           M
     wildlife.  The technology for  reliably treating high  discharge           I
     rivers (such as the salmon rivers of the eastern North American
     coast) is not available.                                                  _

     Swedish experimental liming programs report some  success in              *
     being able to promote the growth and reproduction  of  fish
     populations.  However, all results  to date  are  from experiments          •
     which have been run for five years  or less. The  long-term                V
     effectiveness of liming to protect  aquatic  ecosystems is not
     known.  As a result of liming  acidic waters, aluminum poisoning          «
     of salmon and rainbow trout has been encountered.                         •

     No experimental data on liming are  available for  surface waters
     containing some of the important sport fish species in North              •
     America, such as muskellunge,  walleye and  bass.                          "

     Anthropogenic acidic deposition will alter  the  original
     uniqueness of "wilderness" aquatic  environments.   The additions
     of neutralizing agents will further modify  the  character of
     these ecosystems and will not  preserve the  "wilderness" nature           •
     of these waters.                                                          •
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The liming of  forest  lands  to  neutralize  potential acidic deposition
effects on terrestrial  ecosystems  has  serious limitations.  These             •
include evidence that liming would not  prevent  direct foliar injury;          |
that under certain  conditions  lime additions  can disrupt important
soil biological relationships  and  adversely affect forests; and that          «
the area  coverage required  would tend  to  be so  large as to be                 •
economically prohibitive.
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                                        SECTION 2



                                      INTRODUCTION
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                                                                  2-1
                              SECTION 2
                            INTRODUCTION
World attention was drawn to the problem of transboundary air
pollutants and their deposition on surface waters  in  1972, when
Sweden and Norway reported the so-called "acid rain"  phenomenon.
From these Scandinavian studies, scientists in many other nations
became increasingly aware that, because atmospheric dilution does  not
eliminate waste, there may be effects on "receiving"  aquatic
ecosystems, caused by the transport and deposition of  pollutants.
Since 1972, the acidic deposition phenomenon has become  recognized in
North America, as detailed in many articles by both Canadian and
U.S. scientists.
2.1   THE EXTENT OF RESOURCES EXPOSED TO ACIDIC  DEPOSITION AND
      POTENTIAL FOR LARGE-SCALE EFFECTS


Acidic deposition is currently being observed  over  most  of eastern
North America.  The effects on watersheds  and  aquatic  resources  are
most strongly expressed in the areas where elevated inputs of acid
combine with low natural acid neutralizing capacity (ANC)  of  soils
and water to reduce the pH of surface water, leading to  effects  on
aquatic ecosystems.


Over most of this area, acidic deposition, sulphate particulates,  and
oxidants occur together.  In addition, there are local exposures
occurring to sulphur dioxide, nitrogen oxides  and fluorides,  with
biological uptake and subsequent cycling of these compounds.
Although acidic components of acidic deposition  remain the focus of
this report, due to their important impacts on aquatic/terrestrial
ecosystems and on human health and man-made structures,  the effects
attributable to oxidants are also considered.


Hydrogen ion concentration (acid, H+) is a critical factor
controlling the rate of most chemical reactions. Processes such as
solubilization, corrosion, and mobilization of minerals  and metals
are accelerated by increasing the acid concentrations  in soils and
water.  Soil weathering and nutrient balances  are altered  by  changes
in the acidity of soilwater.  Household water  supplies from shallow
wells, or acidic surface waters, in turn,  can  be modified  by  the
further mobilization of metals from lead and copper pipes. The
hydrogen ion load (mass per area per time) affects  the extent of
chemical reactions in soils and other materials  whereas  the
concentration affects the rates of reactions.  For  example, the  total
amounts of chemical constituents leached from  soils annually  is  more
closely related to the annual load on hydrogen ion  than  to the
concentration in any precipitation event.  The load is also used in
the following ways: (1) in comparison with loads of acid-forming ions
to determine the influence of acid neutralizing  materials  in

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atmospheric deposition;  (2)  to  simulate  the  acidity of streams                  B
receiving snowmelt runoff  from  an  accumulated snowpack;  and (3) to
determine the acidity of lakes  which  average the inflow from a number           _
of runoff events.                                                                fl

The effect of acidic deposition on watersheds is quite different from
one region to another due  to  differences in  climate,  soils and                  B
geology.  Generally speaking, ecosystems seen as sensitive to acidic            B
deposition are characterized  as having thin  soils,  low in exchange-
able bases and cation exchange  capacity, overlying  granitic bedrock             •
(noncalcareous).  Figure 2-1  provides a  small scale overview of areas           B
seen as sensitive based  on bedrock geology.   Efforts  are now underway
and preliminary results  are  presented in Sections 3.5 and 4.5 of                ^
larger scale mapping of  sensitive  areas.  In the United States, the             B
four most susceptible regions are  the Northeast, the  Appalachian                ™
Mountains, the Minnesota-Wisconsin-Michigan  highlands, and the
western mountain areas of  Colorado, Oregon,  Washington,  Idaho and               I
California.  In Canada,  sensitive  regions include parts of the                  B
Atlantic Provinces and portions of the Precambrian  Shield areas of
Ontario and Quebec.  Other areas may  be  considered  sensitive based on           -M
soil characteristics or  other variables.                                        B

What is known of the complexity and geographic range  of acidic
deposition ecosystem interaction and  long distance  transport of air             B
pollutants pose a significant dilemma for federal,  state and                    B
provincial regulatory agencies. Aquatic life is apparently being
damaged by regional air  emissions, but air quality  standards were not           •
designed to protect water  quality. Nevertheless, important resources           B
over a large part of the continent appear to be at  risk and new
multinational control approaches may  be  required.                               ^


2.1.1   Methods of Measuring  Effects

Lakes, rivers, and watersheds act  as  "collectors" of  atmospheric                B
pollution.  Therefore, one research approach has been to study lakes
and watersheds as large-scale "calibrated" collectors since the                 •
surface environment experiences a  total  loading that  is an                      |
integration of all deposition processes.  This approach has led to
establishing "calibrated watersheds"  as  monitoring  sites which are              «
combinations of streams, lakes, and plant communities under intensive           B
measurement.  In these watersheds, hydrologic weirs are set up in
streams entering and leaving  small study lakes or settling pools.
The flows of water and dissolved substances  are measured upon                   B
entering and leaving the lake,  and these data are combined with                 B
measures of atmospheric  inputs  and water loss by evaporation, to
calculate "substance budgets".   The difference between the inputs               •
measured by the budgets  and  inputs measured  from wet  deposition                 £
monitoring can provide a preliminary  estimate of dry and gaseous
deposition.                                                                      .

Detailed sampling of biota within  such a watershed, together with               ™
chemical data, allow an  assessment of the chemical  and biological

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                                                                   2-3
                                               Location of Ten Calibrated Watersheds:

                                                   1. Experimental Lakes
                                                   2. Boundary Waters Canoe Area

                                                   3. Northern Highlands, Wl

                                                   4. Saulte Ste. Marie
                                                   5. Dorset
                                                   6. Sagamore Lake
                                                   7. Hubbard Brook

                                                   8. Laurentide
                                                   9. Kejimkujik Park
                                                  10. Coweeta
Figure 2-1.
Regions of North America  containing  lakes  that may be
sensitive to acidification by  acidic deposition,  based
on bedrock geology, showing where  calibrated watershed
studies on sensitive areas are in  progress (modified
from Galloway and Cowling 1978).

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                                                                  2-4
2.1.2   Hydrologic Cycle
I
I
effects that air pollution can have on the  system.   Calibrated
watersheds have been established at a number of  locations,  such  as
Kenora, Sault Ste. Marie, and Dorset in Ontario;  Laurentide Park,              •
Quebec; Kejimkujik Park, Nova Scotia; Hubbard Brook,  New  Hampshire;            f
Coweeta, North Carolina; and Sagamore Lake, New  York (Figure 2-1).
I
Although the hydrologic cycle seems  to be well-known,  questions  do             fl
emerge as to the potential for high  evaporation/precipitation  ratios          V
to concentrate sulphate, and the availability  of  water for  many  of
the acid-forming reactions, as well  as for  the wet  deposition  and             M
soil flux processes.  For example, in  low-humidity  regions, or during         •
drought periods, long-distance gaseous transport  of SC>2 may provide
a greater fraction  of the deposition than in wet  regions.   Similarly,
conditions of low rainfall and high  evaporation,  or seasonal droughts         •
will alter the soil solution flux processes and associated  reactions.         w
In regions where annual precipitation  is  less  than  potential annual
evaporation, movement of dissolved ions is  upward (calcification).             M
This movement of bases would tend to neutralize acidic deposition             |
falling onto soil surfaces.  Indeed, in regions where  potential
evapotranspiration  approaches total  rainfall,  flushing of H+ or                _
50^2- becomes limited to short-season  processes or  those that                  •
occur only every few years.

Because of the evidence that in many poorly-buffered northern  soils,          I
the sulphate ion is a relatively conservative  substance (Harvey                •
et al. 1981), high  rates of evaporation can leave the  precipitation
sulphate concentrated in the soil solution  (and lake water) by a              «|
factor controlled by the evaporative losses.   The equations for  lake          •
sulphate concentration developed by  Henriksen  (1980),  show  this
factor plus dry deposition to be  1.9 for  central  Norway.  Regions of
proportionately high evaporative losses are expected to have higher           •
observed sulphate concentrations  in  lake  water than are predicted by          ™
the Henriksen equations for a given  atmospheric loading rate (Glass
and Brydges 1981).  These processes  vary  with  precipitation and                •
temperature patterns between regions,  from  one watershed to the                |
next, and from areas having strong topography.

Thus, local processes governing the  hydrologic balance need to be             •
considered as a part of the surface  water acidification process.
Knowledge of the periodicity of atmospheric cycles, and of  the
geographic patterns of these transport processes  and precipitation is         •
essential to understanding what happens over  long periods  to                  •
sensitive aquatic systems, as well as  when  and where it will happen.
                                                                               I

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                                                                  2-5
2.2   ATMOSPHERIC INPUT, TRANSPORT AND DEPOSITION  OF  POLLUTANTS

2.2.1   Emissions of Pollutants to the Atmosphere

Extensive research attributes most of the acidity  in  rainfall  in
eastern North America and elsewhere to the presence of  sulphuric and
nitric acids.  These acids are formed by a complex series  of  chemical
and physical processes during and subsequent  to  the burning of fossil
fuels, ore smelting, and petroleum refining.

Vehicular transportation, construction, agriculture,  municipal
incineration uses of home wood burning stoves  and  natural  processes
also contribute to the atmospheric burden.  Other  substances  are also
emitted to the atmosphere during these processes.  Prevailing  weather
conditions in eastern North America foster the large-scale movement
of pollutants within and between Canada and the  United  States, so
that the movements of pollutants are regional  issues.

Current emissions in the United States and Canada  have  been estimated
by Work Group 3B (Table 2-1).

Substantial increases in these emissions are  expected if consumption
of fossil fuels continues to increase.  Estimated  emission rates for
other constituents from the burning of coal are  presented  in
Table 2-2.  A recent U.S. National Academy of  Sciences  report
(NAS 1978) further estimated that from 25 to  30% of the present  day
atmospheric mercury burden is due to man-made  emissions.

Much study is presently being devoted to the  characterization of
emissions from both natural and anthropogenic  sources.  Table 2-3
presents a comparison of these sources for several gases.   Rasmussen
et al. (1975) estimated that greater than 90%  of the  global
anthropogenic S02 is emitted from the Northern Hemisphere. It is
evident that the natural sources of many gases far exceed  the
man-made sources on a global basis.  However,  because such natural
gases are usually well distributed throughout  the  atmosphere,  their
concentration, known as the background concentration, is extremely
low.  Anthropogenic sources of many pollutants are centered near
urban complexes and, therefore, their local pollutant concentrations
are higher and may pose major threats to the  urban environment.   This
spatial concentration of pollutant emission sources causes many
atmospheric constituents to exceed their natural levels several
fold.
2.2.2   Atmospheric Transport of Pollutants

The fate of a pollutant once emitted into  the  atmosphere  depends  on
several factors, some meteorological and some  a  function  of  the
pollutants themselves.  It is important to have  information  about
these factors since sensitive receptor areas are often located at
considerable distances from the pollutant  source regions.

-------
2-6

TABLE 2-1. CURRENT EMISSIONS IN THE U.S. AND CANADA (106 Tons)

U.S.A.
(1980 Estimated) CANADA 1979a TOTAL
N0x sox N0x sox N0x sox
Utilities 6.2 19.5 0.3 0.8 6.5 20.3
Industrial Boilers/ 7.1 7.3 0.6 1.1 7.7 8.4
Process Heaters/
Residential/
Commercial
Nonferrous 0.0 2.0 0.0 2.2 0.0 4.2
Smelters
Transportation 9.0 .9 1.1 0.1 10.1 1.0
Other - - 0.2 1.1 0.2 1.1
TOTAL 22.3 29.7 2.2 5.3 24.5 35.0
a Inco, Sudbury at 1980 emission rate.

From: Canada/United States Work Group 3A Interim Report "Strategies
Development & Implementation" Feb. 1981, Ottawa, Ont.







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                                                                                 2-7
TABLE 2-2.   AIR EMISSIONS  FROM A TYPICAL 1000  MW COAL-FIRED

                STEAM  PLANT3
Const Ituent



Ash
Total carton

Total su 1 phur
Water
Total nitrogen
Al
Ca
Cl
Fe
K
Mg
Na
SI
Tl
Organic C
Fluoranthane
Benzo(gnl Jperylene
Benzo(a)pyrene
Benzo(a)pyrene
Pyrene
Perylee
Phenanthrene
Corenene
Ag
Au
As
B
Be
Br
Cd
Co
Cr
Cu
F
Ga
Ga
Hg
LI
Mn
Mo
Nl
P
Pb
Ra
Rb
Sb
Se
Sn
Sr
Ta
Te
Th
Tl
U
V
W
Zn
Zr
Mean concentration



11.4
70.3

3.3
9.
1.3
1.3
0.77
0.14
0.9
0.16
0.05
0.05
2.49
0.07
-
-
-
-
-
-
-
-
-
0.1
0.001
14.
102.
1.6
15.4
2.5
9.6
13.8
15.2
61.
3.1
6.6
0.2
9.
49.4
7.5
21.1
71.1
34.8

40.
1.3
2.1
4.8
34.
0.16
50.
3.1
680.
5.
32.7
3.
272.
72.5
In coalb



(*>
(*>

(?)

<*)
<*)
<*>
«)
(I)
<*>
(*)

(%)









(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)

(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
Annual air emission
(kg/yr)


2.5 x 106
1010 (as C02)
107 (as CO)
65 x 106
450 x 106
106 (as NO*)
0.24 x 106
0.14 x 106
7 x 10^ (mostly vapor)
0.31 x 106
0.062 x 106
0.014 x 106
0.02 x 106
0.54 x 106
0.034 x 106
5,000.
35.
14.
13.
7.
13.
6.
3.
0.6
31.
0.3
3,500.
3,100.
80
70,000. (mostly vapor)
680.
640.
1,700.
915.
15,000. (40* as vapor)
172.
1,600.
1,000.
365.
1,500.
940.
1,300.
2,700.
1 1,000.
0.1 (Cl)
1,200.
360.
335. (20$ vapor)
1,200.
1,100.
6.5
2,600.
96.
33,000.
250.
3,400.
90.
37,000.
2,200.
  a   Plant has electrostatic  preclpltator efficiency of 99.5<, no scrubbers, and
      consumes 5 x 10  tons of coal  per year.


  b   Western, midwest and eastern coal mean of 101 samples.
  From:
        A.W. Andren personal  communication; Bauer et al. 1982a, 1982b; EPRI 1980;
        Klein et al. 1975; NAS 1977; ORNL  1977.

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                                                                  2-9
Several types of meteorological factors influence long distance
transport.  The prevailing wind regime over much of the eastern U.S.
and Canada is one of westerly winds.  This pattern is complicated  by
seasonal trends, in that there is a southerly component in the summer
and a northerly component in the winter (Figures 2-2 a and b).
"Long-range transport" is facilitated by tall stacks, high wind, and
a stable lower atmosphere (i.e., where the temperature increases with
altitude).  Absence of precipitation also increases the distance of
transport.  Figures 2-3 a and b show isopleths of precipitation for
the North American continent.  The numbers on the contours represent
the average number of centimetres of water falling on the land during
two periods, warm and cool, over 12 months.  The amount of
precipitation in any particular locality usually varies from  year  to
year, but over a long period its average is fairly constant.  The
precipitation patterns shown in Figures 2-3 a and b partially govern
the removal processes of pollutants from the atmosphere.

The properties of the pollutants also will determine their ultimate
fate in the atmosphere.  Junge (1977) has argued that atmospheric
constituents may be put into three categories, each describing the
fate of a set of compounds: (1) accumulative gases; (2) gases
determined by chemical or physio-chemical equilibria with the earth's
surface; and (3) gases and particulate matter (aerosols) determined
by steady-state conditions of their cycles.

The third category comprises most trace gases and particulate matter
and is the prime concern of this report.  The atmospheric concen-
tration of these constituents is determined by dynamic processes
between sources and sinks.  The average atmospheric residence or
turnover time varies between constituents.  A large percentage of
compounds with relatively short residence times  (a few days)  are
deposited within tens to hundreds of kilometres  from the point of
emission.  Compounds with longer residence times may travel  thousands
of kilometres.  Galloway and Whelpdale (1970) estimate, for  example,
that some two-thirds of sulphur emissions in eastern North America
are deposited there, the remainder being transported out over the
Atlantic Ocean.  Table 2-3 presents typical residence times  for other
selected parameters.
2.2.3   Atmospheric Removal Processes

Substances transported through the atmosphere  are  removed  via  wet  and
dry processes.  There are presently  a number of  deposition models,
both empirical and theoretical, which may  be used  in  delineating
pollutant deposition patterns.  The  suitability  of these models
depends on the time and space scales of  the transport processes under
consideration and the complexity  of  the  chemicals  of  interest. The
transport process models require  knowledge of  the  chemical and
physical characteristics of the airsheds involved, for example,
reaction rates under ambient conditions; the concentration in  the

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                                                                 2-10
Figure 2-2.  Wind patterns for North America based on surface
             stream-lines for (a) January and (b) July (Bryson and
             Hare 1974).
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                                                                   2-11
           Total Precipitation (cm)

               Apr-Oct 1979
                           so

          Total Precipitation (cm)

            Nov 1979-Mar  1980
                                          33
Figure 2-3.  Seasonal  precipitation for North America patterns,  total
             precipitation  as  water depth (cm), shown for (a)
             "Summer"  April -  October 1979,  and (b) "Winter" November
             1979 - March 1980.   Data reporting sites (A) are from
             NADP and  CANSAP precipitation monitoring networks (Glass
             and Brydges 1982).

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                                                                  2-12
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solid, vapour, and liquid states; size distributions, morphology,  and
sorptive characteristics of aerosols; and  the  vertical,  aerial,  and
temporal variability of these parameters.                                      •

Particles and unreactive gases in air may  be removed  by  rainout
(in-cloud processes) and washout (below-cloud  removal).   The  wet flux         •
of these substances is a function of their concentration in                   •
precipitation and the amount of precipitation.  The particle  washout
ratio has been completed by several authors for  different chemicals            ^
(Slinn et al. 1978).  Slinn et al. (1978)  have also summarized data            •
on enhanced solubility coefficients for  reactive gases.   These gases          ™
include SC^, where the dissolution, hydrolysis and oxidation  to
sulphuric acid are considered.                                                 fl|

Accurate and direct measurements of dry  deposition, both for  aerosols
and gases, are not possible at present (Hicks  and Williams 1980).              •
The mass transfer is especially difficult  to estimate for trace                •
chemicals because long sampling times are  required (often greater
than 24 hours) and meteorological conditions may change  drastically
during such a sampling interval.  Dry flux estimates  will undoubtedly         •
change in the future as deposition measurement techniques and models          •
improve.  At the present time, it seems  that the best experimental
strategy is to collect accurate data for atmospheric  constituents              •
with the best possible time resolution,  at an  appropriate reference            £,
height, and with as much meteorological  information as  possible.

Several approaches are available for indirectly  calculating mass              •
transfer of aerosols to the earth's surface.   The most  popular
approach has been to use the relation by Chamberlain  (1966):

                    F = VDCZ          (1)                                      I

where F = flux, VQ = deposition velocity,  and  Cz = pollutant                   •
concentration at a certain reference height.   Deposition velocity             •
data, determined by wind tunnel experiments for  several  particle
diameters, roughness lengths, and friction velocities,  have been
furnished by Sehmel and Sutter (1974), Cawse  (1974) and  Holler  and            •
Schumann (1970).  The data, which have been summarized  by Gatz                 •
(1974), represent time-averaged deposition velocities for a variety
of meteorological conditions and thus do not necessarily give                 •
realistic values for aerosol depositions to water.  Sievering et al.          ^jf
(1979) has used the profile method for estimating fluxes across  the
air/water interface.  Hicks and Williams (1980)  have  proposed a new            «
spray capture model, indicating that very  little (if  any) transport            •
is possible during calm conditions.  Slinn (1980) has proposed  a more         *
sophisticated resistance model, where aerosol  growth  in the surface
layer is included.  Sehmel and Hodgson  (1974)  have presented  a model          fl
based on dimensionless integral mass transfer  resistances.  Surface            V
integral resistances were evaluated with deposition velocities  of
monodispersed aerosols determined in wind  tunnel experiments.                 •
                                                                              I

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                                                                  2-13
Similar models are also available for gaseous  deposition  to  various
surfaces.  Garland (1980), Gramat (1980) and Liss  and  Slater (1974)
have devised models based on resistance of transfer  to various
surfaces, such as grass, snow, water, and forest canopies.   These
models usually include an aerodynamic, stagnant film,  and stomatal
(for vegetation) resistance.  The same caveats are necessary on these
models as are applied to dry particle deposition.


The relative importance of each process (i.e., dry vs. wet
deposition), is still being evaluated.  Although the results are not
fully conclusive, modelling and mean balance studies indicate wet  and
dry deposition of sulphur compounds are of equal importance  in  north
Europe and North America (Fowler 1980; Haines  et al. 1981).   Dry
deposition seems to be of lesser importance in remote  areas. Harvey
et al. (1981) conclude that dry deposition is  relatively  more
important than wet deposition in areas like the Ohio Valley, whereas
the opposite is true in remote Canadian Shield lakes.
2.2.4   Alteration of Precipitation Quality


The seasonal quantity and quality of precipitation  are  important  for
determining the potential for acidic deposition  impacts on the
environment.  Acid pollutants accumulating in  the snowpack have  a
higher potential for causing deleterious  effects on organisms  and
habitats in areas with higher amounts of  snowfall than  in  areas with
lower amounts of snow accumulation.  This is due to the rapid
flushing of accumulated acid during snowmelt.  Large storms, on  the
other hand, tend not to have as  low a pH  for the entire rainfall  as
do light rains.  Thus, the distribution of precipitation during  the
year, the temporal behaviour of  rainfall, and  the location of
pollution sources within rainfall pathways are linked to the
potential for damage to the aquatic ecosystems.  In addition,  many
areas in the east with the greatest annual precipitation have  the
least buffering capacity in soils and waterways.


Distilled water in equilibrium with atmospheric  carbon  dioxide has a
pH value of about 5.6.  Results  of CANSAP + NADP monitoring presented
in Figure 2-4 show large areas of North America which are  receiving
precipitation with a pH less than 5.6.  This results in elevated
concentration and deposition of  acids to  the surface as shown  in
Figures 2-5 a and b.


All precipitation contains a wide variety of chemical constituents
from sources such as sea spray,  dust particles and  the  natural
cycling of carbon, nitrogen and  sulphur.  The  discharge of wastes to
the atmosphere increases the amounts of compounds containing elements
such as nitrogen, carbon and sulphur, and adds to the variety  of
compounds, such as PCBs, PAHs and heavy metals, which are  found  in
rainfall.  The four ions usually of most  importance to  rainfall
acidity are:  hydrogen (H+), ammonium (NH^+),  nitrate (N03~) and
sulphate (S0^^~).  Other ions (e.g., calcium)  may be important

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                      2-14
                                 V  ,1980 pH
Precipitation amount -
weighted mean annual  pH in
North America for the calendar
year 1980.
Figure 2-4.


  Legend
  Canada United States
 •CANSAP »NADP
 QAPN   DMAP3S

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                                                                      Legend
                                                                      Canada   United States
                                                                     •CANSAP  «NADP
                                                                     • APN     "MAP3S
                                                                     »OME
                                                                          1980 CHH
          Figure 2-5a.   Precipitation  amount - weighted mean hydrogen ion
                        concentration  in  1980 ( pmoles per litre).

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                      2-16
  0.01 kg/ha =1 m mole/m2
Precipitation amount-
weighted mean hydrogen ion
deposition for 1980 (m moles
per square metre).
Figure 2-5b.


   Legend
   Canada  United States
   •CANSAP «NADP
   OAPN  QMAP3S
   *OME
                                               I

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                                                                  2-17
under some conditions.   Some  of  the  nitrogen  and  sulphur-containing
pollutants are oxidized  to  nitric  and  sulphuric acids,  so that the
acid content of precipitation is mainly  a  secondary result of the
primary emissions.


Table 2-4 lists the  concentrations of  these four  major  ions in bulk
precipitation and total  bulk  deposition  for various sites in North
America.  Precipitation  at  pH 5.6  has  a  hydrogen  ion content of about
2.5 ueq/L (microequivalents/litre).  It  is evident  that the most
westerly study area,  the Experimental  Lakes Area,  has an acid
concentration of about 4 times this  value, while  Dorset and Hubbard
Brook are about 30 times this value.   Sulphate is  the dominant anion
in terms of eq/L (equivalents/litre).  In  the  wet  precipitation at
Kejimkujik National  Park, Nova Scotia, the most easterly study area,
the pH is about 4.6, while  sulphate  is the second  highest anion,
surpassed by chloride (41 yeq/L),  which  is a  reflection of the strong
maritime influence on the precipitation  in Nova Scotia.


Figures 2-6, 2-7 and  2-8 illustrate  the  concentration and deposition
patterns of sulphate, ammonium and nitrate ions,  respectively.  Both
sulphate and nitrate  ion concentrations  are highest in  the east with
high values also recorded in  southern  Alberta  and  Saskatchewan.
Table 2-5 defines the conversion factors for  ion  deposition and
concentration.


The percent of normal precipitation  for  1980  is shown in Figure 2-9.
While most areas received at  least 75% of the  normal precipitation,
others received up to twice as much  precipitation  as normal.

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                                                                 2-18
TABLE 2-4.   CONCENTRATIONS IN BULK DEPOSITION AND TOTAL BULK
             DEPOSITION OF FOUR IONS AT FOUR CALIBRATED WATERSHED
             STUDIES (concentrations in bulk deposition yeq/L)
Muskoka- Hubbard Kejimkujik3 Sagamore
ELAb Haliburtonc Brookd Park6 Lakef
H+
NH4+-N
N03~-N
so42~
Deposition
H+
NH4+-N
N03~-N
so4 -
11 70-90
21 34-36
18.5 36-41
30 77-89
in meq/m^.yr from
10 55-58
22-28
25-34
20.7 62-64
72-74
12.2
23.7
60.3
bulk deposition
96
16
30.6
79
24
4.4
12.4
33(28.5)

34 80-95
6 20-26
17 37-50
46(40) 81-95
a Wet deposition  only,  (  )  indicating  excess sulphate.


b Schindler  et  al.  1976
c  Scheider  et  al.  1979
d Likens  et  al.  1977
6 Kerekes  1980
   Johannes  and Altwicker 1980


 NOTE:   differences  in values for areas,  compared to the isoplot
        figures are  due to year to year variations.
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2-19
                                                                       Legend

                                                                       Canada    United States

                                                                      •CANSAP  «NADP
                                                                      • APN     "MAP3S
                                                                      • OME
                                                                           1980
           Figure 2-6a.  Precipitation amount - weighted mean sulphate ion
                         concentration for 1980 ( ymoles per litre).

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                       2-20
       • 3.4
   • 7.8
              • 51
         • 10

          • 16
       »3.8
                     .46
 |»49

  • 48
              * 5°

              • 45

              • 22
    \
        \
               27
               •
0.961 kg/ha =1 m mole/m2
                                  • 33
                                             20
                                      1980 D
        SO4=
Precipitation amount -
weighted mean sulphate ion
deposition for 1980 (m  moles
per square metre).
Figure 2-6b.


   Legend
   Canada  United States
   •CANSAP «NADP
   QAPN  DMAP3S
   *OME
                                               I

                                               I

                                               I

                                               I

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                                                                2-21
                                                            Legend

                                                            Canada   United States
                                                           •CANSAP »NADP
                                                           • APN    BMAP3S
                                                           »OME
                                                               1980 CNH4+
Figure 2-7a.  Precipitation amount  - weighted mean ammonium ion
              concentration for  1980 ( ymoles per litre).

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                     2-22
                             \J
                 c
                  0
           \ f

          f?

  0.18 kg/ha =1 m mole/m2
Precipitation amount -
weighted mean ammonium ion
deposition for 1980 (m moles
per square metre).
 ure 2-7b.
 Legend

 Canada  United S
• CANSAP »NADP
nAPN  QMAP3S
*OME

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                                                                 2-23
                                                             Legend

                                                             Canada   United States
                                                            •CANSAP »NADP
                                                            • APN    "MAP3S
                                                            »OME
                                                                1980
Figure 2-8a.  Precipitation amount - weighted mean nitrate ion
              concentration for 1980 ( ymoles per litre).

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                      2-24
  0.62 kg/ha = 1 m mole/m2
Precipitation amount -
weighted mean nitrate ion
deposition for 1980 (m moles
per square metre).
Figure 2-8b.  •
 Legend

 Canada  United States

•CANSAP »NADP
QAPN   nMAP3S
4OME
              »




              I

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                                                                     2-25
TABLE 2-5.   CONVERSION FACTORS FOR CONCENTRATION AND DEPOSITION
             UNITS
   ION
Example for
 CONCENTRATION


mg/L PER  pmole/L
    DEPOSITION


kg/ha PER   mmole/m2
H+
NH+
Na+
Ca2+
Mg2+
so42~
N03
ci-
0.0010
0.0180
0.0230
0.0401
0.0243
0.0961
0.0620
0.0355
0.010
0.180
0.230
0.401
0.243
0.961
0.620
0.355
               2-
     0.0961 mg/L equal 1  ymole/L

                                 f\
     0.961 kg/ha equal 1  miaole/m

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                                                              2-26
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                                                             A 1980 % normal
                                                               precip
Figure 2-9.   Percent of normal precipitation  in North America
             in  1980.
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                                                                  2-27
2.3   REFERENCES


Andren, A.  Personal communication.  Water Chemistry Department,
     University of Wisconsin, Madison, WI.


Bauer, C.; Vern Mark, K.; Price, B.; and Andren, A.W.   1982a.
     Organic vapour emissions from a coal-fired steam plant.  Final
     Report, U.S. Environmental Protection Service, University of
     Wisconsin, Madison, WI.  (in preparation)


Bauer, C.; Andren, A.W.; and Knaebe, M.  1982b.  Chemical composition
     of particulate emissions from a coal-fired steam plant;
     Variation as a function of time and size.  Final Report, U.S.
     Environmental Protection Service, University of Wisconsin,
     Madison, WI.  (in preparation)


Bryson, R.A., and Hare, F.K.  1974.  In World Surveys of Climatology,
     ed. H. Landsberg.  Vol.  VII.  The Climates of North America.
     Elsevier Press.  432 pp.


Cawse, P.A.  1974.  A survey of atmospheric trace elements in the
     United Kingdom.  A.E.R.E. Hawwell Report No. R-7669, HMSO,
     London.


Chamberlain, A.C.  1966.  Transport of gases to and from grass-like
     surfaces.  Proc. R. Soc. Lond.  A296:45-70.


Electric Power Research Institute (ERPI).  1980.  Inventory of
     organic emissions from fossil fuel combustion for  power
     generation.  ERPI Report EA-1394, Palo Alto, CA.


Fowler, D.  1980.  Removal of sulphur and nitrogen compounds from the
     atmosphere in rain and by dry deposition.  In Proc. Int. Conf.
     Ecological Impact of Acid Precipitation, eds. D. Drablos and
     A. Tollan,  pp. 22-32.  SNSF-Project, Sandefjord,  Norway, 1980.


Galloway, J.N., and Cowling, E.B.  1978.  The effects of
     precipitation on aquatic and terrestrial ecosystems - a proposed
     precipitation chemistry network.  J. Air Pollut. Control Assoc.
     28:229-235.


Galloway, J.N., and Whelpdale, D.M.  1980.  An atmospheric sulfur
     budget for eastern North America.  Atmos. Environ. 14:409-417.


Garland, J.A.  1980.  Dry deposition of gaseous pollutants.  In Proc.
     WMO Symp on Long Range Transport of Pollutants and its Relation
     to General Circulation Including Stratospheric/Tropospheric
     Exchange Processes.  WMO (Geneva), 538:95-103.


Glass, G.E., and Brydges, T.  1982.  Problem complexity in predicting
     impacts from altered precipitation chemistry.  In Proc. Int.
     Symp. Acidic Precipitation and Fishery Impact in Northeastern
     North America.  American Fisheries Society, Ithaca, NY., 1981.
     (in press)

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                                                                 2-28
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                                                                               I
Goldberg, E.D., and Bertine, K.  1971.  Fossil fuel combustion and
     the major geochemical cycle.  Science 173:233-235.

Gramat, L.  1980.                                                              I

Gramat, L.; Rodhe, H.; and Hallberg, R.L., 1976.  Global sulfur
     cycle.  In Nitrogen, phosphorus and sulfur global cycle, eds.             •
     V.H. Svensson and R. Soderlund, pp. 89-134.  Scope Report 7,              •
     Ecol. Bull.  (Stockholm) 22.

Raines et al.  1981.

Harvey, H.H.; Pierce, R.C.; Dillon, P.J.; Kramer, J.P.; and                    •
     Whelpdale, D.M.  1981.  Acidification in the Canadian aquatic             I
     environment;  scientific criterion for an assessment of the
     effects of acidic deposition on aquatic ecosystems.  Nat. Res.
     Council Canada Report No. 18475, Ottawa, Ont. 369 pp.                     •

Henriksen, A.  1981.  Acidification of freshwaters - a large-scale
     titration.  In Proc. Int. Conf. Ecological Impact of Acid                 •
     Precipitation, eds. D. Drablos and A. Tollan, pp. 68-74.  SNSF -          |
     Project, Sandefjord, Norway, 1980.

Hicks, B.B., and Williams, R.M.  1980.  Transfer and deposition of             I
     particles to water surfaces.  In ORNL Life Sciences Symposium             *
     Series. (in press)

Johannes, A.H., and Altwicker, E.R. 1980.  Atmospheric inputs to               •
     three Adirondack lake watersheds.  In Proc. Int. Conf.
     Ecological Impact of Acid Precipitation, eds. D. Drablos and A.           •
     Tollan, pp. 256-257.  SNSF - Project, Sandefjord, Norway, 1980.           |

Junge, C.E.  1972.  The cycle of atmospheric gases - natural and               _
     man-made.  Q. J. R. Meteorol. Soc. 98:711-729.                            •

             1974.  Residence and variability of tropospheric trace
     gases.  Tellus 26:477-488.                                                •

             1977.  Basic considerations about trace constitutents in
     the atmosphere as related to the fate of global pollutants.  In           M
     Fate of pollutants in the air and water environments, Part I,             •
     ed. I.H. Suffet.  New York:  J. Wiley and Sons.

Kellogg, W.W.; Cadle, R.D.; Allen, E.R.; Lazrus, A.L.; and                     I
     Kartell, E.A.  1972.  The sulfur cycle.  Science 174:587-596.             •

Kerekes, J.J.  1980.  Preliminary characterization of three lake
     basins sensitive to acid precipitation in Nova Scotia, Canada.
     In Proc. Int. Conf. Ecological Impact of Acid Precipitation,
     eds. D. Drablos and A. Tollan, pp. 232-233.  SNSF - Project,
     Sandefjord, Norway, 1980.
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                                                                 2-29
Klein, D.H.; Andren, A.W.; Carter, J.A.; Emery, J.F.; Feldman, C.;
     Fulkerson, W.; Lyon, W.S.; Ogle, J.; Palmy, Y.; Van Hook, R.I.;
     and Bolton, N.  1975.  Pathways of thirty-seven trace-elements
     through a coal-fired powerplant.  Environ. Sci. Technol.
     9:973-979.


Likens, G.E.; Bormann, F.H.; Pierce, R.S.; Eaton, J.S.; and
     Johnson, N.M.  1977.  Biogeochemistry of a forested ecosystem.
     New York:  Springer-Verlag.   146 pp.


Liss, P.S., and Slater, P.G.   1974.  Mechanism and rate of gas
     transfer across the air-sea  interface.  In Atmosphere-surface
     exchange of particulate and  gaseous pollutants, pp. 345-368.
     ERDA Symposium No. 38, Richland, WA.


Liu, S.C.   1978.  Possible non-urban environmental effects due to
     carbon monoxide and nitrogen oxide emissions.  In Man's impact
     on the troposphere, eds.  Levine and Schryer, pp. 65-80.  NASA
     Ref. Publ. 1022.


Moller, U. , and Schumann, G.J.  1970.  Mechanisms of transport from
     the atmosphere to the earth's surface.  Geophys. Res.
     75:3013-3019.


National Academy of Sciences (NAS).  1977.  Nitrogen oxides:  Medical
     and biological effects of environmental pollutants.   National
     Academy of Sciences, Washington, DC.333 pp.


	.  1978.  An assessment of mercury of the environment.
     National Academy of Sciences, National Research  Council,
     Washington, DC.  185 pp.


Oak Ridge National Laboratory  (ORNL).   1977.   Environmental,  health,
     and control aspects of coal-conversion:   an  information
     overview.  In ORNL-EIS-94, Volume  1,  eds.  H.M. Braunstein,  E.B.
     Copenhaver, and H.A. Pfuder.  Oak  Ridge National Laboratory,  Oak
     Ridge, TN.


Rasmussen, T.M.; Taheri, M.; and Kabel, R.L.   1975.   Global emissions
     and natural processes  for removal  of  gaseous  pollutants.  Water,
     Air, Soil Pollut. 4:33-64.


Robinson, G., and Robbins,  R.C.  1970.  Gaseous nitrogen  compound
     pollutants from urban  and natural  sources.   J. Air Pollut.
     Control Assoc. 70:305-306.


Rodhe, H.  1978.  Budgets and  turnover  time of  atmospheric  sulfur
     compounds.  Atmos. Environ. 12:671-680.


Scheider, W.A.; Snyder, W.R.;  and Clark, B.  1979.  Deposition of
     nutrients and ions by  precipitation in south-central Ontario.
     Water, Air, Soil Pollut.  12:171-185.

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                                                                 2-30
                                                                              I
                                                                              I
Schindler, D.W.; Newbury, R.W.; Beaty, K.G.; and Campbell, P.  1976.
     Natural water and chemical budgets for a small Precambrian lake
     basin in central Canada.  J. Fish. Res. Board Can.                        •
     33:2526-2543.                                                             |

Sehmel, G.A., and Hodgson, W.H., 1974.  Predicted dry deposition               «
     velocities.  In Atmosphere-surface exchange of particulate and            •
     gaseous pollutants,  pp. 339-419.  ERDA Symposium No. 38,
     Richland, WA.

Sehmel, G.A., and Sutter, S.L.  1974.  Particle deposition rates on a          •
     water surface as a function of particle diameter and air
     velocity.  J. Rech. Atmos. 8:911-920.                                     •

Sievering, H.; Dave, M.; Dolske, D.A.; Hughes, R.L., and McCoy, P.
     1979.  An experimental study of lake loading by aerosol                   «
     transport and dry deposition in the southern Lake Michigan                I
     Basin.EPA-905/4-79-016, EPA Progress Report, U.S.™
     Environmental Protection Agency, Governor's State University,
     Park Forest, IL.                                                          •

Slinn, W.G.N.   1980.  Precipitation scavenging.  In Meteorology and
     power production.  U.S. Department of Energy, Washington, DC.             •

Slinn, W.G.N.; Basse, L.; Hicks, B.B.; Hogan, A.W.; Lai, D.;
     Liss, P.S.; Munich, K.O.; Sehmel, G.A.; and Vittori, 0.   1978.
     Some aspects of the transfer of atmospheric trace constituents            •
     past the air/sea interface.  Atmos. Environ.  12:2055-2087.

                                                                               I
Soderlund, R. , and Svensson, V.H.  1976.  The global nitrogen cycle.
     In Nitrogen, phosphorus and sulfur global cycle, eds.
     V.H. Svensson and R. Soderlund, pp. 23-74.  Scope Report 7,
     Ecol. Bull.  (Stockholm) 22.                                              _

Spedding, D.J., 1972.  Sulphur dioxide adsorption by seawater.
     Atmos. Environ. 6:583-586.
                                                                               I
Stewert, R.W.; Hameed, S.; and Pinto, J.  1978.  The natural and
     perturbed troposphere. In Man's impact on the troposphere, eds.
     Levine and Schryer, pp. 27'-74.  NASA Ref. Publ. 1022.                     •

Sze, N.D.  1977.  Anthropogenic CO emissions:  Implications for the
     atmospheric CO-OH-CH4 cycle.  Science 195:673-675.                        _
                                                                               I

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   SECTION 3




AQUATIC EFFECTS

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                                                                  3-1
                              SECTION 3
                          AQUATIC  EFFECTS
3.1   INTRODUCTION


This assessment is  structured  to  address  three  major questions
concerning aquatic  effects  of  acidic  and  pollutant  deposition in
North America:


1.   What is the nature  and extent  of the chemical  alteration of the
     hydrologic cycle due to pollutant  deposition?
2.   What is the nature  and extent  of biotic  alteration in aquatic
     ecosystems as  a result of  acid-induced chemical alterations?
3.   What is the geographical  distribution and  acid-loading
     tolerance of watersheds of various sensitivities?


Several approaches  were  used to evaluate  these  questions.   Firstly,
emphasis was placed on identifying  and  substantiating historical
(long-term) changes in aquatic  systems  possibly related to long-range
transport of acidifying  substances.   This evaluation has required
some consideration  of the complexity  of hydrologic  systems, as well
as of the complexity and the extent of  aquatic  resources that are at
risk.  Included are detailed documentations of  affected aquatic
environments, both  chemical and biotic  components,  and  definition of
time trends for observed changes.


Secondly, consideration  was given to  the  significance of the episodic
nature of atmospheric pollutant loading and flushing processes, such
as snowmelt, as well as  the seasonal  character  of  the receiving
environments and biota,  such as periods of fish spawning.   Thus,
these sections relate pollutant loading levels  to  the observed
extremes in chemical conditions and biological  effects.


Finally, this section focuses  on  the  aquatic  ecosystems and biota
that are sensitive  to acidic deposition.   It  was,  therefore,
necessary to define an acid-loading tolerance,  to  identify regions
sensitive to acid inputs, to identify aquatic resources  at risk from
higher acid-loading levels, and to  discuss recovery possibilities for
aquatic systems showing  apparent damage.
3.2   ELEMENT FLUXES AND GEOCHEMICAL ALTERATIONS  OF WATERSHEDS


For a complete understanding of  the effects  of  acidic  deposition on

aquatic ecosystems, it is necessary to  examine  the  fate of  ions
deposited from the atmosphere, directly on aquatic  systems  and
indirectly through deposition on watersheds.   In  the latter case

deposition may result in geochemical alterations  of watersheds.
These geochemical alterations must be considered  before a complete

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                                                                  3-2
                                                                               I
                                                                               I
understanding of chemical inputs  to and  changes  in  aquatic  ecosystems
can be achieved.


3.2.1   Hydrogen Ion (Acid)

Hydrogen ions (acid) (H+) drive most  chemical weathering  reactions.             |
They are supplied from both  external  and  internal  sources.   The major
external source is acid supplied  by atmospheric  deposition                      •
(meteorological input).  Internal  sources  are biological  and chemical          •
processes occurring within the watershed.

Carbon dioxide (C02) in the  atmosphere represents  a large,  but                 •
                                                                                I
occasionally rate-limited,  reservoir  of  carbonic  acid
Carbon dioxide contributes  to both  internal and external  sources  of
hydrogen ions.  The major process of  chemical weathering  is  the                •
exchange of protons (H+) for cations  (Ca2+, Mg2+, Na+,  and K+) .  The           |
proton source for the weathering process  is derived  from  the external
supply (precipitation) and  from internal  biochemical generation.   In           _
a typical calcium carbonate-or silicate-bearing soil or rock,  this              I
normal weathering process gives rise  to  waters having  calcium and
bicarbonate as the major ionic constituents.  (See standard  texts on
limnology; e.g., Hutchinson [1957]  or Wetzel  [1975].)                           •

The hydrogen ion cycle within soils is quite complex and  not well
understood.  At the Hubbard Brook Watershed, New  Hampshire,  the                •
average external net annual input of  hydrogen ion equivalents                   I
observed over the 1963-74 decade was  86.5 +_ 3.3 meq/m^.yr
(milli-equivalents/ square metre. year)  (Likens et  al. 1977b).  If  this          _
were the only source of H+  ions at  Hubbard Brook  and the  ecosystem             •
were in a steady state, one might expect  this hydrogen  ion input  to            ™
be balanced by hydrogen ion exports plus  the net  rate  at  which ionic
Ca, Mg, K, Na, and Al are leached from the soil.   In fact, there  are           I
more of these cations removed from  the ecosystem  each  year  than there          •
are external hydrogen ions  to replace them.  The  difference  is
statistically significant,  and implies the yield  of  internally                 •
generated H+ and/or an underestimate  of  dry deposition  and/or the              I
influence of ammonium and nitrate ions on the charge balance.
Internal sources of H+ at Hubbard Brook  were  identified as :                     _
(1) nitrogen compounds, particularly  NH4+; (2) reduced  carbon                  •
oxidized in the soil; (3) organic acids,  such as  citric,  tartaric,              •
tannic, and oxalic acids, produced  by biological  activity within the
soil; (4) oxidation of small amounts  of  sulphide  minerals in the                H
bedrock; and (5) the uptake of cations (e.g., K+, Ca^+) by  the                 ||
forest vegetation and the forest floor.

Currently, in eastern North America,  the amounts  of  hydrogen ion               •
being deposited generally are in the  range of 50-100 meq/m^.yr for
areas receiving the highest acidic  deposition.  To neutralize this
acid input, a base equivalent of 25-50 kg/ha. yr  (kilograms/                     •
hectare. year) of calcium carbonate  would be required.   Carbonate               •
soils can neutralize this amount of acid for  an  indefinite  time with
                                                                                I

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                                                                  3-3
only a small percentage increase  in  total  runoff  of  calcium and
magnesium salts which  is  a  small  loss  compared  to the total stored in
the watershed.  However,  in  areas  underlain  by  rocks resistant to
weathering and with  shallow  noncalcareous  soils,  such as much of the
Precambrian Shield region, the  amount  of salts  and alkaline materials
normally leached are on the  order  of  10-100  meq/m^.yr.  External
hydrogen ion loadings  to  these  areas  are of  the same order of
magnitude as this leaching rate.   When hydrogen ion inputs exceed the
levels of available  Ca and Mg,  other  less  available  metals are
leached.  For example, some  of  the acid results in leaching of such
cations as aluminum, iron, zinc and manganese.   In some cases,
hydrogen ion inputs  exceed the  ability of  the soils  to fix hydrogen
ions and excess hydrogen  ions are  exported to surface waters.

In most parts of the Precambrian  Shield, current  levels of hydrogen
ions from rainfall are neutralized within  the soils  of the watersheds
during most of the year.  Retention  (neutralization) of hydrogen ions
deposited in bulk deposition has  been  measured  at 88, 94 and 98% on
an annual basis, at  the Experimental  Lakes Area (Ontario), Hubbard
Brook (New Hampshire)  and Muskoka-Haliburton (Ontario), respectively
(Schindler et al. 1976; Likens  et  al.  1977b; Scheider et al. 1979c).
On the other hand, hydrogen  ions  deposited in snow tend to be
stripped from snow crystals  early  in  the spring snowmelt process, and
much of the total annual  H+  export from a  watershed  occurs during a
brief period in the  spring.  This  large volume  of water, coupled with
less opportunity for infiltration  and  interaction with the soil, has
resulted in some cases in "shock  level" concentrations of acid
exported to streams  and surface waters of  lakes (Schofield 1981).
Hultberg (1977) reported  on  such  shock level pH declines in Swedish
lakes and rivers and demonstrated  that in  some  cases these pH
declines were associated  with fish kills.

The total ionic strength  of  surface waters is determined largely by
the hydrological and geochemical properties  of  the catchment basin.
"Soft" waters, of low  ionic  strength,  occur  within basins having
chemically resistant and  very little  readily-exchangeable material,
often associated with  igneous bedrock or its soil derivatives.
"Hard" waters of higher ionic strength are derived from basins having
greater amounts of carbonate lithology (see  Section  3.5).  The amount
of cations exported  from  a basin  thus  becomes a parameter which,
under similar hydrologic  and acid-loading  conditions, characterizes
the basin in an integrated sense.  The chemical composition of
receiving waters is  dependent on  the  types of weathering reactions
within the surrounding watershed.  If  the  weathering has been the
result of reactions with  C02 and  carbonic  acid, the  major ionic
constituents in surface waters  will be bicarbonate and calcium.  When
strong acids such as ^SO^ are  introduced  (for  example, as acidic
deposition) into a bicarbonate-weathering  system, the generation of
bicarbonate alkalinity may be altered  (see Section 3.3).  Instead of
weathering resulting primarily  from reactions with carbonic acid and
yielding bicarbonate ions as a  major  end product:

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                                                                  3-4
CaC03 + H2C03 —> Ca   +  2HC03                                  (1)
                                 or
(K-feldspar)
       30g + 2H2C03 +  12H20  —»  2K  +  2HC03  + 6H4Si04          (2)
                                   m3Si3°10(°H)2
                                                           I
*•'  i  OTT/irv                                   f 1 \             ^1
                                                           I
                                                           I
the reaction of sulphuric acid with  limestone  or  other rocks  yields           I
sulphate as a major anion:                                                     I

CaC03 + H2S04 —*• Ca2+ + SO^2" + H20 + C02                      (3)            •

Alternatively, the reaction  can be considered  as  a  progressive
titration of bicarbonate alkalinity.                                           _

Ca2+ + 2HC03 + H2S04 —> Ca2+ + S042~ + H20  +  2C02              (4)            •

Alkalinity of waters is a measure of  the reserve  acid  neutralizing            •
capacity (ANC) that remains  to be titrated to  any chosen pH level.            |
Dissolved carbonate species  (HC03 and C03^+),  if  present in
sufficient concentrations, react together as a buffering system,               M
tending to retard or limit changes in pH.  (See Figure 3-1 [Wetzel            •
1975] for the relationship of the inorganic  carbonate  species to  pH.)
For a monoprotic acid  [HA]:

     alkalinity [ANC] =  [A~] +  [OH~]  - [H+]                     (5)            •

For a diprotic acid [H2A]:                                                     •

     alkalinity [ANC] =  [HA"] + 2[A2~]  + [OH~]  -  [H+],         (6)

where the acids are HA and ^A, respectively (Stumm and Morgan                •
1970).  The major source of  buffering in freshwaters is the carbonate
system.  Therefore for surface waters:

     [ANC] =  [HC03~] + 2[C032~] +  [OH"]  + [B~]  -  [H+]           (7)            I

where  £B~ is the sum of all titrable bases  (Lerman 1978).  Thus,             •
the loss of bicarbonate  during  the ^804 titration  represents a               |
decrease in the buffering  capacity of the water (lower alkalinity).

As a result of the above reactions,  804^- replaces  HC03~ in the ionic         •
balance of outflow waters until the  titration  endpoint is reached,            ™
that is, when all the HC03~  has been consumed  (Kramer 1981).   The
HC03~ remaining at any stage above the titration  endpoint largely             I
determines the pH or alkalinity of the waters,  although organic               I
                                                                               I

                                                                               I

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                                                                   3-5
                                     8  9   10  11  12 13
Figure 3-1.  Relationship  between pH and the relative proportions of
             inorganic  carbon species of CC>2 (H2CC>3), HCO^, and
             C0o~ in  solution (from Wetzel 1975).

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                                                                  3-6
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materials may provide some additional  buffering  at  lower alkalinities
(see Section 3.3).  Beyond the  titration endpoint,  large
concentrations of hydrogen ion  will  be present and  other buffers such         •
as aluminum or humic materials  may  also become important in the               J
control of pH of the waters  (see  Section 3.2.4).  Thus,  the
concentration of cations  in  surface  waters  for any  given alkalinity           _
reflects a basin's ability to produce  cations and may be used as an           I
index of its capacity to  neutralize  acidic  deposition added to the            ™
basin.

Henriksen (1980) and Thompson (1982) have used this assumption and            •
the necessity of ionic charge balance  to estimate surface water
sensitivity or the ability of a basin  to respond to an external               •
stress of acidification.  Hesslein  (1979) has applied similar                 I
assumptions and used alkalinity to  estimate acid loadings which would
be required to produce acidification.   Thus,  if  arbitrary "loading"           _
or acidification stress  levels  are  specified, alkalinity can provide          •
a quantified measure of  the  sensitivity of  a  basin  to further                 •
acidification of waters.  For example, HCO^ concentrations of
100 to 200 yeq/L, have been  identified as approximate levels below            H
which a basin may be considered to  be  sensitive  to  acidification              |
(Altshuller and McBean 1979; Glass  and Loucks 1980).   When the flow
rates through a basin are specified, the alkalinity provides a flux           •
or basin yield of reserve ANC.  If  significant loss of alkalinity has         •
not occurred this equates to the  Ca^+  or cation  flux used in the
Cation Denudation Rate (CDR) model  of  Thompson (1982).  Alkalinity
(concentration or flux)  or CDR  therefore provide techniques to                I
estimate quantitatively  the  capacity of a drainage  basin to withstand         •
acid loading (see Sections 3.9.2  and 3.9.3).

Acidification of nonorganic  surface  waters  by external sources of             |
H  may thus be a combination of two  processes:   (1) a retardation
of the development of alkalinity  in  the watershed (Kahl  et al. 1982),         •
and (2) a titration (Henriksen  1979) of surface  water alkalinity.             I

The Calcite Saturation Index (CSI),  was defined  by  Conroy et al.
(1974) as the undersaturation of  waters with respect to  CaC03.  As            I
modified by Kramer (1981):                                                     •

              CSI = log  K -  log [Ca2+] -log [HCOZ]  -pH                        •
        where log K = 2.582  - 0.024t                                          |
              t - temperature (°C)  and [  ] are  concentrations.

The CSI allows for assessment of  pH and alkalinity  on a  single                •
logarithmic scale.  Saturation  with respect to  calcium carbonate
gives a value of zero with degree of undersaturation on  an increasing
positive scale.  Kramer  (1976)  considered values greater than CSI =3         •
to indicate waters sensitive to acidification.   To  date, a                    •
quantitative relationship between acidification  potential and CSI
units has not been developed.
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                                                                  3-7
3.2.2   Nitrate and Ammonium  Ions

Atmospheric deposition  of  nitrate  is  only about  one-third to one-half
as great on an equivalent  basis  as  the  sulphate  deposition in eastern
North America, but in some  areas of the western  United States nitrate
may represent up to 60% of  the annual acid fractions in rainfall
(Lewis and Grant 1979;  Liljestrand  and  Morgan 1978).

Nitrogen deposition can result in  either acidification or
neutralization of surface waters depending on the ionic form.
Nitrogen, as nitrate ions  (N03~),  can be incorporated directly by
vegetation resulting in the release of  hydroxyl  ions (OH~) into the
environment (Figure 3-2).   The hydroxyl ions  neutralize hydrogen ions
and raise the pH of the soil  and water.  Natural decomposition of
nitrogenous plant material  releases hydrogen  ions,  but net annual
accumulation of plant tissue  dominates  in most ecosystems (Bormann
and Likens 1979).  Hence, net production of neutralizing capacity
from nitrate addition is often dominant, especially during warm
periods of the seasons  (see data from Harvey  et  al. 1981; Brewer and
Goldman 1976).  This is particularly  significant where forest harvest
rather than decomposition  removes  plant materials,  because the
neutralizing portion of the cycle  is  left in  the system and a portion
of the acidification source (decomposition) is removed.

Ammonium salts and sulphate particulates are  present in both dry and
wet deposition.  Ammonium  is  a source of hydrogen ions (Figure 3-2)
when the nitrogen is utilized by plants.  This release of hydrogen
ions can be a significant source of acidification in soils and
surface waters.  Nitrogen  is  usually  in short supply in terrestrial
habitats, and is readily incorporated and retained  by ecosystems
(Reuss 1976) (Table 3-1).

Nitric acid and ammonium salts are  stored in  snowpack and released as
acid components to streams  and lakes  during spring  snowmelt and may,
therefore, be partially responsible for the documented episodic
increase in acidity in  aquatic ecosystems.  During  the growing
season, however, both terrestrial  and aquatic vegetation use most of
the deposited nitrate and ammonium  ions,  except  for periods of heavy
rainfall.  Because nitrate  ions  often occur at higher concentrations
in precipitation than do ammonium  ions,  there is often a net
production of alkalinity.
3.2.3   Sulphate

Sulphur, like nitrogen,  is an essential  plant  nutrient and the
incorporation of sulphate into  vegetation  releases  hydroxyl ions
(Figure 3-3).  As opposed to nitrogen, sulphur in soil is  usually in
adequate supply for plant growth.  Additions of sulphur may not be
entirely incorporated into living  tissue.   Sulphate ions can also be
absorbed by soils and reduced by bacterial action.   This reaction
consumes acid and raises the pH of the soil-water environment.

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                                                                 3-8
 PLANT
       NH«
         r
    R-C —I
NH/    «-
NO,
F
SOIL
OR i
? organic nitrogen

r
WATER
T*
R r R -k NH
H +

i

H* *
3^ ^ kj|
2H +
-J
>

OH
2H +
j * .--^ , k Mr



i«~
        R   organic nitrogen
Figure 3-2.  Simplified nitrogen cycle showing chemical changes
             caused by plant and soil processes (from Reuss 1976).
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                                                                        3-9
TABLE 3-1.  THE RETENTION OF NITRATE, AMMONIUM  ION  AND TOTAL NITROGEN
            BY FORESTED WATERSHEDS  IN SEVEN  CALIBRATED WATERSHED STUDIES
             	% Retention  in  the  watershed  on an annual basis	

Substance      ELAa   Muskoka-    Hubbard    Kejimkuiik   Sagamore   Woods    Panther
                     Haliburtonb   Brookc       Park3       Lake6      Lake6     Lake6
             Ontario  Ontario      New      Nova  Scotia  New York  New York  New York
                                Hampshire



N03~           -        75         15          99           43        70        15
                        95          89           98           90        90        90
Total
Nitrogen     81-90
a Schindler et al. 1976.


b Scheider et al. 1979c.


c Likens et al. 1977b.


d Kerekes 1980.


e Galloway et al. 1980 (figures estimated  from  published  bar graphs).

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                                                                 3-10

— c
1
SOIL S
2+
P^ *>
^^\ A
^2H *
/
2OH~^
H 2H +
aerobic ^^^
N ^- 	 k o
^ r VJ
2H +
0 ^ ± 	
2« 4
anaerobic
2-
f%
P4
2-
/^
°4

Figure 3-3.  Simplified sulphur cycle  showing  chemical  changes caused
             by plant and soil processes  (modified  from Reuss 1976).
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                                                                  3-11
Sulphide (S^ ) can subsequently  be  oxidized  back to  sulphate,
resulting in the production of hydrogen  ions.

In spite of these possible  reactions  in  granites and related rock
types, much of the SC>2 and  S0^~ deposited in  acidic deposition is
not retained.  Sulphate is  leached  out of soils  and  is  often the
anion balancing the presence  of  H+  and other cations in surface and
shallow ground waters.  The amount  of 80^2-  in runoff from the
Shield areas is very close  to the amount deposited  in precipitation.
At the Experimental Lakes Area (ELA)  in  Ontario, Schindler et  al.
(1976) found the atmospheric  80^"  input measured in bulk
precipitation and the 804^" export  in the runoff were in balance.
Likens et al. (1977b) found 67%  of  the total input  in runoff at
Hubbard Brook, New Hampshire.  Kerekes (1980)  reported  that outputs
of sulphate were about 80%  of the annual inputs  for  the Lower  Mersey
River system in Nova Scotia.  In the  Adirondack  Mountains of New
York, Galloway et al. (1980b) observed that  sulphate inputs and
outputs were in balance for two  lake/watershed systems, while  for a
third watershed some accumulation of  sulphur may be  occurring  within
the terrestrial system.   In some cases,  the  SO^" in surface
waters is greater than the  total input measured  in  precipitation and
the difference may be due to  sulphur  inputs  in dry  deposition  (see
Section 3.6.1).

Although little sulphate  is retained  in  granitic watersheds, in
certain kinds of soils, such  as  are common in  the southeastern U.S.,
a large portion of sulphate inputs  may be retained  in the soil by
soil adsorption processes (Johnson  et al. 1980). This  will have the
very important effect of  retarding  the movement  of  cations, including
H+, from the soil to aquatic  systems.  (See  Section 4.4.2 for
further discussion.)
3.2.4   Aluminum and Other Metals

Surveys of waters in regions  affected  by  acidic  deposition indicate
elevated levels of aluminum  (Al),  cadmium (Cd),  copper (Cu),  lead
(Pb), manganese (Mn), nickel  (Ni)  and/or  zinc  (Zn)  in many acidic
lakes and streams (Aimer et  al.  1978;  Beamish  1974;  Conroy et al.
1976; Henriksen and Wright 1978; Schofield  1976b).   These  increased
concentrations of metals may  result  from  either  increased  atmospheric
loading (associated with or  independent of  acidic deposition) or
increased metal solubility caused  by increasing  surface water
acidity.  Elevated concentrations  of Cd,  Cu, Pb, and Ni are  probably
derived from increased atmospheric deposition.   For these  metals,
deposition and concentrations significantly above background  levels
occur principally in lakes and  streams in relatively close proximity
to pollutant sources (e.g.,  Sudbury  region  of  Ontario;  Conroy et al.
1976).  Although increased atmospheric loadings  of  these metals may
occur in conjunction with acidic deposition, acidic  deposition and
acidification of surface waters  are  not direct causative factors.  On
the other hand, increased concentrations  of Al,  Mn,  and Zn can occur
without increased atmospheric metal  loadings.  For  example,  addition

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                                                                  3-12
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of acid to limnocorrals in the Experimental Lake  Area,  Ontario,
produced substantial increases in  lake water  concentrations  of Al,
Mn, Zn, and Fe at pH levels  6 and  5  (Schindler  1980).   Elevated              •
concentrations of these metals result from an increase  in solubility        |
at lower pH levels (Stumm and Morgan 1970) and  their mobilization
from the surrounding watershed and lake  and stream sediments                H
(Galloway et al. 1980a).  Elevated concentrations of Al,  Mn, and Zn         •
in acidic waters are for the most  part,  a direct  consequence of
atmospheric deposition and acidification.


cycling of metals have focused on  aluminum.   One  of  the effects  of
soil acidification is the mobilization of aluminum.  The solubility         •
of this metal is pH dependent, with  a minimum solubility at  about           •
pH 6 (May et al. 1979; Stumm and Morgan  1970) (Figure  3-4).   Several
reports have documented elevated aluminum concentrations  in  acidic
surface waters (Figure 3-5)  (Cronan  and  Schofield 1979; Dickson 1978;        •
Driscoll et al. 1980; Richard 1982;  Wright and  Gjessing 1976; Wright        «
et al. 1980), and in effluent from lysimeters in  soils  treated with
acid solutions (Abrahamsen et al.  1977;  Dickson 1978).   While               •
aluminum ordinarily is leached from  the  upper soil horizon of podsol        |
soils by carbonic acid, tannic and humic acids, and  organic
chelation, it is usually deposited in lower horizons.   Under the            •
influence of strong acids in precipitation, however, the aluminum may       •
be mobilized in the upper (slightly  acid) soil  horizons and
transported by saturated flow through the surface layers into lakes
and streams (Cronan and Schofield  1979;  Herrmann  and Baron 1980).           •
Elevated aluminum concentrations in  streams have  been  shown  to occur        •
during the spring melt of the snowpack,  when  large quantities of ff1"
ions are released into the saturated surface  layers  (Driscoll 1980b;        M
Seip et al. 1980).                                                           |

The mechanism supplying Al^+ to soil water, and therefore to                •
shallow interflow water, is  the dissolution of  aluminum minerals or         •
exchange reactions on soil organic matter.  Norton (1976) and Reuss
(1976) suggest the following as an explanation  of weathering
reactions for aluminum minerals:                                             •
     A1(OH)3 + H

     A1(OH)2+ + H+^ A1(OH)2+  + H20                                         -

     A1(OH)2+ + H+^A13+  +  H20                                             "

These reactions are  likely to  occur in watersheds where there are no        •
carbonates  to consume H+.  In  such instances,  the reactions above           •
become the  primary buffering mechanism (N.M.  Johnson 1979;  Kramer
1976).  The pH at which  this buffering occurs  is around 4.5-5.0             •
(Johannessen 1980).  Henriksen (1980)  has  shown that lakes  with pH          |
4.6-4.8 have a higher pH than  expected from a theoretical titration
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                                                                  3-13
    4  -
    5  -
    6  -
    7  -
    8  -
    9
                                PH
Figure 3-4.  Aqueous aluminum in equilibrium with gibbsite
             (after May et al. 1979).

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                                                                  3-14
               1000 r
                500
             O)
             2  200  -

             o
             c
             o
             O

             E
             3
100 -
                 50  -
                 20  -
                 10
                   4.0
          5.0
6.0

PH
7.0
8.0
Figure 3-5.  Relationship of observed stream concentrations  of
             aluminum to the pH of  surface water  (modified from
             Wright and Gjessing  1976).
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                                                                  3-15
curved based only on  bicarbonate  buffering,  and that the extra
buffering  can be explained  by the presence of aluminum.

In aquatic systems, aluminum forms a  variety of complexes with water
and its  constituents,  including hydroxide, fluoride, silicate,
organic matter, and sulphate (Driscoll  et  al. 1980).  In surface
waters of  the Adirondack Region of New  York, Driscoll (1980b) found
aluminum-organic complexes  were the predominant monomeric aluminum
form  (average = 44%).   Concentration  increased linearly with total
organic  carbon content.   Aluminum-fluoride complexes were the most
abundant inorganic form (average  = 29%  of  the total monomeric Al),
with  concentrations increasing with decreasing pH,  although their
formation  was generally limited by fluoride  concentration.
3.3   NATURAL  ORGANIC  ACIDS  IN SOFT WATERS

Surface and ground waters  can  have  low pH values  or become acidified
as a result of natural processes  including:

     1)   natural chemical weathering  of  pyrite  and other
          sulphide-rich rocks  (Herrmann and  Baron 1980;  Huckabee
          et al. 1975);

     2)   net  oxidation of reduced  organic material due  to aerobic
          biological decay (Likens  et  al.  1969);

     3)   oxidation of reduced inorganic  material following a
          lowering of  water  tables,  lake  levels,  with subsequent
          exposure to  oxygen (Urquhart and Gore  1973);

     4)   strong cation exchange, especially by  Sphagnum sp.,  with
          subsequent release of H+  (Clymo  1967);  and

     5)   production of  organic acids  which  are  dissociated in the pH
          range 3 to 6 (Oliver and  Slawych 1982).

Natural acidification  due  to chemical  weathering  (process 1) is
usually identifiable because of local  geologic  conditions (e.g.,
bedrock geology and Fe-rich  secondary  soil and  sediment
mineralization).  Processes  2  and 3 are not  steady-state phenomena
and can generally be related to mechanical disturbances  in the
watershed or meteorological  changes.   Process 4,  common  in humid
temperate or sub-arctic  climates, is normally distinguishable  by
analysis of the local  hydrology, vegetational studies, and the
presence of coloured (humic) waters  (related to  process  5).

A major portion of the dissolved organic  carbon  in natural waters is
organic acids, especially  humic and  fulvic acids.  These acids are
produced (process 5) by microbial degradation of  plant and animal
matter.  They are poorly characterized in  terms  of chemical and
physical properties but  serve  two important  functions.   They display

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                                                                  3-16
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acidic properties and contribute  significantly  to  acidity in some
organic-rich waters.  Secondly, these  organic compounds  chelate
various metals that:  (1) increase  total metal  solubility,  and                •
(2) may decrease the concentration  of  biologically available metals           •
(Reuter and Perdue 1977).

The relationship between  colour (Platinum  units) and  dissolved                •
organic carbon (DOC) has  been evaluated by several workers  (e.g.,
Juday and Birge 1933) and the relationship between DOC and  organic
acid has been evaluated empirically by Thurman  and Malcom (1981).             4
The extent of dissociation of the acid can be estimated  by  methods            •
developed by Oliver and Slawych (1982).  Thus,  the organic  anion
concentration can be estimated with a  knowledge of DOC and  pH, both           •
commonly made measurements.  Alternatively,  the organic  anion                 •
concentration can also be estimated based  on a  complete  chemical
analysis (cations and anions) using an ion balance approach.

Many ' igs and organic rich soils  have  undiluted water pH values in            •
the r^nge of 3.5 to 4.5 due  to high concentrations of DOC and
associated acidity.  The  high IT1"  concentration  is  not totally                 If
balanced by S042~, N03~ Cl~, or HC03~  and  the PH is dearly                   j|
determined largely by organic acid  production and  cation exchange
(Clymo 1967).                                                                  M

The synoptic surveys of acidic clearwater  lakes (Dickson 1980; Haines
1981b;  Haines and Akielaszek 1982;  Norton  et al. 1981a;  Wright and
Henriksen 1978; among others) have  concentrated on lakes that have            •
relatively low or no water colour,  and therefore having  low DOC, low          9
organic acid content, and low organic  anion concentrations.  Ion
balances are achieved largely using only H"1", major cations  and
sulphate for lakes with pHs  below about 5.5 where  HC03~  becomes
relatively unimportant.

Natural soil processes in well-drained terrain  may produce                     •
considerable acidity due  to  soil  respiration (which raises  dissolved
C02 and carbonic acid concentrations)  and  biological  breakdown of
organic material to produce  organic acids  and chelators.  Water               I
percolating through the soil profile may commonly  have pH levels              ™
lowered to near 4.0 in the organic  horizons. As these solutions
descend further, acidity  is  consumed by inorganic  reactions including
mineral weathering and desorption of cations.   Additionally, organic
compounds precipitate with increasing  pH and/or oxidize  to  C02 and
H20.  The result is that  acidic soil solutions  commonly have their            •
pH raised from about 4.0  to  5.5-6.5 within a few vertical meters of           •
travel (Cronan 1982).  Should these solutions emerge as  surface
water, the pH would be elevated,  "nonacidic", and  HC03~  would be
a major charge balancing  anion, along  with sulphate.   However, if             •
soils are shallow and unreactive, solutions may reach streams prior           •
to effective neutralization  (A.H. Johnson  1979) and prior to the
development of the maximum allowable HC03~ alkalinity.  The                   •
addition of excess acidity (as ^804 or  (Nfy^  SO^) to soil waters            |
decreases the pH of soil  solutions  further (even for soils  with pH
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                                                                  3-17
values originally around 4).  As a  result,  given the same flow path,
a smaller proportion of the  acidity will  be consumed.   Therefore,
surface water emerges with a  lower  pH,  lower alkalinity,  and possibly
elevated concentrations of cations  due  to accelerated  cationic
leaching (Abrahamsen 1980).   A  number of  processes  may ameliorate the
impact of increased acid loading, the most  important of which are net
uptake of NC>3~ by plants (Reuss 1976) and SO^" adsorption
by soils (Johnson et al. 1980).

Humic materials have recently been  shown  to have low buffering
capacity even when present in high  concentrations (Wilson 1979).  The
weak buffering capacity they  do exhibit is  between  pH 4 and 5
(Driscoll 1980a; Wilson 1979),  the  pH region in which  the endpoint of
alkalinity titrations occurs.  In systems with low  alkalinity, the
presence of humics can lead  to  a significant underestimation of
alkalinity when the usual acidimetric determination method is used
(Driscoll 1980a).  In addition,  these substances can influence the
bioavailability of acid-leached cations such as Al, Mn, Fe and Zn by
acting as chelators.
3.4   CATION AND ANION  BUDGETS

     "Calibrated lakes  and watersheds,  that  is,  natural catchments
     for which the  input  and  output  rates  of substances can be
     measured, are  an established  research tool  in environmental
     studies.  For  example, the  development  of  strategies for the
     management of  eutrophication  of  lakes by phosphorus control was
     based largely  on mass balance studies and models  (Dillon and
     Rigler 1975; Oglesby 1977a,  1977b;  Reckhow  1979;  Vollenweider
     1975).

     "Common reasons for  the  use  of  this approach include:

     (a)  the relative  importance  of  different inputs  of a  pollutant
          can be assessed and abatement  planned  accordingly;

     (b)  mass balances can be used with mathematical  models  to
          predict the chemical concentrations of compounds  in the
          receiving body, either  the  stream  draining the calibrated
          watershed, or the calibrated  lake  itself;

     (c)  the quantitative accounting of the flow of substances in
          the watershed or lake may  provide  information concerning
          the processes and mechanisms occurring there."
          (Dillon et al.  1982)

Ionic balances of watersheds  have  been used  as a means of quantifying
net basin chemical  fluxes (Figure  3-6).  This approach is being used
to evaluate the effects of acidic  deposition on  element budgets.
Several studies have been underway since the early 1960s.  One of the
earliest studies and the  longest  continuous  record (1963-present) is

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3-18 |
1
1
Allochthonous Sources of Hydrogen Ion
A 1
precipitation J>°|| •
"^x^r^j
dry deposition 't^
drainage water £M
*i^r










% 1
|^
>-«. _
^*!
^YV^,

Hydrogen Ion Sources Hydrogen Ion Sinks

oxidation reduction
cation uptake anion uptake



pyrite oxidation oxide weathering
NH * uptake

Stream Exports
1 H* HCO3", OH - ligands, organic

Figure 3-6. Schematic representation of the hydrogen
(Driscoll 1980a).




anions
1
1
1
1
_
1
1
1
1
1
1
1
ion cycle 1
1
1

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                                                                  3-19
from Hubbard Brook, New Hampshire,  summarized  by Likens  et  al.
(1977a).
3.4.1   Element Budgets at Hubbard  Brook,  New Hampshire

The ionic composition of bulk  precipitation  at the Hubbard Brook
ecosystem is essentially characterized  by  acids,  such as  H2SC>4
and HNC>3.  In contrast, water  leaving the  system  is characterized
mainly by neutral salts, composed of Ca^+, Mg2+ and Na+ balanced in
solution by SO^" and, to a  lesser  extent, by chloride, nitrate, and
bicarbonate species.  The chemical  and  biological reactions of
hydrogen ion, nitrate, ammonium, and sulphate are very important in
driving displacement and weathering reactions.

Observed trends and annual ion budgets  for 11 years at Hubbard Brook
demonstrate the influence of atmospheric inputs on surface water
quality.  High rates of H+,  N03~, and S0^~  inputs were observed
throughout the period.  The  average annual weighted pH of
precipitation from 1964-65 through  1973-74 ranged between 4.03 and
4.21.  The lowest value recorded for a  storm at Hubbard Brook was pH
3.0 and the highest was 5.95.   During the  period  1969-1974 (the
latter being the last year of  the 1977  summary),  no weekly
precipitation average exceeded a pH of  5.0.   Fluctuations in hydrogen
ion deposition can be explained in  large part by  the fluctuation in
total precipitation.  Concentrations for SQ^~ and Nfy"1" varied from
year to year, but showed no  statistically  significant time-trends for
the period.  In contrast, annual weighted N03~ concentrations
were about 2.3-fold greater  in 1971-74  than  they  were in  1955-56
(Likens et al. 1977b).

From 1964 to 1970, there was a general  downward trend in  the
percentage sulphate contribution to the total anion equivalents
(Figure 3-7).  During the period 1970-77,  the rate of decline
decreased or perhaps the trend even reversed.  The proportion of
nitrate to the total anion equivalents  has increased throughout the
period.  Two conclusions were  drawn:  (1) nitric  acid was of
increasing importance in precipitation  at Hubbard Brook (Likens
et al. 1976), and (2) the average annual change in nitrate was
somewhat smaller after 1970, apparently due  to slower increases in
nitrate concentration relative to sulphate in precipitation.  The
proportion of hydrogen ion to  the total cations increased throughout
the period even though the total equivalent  concentration of cations
decreased (Likens et al. 1980).

The Hubbard Brook study site is an  isolated  headwater catchment.  As
a result, the influx of chemicals is limited principally  to
precipitation and dry deposition, and the  outflow to drainage waters.
Theoretically, differences between  annual input and output for a
given chemical indicate whether that constituent  is being accumulated
within the ecosystem, is being lost from the system,  or is simply
passing through the system.  Likens et  al. (1977b) were,  therefore,

-------
                                                                   3-20
    80
    70
«   60
c
Si
"5
.2   50
3
a
UJ

«   40
    30
S   20
    10
                                    i	I	l	(	i	i	i
     1964-65   66-67
68-69    70-71     72-73     74-75    76-77

          Year
  Figure 3-7.   Percent of ionic composition of precipitation for the
               Hubbard Brook Experimental Forest during 1964 to  1977,
               £M+ is sum of all cations (Likens et al. 1980).
 I
 I
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 1
 1
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1
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I

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                                                                  3-21
able to estimate with reasonable  accuracy  the  mean annual budgets for
most of the major ions  (Table  3-2).   Over  the  long term,  there was
considerable variation.  However,  calcium, magnesium,  potassium,
sodium, sulphate, aluminum,  and dissolved  silica budgets  indicated
net annual losses.  Net annual gains  of  ammonium,  hydrogen ion, and
phosphate occurred  in these  undisturbed, accreting watershed
ecosystems.  Nitrate and chloride  budgets  indicated a  net
accumulation in all but 3  of  the  11 years  of  study.

Overall, during 1963-74 there was  an  annual net  loss of  total
dissolved inorganic substances from the  experimental watersheds
amounting to 74.7 kg/ha. yr.  The  average net output of dissolved
inorganic substances minus dissolved  silica  (1963-1974) was
38.4 kg/ha. yr.  The smallest annual net  loss of  dissolved inorganic
substances (27.8 kg/ha, or 7.0 kg/ha  for total material minus
dissolved silica) occurred during  1964-65, the driest  year of the
study.  The largest net losses of  dissolved  inorganic  substances
occurred during the wettest  year,  1973-74  (139.7 kg/ha).

Likens et al. (1977b) also noted  the  complexity  of computation of the
long-term cationic  denudation  rate in the  Hubbard Brook ecosystem
because of the need to  consider accumulations  in living  and dead
biomass.  The net accretion  of biomass should  be viewed as a
long-term sink for  some of the nutrients supplied from the weathering
reactions.  The total amount of cations  sequestered by this means is
72.2 meq/m^.yr.  They concluded that:  (1) cations stored within
the biomass must be included in calculations of  contemporary
weathering ; ( 2) the rate of  storage is a consequence of  the current
state of forest succession and changes with  time;  and  (3) the
existence of the forest and  its state of development must be included
in geological estimates of weathering.

If this appraisal of the biological system at  Hubbard  Brook is
correct, the flux of cationic nutrients  being  diverted into biomass
accretion (72.2 meq/m^.yr) must be added to  that actually removed
from the system in  the  form  of dissolved load  (126.7 meq/m^.yr) and
particulate organic matter (1.0 meq/m^.yr).  Therefore,  the best
estimation of cationic denudation  (net loss  from ecosystem plus
long-term storage within the system)  at Hubbard  Brook  is  about
200
These long-term estimates  of  cationic  denudation at  Hubbard Brook
allow estimation of the relative importance  of  external  and internal
sources of H+ ions.  The external  supply  rate  is 100 meq/m^.yr
and, by difference, the internal source becomes 100  meq/m^.yr.
This suggests that under prevailing biological  and chemical
conditions (perhaps altered by  changes in atmospheric precipitation),
external and internal generation of H"1" ions  play nearly  equal roles
in driving the weathering  reactions at Hubbard  Brook (Figure 3-8).

-------
TABLE 3-2. ANNUAL BUDGETS OF BULK PRECIPITATION INPUTS AND STREAM-WATER
OUTPUTS OF DISSOLVED SUBSTANCES FOR UNDISTURBED WATERSHEDS W
THE HUBBARD BROOK EXPERIMENT FOREST (Likens et al. 1977b)
Substance
(kg/ha)
CALCIUM
1 nput
Output
Net
MAGNESIUM
Input
Output
Net
ALUM 1 NUM
Input
Output
Net
AMMON 1 UM
Input
Output
Net
HYDROGEN
1 nput
Output
Net
SULPHATE
Input
Output
Net
NITRATE
Input
Output
Net
BICARBONATEd
Input
Output
Net
1963 1964 1965 1966 1967 1968
to to to to to to
1964 1965 1966 1967 1968 1969

3.0 2.8 2.7 2.7 2.8 1.6
12.8 6.3 11.5 12.3 14.2 13.8
-9.8 -3.5 -8.8 -9.6 -11.4 -12.2

0.7 1.1 0.7 0.5 0.7 0.3
2.5 1.8 2.9 3.1 3.7 3.3
-1.8 -0.7 -2.2 -2.6 -3.0 -3.0

a a a a a a
1.6c 1.2 1.7 1.9 2.1 2.2
-1.6 -1.2 -1.7 -1.9 -2.1 -2.2

2.6° 2.1 2.6 2.4 3.2 3.1
0.27C 0.27 0.92 0.45 0.24 0.16
2.3 1.8 1.7 2.0 3.0 2.9

0.85C 0.76 0.85 1.05 0.96 0.85
0.08C 0.06C 0.05 0.07 0.06 0.09
0.77 0.70 0.80 0.98 0.90 0.76

33.7b 30.0 41.6 42.0 46.7 31.2
42. 7b 30.8 47.8 52.5 58.5 53.3
-9.0 -0.8 -6.2 -10.5 -11.8 -22.1

12.8° 6.7 17.4 19.9 22.3 15.3
6.7° 5.6 6.5 6.6 12.7 12.2
6.1 1.1 10.9 13.3 9.6 3.1

a a a a a a
6.2b 4.6b 6.2 9.4 9.6 7.0
-6.2 -4.6 -6.2 -9.4 -9.6 -7.0
1969 1970 1971
to to to
1970 1971 1972

2
16
-14

0
3
-3

a
2
-2

2
0
2

0
0
0

29
48
-18

14
29
-14

a

.3 1.
.7 13.
.4 -12.

.5 0.
.5 3.
.0 -2.

a
.2 1.
.2 -1.

.7 3.
.51 0.
.2 3.

.93 1.
.09 0.
.84 1.

.3 34.
.1 51.
.8 -16.

.9 21.
.6 24.
.7 -3.

a
6.0 7.
-6
.0 -7.

5 1
9 12
4 -11

5 0
1 2
6 -2

a
8C 1
8 -1

9 2
23 0
7 2

18 0
14 0
04 0

6 33
1 46
5 -13

6 21
9 18
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a
1b 6
1 -6

.2
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.4
.8
.4

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.7

.8
.05
.8

.97
.13
.84

.0
.8
.8

.4
.7
.7


.6b
.6
1972
to
1973

1.2
15.6
-14.4

0.5
3.3
-2.8

a
2.3C
-2.3

2.5
0.18
2.3

1.08
0.16
0.92

43.4
64.0
-20.6

26.3
19.2
7.1

a
9.0b
-9.0
1973
to
1974

2
21
-19

0
4
-4

a
3
-3

3
0
3

1
0
0

52
84
-31

30
34
-3

a
12
-12

.0
.7
.7

.4
.6
.2

.2C
.2

.7
.42
.3

.14
.20
.94

.8
.7
.9

.9
.8
.9


.5b
.5
3-22
ITHI N

1
1
1
Total Annual
1963-1974 mean •
kg/ha kg/ha •

23.8
151.2
-127.4

6.3
34.6
-28.3

a
21.9
-21.9

31.6
3.7
27.9

10.62
1.13
9.49

418.3
580.3
-162.0

209.5
177.5
32.0

a
84.2
-84.2

2.
13.
-11.

0.
3.
-2.

a
2.
-2.

2.
0.
2.

0.
0.
0.

38.
52.
-14.

19.
16.
2.

a
7.
-7.
a Not measured, but trace quantities.
b Calculated
value based on weighted average concentration
and on amount of precipitation or streamflow during the
c Calculated from weighted concentration for 1964-1966
Based on annual concentration of 0.50 mg/1 (Juang and
d Watershed

4 only.

during
years
when chemical
measurements
— ^
1
7 •
5
1
6
1 •
1

I
0
1
9
34 -
1

96 |
10 •
86
1
0
8 m
81

0 1
i •
9
1

£•
1
1
were made *
specific year.
times precipitation
Johnson 1967).








for 1963-1964.










1

1

-------
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1
1

1

1

1

1

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1

1

t


3-2:

HUBBARD BROOK HYDROGEN ION BUDGET ^

Allochthonous
Precipitation
Dry Deposition

^^^^f,
JnPUtS
+ 362 "M^
Ir 'Hi
	 — 	 n
Weathering Reactions Net Accumulation in Forest Floor and

Ca -1055
Mg - 288
Na - 252
K - 182
S + 25
Al - 211
Fe - 78
P + 83

TOTAL -1957




Stream pH (H*)
Stream Alkalinity (HCOp
Discrepancy in Charge Balance
Forest Biomass
Ca + 475
Mg + 74
Na + 7
K + 156
S - 125
Fe + 103
HQ-- 47
NH4++ 144
P - 90
+ 697


Stream
Exports
-100 '
+126
+ 26
_ (organic anions, hydroxide ligands)
1
•
1

1

SUMMARY
Hydrogen Ion Sources
Hydrogen Ion Sinks
Budget Discrepancy
Figure 3-8. Hydrogen ion budget (meq/m^


1


+ 2541
- 2428
+ 113
.yr) for Hubbard Brook
Experimental Forest (Driscoll and Likens in press).





-------
                                                                  3-24
3.4.2   Element Budgets in Canada
I
I
The calibrated watershed technique  for  measuring rates  of movement of         •
elements has also been used in Canada and  results  have  been                   •
summarized by Harvey et al. (1981):

    "Input-output budgets  (mass  balances)  for  major ions are being            •
     measured at a number  of  locations  in  Canada as described in
     Table 3-7  [Table 3-3  this report].   In  all cases,  mass balance           _
     measurements have excluded  possible contributions  via subsurface         •
     flow, although the evidence available for these lakes suggests
     that these contributions are negligible (Schultz 1951).  Net
     exports of Ca2+, Mg2+ and K1" are shown  in Table 3-8                      It
     [Table 3-4 this report]  for Canadian  watersheds, along with              9
     input of H"1" by precipitation.   Output of  HC03~ and input-
     output data for S042~, NH^+ and NC>3~  are  also included, where            •
     reported.  No Canadian information on inputs  and outputs of              •
     aluminum was found.   Nicolson  (1977)  reported only output of
     major ions from 12 watersheds  in the  Experimental Lakes Area,            _
     northwestern Ontario; input by precipitation to the nearby               •
     Rawson Lake watershed (Schindler et al. 1976) was  used to                ™
     calculate  a net export for  these 12 watersheds."


With one exception, Clear  Lake,  all of  the watersheds studied had a
net output of the major cations  (Ca2+ + Mg2+ + Na+ + K+).  The net            M
export of Ca2+  + Mg2+ dominated  the ion budgets particularly                  •
in the watersheds in British  Columbia which  contain some calcareous
till.  The study sites in  British Columbia received a larger amount
of precipitation (260 to 450  cm/yr) a factor which may increase the           •
export of cations.  Potassium export is low  in all cases reflecting           •
the biological  demand for  this element  in  the  watersheds.  In all
cases there is  a net accumulation of NH4+  +  N03~ in the                       •
watersheds.                                                                    |

The export of cations from ELA and  Rawson  Lake watersheds on the              ^
Precambrian shield in Western Ontario was  about 30-40% of the export          V
from the Hay Lake watersheds  in  the Muskoka-Haliburton area.  The             '
corresponding H"1" inputs were  5-10 times greater at Harp Lake, also
in Muskoka-Haliburton.                                                         I

More sulphate was exported from  the watersheds than entered via wet
or bulk deposition.  In some  cases  (Rawson Lake and Jamieson Creek)           •
the differences may be within experimental error, and in some cases           |
the input may be underestimated  due to  dry deposition and canopy
effects.                                                                       «
                                                                                I

                                                                                I

                                                                                I

-------
                                                                               3-25















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    "The mechanism for cation export  is  apparent  in some  cases.   At
     Carnation Creek, the  output  of HCO^"  is  substantial,  suggesting
     that carbonic acid  is  the  principal weathering agent  responsible
     for cation export.  At Jamieson  Creek,  the output of  cations
     greatly exceeds  the output of HCC>3~ and  supply of IT1", while
     at the Haney watersheds, the opposite situation is observed.  In
     view of these contradictory  observations,  the mechanisms for
     cation export in this  area is uncertain.   At the Experimental
     Lakes Area in northwestern Ontario  (including the Rawson Lake
     studies), the release  of cations  probably  is a result of
     carbonic acid weathering,  although  the H+  loading of
     7-10 meq/m .yr in precipitation  may account  for 20% of the  net
     cation export.   On  the other hand,  in southern Ontario where the
     cation export is ~3 times  greater than  in  northwestern Ontario,
     50% or more of the  cation  yield  probably results from input of
     H* in strong acid form.  Although the evidence is
     circumstantial,  it  appears likely that  the increased  H+ input
     of southern Ontario has resulted  in a two- to four-fold increase
     in net output of cations."
3.4.3   Effects of Forest Manipulation  or  Other  Land Use Practices on
        Watershed Outputs

Land use practices within watersheds  have  been suggested as an
influence on acidification  (Henderson et al.  1980;  Likens et al.
1978; Rosenqvist et al.  1980).   Henderson  et  al.  (1980)  have
summarized results from watersheds  at Hubbard Brook (New Hampshire),
Fernow (West Virginia),  and Coweeta (North Carolina) which were
experimentally manipulated  through  a  series of forest cutting
practices (Table 3-5).   The work was  designed to  estimate changes in
streamflow concentrations of  cations, particularly  the potential
effects of H+ concentrations.  At Hubbard  Brook,  after felling of
all vegetation and herbicide  treatments for three successive years,
nitrogen discharges into stream  flow  increased by 245.9  kg/ha.yr.
Export of dissolved Ca^+ and  K+  increased  by  65.2 and 28.7 kg/ha.yr
respectively compared to a  control  watershed  (Bormann et al. 1974).
Increased acidity from biomass decomposition  amounted to 69.9 x
10^ iJeq/ha.yr of H+.  This  additional acidity is  presumed to have
been a major contributor to the  accelerated loss  of cations from  the
soil, shown in Table 3-5.

Strip cutting of one-third  of the vegetation  at  a second Hubbard
Brook watershed produced significantly  less effect  on soil leaching
rates.  Organic matter decomposition  was about 5% of that of the
total vegetation removal (500 kg/ha.yr  versus 10,500 kg/ha.yr).
Subsequently, internal H+ production  was also less, as was
resultant cation leaching than in the deforestation experiment
discussed above (Likens  et  al. 1977a).

Commercial clear-cutting at the  Fernow  watershed  generated fewer  H+
equivalents possibly because  only economic biomass  was removed,

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                                                                  3-28
TABLE 3-5.   SUMMARY OF TOTAL CATION RELEASE,  HYDROGEN ION PRODUCTION,
             AND THE CATION RELEASE RATIO  FOR  THREE  MANIPULATED
             WATERSHED STUDIES  (Henderson  et al.  1980)

H+ produced
(eq/ha)
Hubbard Brook,
New Hampshire
Deforested 69,960
Strip-cut 8,400
Fernow,
West Virginia
Clear-cut 960
Fertilization 55,710
Coweeta,
North Carolina
Clear-cut and 360
cable-logged
Total cation
release
(eq/ha)


6,850
390


170
2,420


50

Cation release
ff*" produced
(eq/eq H+)


0.10
0.05


0.18
0.04


0.14

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                                                                  3-29
reducing overall decomposition  rates  and  resultant  H"1" formation
(Henderson et al. 1980).  The Coweeta clear-cut  and cable logging
experiments resulted  in  even less  production  of  H+  ions.   When the
Fernow watershed was  fertilized with  260  kg/ha  of urea,  a 10-fold
increase in stripping of  calcium ions occurred,  plus a 6-fold
increase in magnesium, a  50% increase in  potassium  leaching,  and a
3.6-fold increase in  sodium ion denudation (Henderson et  al.  1980.)

The possibility of changes in land  use  causing  acidification  of
surface waters, rather than atmospheric inputs  of acid,  has been
explored in great detail  by two recent  studies  in Norway.  Seip
(1980) concluded that, while land  use changes probably have
contributed to the acidification process  in some areas,  "there is no
reason to doubt that  the  increase  in  the  deposition of acidifying
components has played an  important  role in the  acidification  of
freshwater."  Drablos et  al. (1980) also  reviewed land use changes in
relation to lost fish populations  in  lakes and  could find no
relationship between  the  two.   The  greatest number  of lakes from
which fish populations have been lost occurred  in areas without
farming activity.  Although it  is  well  documented that land use
changes affect the quality of runoff,  including  pH, these reports
conclude that the large  scale acidification of  lakes in Scandinavia
is apparently not due to  land use  changes.

In Canada, all of the surface waters  which have  elevated  excess
sulphate occur only in areas which  have high  atmospheric  deposition
of sulphate (Figure 2-6b).  Land use  changes, such  as logging, have
taken place in many areas, including  those areas which do not have
excess sulphate in surface waters  (see  Section  3.6.1). All of the
surface waters sampled in Northeastern  North  America that have
experienced loss of alkalinity  also have  elevated excess  sulphate
concentrations.  In areas with  less acidic deposition, loss of
alkalinity in surface waters has not  been observed.  These
observations indicate that loss of  alkalinity from  surface waters is
associated with increased sulphates resulting from  atmospheric
deposition rather than land use changes.

Wright et al. (1980)  summarized their observations  as follows:
"Acidified lakes often barren of fish are found  in  southern Norway,
southern Sweden, southwestern Scotland, the Adirondack Mountains,
New York, and southeastern Ontario.   These areas have in  common
granitic or other highly  siliceous  types  of bedrock, soft- and
poorly-buffered surface waters  and  markedly acidic  precipitation
(average pH below 4.5)."

A recent USGS report  (Peters et al. 1981) provided  a 14-year  data
analysis of precipitation in New York state (nine stations) and
stream chemistry.  "Statistical analyses  of chemical data from
several streams throughout New  York yielded little  evidence of
temporal trends resulting from  acid precipitation,  except in  the
Adirondack mountains,  where the soils lack significant buffering
capacity.  In most areas  of the state,  chemical  contributions from

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                                                                  3-30
3.5.1   Mapping of Watershed  Sensitivity for Eastern North America
I
I
urbanization and farming, as well  as  the  neutralizing  effect  of
carbonate soils, conceal whatever  effects acid  precipitation  may have
on chemical quality of streams."   (Peters et  al.  1981)                         m

In summary, the experiments concerning  different  forest and
vegetation-removal practices showed wide  variation  in  the  short-term          —
(less than five years) patterns  of H* produced  and  cation  releases.           •
A survey of European information on land  use  changes  found no                 ™
evidence that land use changes had an important role  in acidification
of water or impact on fish populations.   Therefore, we  conclude that          ft
although land use changes can affect  the  quality  of runoff and loss           •
of alkalinity in surface waters, land use changes do  not appear to
have a major impact on alkalinity  nor pH  changes  in surface waters,
with the exception of some waters  affected by mine  drainage.
I
3.5   AQUATIC ECOSYSTEMS  SENSITIVE  TO  ACIDIC DEPOSITION                       I

The roles of soils, bedrock  and  vegetation  in regulating surface
water chemistry must be considered  when  assessing the  sensitivity of         II
aquatic ecosystems  to acidic deposition.  The geochemical properties          |
of a watershed provide the primary  controls  determining surface water
alkalinity.  Sensitivity  evaluations can be  based on parameters such          mt
as lake and stream  alkalinity  or calcite  saturation index.   These             •
parameters do not necessarily  reflect  the long term capacity of
watersheds to buffer or neutralize  acidic deposition.   Ideally,
aquatic and terrestrial data should be evaluated in combination.              •
Unfortunately, the  present data  base is  not  sufficient to do so for           ™
all of eastern North America.  Data on terrestrial systems
(especially soils and bedrock) are  more  readily available.                     •
Therefore, terrestrial data  have been  used  to identify areas likely           |
to contain potentially sensitive aquatic  ecosystems for all of
eastern North America.  The  mapping of such  areas is based  on an              M
estimation of the capacity or  potential  of  the terrestrial  system             •
within an area to reduce  the acidity of  incoming atmospheric
deposition.  To identify  aquatic regimes  already acidified  and those
most susceptible, in terms of  present  levels of acidic deposition, it         ft
will be necessary to compare terrestrial-based mapping with aquatic           •
chemistry data and  regional  deposition maps  of SO^" in
precipitation (Section 3.9).
I
Cowell et al.  (1981)  considered  a number  of  characteristics of
terrestrial  environments  to  be  essential  for the assessment of
aquatic sensitivity  (Table  3-6).   Important  factors include soil             il
chemistry, soil depth,  drainage,  landform relief,  vegetation type and        W
bedrock geology.  Each  of these  factors plays a significant role in
ameliorating the  effects  of  acidic deposition.  It is important to           m
evalute as many factors as  practical in order to derive an overall           •
assessment for any area.  Single factor assessments can be
                                                                              I

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                                                                  3-32
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misleading, especially in areas where  soil mineralogy  differs  from
underlying bedrock lithology  such  as glacially-derived soils  and old,          •
deeply weathered soils over limestone  (such  as  in  United  States,              •
south of the glacial limit).

In both the U.S. and Canadian mapping,  soils and bedrock  are  the              •
primary factors assessed.  It is assumed  that resultant lake  or               V
stream water chemistry will reflect the combined interaction  of the
varying soil and bedrock characteristics  on  acidic deposition.                 J|
Surface and shallow groundwater flow conditions are assumed to  best           m
characterize the surface water regime.  Groundwater residence  times
and deep groundwater circulation were  not considered.                          ^

Certain types of vegetation,  especially broad-leaved deciduous  trees,          ™
are capable of reducing acidity of intercepted  precipitation  (Fairfax
and Lepp 1975, 1976).  The nature  of chemical modifications by                 9
vegetation species, however,  is not yet fully understood.   Therefore,          •
the effect of vegetation type and  cover on aquatic system sensitivity
has not been included in this analysis.                                        •m

Lucas and Cowell (1982) have  mapped the potential  of soils  and
bedrock to reduce acidity of  atmospheric  deposition across  eastern            —
Canada (east of Manitoba).  A similar  study  has been carried  out by           I
Olson et al. (1982) for the eastern U.S.   The mapping  was  coordinated          ™
in order to produce a comparable basis  for evaluation. Although the
conceptual framework is similar, data  availability and quality  varied          B
considerably both between and within countries.                                0

The maps of eastern Canada and the eastern United  States  presented            •
here combine bedrock, soil and certain  other factors (Table 3-7) in           •
order to interpret the potential ability  of  terrestrial ecosystems to
reduce acidity.  A low potential implies  that acidic deposition could
reach aquatic systems with little  neutralization.   Many of  the  low            •
potential ecosystems are naturally acid and  may contribute  a  high             •
capability to acidify incoming precipitation because of organic
acids, especially in areas receiving low  inputs of mineral  acids.
High potential areas would generally be capable of reducing acidity
such that impacts to aquatic  systems would be minimal.

Specific factors used in the  mapping for  both Canada and  the  United           •
States are listed in Table 3-7.  The assessment of relative potential
to reduce acidity may be inferred  from Table 3-6.   The methodologies
for combining and weighting the variables shown in Table  3-7  are              •
discussed below.                                                               ™

The map of eastern Canada (Figure  3-9  in  map folio) is presented at           •
the compilation scale of 1:1,000,000.   The U.S. map (Figure 3-10 in           J|
map folio) is shown at 1:5,000,000.
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                                                                  3-33
TABLE 3-7.   TERRESTRIAL FACTORS AND ASSOCIATED DATA BASES UTILIZED
             FOR THE INTERPRETATION OF THE POTENTIAL TO REDUCE
             ACIDITY OF ATMOSPHERIC DEPOSITION (After Lucas and
             Cowell 1982; Olson et al. 1982)
            TERRESTRIAL FACTORS/SURROGATES
                             DATA SOURCES3
  EASTERN CANADA

  1)  Soil Chemistry
           Surrogates:
  i) Texture (sand, loam
     or clay) - Quebec,
     the Maritimes and
     Newfoundland/Labrador,
     northern Ontario

 ii) Depth to Carbonate
     (high, low or no
     lime) - Ontario

iii) Glacial Landforms -
     northwestern Ontario

 iv) Organic Soils (^50%
     of mapping unit)
  2)  Soil Depth - shallow (25 cm to 1 m)
                 - deep (>1 m)
  3)  Bedrock Geology - type


                      - % exposed (<25 cm deep)
Ecodistrict Data
Base (Environment
Canada
1981a, b, c)
Ontario Land
Inventory
(MNR 1977)

Pala and
Boissonneau 1979

Ecodistricts
(Environment
Canada 1981a,
b, c) and Ontario
Land Inventory
(MNR 1977)

Ecodistricts
(Environment
Canada 1981a,
b, c) and Ontario
Land Inventory
(MNR 1977)

Shilts et al.
1981

Ecodistricts
(Environment
Canada 1981a,
b, c) and
Ontario Land
Inventory
(MNR 1977)

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                                                                  3-34
TABLE 3-7.   CONTINUED
            TERRESTRIAL FACTORS/SURROGATES
  EASTERN UNITED STATES


  1)  Soil Chemistry
           i) mean soil order pH
              (in distilled water)
          ii) S04~ adsorption
              (assumed for Ultisols only)
  2)  Elevation - landform
                - 2000 ft a.s.l
  3)  Bedrock Geology - type
  4)  Land Use - urban areas
               - cultivated (managed) soils
DATA SOURCES3
Soil Map
(USGS 1970)
Johnson et al.
1980


Hammond's
Landform Map
(USGS 1970)
Topographic Map
(USGS 1970)


Hendrey et al.
1980; Norton  1982


1977 National
Resource
Inventory
(USDA 1978)


1978 Census of
Agriculture
(USDC 1979)
a  All U.S. data sources listed have  been  compiled within  the
   Geoecology Data Base (Olson et al.  1980).
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                                                                  3-35
3.5.1.1   Eastern Canada

The map of Eastern Canada  (Figure  3-9) was  prepared from several data
sources (Table 3-7).   Quebec,  the  Maritimes and  Newfoundland-
Labrador were interpreted  using  the  Ecodistrict  Data Base
(Environment Canada  1981 a,  b, c)  described in Cowell et al.  (1981)
and the bedrock sensitivity  evaluation of  Shilts et al.  (1981).   In
northeastern Ontario,  north  of 50°N  latitude,  Ecodistricts were  used
in combination with  the Ontario  bedrock  geology  maps (Ontario
Ministry of Natural  Resources, Maps  2198 and 2200).  In  northwestern
Ontario, the recent  physiographic  mapping  of Pala and Boissonneau
(1979), and bedrock  geology  mapping  (Ontario Ministry of Natural
Resources, Maps 2199 and 2201) provided  the basis for interpretations
north of 52°N.  Interpretations  for  the  area to  the south are based
on Shilts et al.  (1981) and the Ontario Land Inventory  (OLI) (OMNR
1977; also described in Richards et  al.  1979).  The OLI  was
originally generated at 1:250,000.   As much information  as possible
has been retained in the 1:1,000,000 scale  mapping presented  here.
This partially accounts for  the  apparent variation in map detail.

A cautionary point regarding the use of  the Ecodistrict  data  base in
Quebec, the Maritimes  and  Newfoundland-Labrador  must be  emphasized.
The Ecodistrict delineations are based on  a series of biophysical
factors including geology  and  soils.  However, the units are  not
based solely on these  two  factors.   In an  attempt to isolate  the
critical geological  factor in  sensitivity  assessment, the bedrock
sensitivity evaluation compiled  by Shilts  et al. (1981)  was
superimposed directly  on the Ecodistrict map south of 52°N latitude.
As no similar map is available for soils for eastern Canada and, with
the premise that the ecodistricts  delineate major soil
characteristics the  Ecodistrict  base is  assumed  as the soil base for
the combined map.  Because of  this assumption, for the resultant
subdivisions of ecodistricts,  the  soils  data represent the dominant
characteristics as described for the  original  ecodistrict and not the
more site specific combined  units.   However, the Shilts  et al. (1981)
interpretation was used primarily  to  improve the resolution in areas
where carbonate predominated or  where soils were thin and
discontinuous and the  bedrock  sensitivity was  most important  in  the
overall evaluation.

In assessing map units, each factor  in Table 3-7 is assigned  a high,
moderate or low potential  to reduce  acidity of atmospheric deposition
independently (except  percent  bedrock exposure).  Dominant factors
were then combined and weighted  in order to derive an overall rating
for the map units.   Subdominant  characteristics  were not considered.
Specific combinations  of the factors  mapped as high, low or moderate
potential for reducing acidity are identified  in Table 3-8.  This
table shows 74 classes (of which 65  actually occur) which have been
grouped into high, low and moderate  potentials to reduce acidity.  In
addition there are 10  classes  representing  terrain dominated  by
organic deposits for which no  specific interpretation has been made.

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                                                                                               3-36
I
TABLE 3-8.  TERRESTRIAL CHARACTERISTICS OF AREAS HAVING HIGH,  MODERATE AND LOW POTENTIAL  TO  REDUCE ACIDITY FOR
            EASTERN CANADA (after Lucas and Cowell  1982)
                                                                                                               I
TERRAIN DESCRIPTION
Polygon
Soil
Classification Depth
HIGH POTENTIAL Hla
TO REDUCE ACIDITY Hlb
Hie
H1d
Hie
Hlf
H1g
Hlh
Hli
H1J

Hlk
H2a
H2b
H3a
H3b
H3c
MODERATE POTENTIAL Mia
TO REDUCE ACIDITY Mlb
Mic
M1d
Mle
Mlf
Mlg
Mlh
Mil
Mlj
M1k
Mil
Mlm
Mln
Mlo
Mlp
M1q
Mir
Mis
Mlt

Mlu
Mlv


deep
deep
deep
deep
deep
deep
shal low
shal low
shal low
shal low

bare
shal low
shal low
deep
deep
deep
deep
deep
deep
deep
deep
deep
deep
deep
deep
deep
deep
deep
shal low
shal low
shal low
shal low
shal low
shal low
shal low
shal low

bare
bare


Soil Bedrock
Texture Lithology
clay
loam
sand
clay
loam
sand
clay
loam
sand
clay, loam
or sand

clay
clay
clay
clay
clay
clay
clay
loam
loam
sand
sand
clay
clay
loam
loam
sand
sand
clay
clay
loam
loam
sand
sand
clay, loam
or sand
clay, loam
or sand




Type 1
Type 1
Type 1
Type 1
Type 1
Type 1
Type 1
Type 1
Type 1
Type 1

Type 1
Type 2
Type 3
Type 2
Type 3
Type 4
Type 2
Type 3
Type 2
Type 3
Type 2
Type 3
Type 2
Type 3
Type 2
Type 3
Type 2
Type 3
Type 2
Type 3
Type 2
Type 3
Type 2
Type 3
Type 2
Type 3

Type 2
Type 3


% Bedrock
Outcropping
0-49
0-49
0-49
50-99
50-99
50-99
0-49
0-49
0-49
50-99

100
0-49
0-49
0-49
0-49
0-49
50-74
50-74
50-74
50-74
50-74
50-74
75-99
75-99
75-99
75-99
75-99
75-99
50-74
50-74
50-74
50-74
50-74
50-74
75-99
75-99

100
100


	 •
MAP AREA
•

Km
78,890
65,960
8,105
N/A
1,004
109
7,989
5,305
8,959
1,405

N/A
4,317
5,467
20,567
65,470
101,420
7,104
N/A
83
5,543
N/A
9,615
N/A
N/A
2,325
489
N/A
N/A
N/A
1,038
3,114
740
48
14,345
374
2,218

415
14


% of Eastern
Canada
2.51
2.10
0.26
N/A
0.03
<0.01
0.25
0.17
0.29
0.04

N/A
0.14
0.17
0.66
2.09
3.23
0.23
N/A
<0.01
0.18
N/A
0.31
N/A
N/A
0.07
0.02
N/A
N/A
N/A
0.03
0.10
0.02
<0.01
0.46
0.01
0.07

0.01
<0.01


_!
•









1

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|


1



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3-37
• TABLE 3-8. CONTINUED
	
1




MODERATE POTENTIAL
ITO REDUCE ACIDITY

1

ff




• LOW POTENTIAL
TO REDUCE ACIDITY

1



1

1
*

1
ORGANIC TERRAIN

1

1
1
TERRAIN DESCRIPTION

Polygon
Classification


M2a
M2b
M3
M4a
M4b
M5
M6a
M6b
M7a
M7b
M7c
Lla
Lib
L1c
Lid
Lie
L2a
L2b
L2c
L2d
L3
L4a
L4b
L4c

Ola
Olb
Olc
Old




Soil
Depth3


deep
shal low
shal low
shal low
shal low
shal low
shal low
shal low
deep
deep
deep
deep
deep
deep
shal low
bare
deep
deep
shal low
shal low
shal low
deep
deep
deep








Soil
Texture


clay
clay
loam
sand
sand
clay
loam
loam
loam
loam
loam
clay
loam
sand
clay, loam
or sand

loam
sand
loam
sand
sand
sand
sand
sand

organics
organics
organics
organics




Bedrock
Lithologyc


Type 4
Type 4
Type 4
Type 2
Type 3
Type 4
Type 2
Type 3
Type 2
Type 3
Type 4
Type 4
Type 4
Type 4
Type 4
Type 4
Type 4
Type 4
Type 4
Type 4
Type 4
Type 2
Type 3
Type 4

Type 1
Type 2
Type 3
Type 4




% Bedrock
Outcropping


50-74
50-74
0-49
0-49
0-49
0-49
0-49
0-49
0-49
0-49
0-49
75-99
75-99
75-99
75-99
100
50-74
50-74
50-74
50-74
0-49
0-49
0-49
0-49

0-50
0-50
0-50
0-50



MAP AREA


km


82
982
60,388
15,234
202,167
13,776
14,155
51,297
35,546
104,406
64,804

3,322
6,538
80,800
10,405
47,460
2,150
11,905
156,862
527,190
15,595
161,509
676,252

205,748
40,426
52,949
142,200




% of Eastern
Canada


< 0.01
0.03
1.93
0.49
6.44
0.44
0.45
1.64
1.13
3.33
2.07

0.11
0.21
2.58
0.33
1.51
0.07
0.38
5.00
16.80
0.50
5.15
21.55

6.56
1.29
1.70
4.53




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                                                                                                 3-38
TABLE 3-8.  CONTINUED
                                                                           I
                                                                           1
                                                                           I
TERRAIN DESCRIPTION
                                                                                                  MAP AREA
I
Polygon Soil Soil Bedrock
Classification Depth9 Texture Lithology0
ORGANIC TERRAIN6 02a
02b
02c
02d
03a
03b
03c
03d
organics
organics
organics
organics
organics
organics
organics
organics
Type 1
Type 2
Type 3
Type 4
Type 1
Type 2
Type 3
Type 4
% Bedrock
Outcropping
51-74
51-74
51-74
51-74
75-99
75-99
75-99
75-99
km
34
N/A
207
377
48
N/A
55
327
% of Eastern
Canada •
< 0.01
N/A
< 0.01
0.01
0.01
N/A
< 0.01
0.01






4
a  Soil depth is defined as follows:  deep    -  >1 m average soil thickness
                                      shallow -  25 cm -  1m average soil thickness
                                      bare    -  <25 cm average soil thickness


b  Soil texture is used to  interpret soil sensitivity for most of eastern Canada.   In Ontario  where depth to
   carbonate information is available, the following corresponding classes were used:
                                      clay    -  high or  very high  lime
                                      loam    -  moderate and low  lime
                                      sand    -  low base or no lime


c  Bedrock sensitivity classes were defined by Shilts et al . (1981) on the basis of  lithology.   Specifically:
                                      Type 1  -  Limestone, marble, dolomite
                                      Type 2  -  Carbonate-rich siliceous sedimentary:   shale,  limestone; non-
                                                 calcareous siliceous with carbonate  interbeds:   shale,  si
                                                 dolomite; quartzose sandstone with carbonates
                                      Type 3  -  Ultramafic rocks, serpentine, noncal careous  siliceous  sedimenta
                                                 rocks:   black shale, slate,  chert; gabbro, anorthosite:  gabbro
                                                 diorite; basaltic and associated sedimentary:  mafic volcanic
                                                 rocks .
                                      Type 4  -  Granite, gneiss,  quartzose sandstone, syenitic  and associated
                                                 a I kal ic  rocks.
^  Average bedrock outcropping within each map  unit  is  shown as  a  percent of  map  unit.


e  Organic materials are the dominant soil constituent  wherever  organics are  indicated.
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                                                                  3-39
These are areas of high natural  acidity  which contribute organic
acids to enclosing watersheds.

Percent bedrock exposure  and  soil  depth  were key parameters for
weighting the relative contribution  between bedrock type and soil
chemistry.  Generally, the  emphasis  was  on the bedrock capacity to
reduce acidity where bedrock  exposure  was  greater than 50% of an
area.  If soils were deep (greater than  1  m) and occurred in more
than 50% of the map unit, then soil  chemistry was emphasized.  Soil
and bedrock potentials to reduce acidity in map units having
combinations of shallow soils and  bedrock  exposures less than 75%
were either averaged or assigned the highest potential.  Soil
chemistry was interpreted using  texture  and depth to carbonate
because of the nature of  the  data  bases.  However, in comparing these
with the smaller-scale Soil Map  of Canada  (Clayton et al. 1977) there
appears to be a good correlation with  soil order.  Hence, sand or no
lime soils are dominantly acid Podzols (or "Rockland") and clay or
high lime soils are dominantly Luvisols  and Gleysols.  Loam or low
lime soils tend to be more  varied  including Podzolic, Luvisolic and
Brunisolic orders.

Map units identified as having a high  potential to neutralize acidic
deposition are predominantly  areas underlain by carbonate bedrock
(HI) or areas dominated by  deep  clay or  high lime soils (H3).  These
each cover approximately  6% (Table 3-8)  of the map area represented
in Figure 3-9.  The former  assumes at  least some interaction between
carbonate-rich bedrock and  precipitation prior to entering the
aquatic regime.  This is  probably  valid  for most of eastern Canada
where limestones have either  been  exposed  or buried under carbonate-
rich tills by the latest  glaciation.  In the Hudson Bay Lowland
(northernmost Ontario and part of  northwestern Quebec) organic
deposits blanket the carbonate-rich  substrate.  Although large
streams, rivers and lakes in  this  region intersect mineral soil,
smaller peatland lakes, ponds and  streams  have naturally soft waters
which developed as peat material accumulated over the carbonates.
All such organic terrains are considered separately for this reason.

The two dominant combinations of soil  and  bedrock identified as
having a moderate potential to reduce  acidity are shallow loam or low
lime soils overlying bedrock  of  moderate (M6) and deep loam or low
lime soils (M7).  Each of these  occupy approximately 7% of eastern
Canada.  The distribution of  all moderate  classes is highly variable
across eastern Canada.

All five combinations identified as  having a low potential are
recorded in eastern Canada.   In  Ontario  and Newfoundland-Labrador the
dominant class is deep sand (L4).   Shallow sands (L3) are frequently
found in the more northerly regions, notably in Quebec and Ontario.
These two classes are predominately  acid Podzols.  Areas of high
bedrock exposure (L2) are common to  shore  zones of lakes and northern
areas.

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                                                                  3-40
                                                                              1
                                                                              I
Major areas of organic soils overlying noncalcareous  bedrock (05b,
05c and 05d) are identified  in western New Brunswick,  southern
Labrador and Newfoundland and in  the west  central  portion of Quebec.          •
Large areas of peatland are  identified adjacent  to the Hudson Bay             |
Lowland in northwestern Ontario.   Throughout  central  and  western
Ontario are numerous  small pockets of organic soils.   These areas             M
are, to varying degrees, undergoing natural organic acidification and         V
hence already contribute low pH,  low bicarbonate waters to enclosed
watersheds.  It is not clear to what degree peatlands  and organic
groundwater are affected by, or in turn  modify,  incoming                       •
anthropogenic mineral acids.                                                   •
                                                                              I
3.5.1.2   Eastern United States

The potential for terrestrial  systems  to  reduce  acidity of  atmos-            _
pheric deposition was determined  by  combining  information on soil            M
chemistry, bedrock geology, terrain  characteristics,  and land use
(Table 3-7).  A map covering the  eastern  37  states  (Figure  3-10) was
produced at Oak Ridge National Laboratory to characterize the                •
relative potential for areas to  reduce acidity of  acidic deposition          m
prior to being transferred to  aquatic  systems.   The analysis utilized
available national resource inventories and  was  interpreted according        •
to the current understanding of mechanisms of  transport and                  •
alteration of acid inputs in terrestrial  systems (Seip 1980).
County-level data from the Geoecology  Data Base  (Olson et al. 1980)          H
were used in the analysis to provide a regional  perspective.  As more        •
detailed data or new studies are  completed,  the  resolution  or inter-         ™
pretation of the map may need  to  be  revised.

Initially, counties that were  predominantly  ( > 50%) urban or                 •
agricultural were excluded from  the  analysis.   Management and land
use practices (liming, fertilizing,  etc.) in these  areas would tend          A
to dominate modifications resulting  from  acidic  deposition.  The 1977        H
National Resource Inventory (USDA 1978) was  used to define  land in
urban built-up areas and transportation corridors.   The 1978 Census          _
of Agriculture (USDC 1979) provided  data  on  cropland.  This resulted         •
in 1,648 of the 2,660 counties in the  east being included in the             ™
analysis.  They contained predominantly forest,  range, or pasture.

Rapid surface runoff of precipitation  or  snowmelt  can preclude               9
significant interaction with soils or  bedrock.   Steep areas with
greater than 160 m of relief and  elevation greater than 600 m based          •
on Hammond's landform map (USGS  1970)  and a  general topographic map          •
(USGS 1970) were identified as areas in which  topography dominated
the movement of rainfall to streams  and lakes.

Counties covered by 50% or more  of soil types  with a surface pH of           ^
less than 5.0 were assigned a  low potential  to reduce the acidity of
incoming precipitation.  However, it should  be noted that these soils        •
are naturally acid and could contribute natural  acidity to  aquatic           |
ecosystems.  Criteria for natural acid generation in the soil are
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                                                                  3-41
lacking and thus it is not known how  significantly acidic deposition
adds to the natural acidification  in  areas  with low soil pH (see
Section 3.5.2).  Thus, the interpretation of  all areas having a low
potential to reduce acidity  as  being  highly sensitive ignores natural
acidity contributions.

Chemical and physical soil characteristics  employed in the analysis
represent average values for  the A horizon  (upper 20-25 cm) for the
82 great soil groups occurring  in  the eastern United States.   These
values were obtained from published literature (Klopatek et al.
1980).  The great soil groups were combined to estimate values for
the 195 soil mapping units identified (USGS 1970) in the east.
Although the exact proportions  of  great  soil  groups within map units
are not readily available, the  dominant  great soil group was  given a
weighting factor of 0.66 to  calculate average map unit values.
Proportions of soil mapping units  within counties were estimated from
the 1:7,500,000 scale soil map  of  the United  States (USGS 1970).

Sulphate adsorption capacity  of soils provides additional
neutralization of acidic water  infiltrating the soil.  Sulphate
adsorption prevents H+ transport and  can increase soil cation
exchange capacity (see Section  4.5 on soil  sensitivity mapping).
Ultisols generally have high  sulphate adsorption capacity, although
few studies have determined the current  status of adsorption  capacity
in existing Ultisols, such as occur extensively in the southern
United States (Johnson et al. 1980).   Counties containing 50% or more
Ultisols were identified on Figure 3-10  as  having high potential to
reduce acidity.

Bedrock influence was based on  the occurrence of type 1 (low to no
ability to neutralize acidic  inputs)  and type 2 (medium to low
ability to neutralize acidic  inputs)  bedrock  as defined and mapped by
Hendrey et al. (1980).  Counties having  50% or more area in type 1
and 2 were defined as having  low potential  to reduce the acidity of
acidic deposition which comes in contact with bedrock.  These are
also designated sensitive.  The remaining counties were generally
dominated by type 4 (greater  ability  to  neutralize acid inputs) with
a high potential to neutralize  acid water coming in contact with
bedrock.  Such areas are often  called insensitive to acid rain.

The influence of these factors  on  the ability of the watersheds to
neutralize acid inputs was evaluated  on  a county by county basis.
Although counties are generally uniform  in  size in the eastern United
States, some of the larger counties occur along the Canada-United
States border in Maine and Minnesota. For  each factor, 50% or
greater of land surface area  was used as dominance criterion  to
classify counties.  Therefore,  significant  areas can exist within
counties that differ from the final designated classification.  Thus,
Figure 3-10 displays the broad  regional  patterns but evaluation of an
individual county requires more detailed analysis to determine the
extent and coincidence of the various factors within that county.
The analysis identified the dominant  factor(s) in each county that

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                                                                  3-42
3.5.2   Aquatic - Terrestrial Relationships
                                                                               1
                                                                               I
would determine if a county had  relatively  low,  moderate or high
potential to reduce the acidity  of  acidic  deposition.   The moderate
class would both be between the  extremes in reducing acidity and also         B
may be more variable,  that is, within  a moderate county, there may be         I
both areas of low and  high of sensitivities.

Seven classes were used to describe the combinations that occurred            •
(Table 3-9) with the agricultural/urban areas  shown as blank on the
map (Figure 3-10).  The factors  in  each class  and the  assignment of           _
low, moderate or high  potential  are defined in Table 3-8.  Classes 3,         •
4 and 6 are combinations  of soils and  bedrock  having opposite                 ™
potentials for reducing acidity.  In these  areas, the  soil depth and
other terrain characteristics (such as glaciation or soil pans) will          tt
determine whether soil or bedrock properties dominate.  Class 3               •
consists of low pH soils  overlaying bedrock with high  ability to
neutralize acid.  In the  south these soils  are generally very thick           •
and bedrock would be an insignificant  factor.   However, in northern           •
glaciated areas, the thin, porous soils would  probably result in a
high potential to reduce  acidity of precipitation through the                 —
interaction with the bedrock.                                                  •
                                                                               I
The maps shown in Figures  3-9  and  3-10  identify areas of low,
moderate or high potential  to  ameliorate  the  impact of acidic                 •
deposition on aquatic regimes.  Map  units  having the lowest capacity          I
to reduce the acidity of atmospheric deposition should not be
interpreted as representing  the total land area with acidified lakes
and streams in eastern North America.  These  are the areas where              •
acidification would theoretically  be most  pronounced provided the             •
input of anthropogenic acids add  significantly to natural acid
production or, in the case  of  bedrock dominated systems, exceeded the
acid neutralizing capacity  of  the  strata.   In order to determine
which aquatic ecosystems are already acidified, detailed water
chemistry data are necessary (Section 3.6).   However, as noted                tm
earlier, soil and bedrock  information provides the best indication of         •
the long term capacity of  watersheds to buffer acidic deposition.
                                                                               I
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Many questions remain as to how  the  dilute  acid  in precipitation can          •
be transported through  terrestrial  systems  without being dominated by         ™
organic/soil buffering  mechanisms.   Current knowledge of terrestrial-
aquatic transport fail  to account mechanistically for the large
changes in surface water pH attributed  to acidic deposition.
However, lake and stream acidification  effects are observed in water-
sheds where soils are present  (Section  3.9).  These changes are               «
through mechanisms not  now fully understood.  Such mechanisms                 •
probably relate to rapid drainage through soil macropores as
represented by root  channels,  voids  surrounding  coarse fragments
(such as common in glacially-deposited  soils) and other routes.  Thus         •
at this stage sensitivity criteria  are  hypothetical (e.g., soil               •
texture).  The maps  presented  in this section should not be
                                                                               I

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                                                                  3-43
TABLE 3-9.   CHARACTERISTICS OF MAP CLASSES FOR THE  EASTERN  UNITED
             STATES AS TO THE POTENTIAL TO REDUCE  ACIDITY  OF ACIDIC
             DEPOSITION (Olson et al.  1982)
  Class   Potential to        No. of
         Reduce Acidity      Counties
               Characteristics
           Low



           Low



           Low-High



           Moderate




           High





           Moderate



           High
 72
 89
114
291
326
241
515
Steep slopes, high relief,
high elevation


Low soil pH, sensitive
bedrock


Low soil pH, nonsensitive
bedrock


Low soil pH, sensitive
bedrock, sulphate
adsorption


Low soil pH, nonsensitive
bedrock, sulphate
adsorption


High soil pH, sensitive
bedrock


High soil pH, nonsensitive
bedrock

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                                                                  3-44
I
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considered strictly as sensitivity maps.   They  are  objective
representations of soil and bedrock  characteristics as  provided by
available data bases.  Map units  are  identified by  their  "potentials"        B
to reduce acidity based on one  interpretation of the criteria.   The          II
criteria are plainly visible if anyone  should desire some other
interpretation or sensitivity assessment.   The  application of these          •
maps for surface water sensitivity interpretation can,  at present,           •
only be tested using emprically based surface water acidification
data (Section 3.9).
                                                                              •
Low pH soils (eastern U.S.) and acid  podzolic soils (eastern Canada)         •
are representative of much of the area  identified in Figures 3-9 and
3-10 as having the lowest potential  to  reduce the acidity of                 tt
rainfall.  According to Wiklander (1973/74)  as  reported in Seip              |
(1980) as soil pH decreases below 5.0 there  is  an increasing
probability that streams and lakes within  a  watershed will receive           H
acid and aluminum associated with anion inputs  from the terrestrial          •
systems due to increased acidic sulphate deposition. Because these
soils generally have low quantities  of  basic cations (e.g., Ca^+,            ^
Mg^+) a significant portion of  the increased cation concentration            •
required to balance the increased sulphate input must be  H+ and Al           •
(Johnson and Olson in press).  Because  these soils  are  naturally
acid, they are also the ones most likely to  contribute  natural                B
acidity to surface waters (Rosenqvist 1978). Such  soils  do indeed           0
have the lowest potential to reduce  acidity  of  rainfall,  but they
also have the potential to acidify incoming  rainfall in areas where          •
low acidic deposition occurs (Johnson 1981;  Johnson and Cole 1977).          •
Thus, the question of acidic deposition effect  is one of  quantity,
that is, to what extent does acidic  or  sulphate deposition via the
mobile anion mechanism described  by  Seip (1980) contribute to the            •
natural acidity of waters from  such  soils?                                   •

Aquatic ecosystems most sensitive to  acidification  and  Al mobility,          •
therefore, are those areas identified as having a limited ability to         J|
reduce acidity.  They may also  receive  significant  inputs of anthro-
pogenic acids.  What constitutes  a  "significant input"  can only be           •
determined at present by monitoring  surface  water chemistry in areas         •
undergoing acidification.  It should  then  be possible to  extrapolate
these results to other areas by comparing  watershed characteristics
such as bedrock, soils, proportion of open water to watershed area           •
and vegetation.  This would need  to  be  carried  out  at a more detailed        W
level than the present mapping.   However,  the maps  in Figures 3-9 and
3-10, in combination with acidic  deposition  maps, illustrate the
distribution of the areas within  which efforts  need to  be
concentrated in eastern North America.
I
Groundwaters and  surface waters  which cross  areas of differing               •
capacity to reduce acidity would reflect  the chemistry of the most
reactive bedrock  or  soils upstream from any  sample point (Hendrey
et al.  1980).  Thus, both local  and regional hydrological and hydro-         •
geological conditions  need to  be assessed when comparing measured            •
aquatic chemistry with potential of areas to reduce acidity.
                                                                              I

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                                                                  3-45
It is also important  to  consider  the  topographic  position of streams
and lakes within watersheds.   Generally,  the  most susceptible aquatic
resources are those in the  headwater  portion  of watersheds,  or in
small enclosed watersheds.  During  spring snowmelt runoff reaches
surface waters with little  or  no  contact  with soils or bedrock,
resulting in episodic pH declines.  This  effect may occur even in
watersheds that are not  very sensitive  to long-term acidification.
3.5«3   Geochemical Changes  Due  to  Acidic Precipitation

Nearly all precipitation  is  processed  terrestrially before becoming
surface water.  Thus,  changes  in soil  chemistry might be expected as
a result of atmospheric deposition  of  acids  and metals.  Many
geochemical changes in soils are difficult to  measure directly, due
to large reserves of elements, and  due to complex ecology.  However,
changes in outputs of  soil and groundwaters  from stressed systems may
be manifested as changes  in  surface water chemistry.   In dilute
waters such as found in the  Adirondacks and  New England, any change
should be readily observed,  if historical data cover  the time
interval of change.

Acidification rate (or lack  of)  is  in  part a function of relative
maturity of the water  in  question.  Low order  streams and small
headwater ponds will reveal  acidification effects before major
streams, rivers and lakes (Raines 1981b).   Johnson and Reynolds
(1977) examined the chemistry  of headwater streams in New Hampshire
and Vermont.  These streams  ranged  from pH 5.0 to 7.8.  Streams
situated in sensitive  bedrock  such  as  granite  or quartz monzonite
ranged from pH 5.0 to  6.8.   Total dissolved  solids were generally
very low (12-30 ppm),  lower  than TDS for many  waters  in areas that
are not experiencing acidic  precipitation.   Similar results are
reported for Hubbard Brook (Likens  et  al.  1977a).  The implication is
that cation denudation in New England  is relatively low,  in spite of
acidic precipitation (Johnson  et al. 1972,  1981).  Studies by
Schofield (1982) and Johnson et  al. (1972)  concur that it is not
possible to conclude that increases in weathering (or increases in
dissolved load) have occurred  in areas receiving acidic deposition.

While major cations are generally low  in sensitive terrain, trace
metals such as Zn, Mn, Al and Cu have  been shown to be elevated in
acidified systems (Norton et al.  1981b;  Schofield 1982).   This
increase is a function of the solubility relationships for the
metals, as well as atmospheric inputs  of heavy metals (Galloway
et al. 1980a).  Continued inputs  of acids  may  alter soil pH regimes,
and result in mobilization of metals into  ground- and surface-waters
(Burns et al.  1981; Johnston et  al. 1981; Kahl and Norton 1982).
Aluminum mobilization  may neutralize acids,  as suggested by
N.M. Johnson (1979), but  once mobilization has occurred,  Al species
may buffer acidic waters  at  low  pH  (about  pH 4.9), much like the
carbonate buffer system,  but at  a lower  pH.  Once acidified, recovery

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                                                                  3-46
of waters with high concentrations  of  Al may  be  hindered  by these Al
hydrolysis reactions.
3.6   ALTERATIONS  OF  SURFACE  WATER QUALITY
I
I
Atmospheric inputs of Pb and Zn  can  be  demonstrated in organic soils         |
in New England.  In Massachusetts, Siccama  et  al.  (1980)  report that
Pb is accumulating in the  forest floor  at a rate of 30 mg/m .yr.             •
No increase was reported for Zn,  but  Zn is  much more mobile than Pb.         I
Benninger et al. (1975) estimate that the retention time  for Pb at
Hubbard Brook Experimental Forest (HBEF) is nearly 5,000  years:  thus
Pb is largely being retained terrestrially.  Other studies  have              •
reported concentrations of Pb and Zn  above  background in  the                 •
northeast U.S. (Kahl and Norton  1982; Lazrus et al. 1970; Reiners et
al. 1975; Schlesinger and  Reiners 1974).  Hanson et al. (1982) found         tt
a gradient of Pb in sub-alpine litter,  suggesting  that Pb was more           |
concentrated in litter  (and therefore in precipitation) in  southwest
New England, than in northeast New England  or  the  Gaspe" Peninsula.           «
Concentrations of these metals may be hundreds of  times those found          •
in underlying inorganic soils (Kahl  and Norton 1982).

The study by Johnson and Reynolds (1977) did not reveal any markedly         •
acidic streams in New Hampshire  or Vermont  (low pH = 5.0).   Burns            •
et al. (1981) also report  nonacidic  headwater  streams in  New
Hampshire (mean pH 6.1).   However, they conclude that significant            •
acidification has occurred since the  1930s, based  on historical              jg
colorimetric data.  They report  that  their  colorimetry data agreed
with their pH meter data.  Regardless of the validity of  time trend          «
comparison, they also conclude that  alkalinity to  total base cation          •
ratios are 0.2-0.5 in New  England.  This indicates that some chemical
weathering is occurring through  the  reaction with strong  acids,
rather than by carbonic acid, with implications for surface                  B
alkalinities in the future.  Similar  findings  have been presented by         m
Cronan et al. (1978) for New Hampshire  sub-alpine  soils,  where
sulphuric acid, instead of carbonic  or organic acids, is  supplying           •
most of the hydrogen ion for weathering reactions.  The net result is        £
a replacement of HC03~  by  SOz^    as the dominant anion inwaters of the
Adirondacks and New England.  This replacement is  complete  in very           —
acidic waters, and may  be  used as an  estimate  of acidification when          •
only partial replacement by sulphate  has occurred  (Henriksen 1979).          ™
Schofield (1982) reports an apparent, although not significant,
increase in 80^2" in Adirondack  lakes during the past 15  years,              B
although the validity of the comparison between methods is  unknown.          V
I
The chemistry of  surface water  is  an integrative measure of
precipitation inputs  and watershed influences.  Altered precipitation        •
inputs may  cause  biogeochemical changes and account for differences          "
in regional water chemistry.  The  available data are discussed below
as three topics:   the present chemistry of  aquatic systems; evidence         H
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                                                                  3-47
of time-trends in water quality measures;  and  the patterns of
seasonal or episodic variations in  water  quality.
3.6.1   Present Chemistry  of  Aquatic  Systems

A decade of results  in  Scandinavia  indicates  that as lakes are
subjected to acidic  precipitation  cations  are mobilized and some of
the bicarbonate ions are replaced by  sulphate.   As a result,  the
normal relationship  between the  dominant  cations, calcium and
magnesium, and alkalinity  is  altered.   Although these lakes are not
necessarily acidic,  the alkalinity  will be  less than predicted, from
the sum of calcium plus magnesium  (Henriksen  1980).

The report by Harvey et al. (1981)  gives  a similar evaluation of lake
data for North America.  Their description  is as follows:

    "Comparable data for lakes on  the Canadian Shield are shown in
     Figure 4-3 [Figure 3-11  this report].  Lakes that can be
     considered unaffected by acidic  deposition include those in the
     Northwest Territories, probably  Labrador and Newfoundland, and
     northern Manitoba  and Saskatchewan.   These lakes have close to a
     1:1 relationship between [Ca2+ + Mg2+] and [HCC^"],  as do
     several lakes in calcareous pockets  in the Killarney area of
     Ontario.  [Ca2+ +  Mg2+]  may be overestimated for several
     of the Newfoundland and  Labrador lakes,  because the
     concentrations  are not corrected for  sea salt contributions.
     Many of the other  lakes, however, have a HC03~ deficiency
     relative to Ca2+ plus Mg2+; most of  the  Killarney lakes,
     including all the  La  Cloche Mountain  lakes ... almost all of the
     lakes within a  100 km radius of  Sudbury, Ontario, and all of the
     Muskoka-Haliburton lakes and Nova Scotia-New Brunswick lakes
     (although the latter  data were also not  corrected for sea salt
     contributions), have  HC03~ deficiencies.  The distance below
     the [solid] line in Figure  3-11  may be an indication of  the
     extent of acidification; lakes found  below zero alkalinity [the
     hatched line] are  considered to  be acidified.

     If the other major source of Ca2+ and  Mg2+ in lake water
     is weathering by strong  acids  in precipitation, and  if most of
     this acid is associated  with sulphate, then there should be a
     good relationship  between [S042~] and  [Ca2+ + Mg2+ - HC03~]
     on an equivalent basis.  This  relationship provides  an estimate
     of the Ca2+ and Mg2+  not derived from  carbonic acid  weathering.
     Data for Canadian  Shield lakes are shown in Figure 4-4
     [Figure 3-12 this  report];  the agreement between [S0^2~]
     and [Ca2+ + Mg2+ - HC03~] for  most lakes is very good although
     it can be argued that this may be expected, based on the
     principle of charge balance and  implies  no cause-effect
     relationship.  All of the lakes  in Nova  Scotia and New Brunswick
     have excess Ca2+ and  Mg2+,  suggesting  that Ca2+ and  Mg2+
     may be supplied in part  by sea salt	

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                                                                      3-48
  400
  300
  200
§  100
                                   D •   «
                                             •  MANITOBA, SASKATCHEWAN

                                             A  LA CLOCHE MT LAKES

                                             •  SUDBURY AREA

                                             x  NWT, LABRADOR, NFLD

                                             O  MARITIMES

                                             O  MUSKOKA-HALIBURTON, ONT

                                             ®  ELA

                                             ®  MALI BURTON

                                             ©  OTTAWA R. dromoge

                                             ©  UPPER GREAT LKS. dromog.
                                                                        I
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  -100
100      200     300
           Co2%Mg2*}
                                      400
                               500
600
Figure  3-11.
Total  concentration  of  calcium plus  magnesium with
respect  to alkalinity  for lakes  in Canada.  Average
concentrations for groups of lakes are shown as
letters.   Individual lake data are shown as symbols.
Maritime  lakes are not  corrected  for seasalt
contribution.  Solid line represents theoretical
relationship for lakes  unaffected  by acidic deposition
(see text for explanation and data sources).  The
scatter  of data is due  partly to  the various techniques
used to  measure alkalinity (modified from Harvey  et al.
1981).
                              I

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1
1
1
1
| 600
• 500
400
1 \m
1 i™
200
• 100

1
1
1
H Figur
1
1
1
3-49



/ • .
: •/.
; •••'/
• ^^
.* ; I? ' • MANITOBA, SASKATCHEWAN
I !• »'H-V '• • A LA CLOCHE MT LAKES
* '•/•:' . •
A • .. j& ' :.vr ' ' SUOBURY AREA
.^5® "•". •' * N.Wt, LABRADOR, NFLO.
ah ''Xv." "'" • D MAR1TIMES
**"y&' >^*'* '• * " ° MUSKOKA'HAI-I8URTON. ONT
~ ''/^ ' ' ' ' • ® ELA
„ / * * ® HALIBURTON
s O
~~* . / 9 OO @ OTTAWA R drainagt
/ <6 QcD D
B / ®< • ® UPPE" GREAT LKS drainage
"• /
/ » x
/ 1 1 1 1 1 1 1 1 1 1 1 1
100 200 300 400 500 600
[Co2** Mgz*-ALKALINITYj(/ieq/L)


e 3-12. [Ca2+ + Mg2+ - alkalinity] vs. [S042~] for lakes in
Canada. Solid line represents theoretical relationship
for [Ca2+ + Mg2+] not derived from carbonic acid
weathering reactions (modified from Harvey et al .
1981).



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                                                                  3-50
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     The fact that most lakes or  groups  of  lakes  have  reasonably
     close correspondence between [Ca2+  + Mg2+  -  HC03~]  and
     [S042~] supports the hypothesis  that the Ca2+ and Mg2+                    •
     content of lakes is not derived  from carbonic acid  weathering,            •
     but is related to the  input  of sulphate.   Because the other
     major strong acid anion, NOg", is a nutrient in lakes and                •
     streams, (i.e., is non-conservative),  it is  not possible  to              |
     incorporate it into a  more complete relationship."

In a study of the most recent available  data for  lakes in Quebec,              H
Bob§e et al. (1982) have shown that a similar relationship between            *
[Ca2+ + Mg2+] - [alkalinity] and  [SO^2"] exists on the southern
slope of the Canadian Shield in  Quebec.   Figure  3-13 shows  the                •
different hydrographic regions sampled  and  Figure 3-14 shows the              •
sulphate versus  [Ca] + [Mg] - alkalinity  relationship for six of the
regions.  The highest sulphate concentrations  and greatest  alkalinity         fl|
deficiencies were observed in the  southwest part of  the province              I
(Region 04).  The concentrations of  sulphate and the alkalinity
deficits decrease to the north and east.  In Region  10, sulphate              —
concentrations average about 30  yeq/L and the  alkalinity values were          •
equal to or slightly greater than  the calcium  plus magnesium values           ™
indicating no alkalinity deficit.  This  supports the hypothesis of
atmospherically  deposited sulphur  being a major  influence on lake             B
chemistry.                                                                     •

Current data on  pH, alkalinity,  sulphate, and  other  chemical                  M
variables are available for surface  waters  in  a  wide variety of               I
climatic, geological and biological  conditions in eastern North
America.  These  data give an idea  of the  current chemistry  of aquatic         _
systems, but do  not necessarily  indicate  how or  when that status was          •
achieved, or whether it is currently changing.   Some insight into             •
these questions  is given by comparisons  of  water quality data from
areas with quite different rates of  acidic  deposition.  This approach         I
was used by Thompson and Button  (1982)  for  lakes in  Canada  from ELA           •
(Experimental Lakes Area, Kenora,  Ontario)  eastward  to Labrador and
Newfoundland (Figure 3-15).  The formal names  of the lake regions,            m
data sources , and the range of latitude  and longitude including the           •
sampled lakes are shown on Table 3-10.  Concentrations of sulphate,
and of excess sulphate near the  coast,  were multiplied by the basin
runoff of water, obtained from hydrographic records  of the  basins or          •
were approximated from hydrographic  charts  (Fisheries and Environment         ™
Canada 1978) to  determine the sulphate  flux or specific yield of
sulphate for each basin in units of  mass  per unit area per year.              •
Lakes used for this comparison exclude  those where geological sources         |
and direct industrial or municipal discharges  of sulphur to the water
body were obvious.  Therefore, Thompson and Hutton (1982) assumed             «
that the primary source of the basin sulphate  yield  was atmospheric.          •
As a test of this assumption they  compared  the values of sulphate
flux with the estimated atmospheric  loading of sulphate in
                                                                               I

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                                                                     3-51
         HUDSON

         BAY
                                                        GULF   OF

                                                       ST  LAWRENCE
                          03


                       UNITED  STATES
ONTARIO
Figure  3-13.   Hydrographic Regions of Quebec  (Bobge et al. 1982).

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3-54
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                                                                  3-55
precipitation for the different areas studied.   The  estimated
atmospheric excess sulphate deposition  rates  in  precipitation  (flux
per unit area per year) in units comparable to the basin  specific
yield as well as the range of  estimated  deposition for  1977-80 were
obtained from measurements or  interpolation of measurements  from the
CANSAP precipitation network (Barrie and  Sirois  1982).  These  values
are shown on Figure 3-15 for direct comparison to the basin-specific
yield of surface waters.  Also shown on  Figure 3-16  are dry
deposition of sulphate calculated from measurements  of  sulphur oxides
in air at four Air Pollution Network (APN) stations  (ELA,  Long Point
on Lake Erie, Chalk River, Ontario and Kejimkujik National Park,  Nova
Scotia (Barrie 1982).

The agreement between the estimated deposition and basin  specific
yield of sulphate is generally good but  shows greater yield  than
deposition in the areas of highest yield  (i.e.,  the  region between
Thunder Bay, Ontario and Halifax, Nova  Scotia).  This deficiency of
sulphate measured in precipitation as compared to basin yield  of
sulphate may, at least in part, be due  to dry deposition  of  sulphate
and sulphur dioxide.  The dry  deposition  would be greater  in regions
nearer to or downwind from industrial sources.   There may  also be
some release of sulphate previously stored in the basin.
Contributions from geologic or other sources  cannot  be entirely
dismissed in all cases.  However, in these areas the evidence  is
strong that the atmospheric deposition of sulphate is the  primary
source of the basin yield of sulphate.

In the province of Quebec there exists a  strong  south to north
gradient of lake sulphate concentrations  as illustrated in
Figure 3-17 and Figure 3-14.   The data were obtained from  256  lakes
in the province.  The highest  observed  concentrations are  in the
southwest portion of the Province, and reach  180 yeq/L.  The
concentrations decrease gradually toward  the  north and  to  the  east to
values around 30 yeq/L.  More  than 80% of the lakes  have  sulphate
concentrations higher than 60  yeq/L (Bobee et al. 1982),  equivalent
to the upper background level  for lakes  on the Precambrian Shield
(Harvey et al. 1981).

Haines and Akielaszek (1982) reviewed available  data on surface water
pH distributions in sensitive  regions.   They  found that the  regions
receiving precipitation of lower pH had  higher percentages of  low  pH
lakes (Table 3-11).

A number of other studies have documented the present status of
surface water resources in regions of Canada and the United  States.
They are summarized in the following sections.

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3-57

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                                                                  3-58
TABLE 3-11.   REGIONAL WATER CHEMISTRY SURVEY RESULTS FOR  SURFACE
              WATER pH DISTRIBUTION (Raines and Akielaszek 1982)
LOCATION NUMBEI
OF LAKI
AND STRI
Areas
New England
West Sweden
West Sweden
South Sweden
South Norway
South Norway
Denmark
Scotland
Nova Scotia
Quebec
Central Ontario
La Cloche
Mountains,
Ontario
Sudbury, Ontario
Adirondack
Mountains ,
New York
I PERCENT IN pH RANGE
JO
5AMS <5 5-6
where Precipitation
226
314
15
51
155
719
14
72
21
25
26
152
150
849
Areas where
North Norway
Northwest
Wisconsin
North Minnesota
77
265
85
8
36
27
2
18
64
29
26
52
12
8
28
13
25
Precipitation
0
0
0
21
21
47
20
38
33
57
36
24
40
58
34
15
30
>6
Averages
71
43
27
78
44
3
14
38
24
48
34
38
72
45
Averages >
13
6
0
87
94
100
REFERENCE
pH 4.6
Haines and
Akielaszek 1982
Aimer et al. 1974
Dickson 1975
Malmer 1975
Wright et al. 1977
Wright and Snekvik
1978
Rebsdorf 1980
Wright et al. 1980
Watt et al. 1979
Jones et al. 1980
Scheider et al.
1979a
Beamish and Harvey
1972
Conroy et al. 1976
Pfeiffer and Festa
1980
pH 4.6
Wright and Gjessing
1976
Lillie and Mason
1980
Glass and Loucks
1980
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                                                                  3-59
3.6.1.1   Saskatchewan

Measurements of total alkalinity,  calcium, magnesium and  pH were
analyzed for some 300 lakes  in  Saskatchewan's  Precambrian Shield and
fringe Shield regions (Liaw  and Atton  1981).   Concentrations of
alkalinity in these lakes varied from  10  to  1740 yeq/L.   Forty-four
percent of the lakes surveyed had  alkalinities  of 200 yeq/L or less.

Measurements of lakewater pH, ranged from 5.6  to 8.2, and indicate
that, at present, Saskatchewan's Shield lakes  are circumneutral.
Lakes with pH values between 6.5 and 7.5  accounted for nearly 80% of
all lakes investigated.  Concentrations of calcium ranged from 7 to
630 yeq/L.  About 54% of the lakes  surveyed had calcium of 80 neq/L
or less, while 25% had between  80  and  160 yeq/L.  Concentrations of
magnesium varied from 0 to 130  yeq/L.  Approximately 65%  of the lakes
measured had magnesium concentrations  of  24 yeq/L or less, whereas
32% had between 24 and 36 yeq/L.   Concentrations of  calcium plus
magnesium showed a one-to-one relationship to  alkalinity  (Figure
3-18).  This relationship is expected  in  areas  where alkalinity
production is by bicarbonate weathering in the  absence of strong
acids.
3.6.1.2   Ontario

Alkalinity data for  2,624 lakes  in  Ontario  are  shown in Table 3-12
(OME  1982).  The categories  from 1  to  5  indicate decreasing
sensitivity to acid  deposition.   The 48% of  the  lakes  in categories 2
and 3 had some measurable alkalinity less than  200 yeq/L and may be
regarded as sensitive to acidic  deposition.   The spacial distribution
of the lakes sampled is  shown  in Figure  3-19.   In Precambrian areas,
up to 90% of the lakes are less  than 200 yeq/L.   Five  percent of the
lakes had alkalinity values  less than  zero,  i.e., acidified, these
lakes are located mainly in  the  Manitoulin  and  Sudbury areas which
have been subjected  to deposition from smelting  operations  in
Sudbury.  Scheider et al. (1981) indicate that  acidic  deposition to
the area is substantial.  Chan et al.  (1980)  concluded that much of
the deposition is due to long-range transport of acid.  The influence
of long-range transport  is relative to the  historic local emissions,
with respect to acidifying lakes, cannot  be  determined.

Data from 16 intensively studied lakes in Muskoka-Haliburton are
plotted in Figure 3-20.  The average epilimnetic summer pH  and the
lowest spring pH observed in the surface waters  are plotted against
the mean summer alkalinity values.  The  data  cover 4 years  (1976-
1980) .  Lakes with alkalinity  of less  than  40 yeq/L experienced pH
depressions in surface waters  to values  less  than 5.5.  A few streams
showed pH values below 4.0 in  some  cases  (Figure 3-21).   At Algoma,
spring pH values of  about 5.0  occur in the  surface waters of study
lakes with alkalinities  less than 40 yeq/L  (Scheider 1983).

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                                                                3-60
      1500-
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                y = -18.204 + 0.915x

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                        Calcium+ Magnesium (jjeq/L)
Figure 3-18.   Relationship between alkalinity and calcium + magnesium
              for northern Saskatchewan lakes.  Broken lines indicate
              95% confidence limits of predicted values (Liaw 1982).
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                                                                  3-62
                                                                 I
Figure 3-19.
Distribution of lakes sampled in Ontario Ministry  of
the Environment 1981 and 1982 surveys.  Numbers
indicate number of lakes sampled within each  grid  cell
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per Table 3-12.
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                  Minimum pH Observed in the Streams
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               Muskoka-Haliburton, 1976-80 (Scheider 1983).


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                                                                  3-65
3.6.1.3   Quebec

Vast areas of the Province  of  Quebec  are  composed of non-calcareous
lithology, and glacial  transport  of materials  has not provided
calcareous tills to modify  the  local  soil structures.  Only in the
marine sediments of the St.  Lawrence  Valley and calcareous lithology
of the Gaspe" region and a few  other areas are  sufficient buffering
materials found.  A few local  occurrences of more adequately buffered
waters are found in the Gatineau  Lakes, Lake St.  Jean,  Lake
Mistassini, and the Harricana  River in northwest  Quebec.

It is estimated that  the Province contains  greater than one million
lakes, the vast majority of  which have not  been surveyed.  Present
surveys have been limited to the  southern,  more accessible areas.
Examination of the alkalinity  and CSI values of the surface waters of
the surveyed area gives an  indication of  sensitivity of waters of
Quebec to acidification.

A distribution of calcite saturation  index  (Conroy et al. 1974) of
181 lakes surveyed during the  summer  of 1980 (Bobge et  al. 1982) is
illustrated in Figure 3-22.  Values lower than 3  are not very
sensitive (15% of the lakes  surveyed  have a value less  than 3.5).
Values between 3 and  5  are  potentially sensitive  (48% of the surveyed
lakes have a value between  3.5  and 5.5).  Values  higher than 5 are
extremely sensitive to  acidification  (37% of lakes of the shield have
a value higher than 5.5).   The  distribution of CSI of surveyed lakes
in Quebec, is illustrated in Figure 3-22.  It  is  evident that nearly
all waters, other than  the  St.  Lawrence Valley and the Gaspe" Regions
(Regions 01, 02 and 03, as  per  Figure 3-13), have CSI equal to or
greater than 3 and are,  therefore, sensitive to acidification.
Surveys of the lakes  of Laurentide and La Mauricie Parks appear to
indicate a greater sensitivity  than do lakes in the surrounding
regions.  This may be an actual indication  of  local differences in
terrain geochemistry, but is believed to  result from over-estimation
of alkalinity or pH in  the  older  measurements.  The actual
sensitivity of lakes  in Quebec  may, therefore, be even  greater than
indicated by the older  surveys  (Ahern and Leclerc 1981; Jones et al.
1980).

Bobe'e et al. (1982) have shown  that 19 of 20 of the lakes sampled on
the Precambrian Shield  in Quebec  south of 50°  latitude  have
alkalinities less than  200  yeq/L, and thus  are considered to be
sensitive to acidic deposition.   For  the  same  region, summer values
of pH were below 5.0  for 15% of these lakes, and  below 5.5 for 41%
(Figure 3-23).  The pH  frequency  distribution  has two modes:  one
between 5.0 and 5.5 and one  from  6.0  to 6.5.  In  a lake with only
carbonate species to buffer  the water, a  pH value of 5.5 indicates
that the lake can have  rather  large pH fluctuations.

    "The importance of  the  sulphate anion in the  lakes  of the
     Canadian Shield  (in Quebec)  appears  clear upon examination
     of the relationship between  bicarbonate and  sulphate.

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                                                                  3-68
3.6.1.4   Atlantic Provinces
I
I
     According to Dickson  (1975), this  ratio  should  greatly
     exceed one in lakes not  influenced by  (atmospheric)
     sulphates.  In the southern portion of the  Shield  region                 •
     (in Quebec), the  sulphate  ion  dominates  in  these  lakes.                   |
     For the entire area of the Shield  (in  Quebec),  84% of  the
     lakes have a HC03~/S042~" ratio less than one."                            •
     [Translated from  Bob€e et  al.  1982]  (See Table  3-13  and  Figure           I
     3-24.)                                                                    "
I

I
Except for isolated regions  of  calcareous  lithology,  mostly in
northern and eastern New Brunswick,  the  northern peninsula of
Newfoundland and all of Prince  Edward  Island,  the Atlantic provinces
have soils and bedrock that  provide  limited  acid neutralizing                 _
capacity.  Much of the area  is  of very complex geology which has been         •
indicated in the sensitivity maps (see Section 3.5).   However,
summaries of the surface water  chemistry by  Clair et  al.   (1982),
Wiltshire and Machell (1981), and Thompson et  al. (1980)  have shown           •
that large portions of these waters  are  very dilute and poorly                •
buffered.  Clair et al. (1982)  have  summarized the Atlantic Provinces
water chemistry in terms of  the Calcite  Saturation Index  (Kramer              •
1976).  CSI maps for New Brunswick,  P.E.I.,  Nova Scotia,  Island of            |
Newfoundland and Labrador are illustrated  in Figures  3-25, 3-26 and
3-27.  If CSI of 3 or greater is  taken as  an index of highly                  _
sensitive waters, it is evident that large portions of the surface            I
waters are sensitive to acidification.                                        *

The loss of alkalinity and consequent  decline  in pH of some lakes and         I
rivers of Nova Scotia have been well documented (see  Thompson et al.          m
[1980], Watt et al.  [1979],  Wiltshire  and  Machell [1981]).  Wiltshire
and Machell (1981) applied Henriksen's (1979)  comparative                     •
relationship to data from 16 lakes in  Nova Scotia and suggested that          |
acidification (loss of alkalinity) of  40 to  50 yeq/L  has  occurred
over the past two decades to 1979, which is  consistent with measured          _
pH declines.  Watt et al. (1979)  have  shown  similar  pH declines for           •
lakes near Halifax but attribute  this  decline  to sulphate deposition          ™
from local sources.  Some pH increases have  also been identified in
rivers of southwestern Newfoundland,  (Thompson et al. 1980).                  •
Thompson and Button  (1982) concluded that  lower levels of sulphate            •
deposition over Newfoundland and  Labrador  have apparently resulted in
only moderate alkalinity replacement.                                          •

Bogs are a common feature of the  Atlantic  provinces  and waters often
carry significant organic contents.  Although  there  is a need to more
clearly define the role of these  natural acids in determining the             •
acidity of waters and subsequent  influences  in metal  availability,            ^
ionic balances by Thompson (1982) for  a  number of these waters
suggest that the major acidity  is due  to inorganic ions.                       •
                                                                               I

                                                                               I

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                                                                   3-69
TABLE 3-13.
SOME STATISTICS ON THE RATIOS OF HC03/S042~
FOR WATERS OF QUEBEC DERIVED FROM LEGENDRE ET AL.
(1980), BY HYDROGRAPHIC REGION (see Figure 3-13).



VALUES OF
THE RATIO
0.6
0.6 - 1.2
1.2 - 1.8
1.8
TOTAL
LAKES NORTH OF THE ST. LAWRENCE RIVER
WEST EAST
HYDROGRAPHIC REGION
04 05 06 07
N %N %N %N %
24 21.5 5 8.6 3 50.0 9 64.3
41 36.6 15 25.9 1 16.7 3 21.4
19 17.0 14 24.1 1 16.7 2 14.3
28 25.0 24 41.4 1 16.6 0
112 100.0 58 100.0 6 100.0 14 100.0




VALUES OF
THE RATIO
0.6
0.6 - 1.2
1.2 - 1.8
1.8
TOTAL
LAKES SOUTH OF THE ST. LAWRENCE RIVER
WEST EAST
HYDROGRAPHIC REGION
03 02 01
N % N % N %
21 95.4 13 76.5 5 100.0
1 4.6 3 17.6
- - 0
1 5.9
22 100.0 17 100.0 5 100.0

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3-70
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                                                            3-72
DISTRIBUTION OF CALCITE

  SATURATION INDEX

         VALUES
 Figure 3-26.  Distribution of  calcite saturation index values for
              Newfoundland (modified from Clair et al. 1982).
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                                                          3-73
                                    DISTRIBUTION OF CALCITE

                                       SATURATION  INDEX

                                              VALUES
Figure 3-27.  Distribution of calcite saturation index values for
            Labrador  (modified from Glair et al.  1982).

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                                                                  3-74
3.6.1.5   United  States
                                                                              I
                                                                              I
                                                                              I
The national map of total alkalinity  of  surface  waters  by  Omernik and        •
Powers (1982) illustrates general patterns  of  surface water  sensi-           ™
tivity to acidic deposition  on  the  conterminous  United  States
(Figure 3-28 in map folio).  A  large  number  of regions  in  the  U.S.
have mean annual alkalinity  values  below 200 ueq/L in surface  waters.
In the portion of the country where continental  glaciation resulted
in high densities of natural lakes, these  low  alkalinity areas               M
comprise:  (1) much of New Hampshire  and  central and southern  Maine;          •
(2) the Adirondacks in northeast New  York;  and (3)  the  northeastern
tip of Minnesota and a portion  of northcentral Wisconsin.  An
analysis of 300 headwater lakes and streams  in six northern  New              V
England sites shows that alkalinity values  of  less  than 200  yeq/L            •
cover most of the regions examined, with widespread values <20 yeq/L
as shown in Figure 3-29 (Raines 1981b; Raines  and Akielaszek 1982).           •
In the West, streams and lakes  with average  alkalinity  values  below           |
200 yeq/L are generally found in the  higher  mountainous areas,
particularly the Cascade Range  of Oregon and Washington and  the              ^
Sierra Nevadas in California.                                                 I

Elsewhere in the United States, sensitive  surface waters are
primarily streams, small lakes  and  general  purpose  reservoirs.  For           I
these waters there are several  areas  of  low alkalinity  values:  (1) a        •
discontinuous region extending  from southeastern New York  to western
Pennsylvania and central West Virginia;  (2)  eastern North  Carolina;           •
(3) central South Carolina and  southeastern  Georgia; (4) an  area             |
centered on the southwestern end of the  Blue Ridge  Mountains;  (5) a
band extending from southeastern Louisiana  to northeastern Florida;           _
(6) southeastern Texas and westcentral Louisiana;  and (7)  smaller            I
areas in southern New Jersey, northwest  Alabama,  southern  Arkansas           *
and northern Louisiana, and  the Quachita Mountains  across  the
Oklahoma/Arkansas border.
                                                                              1
As indicated by the cautionary note  on  the  face  of  the  alkalinity
map, the "map is intended to provide a  synoptic  illustration  of  the          •
regional patterns of surface water alkalinity  in the  United  States.          •
As such, it affords a qualitative graphic overview  of the  sensitivity
of surface waters to acidification.  The map should not be used  for          _
making quantitative assessments  of the  extent  of alkalinity  or               I
sensitivity" (Omernik and Powers  1982).                                       '


3.6.2   Time Trends in Surface Water Chemistry                               |

Questions of past and potential  future  changes in surface  water               •
acidification are best answered  by detailed analysis  of available            I
long-term data.  Such studies also give an  indication of natural
trends or an anthropogenic effect.   Care must  be taken  in  any
historical studies, however, to  account for differences between  older        •
methods of measurement and current methods.  Precautions have been           "
taken in the following analyses  to correct  for methodological
                                                                              I

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                  3-75
<20/jeq/L


20-200 ^eq/L


>200 jueq/|_
  states

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                                                                  3-76
differences, but these corrections  add uncertainty  to  some  of  the
comparisons.
3.6.3.1   Time Trends  in Nova  Scotia  and  Newfoundland
I
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I
3.6.3   Time Trends in Representative Areas

Historic water quality data exist  for several  areas  in  eastern North         •
America.  The data must be verified  based  on  sampling and  analytical
methodologies before comparisons with modern measurements  can be
made.  Acidification represents a  loss  of  alkalinity, but  measure-           •
ments of alkalinity are sparse, and  therefore, most  time trend               |
comparisons have been restricted to  pH  changes.   The following
section will review time trends in pH measurements and  alkalinities          •
where available.                                                              •
I
Several rivers in Nova Scotia and Newfoundland  were  sampled  and
analyzed by Thomas (1960) during the  period  1954-55  in Newfoundland         flj
using carefully described analytical  methods.   Several of  the same          |
sample locations were continued under the  Environment  Canada,
National Water Quality monitoring program  in 1965.   This monitoring         w
on a monthly basis was continued through 1974 after  which  most              •
stations were reverted to seasonal  sampling.  Monthly  sampling was
reinstated for some  stations in 1979.  The methodologies are
described and data are archived in  the Environment Canada  National          I
Water Quality Data Archive, NAQUADAT.  pH  has been determined               •
potentiometrically throughout the period of  record.  Laboratory
samples from the early data of Thomas were stored  in soft  glass             •
sample bottles which may have caused  a small increase  in the                |
laboratory measured value of pH.  This factor would  be unimportant
for the field measured pH values.   Sulphate  was measured by  a               •
BaCl2 precipitation  gravemetric method prior to 1954.   Later                •
determinations were by the colourimetric procedure which was
automated in 1973.

This data set has been employed in  several studies to  analyze trends        »
and changes that may have occurred  in the  chemistry  of the waters
during the period of record.  Thompson et  al.  (1980) examined the pH        •
records for three rivers of Nova Scotia and  three  rivers of                  |
Newfoundland.  The pH values were accepted as  comparable and, while
statistical analysis was not undertaken, there  appears to  have been a       •
decrease in the discharge-weighted  mean pH of  the  Tusket,  Medway and        I
St. Mary's Rivers of Nova Scotia during the  period  1966 through 1974.
The one year of record 1954-55 indicates a discharge-weighted mean pH
greater than the following years of record.  The Isle  aux  Morts,            •
Garnish, and Rocky Rivers of Newfoundland  indicate minimum discharge-       •
weighted pH in 1972  or 1973 in the  period  of record  1966-1980 or
1981.  Values have increased since  that period.                             •
                                                                              I

                                                                              I

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                                                                  3-77
Glair and Whitfield  (1983) have  subjected  portions  of  the record of
several of these rivers  ta statistical  analysis,  where the record was
continuous and uniform.   They  classified  the  rivers by the CSI
sensitivity  index  (greater than  -3,  insensitive  and less than -3
sensitive).  Periods of  record were  limited to  1965-66 through
1978-79 and  some records  terminated  in  1973-74.   They  have reported
decreasing trends  for pH of  the  Medway, Isle  aux Morts,  and Rocky
Rivers and stationary records  for  the Piper's Hole, Lepreau and
Mersey.  Among the insensitive rivers,  all were  either stationary or
increasing in pH records.  Glair and Whitfield  (1983)  also analyzed
the trend of sulphate but did  not  apply a  correction for seasalt
contribution.  While some trends were reported,  they are likely to be
strongly influenced  by seasalt in  this marine coastal  environment and
cannot be interpreted as  trends  in excess  sulphate.

Watt et al.  (1983) has compared  the  major  ion concentrations
(corrected for seasalt)  for  several  Nova  Scotia  rivers for the
1954-55 through 1980-81  period using the  same data  set.   He has found
smaller values of  bicarbonate, greater  values of  sulphate and greater
hydrogen ion concentrations, all at  greater than  1% significance
level for the Roseway, Medway, Mersey,  and La Have  Rivers as shown in
Table 3-14 (from Watt et  al. 1983).  While caution  is  required in
interpreting SO^- trends due  to interference of  organic anions
in measurement procedures, the bicarbonate and hydrogen  ion
concentration trends are  not subject to such  caution.   Other major
ions did not show  significant  changes.  Farmer et al.  (1980), using
the same data base,  has  compared major  ion concentrations
(unweighted) for 1954-55 with  1978-79 for  the Mersey River.  The pH
has decreased from 5.8 (range  5.4  to 6.6)  in  1954-55 to  5.2 (range
4.9-5.4) in  1978-79 while sulphate has  increased  from  1.6 mg/L (range
0.1 to 3.0 mg/L) in  1954-55  to 3.3 mg/L (range  1.0  to  5.0 mg/L) in
1978-79.  Other rivers of Southwest  Nova  Scotia  examined by Farmer et
al. (1980) include the Tusket, Clyde, Roseway, Jordan, and Medway.
Decreased pH values were  observed  in all  these rivers.  pH of the La
Have River has changed little  over the  same time  period  "...
reflecting deposits  of sandstone in  this  area."

Farmer et al. (1980) have stressed that the Nova  Scotia  rivers having
the greatest pH change and the lowest pHs  in  1978-79 were also the
most highly  coloured.  Thus  the  contribution  of humic  and/or fulvic
acids to the total acidity may be  significant.  Extensive direct
measurements of the  organic  anion  concentration  have not been
reported.  Preliminary measurements  by Oliver and Slawych (1982) of
samples from the West, Medway  and  Mersey  Rivers  indicated an organic
acidity of 95, 94 and 53 yeq/L respectively as compared  to an
estimated precipitation  acidity  of 29 yeq/L.  Thompson (1982) has
observed that for the Roseway, Mersey and  Medway  rivers  while "their
pH's have been thought to be dominated by  naturally occurring organic
acids, their low pH's can be explained quite  well on the basis of
simple inorganic chemistry."  More direct  measurements of the organic
anion concentrations are needed  to define  the relative contributions
to these waters of very  low  total  ionic strength.

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                                                                      3-78
                                     Ion Concentrations
LeHave   1954-55  0.072  0.040   0.019   0.008   0.001   0.070   0.017   0.007

         1980-81  0.036  0.081   0.024   0.006   0.001   0.069   0.030   0.017
Average
 difference      -0.036 +0.039  +0.010  -0.004  +0.009  -0.012 +0.006 +0.009
Significance
 level           <0.001  <0.001   N.S.    N.S.   <0.001   N.S.    N.S.   <0.001
I
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TABLE 3-14.  MEAN CONCENTRATIONS (meq/L) OF IONS IN THE WATER OF FOUR NOVA
             SCOTIA RIVERS IN  1954-55 AND  1980-81.  AVERAGE DIFFERENCES           _
             WERE CALCULATED AS 1980-81 CONCENTRATION MINUS 1954-55.  THE         I
             SIGNIFICANCE LEVELS (EXCEPT H+) ARE FROM THREE-WAY VARIANCE          •
             ANALYSES.  THE S042~, Na+, K+, Ca+, AND Mg2+  IONS HAVE BEEN
             CORRECTED FOR SEASALT INFLUENCE (Watt et al.  1983)
I

I
River     Years   HCO^    So£~*  Na+     K+    H+     Ca2+   Mg2+    A13+           •



Roseway  1954-55  0.049  0.033  0.002  0.016  0.014   0.060  0.004   0.014          I

         1980-81  0.007  0.089  0.031  0.007  0.040   0.028  0.010   0.027


Medway   1954-55  0.055  0.031  0.016  0.006  0.001   0.047  0.016   0.007

         1980-81  0.013  0.059  0.018  0.005  0.005   0.045  0.017   0.014          I


Mersey   1954-55  0.044  0.023  0.014  0.008  0.002   0.045  0.010   0.009          •

         1980-81  0.022  0.053  0.017  0.005  0.006   0.031  0.012   0.016
 I

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* Caution  is  required  in  interpreting SO^   trends  due to the
  interference  of  organic anions  in  measurement  procedures.                        •
                                                                                   I

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                                                                  3-79
The time records of the median pH  and  excess  sulphate  discharge for
two rivers of Nova Scotia  (Medway  and  St.  Mary's)  and  for two rivers
of Newfoundland (Rocky and Isle  aux Morts)  are  shown in Figure 3-30.
The pH values are the median  value for the n  observations of the
calendar year.  Maximum and minimum pH observed are  also shown.
Excess sulphate (seasalt corrected) discharge calculated from the n
observations of sulphate concentration and  the  measured run off
(calculated as indicated on the  figure)  are also shown.  Figure 3-30
illustrates the difficulty in making statistical analysis of the
observations.  Record breaks  are present and  unevenly  spaced
observations render statistical  analysis to establish  trends over
time impossible.  Thus Clair  and Whitfield (1982)  could treat only
portions of the record.  Figure  3-30 may be examined to illustrate
the temporal variability of pH and excess  sulphate discharge which is
not revealed by the statistical  trend  analysis  or  the  changes between
two time periods as reported  by  Watt et al. (1983) or  Farmer et al.
(1980).  The dominant feature is the minimum  pH that occurs in the
1971-73 period.  Excess sulphate discharge  reaches a maximum for the
Newfoundland rivers during the same period.

Wiltshire and Machell (1981)  have  reported  on a re-survey of 16 lakes
in Nova Scotia and New Brunswick,  which had historical data going
back to the 1930s in some  cases.   Eleven of the lakes  are remote from
local sources in Halifax and  Saint John.  The data for 10 remote
lakes with the most reliable  historical information  are summarized in
Table 3-15.  Between 1950  and 1979 data indicate that  there has been
a decline in pH in all cases, most notably since the 1950s.  All but
one of the 10 lakes, however, still had  a  pH> 5.5  in 1979.

Calculated alkalinity changes (Table 3-15)  show declines ranging from
5.5 to 55 P eq/L.
3.6.3.2   Historical Trends  in Northern Wisconsin

Juday et al. (1935) described the  pH-C02  relationships of  lakes in
northeastern Wisconsin.  Between the  period  1925-41,  measurements
were made of pH, alkalinity  and conductivity in 518 lakes.   Historic
pH was measured colorimetrically between  1925 and 1932;  from 1932 to
1941 a quinhydrone electrode was used.  Two  groups  have  remeasured
pH, alkalinity and conductivity in separate  subsets of the  518 lakes
(Bowser et al. 1982; Eilers  et al.  1982).  The 53 lakes  sampled by
Bowser et al. (1982) ranged  from alkaline, mesotrophic lakes to
brown-water bogs to clear-water, oligotrophic lakes.   Multiple
historical measurements were available and modern-day sampling was
adjusted to a similar seasonal sampling period.   All  three  lake types
showed increases in pH, alkalinity, and conductivity  over  the 50-year
period.  Bowser et al. (1982) attributed  their results to:   (1) short
duration of acidification  of precipitation in Wisconsin;  (2) changes
in vegetation and shoreline  land use; and (3) the importance of
groundwater to many of the lakes.   Eilers et al.  (1982)  sampled 275
of the lakes surveyed by Birge and  Juday.  They selected  180 for
analysis and comparison with earlier  measurements.   They also found

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                                                                            3-80
   8.8-
X
a
                                                                        -100
                                i	1	1	1
                                                    i	1	1	1	1
               5  10  12  14  24  12   12  12  12   4
                                                         —•	Excess SO
       ST. MARY'S RIVER
               5  14  1 1   1 1  13  12   8   12  11   4   4  4   3   4  5  18
      1984/88    98  86  87  68  69  70  71  72  73  74  75  76  77  78  79  80  81
                                                       S  •
                                                       S  ?
                                                       CO  <
                                                      *p  J

                                                       71
                                                       ?  a
                                                       o  °-
                                                       S.  5
                                                                        -100
   6.6-
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a
                                                    9   9111   3  4
        ISLE AUX MORTS RIVER
—I	1	1	1	1	1	1	1	1	1	1  -  •
 10  12  13  12  12  13   11  11  10   12  10  10
        ROCKY RIVER
               66 66  67  68  69  70  71  72  73  74  75  76  77  78  79
                                                                              p
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                                                                 80  81
                                      Year
  Figure 3-30.   Annual changes in median pH and  mean discharge-
                  weighted  excess SO^" for the  St.  Mary's  and
                  Medway Rivers, Nova  Scotia, and  the Isle  aux Morts  and
                  Rocky Rivers, Newfoundland.  Data  are from the sources
                  indicated.   Upper and lower numbers shown represent
                  range of  values, (•) is median and n is  the number  of
                  samples for each year.
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                                                                  3-81
Figure 3-30.   CONTINUED


Data for Figure 3-30 were calculated according  to  following format:


1. Excess SO^2~ = Total S042~ -  0.14C1"  (both in mg/L)


2. Mean discharge-weighted excess  S042~  =  ^(Excess  S042~  times  Sample Date
                                             Discharge)	
                                            Z Sample Date  Discharge


3. Runoff = Mean Annual Discharge  (m-Vyr)  divided by drainage area (m2)
          = m/yr = m-Vm2.yr.


4. Runoff for Water Years 1954/07  -  1955/06 and  1955/07 - 1956/06 were
   calculated from mean monthly  discharges.  For the Mersey the long-term
   runoff times simple mean SO^2"  concentration was used.


5. Excess SO^2" (meq/m.yr) = Mean discharge-weighted excess
   SC>42~ times Runoff.


6. Chemical data are from NAQUADAT.  Discharge  data are from various
   reports of the Water Survey of  Canada,  Ottawa.

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3-82

1
•
1
TABLE 3-15. APPARENT CHANGES IN SUMMER pH VALUES IN LAKES IN NOVA SCOTIA AND SOUTHERN
NEW BRUNSWICK DURING THE PERIOD 1940-79 (Wiltshire



pH pH change
ca 1940a 1950sb 1979C pre-1950s post-1950s
Boarsback N.S. 4.7 4.7 4.4 .0 -.3
Jesse N.S. 6.5 6.5 5.8 .0 -.7
Lily N.S. 6.5 5.8 -.7
Kerr N.B. 6.8 6.6 6.0 -.2 -.6
Creasey N.B. 6.7 6.7 6.0 .0 -.7
Tedford N.S. 6.3 6.6 6.3 +.3 -.3
Sutherland N.S. 7.0 6.3 -.7
Gibson N.B. 7.0 6.7 6.4 -.3 -.3
Black Brook N.S. 6.8 6.4 -.4
Copper N.S. 7.3 7.0 -.3


a Data from Smith 1937a, 1937b, 1948, 1952, 1961.
k Data from Hayes and Anthony 1958.
c Wiltshire and Machell 1981.
^ Calculated by Liljestrand pers. comm. PCO~ assumed as 10~^
mean) with bicarbonate as major buffer.





and Machell 1981)

Calculated
alkalinity change
in yeq/L
pre-1950 post-1950
0 -20
0 -14
-14
-12 -16
0 -21
5.5 -5.5
-41
-25 -18
-20
-55





•5 atm. (a global






1



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*


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                                                                  3-83
that most lakes had increased in pH, alkalinity  and  conductivity.
The lowest pH values were  found in  lakes  having  no  inlet  or outlet
and no contact with groundwater (Eilers et  al.  1982;  Schnoor et al.
1982).
3.6.3.3   Historical Trends  in New York  State

Peters et al. (1981) analyzed precipitation  data  and  stream water
chemistry data from a nine-station monitoring  network in New York
State.  The data covered  the years 1965-78.  Sulphate concentration
in precipitation decreased 1-4%/yr, while N(>3~ increased by 4-13%
each year.  An increase in the total amount  of precipitation over the
period resulted in an increase in total  acid loading.  Variable
neutralization of hydrogen ion, perhaps  by particles  in dry depo-
sition, was suggested because the observed trends in  hydrogen ion
concentration do not correlate well with those for  sulphate or
nitrate.

In most areas of New York, urbanization, farming  and  carbonate soils
have masked any effects of increased acid loading.  For the East
Branch of the Sacandaga River in the Adirondacks, nitrate increased
0.004 meq/L.yr, while sulphate decreased 0.0041 meq/L.yr.   Sulphate
concentrations exceed bicarbonate for  the stream  indicating little
interaction with soils or ground water.  Consequently,  with the
increases in acid loadings in precipitation  over  the  period,
alkalinity has decreased  0.083 meq/L.yr  (Peters et  al.  1981).

In a survey designed to identify acidic  lakes  in  the  Adirondacks,
Schofield (1976c) sampled 214 high altitude  lakes (Figure 3-31).  A
complete set of chemical  analyses was  obtained, but no  internal
checks can be made on the data, because  sulphate  was  determined by
difference.  The pH range of sampled waters  was 4.3-7.4.  Fifty-two
percent were listed as pH <5.0; 7%, pH 5.5-6.0.  pH measurements were
made in the laboratory following aeration of the  sample.

Increased elevation and low  pH of ponds  and  lakes were  positively
correlated.  The combined influences of  heavier precipitation at
higher elevations, the smaller surface area  and watershed size which
characterizes most headwater ponds, the  prevalance  of granitic
bedrock and shallow soil deposits in the higher elevations,  and the
direct impingement of acidic cloud water are all  possible factors.
In addition, N.M. Johnson (1979) showed  that neutralization occurs as
contact time with the substrate increases, such as  occurs as water
flows downhill into progressively larger streams.

For a subset of 40 of these  214 high elevation lakes, historical data
on pH are available from  the 1930s (Schofield  1976c;  Figure 3-32).
These early pH values represent colorimetric measurements.   Several
authors (Norton et al. 1981a; Pfeiffer and Festa  1980;  Schofield
1982) have examined the agreement between the  two pH  methods.
Although certainly not exact, qualitative comparisons appear
appropriate.  For this subset of 40 lakes, in  1975, 19  lakes had pH

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                                                                   3-84
                                                      (Ouake
                                                      V placid
                                                   0  S  10 15  20
                                                               Km.
Figure 3-31.  Geographic distribution of pH levels  measured in
              Adirondack lakes higher than 610 metres  elevation,
              June  24-27, 1975 (Schofield 1976c).
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                                                                 3-85
                         20
                          10
                     W
                     o>
                    x.
                     
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                                                                  3-86
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below 5.0 and all of these  lakes had no  fish.   In  the 1930s,  only 3
lakes had values below 5.0  and  a total of  only 4 lakes  had  no fish
(Schofield 1976c).                                                             •

In a larger survey that  included Schofield's  1975  sites (Schofield
1976c), a 1980 report by the New York Department of  Environmental             —
Conservation (NYDEC) (Pfieffer  and Festa 1980)  reported that  264 of           •
849 (25%) lakes sampled  in  the  Adirondacks  had  a pH  <5.0.   The report         *
linked this acidity to fish losses in these lakes.   Since  publication
of this report, however, both the NYDEC  (1982)  and others  (Schofield          •
1982) have recognized that  many of the pH values reported  were too            9
low (due to problems with the pH meter).  Pfeiffer and  Festa  (1980)
also presented a comparison of  colorimetric pH measurements for the           •
1970s and 1930s for a set of 138 Adirondack lakes.   In  general,               •
historic pH readings were higher than the  comparable current
measurements.


3.6.3.4   pH Changes in  Maine and New England

Several synoptic studies have been done  for New England surface               |
waters.  Davis et al. (1978) studied 1936  pH readings taken from
1,368 Maine lakes during the period  1937-74 in  an  effort to see if            m
they could find pH decreases associated  with the acidic precipitation         •
of that area (4.4
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                                                                  3-87
lakes and then mean slopes from  1937  to  1974.   The  mean slopes were
added to obtain a total H"1" concentration change for the entire
period.  Given a starting pH of  6.89  (mean  of  123 values 1937-42),
the final (1974) pH would be 5.79,  an increase in acidity of 12.6
times.  Using a t-test, the authors also found that the mean annual
increase in H+ concentration based  on the mean slopes  for each year
was significantly different from zero change with p <0.0001.  The
authors noted, however, that this procedure more strongly weights
data pairs with long time separations, thus possibly invalidating the
use of a t-test.

The second procedure Davis et  al. (1978) used  was to average the 376
single slope values.  This gave  a mean of 0.115 peq/yr H+ concen-
tration change.  By t-test, this  mean is significantly different from
zero p <0.1, but not at p <0.05.  If  a disproportionately greater
decrease in pH occurred in the 1950s  (as the authors hypothesized),
this procedure would give greater weighting to the  more frequent data
pairs beginning about that time  and would thus overestimate total
change (Davis et al. 1978).

Procedure III the authors used was  to weight each data pair (H+
concentration) slope linearly  in  inverse proportion to the time
interval between each reading.   These weighted slopes  were then
averaged for each year that they  applied.   Using an initial pH of
6.89 in 1937, the authors noted  that  pH  decreases by 1950 to only
6.83.  By 1961, however, the pH  has decreased  to 5.91, so that 73% of
the increase in acidity has occurred  in  this latter time period.  The
authors believed that this 73% increase  in  acidity  was actually an
underestimate for this time period.

Davis et al. (1978) also discussed  some  alkalinity  data they had for
44 of the 258 lakes cited above.  These  data were from the period
1939-71, a total of 96 values  and 52  pairs.  No information was given
on the analytical method(s) used  to determine  alkalinity.  Applying
their Procedure I to those data,  they obtained a decrease of about
6.34 ppm (as CaCC^; from 11.82 to 5.48 ppm, typically; corresponding
to a decrease of 127 yeq/L from  236 to 109  yeq/L) over the period.
This was much less than expected  from pH changes from the same period
and observed relationships between pH and alkalinity.   The authors
noted that "the discrepancy may  be  due in large part to the
inadequate sampling and great  variance of the  alkalinity data,
including the fact that 67% of the  pairs had their  initial member in
1960 or later" (Davis et al. 1978).

The authors concluded from their  study that between the years 1937
and 1974 H* concentration in Maine  lakes increased  about 1.0 peq and
pH decreased from about 6.85 to  5.95.  Further, nearly three-quarters
of this change occurred in the 1950s.  "This is the first demonstra-
tion of a pH decrease due to acidic precipitation on a large region
of lowland lakes in the United States" (Davis  et al. 1978).

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                                                                  3-88
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I
Norton et al. (1981a) measured pH in  94 New England  lakes  (82 in
Maine, 8 in New Hampshire, 4 in Vermont) for  which historical pH
existed from the period  1939-46.  Eleven (12%)  of  these  lakes had            •
pH <5.0 in 1978-80.  The lakes sampled were small, oligotrophic-             •
mesotrophic, and located in forested  areas on noncalcareous  bedrock.
The recent sampling  (1978-80) was done during July-October but not  on        •
the same monthly dates as the historic sampling.   These  samples were          •
collected at 1 m depths, and the lakes were stratified at  the time  of
sampling.

The pH values of the recent samples were measured  in the field with          •
(1) a portable pH meter with combination electrode,  and  (2)  a Hellige
color comparitor.  Except for three spurious  cases of low pH lakes,          U
the authors found that "reasonable agreement  exists  for  these two            jj
methods, especially  at higher pHs"  (Norton et al.  1981a).

The authors presented their results in plots  of:   (1) old  colori-            •
metric pH vs. recent  colorimetric pH,  and (2)  recent  colorimetric pH
vs recent electrometric pH.  They concluded that their study
"confirms the results of Davis et al.  (1978)  regarding an overall            •
decrease in the pH of Maine lakes"  (Norton et al.  1981a).                     ™

Norvell and Frink (1975) found that the pH and  alkalinity  in                 :fl
sensitive (alkalinity <200 peq/L) lakes in Connecticut had not               |
changed significantly from 1937 to  1973.  Haines (1981a) reports a
number of Connecticut rivers as being  "sensitive", due to  alkalin-            M
ities <200 ueq/L, but pH in these waters is 6.4-7.1  except in smaller        •
lower order streams.  In Maine, the pH of major rivers is  greater
than 6.5, with the lowest values in eastern Maine  (the area with the
highest precipitation pH in New England) (Haines 198la).                     •

Haines and Akielaszek (1982) sampled  95 lakes for  which  there were
historical pH data from the 1930s to  the 1960s. Of  these, 36% either        •
had the same or higher pH while 64% were lower. For 56  lakes there          |
were also fixed end  point titrations  of alkalinity.   A comparison of
historical alkalinities  to modern values indicated that  30% of the            ^
lakes had increased  and 70% had decreased in  alkalinity.  The                •
historical alkalinity values averaged 166 yeq/L and  recent samples
68 peq/L.

                                                                              I
3.6.3.5   Time Trend in New Jersey

A.H. Johnson (1979)  described a 17-year decline in pH of headwater            |
streams in the New Jersey Pine Barrens which  drain relatively
undisturbed watersheds (Figure 3-33).  The trend is  statistically            _
significant and has  amounted to approximately 0.4  pH units over the          •
period.  In the sandy soils of this region, relatively little                "
neutralization of acid inputs occurs  by ion exchange or  mineral
weathering as precipitation moves through the soil.   The low level  of        H
neutralization is evidenced by the  low pH of  shallow groundwater,            |
averaging 4.3 for 78 samples in 1978  through  1979.  The  great
                                                                              I

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                                                                 3-89
       6
°- 6



  5
          OYSTER CREEK
                             O
                              O
                                       o
          MCDONALDS BRANCH
O
              1960
                                 1970
                       1980
Figure 3-33.
         New Jersey stream pH, 1958-1979,  Oyster Creek  and
         McDonalds Branch.  Closed circles represent  samples  in
         which anion and cation equivalents balanced, and
         calculated and measured specific  conductances  were
         equal.  Open circles are samples  for  which the chemical
         analyses were incomplete, or for  which discrepancies  in
         anion and cation and conductivity balances could not  be
         attributed to errors in pH.   The  closed triangle
         represents the average pH determined  in a  branch of
         Oyster Creek in a 1963 study.   Open triangles  are
         monthly means of pH data collected weekly  from May  1978
         to January 1979 during a University of Pennsylvania
         trace metal study (A.H. Johnson 1979).

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                                                                  3-90
variability in pH values of streams in  1978-79  is  thought  to  be  due
to storm events.
3.6.4   Paleolimnological Evidence for Recent Acidification and
        Metal Deposition
                                                                             I
                                                                             I
Some precipitation pH data suggest a  trend  toward  lower  pH values  in
southern New Jersey (A.H. Johnson 1979).  Precipitation  samples,
collected at several sites in  the Mullica and Cedar  Creek  basins  in         _
1970 through 1972, had an average pH  of 4.4.  Samples  collected near        •
Oyster Creek for seven months  in 1972 had an average pH  of 4.25.             *
From May 1978 to April 1979, the average pH of weekly  precipitation
samples at McDonalds Branch was 3.9.                                         •
                                                                             I
To supplement the sparse information  from  long  term  records  on water        _
quality in eastern North America alternative  techniques  have been           •
developed to define time trends related  to  surface water acidifi-           *
cation.

Paleolimnological analyses of  lake  sediments  have traditionally been        •
used to reconstruct many aspects of the  evolution of lake/drainage
basin ecosystems including terrestrial and  aquatic vegetational             M
succession (Bradstreet et al.  1975),  fire  history (Patterson 1977),          •
trophic status (Davis and Norton 1978; Stockner and  Benson 1967) and
even the occurrence of blight  or disease (Bradstreet and Davis 1975).        ^
Long-term changes in meteorology, morphology  of the  lake basins, soil        I
development, land use, or surface water  chemistry can be partially           *
determined from the sediment record.
                                                                             I
Both chemical and biological records are  left  in  the  sediment  record.
By studying modern biota in relation to modern water  quality for many
lakes, changes in ecosystems which have taken  place over  time  can be        •
reconstructed for water quality  parameters,  for example,  pH (Davis          •
and Berge 1980; Davis et al. 1980, 1982;  Renberg  and  Hellberg  1982).
Normally, measurable changes in  natural acidity are on  the  order of          ^
centuries and are accompanied by changes  in  other sediment  character-        •
istics.  Land use changes such as logging followed by reforestation          •
can bring about perturbations in pH of surface waters (both increases
and decreases) with a general return to equilibrium in  10 to perhaps        •
as much as 50 years (Likens et al. 1978;  Pierce et al.  1972).                |

Davis and Berge (1980) and Davis et al. (1980,  1982)  have demon-            M
strated, using fossil diatom data, pH declines in the last  30-70            •
years from pH values of greater  than 5.5  to  values less than 5 in
lakes in Norway with relatively  undisturbed  drainage  basins.  The
present pH of these lakes is too low to be explained  by the concen-          fl
trations of naturally occurring  organic acids.  Sulphate  is the             •
dominant anion and is apparently atmospheric in origin  (Wright and
Henriksen 1978).                                                             •
                                                                             I

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                                                                  3-91
Norton et al. (1981b), Davis  et  al.  (1982),  Evans  and Dillon (1982),
Dickson (1980), and others  have  demonstrated that  heavy metal
(especially Pb, Zn, and Cu) deposition  rates started increasing over
100 years ago in eastern North America  and  Scandinavia indicating
polluted air masses existed in the  late 1800s.   Cores from Swedish
Lapland (Davis et  al.  1982) do not  show these increases.  There, the
pH of precipitation is approximately 5.0.   By inference,
precipitation in eastern North America  was  probably somewhat
acidified by the late  1800s.  No change in  the  biology, defined from
the sediment cores is  observable until  at  least the early 1900s.
Thus biological effects appear to lag behind definable chemical
changes (Brakke et al. 1982;  Davis  et al.  1982).

As the acidity of  precipitation  increases,  leaching of Zn,  Cu,  Ca,  Mg
and Mn from organic matter  and soils of the terrestrial ecosystem
also increase.  At near neutral  surface water pH (greater than
pH 5.5), Zn and Cu from the terrestrial leaching processes  are
accumulated in the sediments.  However,  as  surface waters become more
acidic, Zn and Cu  from the  watershed remain in the water column to be
exported from the  lake.  As a result, acidification of surface waters
will decrease sedimentation of Zn and Cu.   Lead,  on the other hand,
accumulates in sediments independently  of  pH (Davis et al.  1982).

Calcium, Mg and Mn also decline  in  lake sediments  as acidity
increases for two  reasons.  Firstly,  as a  result  of acidic  deposition
falling on the watershed, terrestrial detritus  becomes depleted of
Ca, Mg, and Mn prior  to entry into  the  aquatic  ecosystem and
incorporation into the sediments.   Secondly,  acidified waters prevent
these metals from  being resorbed to  sediment organic matter and, like
Zn and Cu, are exported from  the lake system (Norton et al. 1981b).

Experiments on lake sediment  microcosms (Kahl et  al. 1982)  indicate
that if lake water pH  is increased,  the sediments  absorb Ca, Mg, Mn,
and Zn from the water  column  at  a rate  which would enrich the
sediments.  The observations  and information from  field studies
suggest that acidification  strips cations  from  terrestrial  detritus
and prevents them  from resorbing onto the  detritus (Dickson 1980;
Kahl et al. 1982;  Norton et al.  1980).   Norton  et  al. (1980) showed
that the chemistry of  soil  organic  matter  in New England, New
Brunswick, and Quebec  is partly  controlled  by atmospheric deposition
of acids and metals.   They  found decreased  Zn,  Mn, Ca, and  Mg in
regions receiving  high H+ loading.

Cores from acidic  clear water lakes  in  New  England (pH less than 5.5)
with undisturbed drainage basins (5  of  the  30 lake samples  taken over
at least the last  50 years) show declines  in sediment concentrations
of Zn, Ca, Mg, and Mn  starting as early as  about 1880 suggesting
increased leaching of  sediment detritus prior to  entry into the lakes
(Davis et al. 1982; Kahl et al.  1982) or reduced  sedimentation rate.
All acidified lakes in Norway and New England with pH less  than 5.0
have shown declines in Zn and Cu in  recent  sediment.  Lead, on the
other hand, is not released from surficial  sediments unless the pH is
less than 3.0 (Davis et al. 1982).

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                                                                  3-92
                                                                              I
                                                                              I
Measurement of atmospheric loadings via  both wet  and  dry  deposition
techniques is plagued by a variety of  uncertainties  (Section 2.2.3).
The lake sediments integrate materials deposited  directly on the lake        flj
surface from the atmosphere with  elements  leached from the terres-           |
trial watershed.  Increased mobilization of metals  from watersheds
during hydrologic events when  pH  is depressed  has been discussed             •
(Section 3.2.4).  The calibrated  watershed approach  to measuring             •
deposition is ineffective for  trace metals because metal  levels found
in lake and stream water are often below analytical  detection limits
usually employed.  Trace metals are rapidly removed  from  the water           •
column in most lakes (residence times  are  typically  of the order of          ™
days), and stored in the sediment.  Calculation  of metal  loadings to
lakes may sometimes be derived from information  collected from the           M
lake's sediments.  Profiles of lead concentration in four sediment           |
cores from Jerry Lake, Ontario are shown in Figure  3-34.

Dillon and Evans (1982) demonstrated that  input  of  lead from                 •
anthropogenic sources to eight lakes in  southern Ontario  resulted
only from atmospheric deposition  directly  on  the lakes' surfaces;
that is, deposition on the lakes' watersheds was  effectively retained        •
in the watersheds.  The whole-lake lead  burdens  estimate  the total           •
atmospheric deposition of lead during  the  period when anthropogenic
emissions have existed.  Regional anthropogenic  lead burdens measured        •
for Muskoka-Haliburton, Ontario (Dillon  and Evans 1982) and a remote          ||
northern site, Schefferville,  Quebec (Rigler  1981)  are 680 (range
610-770) mg/m^ and 37 (range 31-59) mg/m^, respectively.                      •


3.6.5   Seasonal and Episodic  pH  Depression
                                                                              I
Although survey data, both current and historical,  can  be  used to
document long-term trends in  a  synoptic  sense,  the  samples usually
represent one or a few measurements  at any  one  location and are often
collected during the summer.  This limited  sampling period provides
no record of pH and other chemical changes  which  take place in
relation to seasonal cycles or  major weather  events.   Individual pH          _
values during the summer do not  reflect  these cyclic and episodic            •
aspects of the loading/episodic response relationship.   If short-term        *
changes in water chemistry coincide  with sensitive  periods in the
life cycles of fish (e.g., spawning  and  hatching),  significant               I
mortality and reduced reproduction can occur.   The  following data            m
describe recent results on episodic  pH declines;  the extent to which
these phenomena occurred in the  past is  not known.                            ••


3.6.6    Seasonal pH Depression in Northern Minnesota                         _

                                                                              I
Siegel (1981) reported on the effect of  snowmelt  on Filson Creek and         ™
Omaday Lake in northeastern Minnesota.   He  found  concentrations of
sulphate increased in Filson  Creek and Omaday Lake  during  snowmelt           B
from less than 2 to 12 mg/L in  1977  and  from  less than  2 to 4 mg/L in        |
1979.  During snowmelt, pH decreased from 6.6 to  5.5 in 1979.
                                                                              I

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    300
    250
    200
T3

D)
*«,
O)
c
O
0)
O
c
O
O
.a
a.
150
100
     50
                Jerry Lake Sediment Cores 1979
                                                                3-93





                                                  LAKE DEPTH AT CORE SITE


                                                       	 11.0 m

                                                       	20.2 m

                                                       	17.3 m

                                                       	32.3 m
       0.0
   Figure 3-34.
                         0.8                    1.6

                                CDWA (g/cm2)


             Profiles of the lead concentration in four sediment
             cores from Jerry Lake, Muskoka-Haliburton.  Depth
             within core is expressed as cumulative dry weight per
             unit area (CDWA) (modified from Dillon and Evans
             1981).
2.4

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                                                                  3-94
3.6.8    pH Depression  During  Flushing Events in West Virginia
                                                                              I
                                                                              I
Alkalinity and concentrations of  total  calcium,  magnesium,  and sodium
in the creek during snowmelt reflect  the  simple  dilution of stream-
flow with more dilute precipitation.  Depression of  pH values to less        •
than about 5.7 indicate  that base  flow  (pH~6.5) has been diluted            •
with meltwater that contains some  mineral  acids.
                                                                              I
3.6.7    pH Declines During  Spring  Runoff  in  Ontario and Quebec

Detailed surface water chemistry  studies have  been conducted in lakes        •
near Muskoka-Haliburton, Ontario, on  the Precambrian Shield.
Jeffries et al. (1979) compared pH  values  of  a series of small
streams in the study area, before and during  spring runoff.   The pH          •
declines of the lake outflows demonstrated that the top portions of          I
the entire lakes were acidified.  The lowest  stream pH values
observed, 4.1 to 5.1 (Table  3-16),  were within a range capable of            •
causing damage to  some aquatic organisms,  particularly fish (see             •
Section 3.7.7 for  discussion).  As  much as 77% of the measured annual
acid export of the streams occurred in April  (Table 3-17).   A typical        m
hydrograph and pH  response for one  of the  streams during the snowmelt        •
period is illustrated in Figure 3-35  and Table 3-17.                         ™
                                                                              I
The pH. of streams was depressed  for periods  of  as  little  as  a few
hours during times of heavy  runoff, during  the  summer months
(Figure 3-36; Scheider et al.  1979b).  Heavy fall  rains also cause
depressed pH in runoff for days  at a  time.   Jeffries  et al.  (1979)           *
observed as much as 26% of the total  annual  hydrogen  ion  runoff,  from        •
small watersheds, in October.

As a control for eastern work, ELA is probably  one of the best that          •
can be obtained at temperate latitudes.  Mean annual  pH of bulk              •
precipitation ranged from 4.9  to 5.2  over  the past 10 years,
calculated on a volume-weighted  hydrogen ion basis.   No directional          •
trend was observed in pH values.  There is  a pH depression in the            |
area related to spring snowmelt,  of about  0.2 to 0.5  pH units in
inflow streams and about 0.2 to  0.3 in lake  outlets.   Minimum values         M
observed in spring runoff have been as low  as 4.5 but are generally          •
above 5.0 (data from ongoing studies  at the  Freshwater Institute,
Fisheries and Oceans, Winnipeg,  Canada).

A comparison of the water chemistry of 70  lakes in Quebec, sampled at        W
the spring isotherm and at a summer stratification of 1980,  has been
performed by Bob£e et al. (1982).   [This information  is  summarized in        •
their table 5.2, Table 3-18  in this report.]  The authors observed           |
that the mean values of conductivity, alkalinity and  pH were
generally lower during the spring than during the summer  while the           _
ratio [804^"]/[HC03~] was much higher in the spring.                          •
                                                                              I
Seasonally low pH  and  regular  patterns  of  pH declines have been
documented for the Little  Black Fork and Shavers Fork Rivers by the          •
                                                                              I

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                                                                  3-95
TABLE 3-16.  pH OF STREAMS IN MUSKOKA-HALIBURTON,  ONTARIO,  CANADA:
             STREAM pH IS GIVEN  PRIOR  TO  SPRING  RUNOFF (MID-MARCH
             1978) AND AT MAXIMUM  RUNOFF  (MID-APRIL 1978)
             (Jeffries et al. 1979)
PH
Watershed
Harp Lake





Dickie Lake



Chub Lake


Red Chalk Lake




Maple Lake
Lake Simcoe

Lake of Bays
Stream
3
3A
5
6
6A
Outflow
5
6
11
Outflow
1
2
Outflow
1
2
3
4
Outflow
Maple Creek
Black River
(at Vankoughnet)
Oxtongue River
Mid-March
6.1
6.0
5.9
6.2
5.4
6.3
4.6
4.6
4.9
5.6
5.8
5.2
5.5
6.1
4.5
6.0
6.2
6.1
6.2

6.3
6.3
Mid-April
5.1
5.6
4.8
5.3
5.0
5.0
4.3
4.4
4.1
4.9
5.1
4.7
4.8
5.6
4.3
5.5
5.5
5.9
5.8

5.9
6.1

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                                                                                                                            3-96
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                         333
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                                                                  3-97
                           HARP LAKE No. 4
                                                5  10 15

                                                 May
Figure 3-35.
Discharge (upper line),  hydrogen  ion load per unit area
(middle line), pH  (lower line), and depth of
precipitation for  each day  that a precipitation event
occurred for Harp  Lake No.  4.  Daily H"1" load to the
respective lakes can be  calculated by multiplying by
the watershed area:  lake area (A
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                                                                3-98
30
20
10
n
RED CHALK No. 4
-
^^\
_l 	 1 	 1 	 1 	 1 	 1 	 1 	 L. __L. ±....1111 II 1 II II
 70 r

 60

 50

 40

 30

 20

 10
                                                  RED CHALK No. 3
1900  2100  2300 0100  0300  0500  0700  0900  1100   1300  1500

July 12 / 77
Rain Event
                      Time  (hr)
                                                  July  13 177
                 pH 4.06 ~2cm
Figure 3-36.
Hydrogen ion content  of streams draining Red Chalk Lake
watersheds No.3 and No.4  (Muskoka-Haliburton, Ontario)
showing effects of a  2 cm rainfall (pH 4.06) between
11:00 p.m.  July 12,  1977 and 3:00 a.m. July 13, 1977
(Scheider et al. 1979b).
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3-99


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                                                                  3-100
3.7   ALTERATION  OF  BIOTIC  COMPONENTS IN AQUATIC SYSTEMS RECEIVING
      ACIDIC DEPOSITION
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U.S. Forest Service in Monongahela  National  Forest  (Dunshie 1979).
Due to the sandstone geology  of  the watershed,  the  tributaries and
the river are poorly buffered and subject  to rapid  changes  in water           •
quality.  The lowest pH values in both  streams  (Little  Black Fork is          •
a control area, with no logging  or  coal mining)  normally occurred
during the winter and early spring, apparently  because  of snowpack             IB
melting.  The highest pH occurred during  low stream flow periods in           jf
the summer and fall.  Even though summer  and autumn are the periods
of highest precipitation inputs  (see  below), more extensive contact           H
between soils and precipitation  may have  lead to greater neutrali-             •
zation at these times than during either  winter  or  spring flushing
events.

The effect of rainfall on river  pH  is more apparent when individual           «•
events are examined.  A graphic  presentation pairing daily  river and
precipitation events with pH  during summer periods  is shown in                •
Figure 3-37.  During the growing season,  a storm event  with a                 j§
subsequent increase in discharge can significantly  lower river pH
below the natural nonstorm daily variation.   The magnitude  of this             •
downward shift is dependent upon rainfall  characteristics (pH,                •
amount, intensity, and area distribution)  and antecedent soil
moisture.  Downward shifts in river pH  ranging  from 0.6 to  0.9 pH
units, occurred on July 11 and 26,  and  on August 15 and 25, 1977.  On         •
three of these days, at least 3.3 cm of  rainfall fell within a                •
48-hour period; pH of the rainfall  for  these dates  ranged from 3.7  to
4.2.                                                                           •

Nearly 13 years of pH data have  been collected  at the Bowden Fish
Hatchery river intake on the  Shavers Fork River, showing lower pH             .
values during winter and spring  compared  to  summer  conditions.  This          •
is important for aquatic organisms  and  has been  measured in other
poorly buffered streams.  This pH trend  occurred in streams and
tributaries independent of watershed disturbance by mining  (Dunshie            •
1979).                                                                          I
 I
Many changes in biota  have  been  linked  to  acidification of surface             •
waters.  In some  controlled whole  lake  and laboratory experiments a            *
causal relationship with  decreased  pH has  been established.   In the
majority of cases, the observed  changes in biota have simply been              fl
correlated with observed  changes  in pH  and other parameters, but               |
causality has not been established.  For many biological communities,
acidification has been accompanied  by decreases in species diversity           •
and changes in species dominance.   Acidification may also be                   •
accompanied by species extinctions, or  decreases in overall  community
standing stocks.  This topic  has  been reviewed recently by Raines
(1981c).  Generalized  summaries  of  responses  of aquatic organisms to           •
low pH are given  in Figures 3-38  and 3-39  (Eilers and Berg 1982), and          ™
are presented here as  a simplified  overview of the complex
                                                                                I

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                                                                    3-101
                                                                  A Rainfall pH

                                                                  I Rainfall Accumulation
                                              10    15   20    25    30
5    10    15

         7/77
Figure 3-37.
         Mean daily pH for the Shavers  Fork River at Bemis, West
         Virginia and precipitation  event  pH and accumulation at
         Arborvale, West Virginia  (Dunshie 1979).

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                                                                 3-102
 Algae
 Insects
 Molluscs
 Sponges
 Leeches
 Zooplankton
 Fish
 Frogs
75

50

25



75-

50

25



75

50-

25



75

50

25



75

50

25



75

50

25



75

50

25
                                        PH
Figure 3-38.  Relative  number  of  taxa of the major taxonomic groups
              as a function  of pH (Eilers and Berg 1982).
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                                                                     3-103
  c
  0
  O
  L_
  CD
 a.
      100
       75  -
50  -
       25  -
        0
            Major Aquatic

            Community Impacts
                                 yMi i n*lit*i i      I    f-
                                  1 I       3  snails5
                           zooplankton I   insects  I  I    phytoplankton
                                                                          CO
                                                                          •^
                                                                          CO
1  Sprules  (1975) - Ontario
2  Beamish  (1976) - Ontario
3  Bell  (1971) - Laboratory TL50


4  Yan and  Stokes (1978)  -
     - Ontario
                                     PH
                               5   0kland (1969)  -  Scandinavia
                               6   Wright et al.  (1976)  - Norway
                               7   Kwiatkowski and  Roff
                                    (1976) - Ontario
                               8   Snekvik (1974) - Norway
Figure  3-39.   Generalized  response of aquatic  organisms  to  low pH
               (Eilers and  Berg 1982).

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                                                                  3-104
3.7.1   Effects on Algae
I
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interactions described below.   It  is  important  to  note  that the data
were derived from literature  surveys  of  the  relationship between the
distribution of groups of organisms versus lake and  stream pH values.         •
The quantitative description  of  these relationships  may not reflect           •
the response of individual taxa.

Definitive experiments are required to demonstrate whether such               •
changes are directly attributable  to  increases  in  hydrogen ion                •
concentration or whether they are  attributable  to  secondary ecosystem
interactions, such as elevation  of trace metal  levels or disruptions          B
of normal food chains.  In spite of incomplete  understanding of the           |
actual mechanisms underlying  observed changes accompanying pH
declines, it appears that acidification  of surface waters brings              •
about major quantitative and  qualitative changes in  structure and             •
function of aquatic ecosystems.  Disruption  of  the normal food chains
may occur long before the lakes have  been acidified  in  a chemical
sense.                                                                         •
I
The free-floating  (planktonic) and  attached  (benthic  and epiphytic)
algae are the major primary producers  in most  aquatic ecosystems and          «
directly or indirectly provide most of the food for zooplankton and           •
ultimately for fish.  Evidence gathered mainly from synoptic surveys
in Scandinavia, Canada and  the United  States  has indicated that the
species diversity  of benthic and  planktonic algal communities is less         •
in acidified lakes.  Yan  and Stokes (1976) observed only nine species         •
of phytoplankton in a single sample from Lumsden Lake (pH 4.4;
Beamish and Harvey 1972), in the  La Cloche Mountains  in Ontario, but          •
observed over 50 species  in each  of two nearby nonacidic lakes,               |
having pH over 6.0.  Diversity indices for phytoplankton populations
in the La Cloche Mountain lakes are much less  in lakes with pH values         •
below 5.6 (Kwiatkowski and Roff 1976).  In Scandinavian lakes numbers         •
of phytoplankton species  are also much less in lakes  with pH values
below 5.5 (Aimer et al. 1978; Leivestad et al. 1976).

Some long-term functional adaptations  to certain acidic environments          •
may occur.  Raddum et al. (1980)  have  suggested that  such a mechanism
explains the observation  that a group  of relatively recently                  •
acidified clearwater lakes  in Norway have  less diverse phytoplankton          Jj
assemblages than naturally acidic,  humic lakes.  Additionally,  the
bioavailability and toxicity of trace  metals  may be lower in the              «
brownwater acidic  lakes because metals may be  complexed with humic            •
materials.

Although species diversity  of phytoplankton generally decreases with          •
increasing acidity, biomass (Yan  1979) and productivity (Aimer                •
et al. 1978; Schindler 1980) are  often not reduced by acidification.
However, if phosphorus (the nutrient that normally limits phyto-              •
plankton productivity in  soft-water lakes) is  immobilized to some             •
degree in acidic lakes because of complexation with aluminum and
                                                                               I

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                                                                  3-105
humic material  (Aimer  et  al.  1978),  this  would  result  in reduced
primary productivity.   To date,  data from lakes in Scandinavia and
eastern Canada  indicate no  significant  correlations between pH and
phytoplankton biomass  or  productivity (Harvey et al.  1981).

Phytoplankton communities of  nonacidic  oligotrophic lakes in eastern
Canada are typically dominated  by  chrysophytes  (Schindler and
Holmgren 1971)  or by diatoms  (Duthie and  Ostrofsky 1974).  In
contrast, strongly  acidic lakes  are  generally dominated by dino-
flagellates.  In Sweden,  the  dinoflagellates,  formed 85% of the
biomass in lakes of pH 4.6-5.5  (Dickson et  al.  1975).   Of 14 lakes in
central Ontario, dinoflagellates formed between 30 and 70% of the
phytoplankton biomass  in  4  lakes having pH 4.2-4.8, but only 2-30% of
the biomass in  10 lakes with  pH levels  of 5.8-6.8 (Yan 1979).

In certain poorly buffered  lakes,  some  of the phytoplankton species
may interfere with  recreational  use  of  the  lakes.  For example, in
five lakes in Ontario  and New Hampshire with pH 5.5-6.2, obnoxious
odours developed during the summers  of  1978,  1979,  and 1980 (Nicholls
et al. 1981).   The  odours have  been  shown to be caused by the growth
of the planktonic Chrysochromulina breviturrita.  This species was
first discovered in 1976, but it is  now known to inhabit more than
40 lakes in Ontario, most of  which are  acidic (Nicholls et al. 1981).
The "invasion", and associated  odour production, by this organism is
apparently a recent phenomenon.  Although the relationship between
lake acidification  and the  proliferation  of this species has not been
proven, data collected thus far  indicate  that  dominance of this
species to an extent causing  the serious  odour  production, is
restricted to acidic lakes.

Acidified lakes and streams are  often characterized by increased
growth of benthic filamentous algae.   In  Sweden, Ontario and Quebec,
unusually dense and extensive masses  of filamentous algae (mainly
Mougeotia, Zygogonium  and Zygnema  sp.)  proliferate  in  the littoral
zones of many lakes with  pH values of 4.5-5.5 (Blomme  1982; Grahn
et al. 1974; Hendrey et al. 1976;  Hultberg  and  Grahn  1975;  Schindler
1980; Stokes 1981).  These  filamentous  algal  growths  are associated
either with macrophytes or  other substrates or  exist  as floating
"clouds" near the lake bottom.   The  accumulations of  algae may reduce
light availability  to  macrophytes, change microclimates for benthic
macroinvertebrates  and restrict  fish feeding  and spawning.  Some
depreciation of shoreline recreational  values and activities,
especially swimming, may  result  from this growth of algae.
3.7.2   Effects on Aquatic Macrophytes

Information on the effects of acidification  on macrophyte  communities
of soft-water lakes is still incomplete.   Scandinavian investigators
have suggested that when lake water pH declines,  typical macrophyte
dominants are replaced by very dense beds  of  Sphagnum  (Grahn et  al.
1974; Hendrey et al. 1976; Hultberg and Grahn 1975).   The  loss  of

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                                                                  3-106
3.7.3   Effects on Zooplankton
                                                                              I
                                                                              I
some macrophyte species and the correlative increase  in  Sphagnum
abundance may be indirectly related to depressed  pH,  through  changes
in inorganic carbon availability  (Raven  1970;  Steemann-Nielsen  1944,          I
1946).  In Scandinavia, the decline of macrophyte species  and the             •
concurrent Sphagnum invasion begins as pH falls to about 6.0, and
proceeds rapidly when pH falls below 5.0.  In  Lake Golden  in  New York         •
(pH 4.9), Sphagnum is abundant (Hendrey  and Vertucci  1980), and  in            •
Beaverskin Lake in Kejimkujik National Park in Nova Scotia, a clear
lake of pH 5.3, Kerekes (1981) has reported extensive Sphagnum                _
growth.  In Ontario lakes, some species  of Sphagnum have been                I
identified (Harvey et al. 1981),  but accumulations as dense as  those          ™
recorded in Scandinavia have not  been observed.
                                                                              I
Sphagnum moss coverage of littoral zones  creates  a  unique  habitat
that is considered unsuitable  for some  species  of benthic  inverte-
brates or for use as fish spawning and  nursery  ground  (Hultberg  and          •
Grahn 1975).  It may reduce  the  appeal  of  freshwater  systems  for             •
certain recreational activities.  Through  the release  of hydrogen
ions and polyuronic acids, Sphagnum  could  acidify their  immediate            _
surroundings should they accumulate  (Clymo 1963;  Crum 1976).                  •
                                                                              I
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Four major groups of animals  contribute  to  zooplankton  communities:
protozoans, rotifers, crustaceans  and  insects.   Zooplankton are an           m
important food for many species of  fish,  particularly for  younger            •
individuals.  Thus,  they  are  an essential component  of  the aquatic
food chain, transferring  energy and materials  from the  primary
producers (algae) to consumers, including fish and man. Acidifi-            •
cation apparently results in  reduced zooplankton biomasses,  as both           •
the numbers and average size  of community members are reduced (Yan
and Strus 1980).  As a result, food availability to  higher trophic
levels may be decreased.

Acidification of lakes is accompanied  by changes in  the occurrence,           «
abundance and seasonal succession  of species,  and in the diversity of        •
crustacean (and other) zooplankton.  It  is  often assumed that the
direct cause of these changes  is differences  in tolerance  among
zooplankton species  to increased H+ concentration.   However,                 •
acidification also increases  the transparency  of lakes, increases the        9
concentration of potential  toxicants such as  Cd^+ (Aimer et al. 1978)
which is toxic to zooplankton  at less  than  1 Pg/L (Marshall and              •
Mellinger 1980), and produces  quantitative  and qualitative changes in        |
zooplankton predator and  prey  species  (Harvey  et al. 1981).   Hence,
the immediate causes for  the  changes in  zooplankton  communities that         _
do occur, while linked to increased acidity, may be  quite  complex.           •

The most important components  of zooplankton  communities are usually
the rotifers and crustaceans.  Of  these,  the  crustaceans usually form        I
90% of the biomass (Pederson  et al. 1976),  while rotifers, because           I
they have shorter generation  times, may  be  responsible  for 50% of the
                                                                              I

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                                                                  3-107
zooplankton productivity (Makarawicz and Likens  1979).   Available
studies on the effects of acidification on  rotifer  populations  are
contradictory; both smaller  (Roff and Kwiatkowski  1977)  and  larger
(Malley et al. 1982; Yan and Miller  1981) standing  stocks  have  been
observed in acidic lakes.  Studies from very  acidic lakes  (Smith and
Frey 1971) and the Smoking Hills Lakes of the Northwest  Territories
(Havas 1980) indicate, however, that some species of  rotifers can
survive when all crustacean  zooplankton have  been eliminated or could
not survive at the low pH conditions.

The diversity of zooplankton communities has  been reported in several
studies to be greatly reduced by acidification  (Raddum et  al.  1980;
Sprules 1975).   Whereas nonacidic lakes typically  contain approxi-
mately ten species of planktonic Crustacea  in mid-summer collections,
Sprules (1975) observed that the number of  species  and species
diversity of acidic lakes in the La Cloche  Mountains  in  Ontario was
drastically reduced.  In several cases only a single  species,
Diaptomus minutus, remained.

The diversity of littoral cladocerans has also  declined  with
acidification (Brakke et al. 1982).  The decrease in  number  of
species and diversity is apparently related to  low  pH and  not to
changes in aquatic macrophytes  (Kenlan et al. 1982).  Sediment  core
studies in New England and in Norway suggest  that changes  in littoral
cladoceran assemblages occurred simultaneously with calculated  dates
of pH declines based on diatom  analyses (Brakke  et  al. 1982; Davis
et al. 1982).

Some predacious zooplankton, for example cyclopoid  copepods  (Raddum
et al. 1980) and Epischura lacustris (Malley  et  al. 1982),  are  very
sensitive to acidification,  and are often absent from acidic lakes.
Densities of other predators, such as some  species  of Chaoborus
(Eriksson et al. 1980a) and Heterocope saliens  (Raddum et  al. 1980),
apparently increase.  The significance of these  changes  in predator
populations to zooplankton community structure  is not yet  understood
although it may be important (Eriksson et al. 1980a).
3.7.4   Effects on Aquatic Macroinvertebrates

Numerous aquatic macroinvertebrates are known  to  be  affected  by  low
pH conditions.  In some cases an entire phylum appears  to  be
affected, while in other situations susceptibility is species-
specific.  Evidence indicates that molluscs, in general, are  highly
susceptible to reduced pH (J. 0kland  1980; Raddum 1980; Wiederholm
and Eriksson 1977), often being restricted to  habitats  with pH
greater than 5.8-6.0.  Similarly, all species  of  oligochaetes studied
thus far have been found at  lower densities in acid  waters
(Wiederholm and Eriksson 1977).

Sensitivity to low pH has been inferred from field investigations  for
certain Arachnids, Crustaceans and Insects.  Arachnids  were only

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                                                                  3-108
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briefly mentioned by Grahn and his  co-workers  (1974);  acarinids  were
absent in waters with pH values below 4.6.   No  macro-crustaceans were
found below pH 4.6 (Grahn et al.  1974).   Gammarus  lacustris  was               •
absent from waters with pH below  6.0 (J.  j&kland 1969),  while the             |
crayfish, Astacus astacus was rare  in lakes  where  the  summer pH  value
was less than 6.0 (Svardson 1974).  Orders of  Insecta  exhibit a  wide         •
range of sensitivities to pH.  While the  numbers of  species  of               •
Ephemeroptera and Plecoptera appear to  be positively correlated  with
pH, larvae of Chironimidae (Diptera), Hemiptera and  Megaloptera  are
often abundant in acid lakes (Aimer et  al. 1978).  Hutchinson et al.         •
(1978) reported an example of extreme tolerance by larvae  of red             •
chironomids, Chironomus riparius,  to waters  of  pH  2.2  in  the
Northwest Territories.
                                                                              I
Although the field studies mentioned  above  provide  evidence  of  the
effects of acidification on certain species,  the  pH of  a  natural              &
system has rarely been altered experimentally,  and  the  impacts  on            •
invertebrates noted.  The documented  effects  of decreased pH include
the disappearance of Mysis relicta in Lake  223, an  experimentally
acidified lake in the Experimental Lakes Area (Malley et  al. 1982),           •
elimination or reduction of Ephemeroptera populations in  a stream in         •
the Hubbard Brook Experimental Forest in New  Hampshire  (Fiance  1978;
Hall et al. 1980), and decreased  emergence  of some  species of                •
Plecoptera, Trichoptera and Diptera in  the  same stream  (Hall et al.           •
1980).  Those species with acid-sensitive life  stages (such as
emergence in insects) which can coincide with low pH snowmelt,  or            ^
other events, such as low pH flushing,  may  be especially  sensitive to        •
acid deposition.                                                              ™

In considering the distribution of the  above  species in relation to           B
waters of varying pH no causative relationship  between  hydrogen ion           •
concentration and the observed changes  has  been determined as yet.
Other factors vary with pH, including concentrations and  availability        •
of nutrients, bicarbonate, and various  metals.  From the  results              •
available, however, it appears that molluscs  (perhaps because of
their requirement for calcium) and moulting crustaceans (perhaps              _
because of their large demand for calcium at  the  time of  moult) are           •
the macroinvertebrates most sensitive to low  pH levels.  It  is  still         •
unclear why certain groups of aquatic insects are more  sensitive  than
others.                                                                       H


3.7.5   Effects on Bacteria and Fungi                                        •

The decomposition rate of fixed carbon, both  allochthonous and
autochthonous organic matter, is  largely determined by  microbial
processes in the water column and in  the surface  layers of sediment.         •
Several studies have demonstrated that  rates  of decomposition of              •
organic matter are decreased at low pH  values.  In  a laboratory
study, for example, Bick and Drews (1973) demonstrated  that as  pH was
lowered, the number of bacteria and protozoans  decreased, populations
of fungi increased, and the rates of  decomposition  and  nitrification
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                                                                  3-109
were reduced.  Traaen and Laake  (1980) measured  decomposition rates
of homogenized birch litter  and  glucose/glutamate  mixtures.   When the
pH was decreased from 7.0 to 3.5,  litter  decomposition dropped to 30%
of control levels, and  a shift from  bacterial  to fungal dominance was
observed.  Traaen (1980) further observed that  rates  of weight loss
of decomposing birch leaves  and  aspen  sticks after one year  in the
laboratory or one to two years in  field situations were significantly
lower at pH levels less than 5.0.

Reductions in numbers of heterotrophic bacteria  have  been observed
previously in aquatic habitats acidified  by acid mine drainage
(Guthrie et al.  1978;  Thompson  and  Wilson 1975; Tuttle et al. 1968,
1969).  Caution must be exercised, however, in extrapolating results
from such studies to situations  where  the source of protons  is
atmospheric because the pH is often  much  lower  in  acid mine  drainage
lakes, and the concentration of  dissolved substances, including
metals, much higher.

Rao et al. (1982) studied the effects  of  acidic  precipitation on
bacterial populations of the Turkey  Lakes,  Ontario and Kejimkujik,
Nova Scotia.  They observed  reduced  numbers of  nitrifying bacteria
and sulphur cycle bacteria in low  pH lakes  and  streams.  Bacterial
activity as measured by oxygen consumption rate  and biodegradation or
organic material was 50% less and  30-40%  less  respectively in
acid-stressed environments compared  to nonacid-stressed areas.

Microbial transformations of sulphur and  nitrogen  species may
influence lake acidity  and alkalinity  (Brewer  and  Goldman 1976).
Schindler (1980) showed that increases in SO^-  concentrations
stimulated sulphate-reducing bacteria  in  lakes that develop  anoxic
hypolimnia.  The reduction of SO^"  yields  OH~ thereby increasing
akalinity.  Stimulation of SO/^- reduction has  been used with success
to reclaim acid mine drainage waters.  Sulphate-reducing bacteria
require anoxic conditions, and are stimulated  by large quantities of
organic matter (i.e., they prefer  conditions typical  of eutrophic
lakes).  However, acidified  lakes  are  not eutrophic and many have
oxygenated hypolimnia.
3.7.6   Effects on Amphibians

Many species of frogs,  toads, and  salamanders  breed  in temporary
pools.  These pools are formed by  a mixture  of  snowmelt water and
spring rains and may have low pH values  during  the spring.   Because
of the vulnerability of this habitat  to  pH depressions, amphibian
populations are expected to be one of  the earliest forms of  wildlife
to be affected by the acidification of fresh waters.   Temporary pools
used as breeding sites by Jefferson's  (Ambystoma  jeffersonianum) and
yellow-spotted salamanders (A. maculatum) in New  York were  found to
have pH values 1.5 units lower than nearby permanent  ponds  (Pough and
Wilson 1977).  The amphibian species  of  eastern Canada considered
most susceptible to the effects of acid  deposition because  of their
breeding habitat are listed in Table  3-19.

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                                                                      3-110
TABLE 3-19.  SUSCEPTIBILITY OF BREEDING HABITAT TO pH DEPRESSION
             FOR THOSE AMPHIBIANS IN NORTHEASTERN NORTH AMERICA WHOSE  RANGE
             OVERLAPS AREAS RECEIVING ACIDIC DEPOSITION (modified  from
             Clark and Fischer 1981)
Potential for
acidification
of egg-laying
habitat	Habitat	Species
high
meItwater
pools
moderate
permanent
ponds
low
streams



lakes

bogs
                   logs and
                   stumps
Ambystoma maculatum - Yellow-spotted
                      salamander
Ambystoma laterale - Blue-spotted
                     salamander
Ambystoma tremblayi - Tremblays
                       salamander
Bufo americanus - American toad
Pseudacris triseriata - Chorus frog
Rana sylvatica - Wood frog
Rana pipiens - Northern leopard frog
Hyla crucifer - Northern spring peeper
Hyla versicolor - Gray tree frog

Necturus maculosus - Mudpuppy
Notophthalmus viridescens - Red-spotted
                            newt
Bufo americanus - American toad
Hyla versicolor - Gray tree frog
Pseudacris triseriata - Chorus frog
Rana catesbeiana - Bullfrog
Rana clamitans - Green frog
Rana pipiens - Northern leopard frog
Rana septentrionalis - Mink frog

Eurycea bislineata - Northern two-lined
                     salamander
Necturus maculosus - Mudpuppy

Rana catesbeiana - Bullfrog

Hemidactylium scutatum - Four-toed
                         salamander

Plethedon cinereus - Red-backed
                     salamander
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                                                                  3-111
Detrimental effects of acidity  on  adult  amphibians  have  been shown in
a number of field surveys.   In  England,  Cooke  and Frazer (1976)
reported that no adult newts were  caught from  ponds of  pH less than
3.8.  The natterjack  toad  (Bufo calamita) was  not  found  in ponds
below pH 5 (Beebee and Griffin  1977)  in  England.  The  common toad
(Bufo bufo) did not occur where pH was less  than 4.2,  and the smooth
newt (Triturus vulgaris) occurred  only rarely  in ponds  at pH values
less than 6.0. Hagstrom  (1977)  observed  that the common  toad and
common frog (Rana temporaria) disappeared when pH levels reached
4.0-4.5.  In New Hampshire,  when a section  of  Hubbard  Brook was
artificially acidified to mean  pH  4.0, salamanders  disappeared from
the study area (Hall  and Likens 1980).

Pough (1976) noted heavy embryonic mortalities and  deformities in the
yellow-spotted salamanders which breed in temporary meltwater ponds
with pH less than 6.0.   In central Ontario,  Clark and  Euler (1981)
reported that the numbers of egg masses  of  yellow-spotted salamanders
and male calling densities (an  estimate  of  population  size) of spring
peepers (Hyla crucifer) were positively  correlated  with  pH.  This
latter species often  breeds  in  stream inflows  and outflows or along
the littoral zone of  lakes,  habitats  also subjected to  particularly
heavy acid loads as a result of snow  melt (Clark and Euler 1981).
Bullfrog (Rana catesbeiana)  and wood  frog (Rana sylvatica) densities
were also reduced in  acidic  streams and  ponds  (Clark and Euler 1981).
Strijbosch (1979) reported a negative correlation between pH and
percentages of dead and moulded egg masses  of  frogs and  toads in the
Netherlands.

Laboratory experiments have  demonstrated that  reductions in pH are
both directly and indirectly responsible for mortalities and
deformities found during amphibian embryonic development.  Gosner and
Black (1957) studied  the sensitivity  of  11  species  of  frogs and toads
to conditions of depressed pH and  found  that the embryos were more
sensitive than adults.  Frogs may  undergo iono-regulatory failure due
to acidic conditions  (Fromm  1981)  similar to that reported for fish
(Leivestad and Muniz  1976; McWilliams and Potts 1978; Muniz and
Leivestad 1980; Packer and Dunson  1970). In the case  of the cricket
frog (Acris gryllus)  and northern  spring peeper, an exposure of
embryos to water in the vicinity of pH 4.0  for a few hours resulted
in greater than 85% mortality.   Beebee and  Griffin  (1977) noted
abnormalities in natterjack  toad spawn exposed to low  pH, and Noble
(1979) observed delayed development and  embryonic mortality in the
leopard frog (Rana pipiens) at  pH  less than  4.75.   The  leopard frog
may be more sensitive to low pH than  the latter study  indicates.
Schlichter (1981) found decreased  sperm  motililty at pH  values less
than 6.5 and the percentage of  eggs which formed healthy embryos
decreased below pH values of 6.3.   A  similar study  using the common
frog reported that sperm motility  was reduced  to 50% of  maximum at pH
values of 6.4-6.7 and to 0% at  pH  values less  than  6.0  (Gellhorn
1927, cited in Schlichter 1981).

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                                                                  3-112
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Cook (1978) found no significant correlation  between  pond  pH and
percent embryonic mortality in  either  the  yellow-spotted  salamander
or Jefferson's salamander studied  in six ponds with mean  pH values  of         I
5.3-5.6.  In contrast Pough (1976) found heavy embryonic  mortalities          I
and deformities for both species in waters with  pH values  less  than
6.0.  Egg transplant studies  suggest that  yellow-spotted  salamander           •
eggs from acidic ponds are more tolerant to acidity than  eggs from             •
neutral ponds (Nielsen et al. 1977).   While Hagstrom  (1977) reported
the elimination of the common toad at  pH values  of 4.0-4.5, Cooke             _
(cited in Beebee and Griffin  1977) found this species in  waters of             •
pH 4.2 and noted that tadpoles were able to tolerate  this  hydrogen             •
ion level.

It is likely that other factors influenced by the  acidity of the               |
water may cause detrimental effects upon amphibian development.  For
example, Huckabee et al. (1975) suggest that  the combined effects of          m
low pH and increased concentrations of aluminum, manganese and  zinc           •
may be the cause of the high mortality of  shovel-nosed salamander
(Leurognathus marmoratus) larvae in Great  Smoky  Mountain  National
P ark";•

Frogs, toads, and salamanders are  important components of  both
aquatic and terrestrial ecosystems.  Orser and Shure  (1972) reported          •
that amphibians are among the top  carnivores  in  temporary ponds and           |
small streams, and are important predators of aquatic insects.   In
turn, they serve as a high protein food source for other  wildlife             M
(Burton and Likens 1975b).  Many birds and mammals depend heavily on          •
these species for food (Burton  and Likens  1975a; Cecil and Just
1979; DeBenedictis 1974).


3.7.7   Effects of Low pH on Fish

The purpose of this section is  to  review briefly how  fish respond to          |
low pH conditions.  This will be done  on the  basis of documented
changes in fish population related to  acidification,  other field               _
evidence and laboratory substantiation.  For  more  comprehensive               •
treatments of this subject, the reader is  referred to reviews by               ™
Fromm (1980), Haines (1981c) and Spry  et al.  (1981).   In  addition,
there is extensive literature available on laboratory studies (see             •
Doudoroff and Katz 1950; EIFAC  1969),  that were  designed  to elucidate         •
mechanisms of pH toxicity.  These  laboratory  results  are  reviewed,  as
they are useful in explaining field observations and  suggesting new           •
directions for field studies.                                                  •

Results from laboratory experiments demonstrate  how overall water             ^
quality (i.e., hardness, ionic  strength) can  affect pH toxicity.   For         •
example, as ionic strength and  water hardness increase, the short-             ™
term sensitivity of fish to waters with pH values  of  4 is decreased
(reviewed in Spry et al. 1981).  The ameliorative  effects of high             B
Ca^+ and ionic strength appear  most beneficial  to  early larval stages         •
at intermediate pH values (^5).  This  is consistent with  field
                                                                               I

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                                                                  3-113
observations that fish communities disappear  from more  dilute  waters
at higher pH levels than  they  do  from  lakes with higher concentra-
tions of salts (Leivestad and  Muniz  1976).  In  addition to  hardness
and ionic strength, survival of fish in water of low pH is  influenced
by the type of acid present (Packer  and Dunson  1972;  Swartz et al.
1978), temperature (Kwain 1975; Robinson  et al.  1976),  the  level of
dissolved carbon dioxide  in the water  (Neville  1979), and by the
presence of metals (Baker and  Schofield 1980; Swartz et al. 1978).

Salts are lost from plasma and body  tissue of fishes exposed to low
pH conditions.  Leivestad et al.  (1976) found that Na+  and  Cl~ in
blood plasma and K+ in muscle  tissue declined in brown  trout at low
pH levels.  Increases in  the concentration of Ca2+ enabled  the trout
to regulate better ionic  balances  (Leivestad  et  al.  1980).   Recent
studies by Saunders et al. (1982,  in press) have shed light on
possible mechanisms affecting  survival, growth,  and  the smelting
process in Atlantic salmon.  Under low pH laboratory conditions it
was found that parr-smolt transformation  was  impaired,  and  ATPase
activity was lowered, resulting in a decreased  salinity tolerance of
smolts.  Salmon raised under low  pH  regimes (i.e., pH 4.2-4.7) were
found to have significantly lower  plasma  Na+  and Cl~ levels, which
was indicative of an impaired  osmoregulatory  ability in fresh  water.

Field evidence suggests that the  susceptibility  to low  pH appears to
be species-specific.  From his studies of La  Cloche  Mountain lakes,
Beamish (1976) estimated  the pH at which  reproduction ceased in 11
species of fishes (Table  3-20).  As  well  as interspecific differences
in sensitivity, variability in sensitivity has  also  been observed
among different strains of the same  species (Robinson et al. 1976;
Swartz et al. 1978).  However, it  is likely that the acidification of
lakes and rivers in North America  is proceeding  too  rapidly to enable
genetic selection for acidic tolerant  strains to occur  naturally
(Schofield 1976b).

Results of laboratory and field studies have  demonstrated that some
species of fish are particularly  sensitive to low pH levels in
certain reproductive stages (reviewed  by  Spry et al.  1981).  Low pH
can inhibit gonadal development (Ruby  et  al.  1977, 1978), reduce egg
production (Craig and Baksi 1977; Mount 1973) affect egg and sperm
viability (EIFAC 1969; Menendez 1976)  and inhibit spawning  (Craig and
Baksi 1977; Menendez 1976).  Embryonic development may  also be
affected by low pH (Swartz et  al.  1978; Trojnar  1977) and low
environmental pH can affect egg internal  pH (Daye and Garside  1980).
Generally, fry appear less resistant to low pH  than  eggs (Spry
et al. 1981), and therefore fry may  be particularly  vulnerable to low
pH conditions associated with  spring melt and storm  events.

Hulsman and Powles (1981) conducted  experiments  on walleye  eggs.  The
eggs were incubated in situ in a  series of small streams in the
La Cloche area of Ontario.  The various sites ranged in pH  from 4.60
to 6.72.  Hatching success was significantly  reduced in the clear
dilute streams with pH values  less than 5.40.

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                                                                  3-114
TABLE 3-20.   APPROXIMATE pH AT WHICH FISH IN THE LACLOCHE MOUNTAIN
              LAKES STOPPED REPRODUCTION (Beamish 1976)
6.0 to 5.5
5.5 to 5.2
5.2 to 4.7
4.7 to 4.5
                         Species
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 flaveseens


Lake chub
Couesius plumbeus
                              Family
Centrarchidae



Percidae



Gadidae



Salmonidae



Percopsidae



Ictaluridae



Catostomidae



Centrarchidae



Salmonidae



Percidae



Cyprinidae
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                                                                  3-115
One mechanism which appears  to  contribute  to  species  extinction in
acidified systems is  the  failure  of  recruitment  of  year classes.  In
a study of 38 La Cloche lakes,  Ryan  and  Harvey (1980) reported
evidence of recruitment failure in yellow  perch  (Perca flavescens)
populations in the two lakes  of lowest pH  values:   Patten Lake
(pH 4.1) and Terry Lake (pH  4.3).  The age group composition of
yellow perch in Patten Lake  is  illustrated in Figure  3-40.   Ryan and
Harvey (1981) also found  evidence of  reduced  and missing year classes
of young fish in five populations of  rock  bass (Ambloplites
rupestris) in acid-stressed  La  Cloche lakes.

The absence of older  individuals  in  populations  of  fish in  some
acid-stressed lakes has also  been reported (Harvey  1980; Ryan and
Harvey 1980).  This effect is illustrated  by  the changes in age
composition of white  suckers  in George Lake,  Ontario  from 1967 to
1979 (Figure 3-41),   Rosseland  et al. (1980)  also reported  the
absence of post-spawning  age  perch and brown  trout  in three lakes
within the Tovdal River System, Norway.

In the field, there have  been several reports of fish kills appar-
ently related to the  low  pH  of  rivers and  lakes. In  Scandinavia, for
example, Jensen and Snekvik  (1972) reported mass mortality  of
Atlantic salmon (Salmo salar),  and Leivestad  and Muniz (1976)
reported a brown trout (Salmo trutta) kill.   Both fish kills have
been correlated with  reduced water pH, although  Al  was not  measured
in either case.

In North America, Harvey  (1979) reported mortalities  of several
species, primarily pumpkinseeds (Lepomis gibbosus)  in Plastic Lake,
Ontario, during spring snowmelt runoff and pH depression.  Surface
water pH was 5.5, while the  pH  of the major inlet stream was 3.8.
During the spring of  1981, some in situ  bioassays were conducted in
Plastic Lake (Harvey  1981).  Rainbow  trout, Salmo gairdneri,  were
placed in cages at four locations in  Plastic  Lake and at four
locations in the control, Beech Lake.  Three  nonmetal cages of
35 fish were situated at  each location.  No mortality occurred at any
of the cage sites in  the  control lake (pH  6.09-7.34,  alkalinity
132-390 ;ieq/L).  In Plastic  Lake, however, mortality  ranged from 12%
at the lake outlet site (pH  5.0-5.85) to 100% at the  inlet  site
(pH 4.03-4.09).  Although aluminum concentrations were not  measured
at the time of the 1979 fish kill and aluminum data for 1981 is not
yet available, total  aluminum concentrations  in  Plastic Lake during
the 1979 and 1980 ice-free season varied between 9  and 30 ug/L in the
lake, and between 240 and 490 Pg/L in the  major  inlet.
3.7.8   Effects of Aluminum and Other Metals on  Fish

Concentrations of metals can be elevated  in acid-stressed  lakes
(Beamish 1974a; Raines 1981c;  Scheider  et  al.  1979b)  because  of
increased atmospheric deposition, increased mobilization from the
sediments and/or mobilization  from the  watershed (see Section 3.2.4).

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3-116


35
30
25
x:
0)
b 20
"o
0>
1 15
z
10
5
0

PATTEN LAKE

-
-

c$$w i i i
012345
Age in










•

1
1
1
1



1

678
Years


Figure 3-40. Age composition of yellow perch
(Perca
captured in Patten Lake, Ontario, pH 4
Harvey 1980).












1
Q


1
1






10
1
1
1
1
1
1
1
1
1
1
1
1
1
f lavescens)
.1 (Ryan and •


1
1

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                                                                   3-117
           w
          il
          E
          3
          •z.
                     0  1 2  3 4 5  6 7 8  9 10 11  12 13 14 15
                                 Age in Years
Figure 3-41.  Changes  in  the  age  composition of the white sucker
              (Catostomus commersoni)  in George Lake, Ontario
              (Harvey  et  al.  1981).

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3-118
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One of the most important consequences  for  fishes  of watershed
acidification is the mobilization  of  aluminum from the  watershed to
the aquatic environment  (Cronan and Schofield 1979).  Elevated levels
of aluminum in waters have been shown to have serious effects  on fish
within the pH range normally considered not harmful  to  aquatic biota
(Baker and Schofield 1980).                                                    _

Spry et al. (1981) give  a simplified  description of  the complex
chemistry of aqueous aluminum.  The solubility of  aluminum is  minimal
at pH 5.6-6.0, increasing as pH increases or  decreases  outside this           •
range (Figure 3-42).  At pH greater than 5.5,  soluble aluminum is             •
mostly anionic; at pH less than 5.5 it  exists increasingly as  a
cation.  The solubility  of aluminum is  apparently  regulated by some           •
form of aluminum trihydroxide  solid,  Al(OH)3(s), which  is  minimally           ||
soluble at pH values of  5.6-6.0 (Driscoll 1980b).   Fewer hydroxyl
ligands at lower pH allow the  aluminum  to become cationic, eventually         •
becoming Al^+ at pH values less than  4.5 to 5.0.   Cationic aluminum           •
is able to form complexes with a number of  ligands,  including  soluble
organics and fluoride, decreasing  its toxicity (Figure  3-42) (Baker
and Schofield 1980; Driscoll et al. 1980).                                     •

Laboratory studies have  shown  significant reductions  in fish survival
at inorganic aluminum concentrations  of 100 and 200 pg/L and greater
for white suckers (Catostomus  commersoni) and brook trout  (Salvelinus
fontinalis), respectively (Baker and  Schofield 1982;  Schofield and
Trojnar 1980).  Inorganic aluminum levels as  high  as  600 yg/L  have            «
been measured in acidic  Adirondack waters (Driscoll 1980b).  Baker            •
and Schofield (1980) note that fry exposed  soon after initiation of
feeding and yolk sac absorption were  more sensitive  to  elevated
aluminum concentrations  than were  eggs  and  sac fry prior to yolk              •
absorption.  They also found that  the presence of  aluminum actually           •
mitigated the toxic effects of low pH to fish eggs.   The survival of
brook trout and white sucker embryos  through  the eyed stage at pH             •
levels below 5 was significantly better in  treatments with aluminum           •
than without.  After hatching, brook  trout  fry were  more susceptible
to aluminum at the extremes of the pH range tested (4.2 to 5.5) than
at intermediate pH levels (Figure  3-43).  The greater susceptibility          •
of fry at these extreme  pH values  may reflect a dual  mechanism of             ^
aluminum toxicity.  At low pH, aluminum (probably  Al-'"*") appears to
cause osmoregulatory stress and loss  of salts from blood plasma               H
(Baker 1981; Leivestad and Muniz 1981).  At higher pH values (5.5),           |
precipitation of Al(OH)3(s) damages the gills and  leads to clogging
by mucous (Baker 1981; Schofield and  Trojnar  1980).   Baker and                mt
Schofield (1980) also found that,  at  all stages, white  suckers were           •
substantially more sensitive to low pH  levels and  elevated aluminum
concentrations than brook trout.

Schofield and Trojnar (1980) suggested  that levels of aluminum,               •
rather than pH alone, may be the primary factor limiting survival of
brook trout stocked in Adirondack  lakes.  Muniz and Leivestad  (1980)          •
and Schofield and Trojnar (1980) suggested  that mass mortalities of           |
fish, observed during episodes of  acidification in the  spring, were
             I

             I

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                                                                 3-119
        100
         80
         60
   CO
   3
   CO
         40
         20
                                                     10
                                                       14  15
                                        Time (days)
Figure 3-42.
Percent survival of brook trout fry plotted as  a
function of time in treatment waters at pH level 5.2
with no aluminum (control) or with 0.5 mg Al added  per
liter with no additional complexing agents (Al) or  with
0.5 mg fluoride/litre (Al + F) or with 30 mg (Baker and
Schofield 1980).

-------
                                                                   3-120
       + 100
   C

  1
   C
   o
   4-f
   o
   C
   3
   u_

   CO

   0}
   (0

   ~G   -100
   3
  CO

   C
   o
  'w
   0)
   0)
   t_
   O)
   o
  QC

  •5  -200

   0>
   a
   o
  CO

                             \


                                 \
                                  X

          4.0
Figure 3-43.
                4.5
                                                  5.0
                                                        5.5
                                     PH
Slope of the regression  line  of  brook trout survival
(arcsin transformation)  as  a  function of total aluminum
concentration at each  pH level,  plotted as a function
of pH level.  A positive slope indicates presence of
aluminum improved survival: a negative slope indicates
detrimental effects of aluminum (Baker and Schofield
1980).
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                                                                  3-121
most likely a result of elevated  concentrations  of  inorganic
aluminum, mobilized from  the  soils  by  strong  acids  present in
snowmelt water.  The former study demonstrated  that pH declines alone
(to levels of pH 4.7-5.0)  did not induce  physiological stress in
fish, as determined from  changes  in plasma  chloride levels.   However,
associated increases in aluminum  levels  to  0.2 mg/L or more  were
found to be sufficient to  induce  severe  stress  and  eventual  mortality
(Muniz and Leivestad 1980).

Aluminum levels in streams in the Adirondack  Region of New York
State (Driscoll 1980b), in the  Great Smoky  Mountains National Park,
U.S.A. (Herrmann and Baron 1980), and  in  the  Muskoka-Haliburton area
of Ontario (total aluminum levels from 1976 to mid  1978 ranged
between 5 and 1000 yg/L in 60 streams)  (Ontario  Ministry of  Environ-
ment data from ongoing studies),  fall  within  levels demonstrated to
be lethal to fish in laboratory conditions.  However, as the
laboratory studies have demonstrated,  the evaluation of aluminum as a
toxic element in acidified waters is not  a  simple function of total
concentration.  In evaluating the survival  of indigenous fish
populations one must consider the form of aluminum, the level of
hydrogen ion, the fish species  present  and  their life history stage.

Other metals besides aluminum also  occur  at elevated levels  in acidic
waters (Section 3.2.4).   Harvey et  al.  (1982) reported increased
lakewater concentrations  of manganese  were  associated with decreasing
pH for 50 lakes in the Wawa area  of Ontario.  They  found Mn  was
elevated when pH values were  less than 5.0  and  reached very  high
concentrations in strongly acidified lakes.  In  the La Cloche
Mountain lakes, Mn was correlated inversely with pH and Mn declined
in acidified lakes in the  Sudbury area  following neutralization
(Harvey et al. 1982).

Manganese has been considered a relatively  non-toxic element, and
thus toxicological data are very  limited.   Lewis (1976) determined
that manganese concentrations up  to 770 yg/L  had no effect on
survival of rainbow trout  in  soft waters with pH levels 6.9  to 7.6.
Concentrations of manganese in  acidic  waters  have been measured up to
130 to 350 ug/L (Dickson  1975;  Schofield  1976c). Available  data
suggest that manganese levels,  by themselves, have  no apparent
adverse effects on fish,  although Harvey et al.  (1982) found elevated
Mn concentrations in the  vertebrae  of  white sucker  (Catostomus
commersoni) from acid lakes.

Although laboratory bioassays examining  effects  of  zinc on fish are
numerous, none of these studies considered  soft  waters with  pH levels
below 6.  Chemical models  predict that  as the pH level declines, an
increasing proportion of  the total  zinc  concentration should exist as
the free aquo ion (Stutnm  and Morgan 1970).  For  many metals, the free
aquo ion (i.e., Me^"1") is  considered the most  toxic  form (Spry
et al. 1981).  This has not been  confirmed  to be true for zinc but
care should be taken in extrapolating  bioassay  data and maximum
acceptable toxicant concentrations  (MATC) determined for pH  levels

-------
                                                                  3-122
                                                                             I
                                                                             I
                                                                             I
above 6 to conditions in acidic waters.  For  the most  part,  however,
lethal concentrations of zinc  in  bioassays  are  10  times  the  zinc
concentrations found in acidic lakes  (Spry  et al.  1981).   Sinley
et al. (1974) estimated that the  MATC  for rainbow  trout  (Salmo
gairdneri) exposed to zinc in  soft, circumneutral  water  was  between
140 and 260 yg/L.  Benoit and  Holcombe  (1978),  in  life cycle                 •
experiments with fathead minnows  (Pimephales  promelas) in  soft  water,         I
determined that the threshold  level for  significant  adverse  effects
on the most sensitive life history state was  between 78  and  145 yg/L.
Zinc concentrations in acidic  waters  range  up to 23  to 56  yg/L                •
(Henriksen and Wright 1978; Norton et  al. 1981a; Schofield 1978;  Spry         •
et al. 1981).
                                                                             I
In some regions, concentrations  of  cadmium,  copper,  lead  and  nickel
(see Section 3.2.4) are also elevated  in  acidic  lakes.  Relation-
ships between pH levels and cadmium, copper,  lead,  and  nickel                •
concentrations, however, vary markedly between regions.   High                I
concentrations of these metals probably result primarily  from
increased atmospheric loading and deposition, and occur principally
in surface waters in close proximity to pollutant sources (e.g.,              I
Sudbury, Ontario, Nriagu et al.  1982).  Concentrations  of some  of            I
these metals in lakes in the vicinity  of  Sudbury have been demon-
strated to have definite adverse impacts  on  fish and other aquatic           •
biota (Conroy et al. 1976; Yan and  Strus  1980).  Excluding lakes              |
within 50 km of Sudbury, acidic  Ontario surface  waters  have concen-
trations of metals ranging up to about 0.6 yg/L  Cd,  9 yg/L Cu,                _
6 yg/L Pb and 48 yg/L Ni (Spry et al.  1981).  Spry  et al.  (1981)            •
reviewed bioassay data available and noted no significant adverse
effects on fish survival and reproduction at  concentrations up  to
0.7-11.0, 9.5-77, 13-253, and 380 yg/L for cadmium,  copper, lead, and        •
nickel, respectively.  In general,  concentrations of metals in  acidic        I
waters are below these "safe" concentrations  (unless there is a local
source of metal emissions).  However:  (1) most of these bioassays            •
were conducted in waters with pH levels above 6, and (2)  the                  I
possibility for synergistic effects has not  been evaluated.

In some regions, bioaccumulation of mercury  in fish has been                 I
correlated with low pH levels in lakes.   These elevated levels  of            ™
mercury in fish may have adverse effects  on  consumers (e.g.,  man or
fish-eating birds and mammals; Sections 3.7.12 and  5.2).   However, no        I
data have been reported to indicate that  this bioaccumulation has any        I
adverse effects on the fish themselves (Haines 1981c).

Survival of fish populations in  acidic waters is determined primarily        I
by levels of pH and inorganic aluminum (Baker 1982;  Schofield and
Trojnar 1980).  Although concentrations of a number of  metals are            _
increased in acidic lakes and streams,  definite  effects on fish have         •
been demonstrated only for aluminum (except  for  lakes immediately            ™
around Sudbury, Ontario).  Other metals may  play a  lesser, but  as yet
undefined, role.                                                              I
                                                                              I

                                                                              I

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                                                                  3-123
3.7.9   Accumulation of Metals  in  Fish

3.7.9.1   Mercury

There is substantial evidence of the  effect  of  pH on mercury content
in fish (Brouzes et al. 1977; Hakanson  1980;  Landner and Larsson
1972).  Bisogni and Lawrence  (1973) and Jernelov  et  al.  (1976) have
argued that one reason  fish  in  waters of low pH contain  more
methylmercury than fish in waters  of  comparable mercury  contamin-
ation, but higher pH,  seems  to  be  that  more  acidic waters retain the
monomethyl-form of mercury in solution.   It  is, however, important to
recognize that pH is not  the  only  variable which  determines the
mercury burden in fish.   Other  factors  include  mercury availability,
level of bioproduction  (i.e., lake trophic state), lake  flushing
rates and lake/watershed  drainage  area  ratio (Hakanson 1980).

Few data exist to link mercury  concentrations in  fish to lake
acidification.  However,  an  increase  in concentrations of mercury in
fish from 1970 to 1978  is evident  in  some lakes in the Adirondack
Mountains (Schofield pers. comm.).  In  Ontario, Suns et  al. (1980)
sampled young-of-the-year and yearling  fish  for contaminant studies.
Their data (Figure 3-44)  demonstrate  increased  mercury concentrations
with decreasing pH in  lakes  in  the Muskoka-Haliburton area.  At any
given pH level, however,  the variation  of mercury concentrations in
fish is substantial.  For lakes with  similar pH,  the mercury
concentrations were higher in fish from lakes with a higher ratio of
drainage area/lake volume.   This result  implies that a quantity of
mercury from either direct atmospheric  deposition or from watershed
leaching is influencing the  concentrations in fish.   Data for  1981
are shown in Table 3-21 (Suns 1982).  In 1980,  the survey was
extended to include adult smallmouth  bass.   Fish  from six of the nine
lakes studied had average mercury  concentrations  above the Canadian
guideline (500 ng/g) for  unlimited human consumption. In one  lake
mercury concentrations  in fish  exceeded  the  U.S.  guidelines of
1000 ng/g (Suns 1982).

Because of increased mobility and  leaching under  acidic  conditions
and/or deposition, it is  possible  that  metals other  than mercury may
be accumulating in fishes.   At  present,  however,  the data base is
extremely limited (Haines 1981c).

In a survey of Ontario  lakes by Suns  (1982),  yearling yellow perch
were analyzed for body burdens  of  lead,  cadmium,  aluminum, and
manganese.  The data are  shown  in  Table  3-21 and  are summarized
below.
3.7.9.2   Lead

A significant (p less  than 0.01;  r =  -0.74)  correlation was  found to
exist between lead residues  in  perch  and  lake  pH.   Mean lead residues
as high as 428 ng/g were found  from Moot  Lake  (pH  5.5)  and 403 ng/g
from Fawn Lake (pH 5.4).

-------
                                                                   3-124
    200
    180
    160
    140
  o>
  c
    120
  CO
  ^
  +*
  0)
  o
  i 100
  o
  I  80
     60
     40
     20
                                      13
               4.5
LAKE #, NAME


1.  Duck Lake
2.  Little Clear Lake
3.  Harp Lake
4.  Bigwind Lake
5.  Nelson Lake
6.  Chub Lake
7.  Crosson Lake
          5.0
5.5
6.0
                                      PH
6.5
                                                  A = 0.63

                                                  p < 0.05
                                                                 11
          TWP.         LAKE  #,  NAME


          Minden       8.  Dickie  Lake
          Sinclair     9.  Leonard Lake
          Sinclair     10.  Heney Lake
          Oakley       11.  Cranberry Lake
          Bowell       12.  Healey  Lake
          Ridout       13.  Clear Lake
          Oakland      14.  Fawn Lake
7.0
                          TWP.


                          McLean
                          Mo nek
                          McLean
                          Guilford
                          McCauley
                          Stanhope
                          McCauley
Figure 3-44.
Mercury concentrations in yearling  yellow perch vs.
epilimnetic pH for selected  lakes in Ontario (Suns
et al. 1980).
7.5
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3-125
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                                                                  3-126
3.7.9.3   Cadmium
3.7.10   Effects on  Fisheries  in Canada and the United States

3.7.10.1   Adirondack  Region of New York
                                                                               I
                                                                               I
Although there is evidence  that  lead  concentrations  in water as low
as 8 ng/L can cause neurological  disorders  in  fish (Davies  et al.
1976; Hodson et al. 1978; Holcombe  et  al.  1976),  no  data are                  •
available to relate body-burden  accumulations  to  any significant              •
biological response.
                                                                               I
A statistically significant  (p  <0.05;  r  =  0.60)  correlation exists            I
between cadmium residue  levels  and  lake  pH (Table  3-21).   Little              |
reference material is available  at  this  time  to  evaluate  the
environmental significance of these cadmium accumulations.   However,          *j
a laboratory study using  relatively hard water  (pH 7.5;  alkalinity            •
980 yeq/L) showed that 80 yg/L  killed  50%  of  the test population of
young-of-the-year largemouth bass in 82  days.   The same  study                 _
discovered that 8 iig/L induced  "abnormal behaviour" in the young fish         I
in 12-week exposure  (Clearley and Coleman  1974).  The young bass              •
average body-burden  accumulations of cadmium were   38 ng/g after a
four month exposure  to a  concentration of  80 yg/L.  Although it is            fl
difficult to apply these  laboratory data to field  conditions, it is           ||
apparent that cadmium residue accumulations in  fish tissue from
Ontario lakes, particularly  in  the  more  acidic  lakes, were consider-          •
ably higher than accumulations  observed  under laboratory  conditions           •
to cause biological  effects.
                                                                               I
3.7.9.4   Aluminum and Manganese

No correlations between  lake  acidity  and  mean residue accumulations           •
were apparent in the  1981 collections.   It  is likely that differences         |
in lake complexing capacities  influence  aluminum availability for
uptake.  Therefore factors  other  than pH and  alkalinity will have to          «|
be considered to evaluate fully residue  accumulations.                         •

Moreau et al. (1982)  compared  the chemical  content  of opercula and
scales of brook trout from  lakes  in Laurentian Park classified by             •
Richard (1982) as more acidic  (Group  1,  described in Section 3.7.10)          •
with the same calcified  tissue from brook trout from three nonacidic
lakes (Group 3, also  described in Section 3.7.10).   They reported             ij
that the content of manganese, zinc and  strontium was significantly           ||
higher in the calcified  tissue of brook  trout from  the acidic lakes.
                                                                               1

                                                                               I
The Adirondack  region is  one of the largest sensitive lake districts
in the  eastern  United States, and it is also receives the highest              •
annual  loading  of wet sulphate.  A recent inventory of Adirondack              I
waters  classified lakes  by type of fishery supported (Pfeiffer and
                                                                                I

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Festa 1980).  These authors  suggest  that  acidic  deposition has
exerted the greatest negative  impact on  the  brook trout  fishery.
Brook trout are frequently the only  game  fish  species  present  in  the
many small headwater ponds located at high elevations  in the
Adirondacks and particularly susceptible  to  acidic deposition.

It is difficult to evaluate  exactly  how many fish populations  have
been lost from Adirondack waters  as  a result of  acidification. The
Adirondack region encompasses  approximately  2877 individual lakes and
ponds.  Pfeiffer and Festa (1980) note that  180  Adirondack ponds  that
formerly sustained brook trout populations (either naturally or by
stocking) no longer support  such  populations.  It has  not  however
been formally demonstrated that all  (or most of) these populations
extinctions occurred as a result  of  acidic deposition.  For at least
a few lakes (reviewed  in Pfeiffer and Festa  [1980])  historic records
of fish population status, fish management procedures, and water
chemistry do suggest that population declines  were associated  with a
decrease in pH level and that  alternative explanations for the loss
of fish other than surface water  acidification seem unlikely.
Schofield (1976a) surveyed high elevation Adirondack lakes (total 214
lakes).  For 40 of these lakes, historical data  on fish and pH were
available (Figure 3-32).  In the  1930s, only 8%  of these lakes had pH
<5.0, 10% had no fish  whereas  in  the 1970s,  48%  had  pH <5.0 and 52%
had no fish.  In some  cases, entire  fish  communities consisting of
brook trout, lake trout, white sucker, brown trout,  and  several
syprinid species apparently  have  been eliminated over  the  40-year
period (Schofield 1976a, 1981, 1982).

The present-day distribution of fish in Adirondack lakes and streams
in relation to pH provides additional circumstantial evidence  of  the
impact of acidification on fish.  For high elevation lakes,  Schofield
(1976b, 1981, 1982) noted that the occurrence  of fish was  reduced at
pH levels below 5.0 (Table 3-22 and  Figure 3-32).   Brook trout occur
less frequently in lakes with  pH  <5.0, white suckers at  pH <5.1,
creek chub at pH <5.0, lake  chub  at  pH <4.5  to 5.0,  and  brown
bullhead at pH <4.7 to 5.0 (Schofield 1976b).  About 50% of high
elevation lakes had pH levels  below  5.0 in 1975  and  82%  of these
acidic lakes were devoid of  fish  (Schofield  1976b).   High  elevation
lakes, however, constitute a particularly sensitive  subset of
Adirondack lakes.  It  cannot be inferred  that  50% of all Adirondack
lakes have pH<5.0, nor that all  lakes currently without fish  once
had fish and have lost their fish populations  as a result  of
acidification.

Indices of fish population status in Adirondack  streams  (sample of 42
streams) were also found to  be positively correlated (p  < 0.05) with
pH measurements (Colquhoun et  al. 1980).

In addition to these observations of  fish population status in
Adirondack waters as related to acidity,  Schofield and Trojnar (1980)
examined the effect of water quality  on fish stocking  success. Poor
survival of brook trout fall fingerlings  stocked into  Adirondack

-------
TABLE 3-22. DISTRIBUTION AND FREQUENCY
DURING SURVEYS OF
BRACKETS
pH <4.5

Total lakes 16
% of total 7.1
No fish 16
% 17.2
Fish 0
%
Brook trout 0
f .80
Lake trout 0
%
f
Bullhead 0
%
f
White sucker 0
%
f .15
Creek chub 0
%
f
Golden shiner 0
% 15.0
f .15
Common shiner 0
f
Lake chub 0
%
f
Redbreast
sunfish 0
%
f
Common sunfish 0
%
f
REFER TO
4.5-4.99

95
44.2
74
79.6
20
20.0
16(26)
19.5
.72
0(5)


8(8)
16.0
.40
3(1)
8.3
.28
0(7)


3(4)
15.0
.12
9(2)
9.1
.05
KD
14.3
.05
0

0(1)


OF OCCURRENCE OF FISH
SPECIES
3-128
COLLECTED
1
1
ADIRONDACKS LAKES >610 METRES ELEVATION. NUMBERS IN
EXTINCT
5.0-5.49

36
16.7
2
2.1
25
25.0
18(1)
21.9
1.00
1(2)
7.7
0.4
11(1)
22.0
.44
7(1)
19.4
.73
5
18.5
.20
3
5.0
.09
0(1)
0
0


0

0


POPULATIONS
5.5-5.99

15
7.0
1
1.1
11
11.0
11
13.4
.77
4
30.8
.36
5
10.0
.45
8
22.2
.32
7
25.9
.64
1
40.0
.36
3(1)
27.3
.27
2
28.6
.18
0

1
16.7
.09
(Schofield
6.0-6.49 6

28
13.0
0

22
22.0
17
20.7
.89
2
15.4
.09
14
28.0
.64
7
19.4
.42
5(1)
18.5
.23
8
15.0
.16
1
9.1
.05
0


0

1
16.7
.05
1976b)
.5-6.99

22
10.2
0

19
19.0
17
20.7
1.00
4
30.8
.21
9
18.0
.47
8
22.2
1.00
8
29.6
.42
3
10.0
.67
3
27.3
.16
1
14.3
.05
3
100.0
.16
2
66.7
.11

>7.0

3
1.4
0

3
3.0
3
3.7

2
15.4
.67
3
6.0
1.00
3
8.3

2
7.4
.67
2

3
27.3
1.00
3
42.9
1.00
0

2
66.7
.67

TOTAL

215

93

100

82

13


50


36


27


20

11

7


3

6


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lakes was significant, (p  <0.05) associated with  low  pH  levels  and
elevated aluminum concentrations.

Schofield (1982) summarized  available data  relating  water acidity and
fish population status for the eastern United  States.  With  the
exception of studies in the  Adirondack region, very  few of these
studies included comprehensive inventories  of  fish populations and no
adverse effects of acidic deposition on  fish have  been definitely
demonstrated.  Discussions generally refer  only  to "potential
impact".
3.7.10.2   Ontario

More data on inland fisheries  resource effects  resulting  from lake
acidification are available from Ontario  than from  any  other  province
in Canada.  The case study of  lakes  in the La Cloche  Mountain range
by Beamish and Harvey (1972) is best known.  These  lakes  have a
naturally low buffering capacity and are  only 65 km southwest of  the
Sudbury smelters.  Some of the lakes had  no  fish populations  at the
time of the first survey, 1965-66; others had populations that were
endangered, and still others were apparently in a healthy condition
(Beamish 1976).

The fish community of Lumsden Lake (one of 68 examined) has been
studied for 14 years.  The following chronology of  fisheries  losses
has been assembled by Harvey (1980)  from  his studies  with Beamish
(Beamish and Harvey 1972), from provincial government fish capture
records dating to the early 1960s, and from  observations  by local
anglers and residents for some species prior to 1960:

  1950s     -   8 species present

  1960      -   last reported capture, yellow perch,  Perca flavescens
                and burbot, Lota lota

  1960-65   -   sport fishery fails  (pH 6.8, Sept.  1961)

  1967      -   last capture of lake trout,  Salvelinus namaycush  and
                slimy sculpin, Cottus cognatus

  1968      -   tagged population of white sucker,  Catostomus
                commersoni disappears

  1969      -   last capture of trout perch, Percopis omiscomaycus
                and lake herring, Coregonus artedii

  1971      -   last capture of lake chub, Couesius plumbeus  (pH  4.4,
                Aug. 1971)

In their study, Beamish and Harvey (1972) also  reported the loss  of
fish from nearby Lumsden III, Lumsden II  and O.S.A. lakes.  They

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                                                                  3-130
                                                                               I
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interpreted these observations as evidence  that  the  factor(s)
affecting the fishes of Lumsden Lake were probably widespread.   They
also noted that both sport and nonsport  fishes had disappeared  from
the lakes, suggesting that overfishing was  not responsible.   The loss
of populations of lake trout, lake herring, white suckers  and other
species was attributed to decreasing pH.  Historical data  available           •
for Lumsden Lake indicated that in one decade  (1961-1971)  the lake pH         I
had decreased from approximately 6.8 to  4.4.  Measurements of pH from
1961 or earlier were available for eleven other  La Cloche  Mountain
Lakes, and corresponding 1971 measurements  for these lakes indicated          4
that pH had decreased one to two units in  the  decade.

                                                                               I
Beamish (1974a) also examined  fish  populations  in O.S.A.  and Muriel
Lakes.  He found that few fish remained  in  O.S.A.  Lake.   While
several species were present in Muriel Lake,  only the  yellow perch
population appeared unstressed.  A  case  history of another La Cloche          «
Mountain lake, George Lake, was compiled by Beamish et al. (1975) for         •
the years 1966 through  1973.   They  estimated  that  the  pH of George            *
Lake decreased at an annual rate of 0.13 pH units.  Coincident with
the reduction in lake pH, populations of lake trout, walleye, burbot          IB
and smallmouth bass were lost  in this period.  In 1973,  most brown            m
bullheads, rock bass, pumpkinseeds  and northern pike did  not spawn.


Mountains and the concomitant  loss  of fish  populations.   He also
examined other possible explanations for the  response  of  fishes in            —
these lakes.  He concluded that decreased pH appeared  to  be the               •
principal agent stressing the  fish  populations, as well  as controll-          ™
ing the concentrations  of metals.

Examination of the age  distribution of white  suckers  in  George Lake           I
in 1972 indicated no missing year classes and it was concluded that
no major reproductive failures had  occurred prior to  1972 (Beamish et         •
al. 1975).  The pH of George Lake was measured  colorimetrically In            •
1960 as 6.5, ranged between 4.8 - 5.3 in 1972-73 and was  5.4 in 1979
(Harvey et al. 1981).   In 1967, the white sucker population contained         _
fish up to 14 years of  age.  By 1972, almost no fish were older than          •
6 years.  Sampling in 1979 revealed that 90% of the population was            ™
composed of two- and three-year old fish (Figure 3-41).
                                                                               •
Harvey (1980) also showed that the  white sucker population of Crosson         0
Lake (pH 5.1; Muskoka-Haliburton) had a  truncated age  distribution
with few fish older than five  years (Figure 3-45)  compared with the           m
age composition of white suckers in less acidic Red Chalk (pH 6.3)            I
and Harp (pH 6.3) lakes.  Such a comparison must be viewed with
caution due to the natural variability of age structure  between
lakes.  However a change to a  similar age structure patten was                •
observed, coincident with declining pH,  in  George Lake (Harvey et al.         •
1981).

Kelso et al. (1982) have recently reported  on a survey of 75                  |
headwater lakes varying in size from 1.6 to 120 ha in  the Algoma area
                                                                                I

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           W
           il
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           E
           3
           Z
               100
                                      RED CHALK LAKE
                    0  1 2  3 4  5  6  7  8  9  10 11 12 13 14

                                Age in Years
Figure 3-45.  Age composition of  the  white  sucker  population  of
              three lakes in the  Muskoka-Haliburton Region  of
              Ontario (Harvey 1980).

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                                                                  3-132
of central Ontario.  Most were  found  to  be  poorly  buffered with 65%
of the lakes having alkalinities  less  than  200  yeq/L,  26% less than
40 yeq/L and 8% less than or equal  to  0  yeq/L.   In 55  of  the  lakes
sulphate concentrations were found  to  exceed  bicarbonate.  None of
the eight lakes with alkalinity values less than zero  were found to
contain any sport fish, including brook  trout,  the primary sport fish
in this area of the Province.

Minns (1981) analyzed the Aquatic Habitat Inventory data  base of the
Ontario Ministry of Natural Resources  (OMNR).   This data  base
contains conductivity, pH, lake morphometry and fish species  presence
information for 6,393 Ontario lakes (as  of  September 1980, the time
of analysis).  The lakes contained  in  the data  base were  assumed to
be representative of lakes in the area surveyed.  Analysis of the
data base for the presence of dystropic  lakes  indicated that  very few
were included and therefore their affect on the analysis  would be
minimal.  Using relationships beween  alkalinity, conductivity and pH,
lakes were classified into categories  in terms  of  their acidification
status and the results were extrapolated to areas  represented by the
sample.  Minns estimated that 1,200 lakes in  the province are too
acidic to sustain fish communities  (lake pH less than  4.7) and
approximately 3,500 other lakes are approaching that condition (lake
pH 4.7-5.3).  Most of these lakes are  situated  in  watersheds  in the
region of Sudbury and are small (i.e., less than 10 hectares).  Minns
suggested that esocid and most  percid  communities  are  not currently
at risk whereas the brook trout,  lake  trout and bass communities
represent the most vulnerable resources.
3.7.10.3   Quebec

Fisheries investigations  in  the  province  of  Quebec have concentrated
in the Laurentian Park.   To  determine  the relationship between the
level of acidity and  fish productivity in these lakes, the Quebec
Ministry of  the Environment  sampled  158 lakes  in the area.  Water
samples were collected  through the ice, three  weeks after the
beginning of snowmelt in  March 1981.   Most of  the lakes sampled were
headwater lakes ranging in size  from 10 to 25  hectares, with brook
trout populations.

Richard (1982) classified the lakes  into  three groups using a
multivariate analysis.  The  variables  accounting for the greatest
between group variance  are described following:

Group
1
2
3

Number
of Lakes
23
65
57

pH
5.2
5.9
6.4

Alkalinity
(WS/L)
8.5
45.6
130.6

HC03-/SO
0.1
0.6
1.8
Total
,2- Aluminum
(yg/L)
230.0
143.8
71.2
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In each group of lakes the average annual  yield,  the  angling effort
and the mean weight of the fish  caught  (from detailed daily records
prepared by all fishermen) were  compared  (Richard 1982).   Only those
lakes with nine years of  continuous  exploitation  were included in the
analysis (12 lakes in Group  1, 30 lakes in Group  2,  36 lakes in
Group 3).  During the last four  years of  study (1978-81)  the mean
yield from Group 1 lakes  (the most acidic) was not  statistically
different from that of Groups 2  and  3.  This conclusion was corrobor-
ated by examination of data  from 34  additional lakes  that had been
fished continuously for from four to six  years (Richard 1982).

Fisheries management practices within the  Laurentian  Park provide for
closure to fishing when angling  success was reduced  as defined by a
lower mean weight or lower number of fish  caught, or  when spawning
habitat was disrupted.  Forty-four lakes  were not included in the
analysis as they had been closed to  fishing for one  or more years
preceding 1981.  The 44 lakes which  were  closed to  fishing included
43.5% of the most acidic  lakes (Group 1)  as compared  with 36.9% of
Group 2 lakes and 17.5% of the Group 3  lakes.   This  comparison
suggests lower productivity  in lakes in Groups 1  and  2, the more
acidic and acid-stressed  lakes,  than in Group 3 lakes.

Although the frequency of fisheries  management problems was higher in
the more acidic and acid-stressed lakes,  one cannot  assume a direct
cause-and-effeet relationship with low  pH, but only a general
association between fish  productivity,  pH and the oligotrophic
conditions of these waters.
3.7.10.4   Nova Scotia

There are 37 rivers flowing  through Nova  Scotia for which there are
records to verify that they  are  (or once  were)  Atlantic  salmon rivers
(Farmer et al. 1980).  For 27 of  these  rivers,  almost  complete
angling catch records are available (annual  reports from federal
fishery officers) from 1936.  Of  these  27 rivers,  5 have undergone
major salmon stock alterations since  1936 by dam construction/
removal, and/or extensive hatchery stocking. Watt et  al. (1983)
examined the effect of low pH on  angling  by  dividing the remaining 22
rivers into two groups, based on  1980 pH  levels.   For  the 12 rivers
presently at pH values greater than 5.0,  only one  shows  a statistic-
ally significant decline in  angling success  since  1936,  another shows
a significant increase, and  10 show no  significant trend.  Of the 10
rivers with pH values less than  5.0,  9  show  significant  declines, and
one shows no significant trend.

To combine the data so as to form averages for  the two groups, the
records were first normalized by  expressing  each river's angling
catch as a percentage of the average  catch in that river during the
first five years of record (1936-40).   These percentages were then
summed and averaged for each of  the two pH groups.  The  results
(Figure 3-46) reveal virtually identical  angling  catches in the two

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                                                                         3-134
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•£  10
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            Mean for 12 rivers with pH>5.0(1980)

            Mean for 10 rivers with pH£ 5.0 (1980)
                j_
                      _L
          _L
                    JL
     1935
           1940
1945
1950
1955
1960
1965
1970
                                               Year
        Figure 3-46.
                   Atlantic salmon angling data normalized to facilitate

                   the comparison between high and low pH rivers.   Each

                   river's catch was expressed as a percentage of  the mean

                   catch in 1936-40 so as to give all rivers equal

                   weighting, and the two groups were then averaged by

                   year (Watt et al. 1982).
1975
19f
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                                                               I


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                                                                  3-135
groups until the early  1950s;  after which  the  angling catches in
rivers of pH less  than  5.0  declined,  while the catch in rivers of pH
more than 5 continued to  show  no  significant  trend with time.
Factors other  than pH (e.g.,  stream flows  and  sea survivals) also
affect the angling success.  Variation  from these other factors
should, however, affect both  groups similarly.  The apparent reason
for the difference in angling  success between  the two groups of
rivers is a difference  in pH  since the  1950s.

Historical water chemistry  data are available  for some of these
affected rivers from surveys  performed  in  1954 and 1955 (Thomas
1960).  In the past 25 years,  the pH  of  the Tusket River has
decreased from an  annual  range of 4.9-6.1  to  4.6-4.9; the Roseway
from a range of 4.4-6.4 to  4.3-4.5; the  Jordan River from about 5.1
to a range of  4.4-4.6;  the  Medway River  from a range of 5.5-6.5 to
5.1-5.8; and the Clyde River has  decreased from 5.0 to 4.6.
Alkalinity values  were  below  zero in  the Tusket,  Clyde, Roseway and
Jordan rivers in 1979-80  (Watt et al. 1983), but  was greater than
zero during Thomas' study 25 years earlier. Although Thomas (1960)
sampled some of these rivers only once,  his data  on river pH suggest
that salmon reproduction  in a  few rivers may  have been adversely
affected due to acidity by  the early  1950s, consistent with  the catch
data presented in  Figure  3-47.

Within Nova Scotia, the pH  of  surface waters  xs well correlated with
geology (Watt  1981).  Seasonal variation in the pH of those  rivers is
about 0.5 units, with the annual  minimum occurring in mid-winter, and
a maximum in late  summer.   At  present there are seven rivers with pH
less than 4.7 that previously  had salmon but now have no salmon or
trout reproduction; 11 rivers  are in  the pH range 4.7-5.0, where some
salmon mortality may be occurring; and  seven  rivers are in the pH
range 5.1-5.4, which is considered borderline  for Atlantic salmon
(Figure 3-48).  Those rivers  represent  2%  of  the  total Canadian
habitat potential  for Atlantic salmon, and 30% in Nova Scotia.

The numbers of salmon angled,  recorded  by  Canadian federal fisheries
officers since 1936 in six  Nova Scotia  rivers  are illustrated in
Figure 3-47.  The  Clyde River  with a  mean  annual  pH of 4.6 in 1980-81
has produced no angled salmon  since 1969.   Electroseining in the last
several years also produced no salmon.   The Ingram River with a mean
annual pH of 5.0 (range 4.8-5.8)  apparently still has a small
reproducing population; it  was at one time a good producer of
Atlantic salmon.   Federal fisheries officials  consider this  river to
be in imminent danger of  losing its remaining  stock.  This river has
been identified by Canada Department  of  Fisheries and Oceans
personnel as a candidate  for  liming in order to create a refuge for
maintaining the gene pool of this stock.

One of the Nova Scotia rivers  "threatened" by  pH declines,  the
Mersey, contains an Atlantic salmon hatchery.   The Mersey watershed
has poorly developed soils, and its underlying geology is Devonian
granite.  The mean total  alkalinity of samples collected from the

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                                                                      3-136
               MIDDLE RIVER
Q
UJ
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O
z
       i    r ~~ii    i
  1935 40  45 50  55  60 65  70  75 80

               Year
z
O
<
CO
300-

250-

200-

150-

100-

 50-
               TANGIER RIVER
DC
til
m
  1935 40  45 50  55  60 65  70  75  80

                Year
200-i



150-



10O-



 50-
               SALMON RIVER
  1935 40  45 50  55  60 65 70  75  80


               Year
                                                    INGRAM RIVER
                                              "IIIII
                                          193540 45  50 55 60  65  70 75 80


                                                       Year
                                                     EAST  RIVER
                                              40 45  50  55  60 65  70 75  80
                                             1935
                                                       Year
                                                    CLYDE RIVER
                                              193540 45 50  55 60 65  70
                                                          Year
                                                                      75  80
    Figure 3-47.  Angling records for six Nova Scotia Atlantic  coast
                  rivers with mean annual pHs (1980) <5.0  (Watt et  al.
                  1983).


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                                                  pH <4.7 (no natural salmon reproduction)

                                                  pH range 4.7 - 5.0  (some mortalities likely)

                                                  pH range 5.1 - 5.4 (fisheries threatened)

                                                  pH > 5.4 (no immediate acidification threat)
Figure  3-48.
The Altantic salmon rivers  of  the Maritimes have been
divided  into 4 pH (estimated mean annual)  categories
based on significance to  salmon reproduction.   Present
evidence indicates that salmon cannot reproduce at pHs
below 4.7.   Juvenile mortalities of 30% or more are
expected in the pH range  4.0-4.7.  Rivers  in  pH range
5.1-5.4  are considered threatened.  Above  pH  5.4 there
is no immediate acidification  concern with regard to
Atlantic Salmon (Watt 1981).

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                                                                  3-138
I
river in 1978-79 was less than  10 yeq/L, while  mean pH was 5.2 (range        •
of 4.9-5.4) (Farmer et al.  1980).   In  1954-56 the  river had a mean pH
of 5.8, with a range of 5.4-6.6, and a mean  total  alkalinity of              —
48 yeq/L CaC03, with a range  from 20 to 88  (Thomas 1960).   Mean              •
sulphate values have been estimated to have  increased  from 76 yeq/L
in 1954-55 to  158 yeq/L in  1978-79.  During  the period 1975-78,
mortality of Atlantic salmon  parr reared at  the Mersey hatchery              I
typically occurred during the third and fourth  weeks after first             •
feeding.  This higher-than-expected mortality was  attributed to
increased acidity in spring river water supplying  the  hatchery.  In          •
1979, by treating the water with CaC03, the  salmon fry mortality was         •
reduced from 30% to 3% (Farmer  et al.  1980).  In 1980, the water was
again treated  and produced  the  same increase in survival of parr.            ^

Farmer et al.  (1980) noted  that, even  though all rivers classified as        ™
presently unsuitable for salmon historically sustained Atlantic
salmon populations, these rivers are all also naturally somewhat             •
acidic and historically had relatively low  fish production.  Of the          |
20 readings of apparent water colour (rel. units)  (an  indicator of
the presence of organic acids)  presented for the 7 rivers  classified         m
"unsuitable" by Farmer et al. (1980),  16 were 100.  For "threatened"         •
rivers, only one of 21 readings was 100; the remaining readings
averaged 69.   For rivers classified neither  "unsuitable" nor
"threatened,"  and with pH readings  above 5.5, the  mean measure of            •
apparent colour was 44.  High degrees  of colour are largely attribut-        •
able to humates from peat deposits  and bogs  common in  this area.
Inputs from these materials probably contribute to the low pH levels         •
in "unsuitable" and "threatened" rivers.  Historical records of pH in        |
these rivers do, however, indicate  that acidity has increased in
recent years.  Watt et al.  (1983) concluded  "the Atlantic coast              am
rivers of Nova Scotia have  become more acidic over the past 27 years         •
in response to increased acid loading  in the precipitation."  This
increase in acidity has been  clearly correlated with declines in
populations of Atlantic salmon  in the  same  rivers.                           •
3.7.10.5   Scandinavia
1
Hendrey and Wright  (1976)  reported  that  "acid  precipitation has
devastated the salmonid  fish  in southern Norway."   Massive fish kills       tm
of adult salmon and  trout  have  been reported  in their river systems,        •
usually occurring during the  spring snowmelt  or after heavy autumn
rains.  An intensive  survey of  50 lakes  in southern Sweden showed
that inland freshwater species  are  also  threatened.  The decreases in       •
pH have resulted in  the  elimination of Atlantic salmon from many            •
Norwegian rivers in  the  past  20 years.   Scandinavian scientists have
concluded that, directly or indirectly,  the principal cause of the          •
fish losses is acidification  of the waters, due to acidic deposition.       ||
Portions of Canada's  Atlantic salmon fishery  appear to have declined
as a result of acidification  as has been experienced in Norway and          .
Sweden.                                                                      •
                                                                             I

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3.7.11   Response to Artificial Acidification

While we know that the end-product  of  acidification includes  the
disappearance of important  fisheries,  many of  the early changes which
occur in acidified ecosystems  are  relatively unstudied.  Furthermore,
it is not known whether declines in fish  stocks  are due singly or in
combination to the toxic  effects of hydrogen ion, to hydrogen ion and
aluminum or other metals  synergisms, to food-chain effects  resulting
from elimination of critical species of animals  and plants  or
disruption of nutrient cycles.

A whole-lake acidification  experiment  was  done in Lake 223  in the
Experimental Lakes Area,  Ontario,  in order to  examine some  of these
possibilities.  The pH of the  lake  was progressively lowered  from a
natural value of 6.5 to 6.9 (x = 6.7)  to  an average value of  5.1
by additions of sulphuric acid between 1976 and  1981.  Detailed
monitoring of chemical, physical and biological  changes,  as well as
physiological and ecotoxicological  studies,  were done throughout this
period.  Earlier biological results were  summarized by Schindler
et al. (1980), Schindler  (1980), Malley and Chang (1981), and
Schindler and Turner (1982).

Biological changes in the lake as  it was  artificially acidified and
the pH thresholds at which  these changes  occurred are summarized in
Table 3-23.  The first changes which could have  adversely affected
lake trout and white sucker populations occurred in 1978-79,  when
populations of two species  which are the  usual prey of trout, fathead
minnow (Pimephales promelas) and oppossum  shrimp (Mysis relicta),
collapsed.  Despite these changes,  no  effects  were detected in trout
populations.  A succession  of  strong white sucker year-classes in
1978-80 and greatly increased  abundance of pearl dace were  adequate
food alternatives for trout.   Apparently,  the  pearl dace  partially
occupied the vacated fathead minnow niche, while the primary  food
source of white suckers,  benthic dipterans,  increased in  abundance
(Davies pers. comm.).  In addition, the appearance of excessive
growths of Mougeotia in the littoral beaches probably provided
excellent nursery areas for sucker  fry, but  increased water transpar-
ency (Schindler 1980) perhaps made  prey capture  easier for  trout.

Even though many changes  have  occurred in  lower  trophic levels,
juvenile and adult white  sucker and lake  trout populations  have shown
little indication of stress, except for recruitment failures  in the
very recent years of acidification, at pH values of 5.35  and  below.
Up to 1981, populations of  both species increased, and their  growth
rates have remained high.   Relative condition  (a quantitative measure
of fish fatness) has decreased progressively for trout from 1977 to
1980, and for white suckers  from 1978  to  1980, but this would be
expected due to the increased  abundance of both  species over  the same
time period.

The relatively swift collapse  of the fathead minnow population is due
to two factors.  Firstly, a  recruitment (year-class) failure  occurred

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3-140





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                                                                   3-141
in 1978 (pH  -5.8).  This  agrees  well  with  the  results of Mount
(1973), who found that  impaired reproduction of the same species
occurred at this pH  in  laboratory studies done  at a variety of pH
values.  Secondly, even under  preacidification  conditions, this
species had a very short life  span of  three years in Lake 223.  Even
under natural conditions,  during  the  second and third years of life
an extremely high natural  mortality rate occurred, over 50% per year
(Mills pers. comm.), presumably caused in large part by trout
predation.  Very few individuals  remained after the second year of
life.  Therefore, the failure  of  one  year class in 1978 would leave
few spawning adults  (age 2 and 3) the  following year.  Population
recovery was, therefore, almost impossible.  The combination of
successive year class failures in 1978 and  1979 assured the rapid
disappearance of this species  from Lake 223.

The thresholds observed for disappearance of key species and
appearance of others in Lake 223  agree well with observations made in
other acidified lakes.

For example, Mysis in Lake 223 disappeared  in the same pH range as
benthic crustaceans  with similar  food  habits disappeared in
Scandinavian lakes (0kland and 0kland  1980). Mougeotia epidemics in
Lake 223 began at almost the same pH values as  in Swedish waters
(Hultberg  pers. comm.).   Recruitment  failures  in lake trout and
white sucker began in the  same pH range that year classes began to be
absent in lakes near Sudbury and  in Scandinavia (Harvey 1980; Muniz
and Leivestad 1980;  Raines 1981b,c).

The Lake 223 results also  demonstrate  the danger of assessing
biological damage from  acidification  solely on  the basis of game fish
populations.  Major  alterations to fish habitats and prey species
occurred several tenths of a pH unit above  where initial damage to
lake trout was detectable, even with  an extremely intensive study of
the trout population.   The predation habits of  lake trout appeared to
allow them to easily switch to pearl dace after the disappearance of
the fathead minnows  which  had  been their normal prey.

In summary, the Lake 223 experiment clearly shows that alterations to
aquatic food chains  begin  at pH values slightly below 6.0.  The
remarkable agreement between these whole lake experiments and
observational studies in Scandinavia and eastern North America
provides strong evidence that  the observed  declines in fisheries are
caused by acidification and not by other ecological stresses.
3.7.12   Effects of Acidic Deposition  on  Birds  and Mammals

While birds and mammals are not  affected  directly by acidic depo-
sition they are vulnerable to  changes  in  their  habitat caused by
acidification, particularly to changes affecting the availability and
quality of their food.  Although adults may  continue to find
sufficient food in areas adjacent  to their traditional nesting or

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                                                                   3-142
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breeding sites, they may be unable  to  obtain  sufficient  food to raise
young.  In Scandinavia there have already  been reports of  such
effects on aquatic bird populations.   Aimer et al.  (1978)  reported            4
that, "fish-eating birds,  such  as mergansers  and loons,  have been             •
forced to migrate from several  acidic  lakes,  with decreasing fish
stocks, to new lakes with  ample  food  supply.   In this way,  many               _
territories will become vacant  and  this  will  lead to decreasing               •
stocks."  While the extent of the problem  has not yet been documented         ™
in Sweden, Nilsson and Nilsson  (1978)  found a positive correlation
between pH and "water" bird species richness.  "Water" birds were
defined as those species dependent  upon  open  water,  and  included a
loon, and several species  of waterfowl and gulls.  From the results
of this study it was suggested  that a  reduction in  young fish, a very         «|
important food source for  aquatic birds, may  lead to low reproductive         •
success and local extinction in  some  bird  species (Nilsson and
Nilsson 1978).  Eriksson et al.  (1980) also proposed that  reduced
reproduction of fish in acidified lakes  may decrease the availability         •
of fish of the size classes appropriate  to young diving water birds.          ™
                                                                               I
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Losses of other aquatic organisms  such  as  clams,  snails,  and
amphibians have been documented  in acidified  lakes  and ponds (Section
3.7.6; Hagstrom 1977; Hall and Likens  1980; J.  0kland 1980;
K.A. 0kland 1980).  While wildlife are  largely  opportunistic feeders,         «
reductions of these organisms could affect the  food availability for          •
many wildlife groups such as waterfowl  and semi-  aquatic  mammals.
The effects of changes in food and habitat will be  difficult to
witness in the short term but, in  time,  breeding  densities may                •
decline and eventually productivity could  fall  in response to reduced         9
food availability.

The diet of the common loon  (Gavia immer)  is  approximately 80 percent         (
fish, the remainder being made up  of crustaceans, molluscs,  aquatic
insects, and leeches (Barr 1973).   Because the  food requirements of           «
loons while rearing young are high and  many of  their food organisms           •
are quite sensitive to acidification,  the  nesting densities  of this           *
species may be reduced.  In  eastern Canada, the common loon nests on
lakes throughout  the susceptible terrain of the Precambrian Shield            •
(Godfrey 1966).   In central  Ontario and Quebec  as well as in the              0
Adirondack Mountains of the  northeastern U.S.,  a  number of lakes have
already been reported as devoid  of fish as a  result of acid  loading           •
(Beamish 1976; Schofield 1976a).   Studies  in  New  York indicate that           |
loon productivity has remained high but  nesting densities have
declined in the Adirondack region  (Trivelpiece  et al. 1979).  To              •
date, however, changes in loon populations in the Adirondacks have            •
been interpreted  only with respect to  human disturbance;  the probable         *
role of food depletion has not been investigated.  In Quebec,
fish-eating birds were found more  often on the  nonacid lakes                  •
(DesGranges and Houde  1981).  The  common merganser (Mergus merganser)         |
and the kingfisher  (Megaceryle alcyon)  were observed only on those
lakes where the summer pH is higher than 5.6.  In the vicinity of             m
Schefferville, Quebec, important differences  in numbers and composi-          •
tion of lake-dwelling bird communities  were found:   a third as many
                                                                               I

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                                                                   3-143
species and a quarter of the  total  number  of  aquatic birds were
observed on lakes with  pH  less  than 4.5  compared to lakes with pH
greater than 6.0 (DesGranges  and  Houde  1981).   The situation is less
clear, however, for  lakes  of  pH 4.5-5.5.   It  has been suggested that
the biomass of some  forms  of  benthic invertebrates increases with low
to moderate inputs of acid because  there are  fewer fish predators
(Henrikson and Oscarson 1978; Eriksson  1979;  Henrikson et al. 1980).
This may explain the larger number  of invertebrate-feeding ducks
which are found on moderately acid  lakes  in southern Quebec
(DesGranges and Houde 1981) and in  central Ontario (McNicol and Ross
1982).

Insectivorous birds  such as swallows, flycatchers, and kingbirds may
be affected by lake  acidity since this group  of birds feed on
emerging insects and it is during the emergence that many insects are
most sensitive to high  acid levels  (Bell 1971).  Because a number of
species of aquatic insects emerge in early spring during the peak of
acid input to lakes  and ponds they  are particularly vulnerable to the
effects of acid loading.   It  is also in  early spring that the birds
have higher food requirements in  nesting and  raising young.  In
southern Quebec, the tree  swallow (Iridoprocne bicolor) was more
common during the breeding season in the  vicinity of lakes of
pH  >6.0 while in northern Quebec this  species was not observed in
the area of lakes of pH <4.5 (DesGranges  and Houde 1981).  This was
also the finding from the  studies of insectivorous birds in the
Killarney area of Ontario  (Blancher 1982).   The presence or absence
of these birds will  largely be  determined by  the biota of the nearby
lakes.

Effects of acidification on lower life  forms  such as microorganisms,
essential to decomposition and  nutrient  cycling have been found
(Hendrey et al. 1976; Leivestad et  al.  1976).   A loss in productivity
at the base of the food chain due to decreased nutrient availability
could result in progressively larger reductions at each succeeding
trophic level.  The  implications  for wildlife  at the top of the chain
are a critical loss  in  biological production  and severely reduced
carrying capacity of their habitat  (Clark and Fischer 1981).

Increased solubility and mobility of metals from sediments have been
reported as a result of acidification (Schindler et al. 1980).  The
higher concentrations of metals produced in lake waters have
important implications  for biological organisms as described in
previous sections.   Studies by  Nyholm and Myhrberg (1977) and Nyholm
(1981) have implicated  aluminum in  the impaired breeding of four
species of passerines.  Reductions  in the  reproductive success of
these birds was highly  correlated with the  distance of their nests
from acid-stressed lakes in Swedish Lapland.   Breeding impairment was
manifested as abnormal  egg formation producing thin and porous
shells.  In addition, clutch  size and hatching success of the
"affected" birds were reduced and egg weights  were lower in the birds
closer to the acid-stressed lakes.   The  link  between the acidified
lakes and the breeding  impairment has been  related to the high

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                                                                   3-144
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aluminum content of the limnic insects upon which  the  birds  feed
(Nyholm 1981).  Birds feeding closest  to  the  stressed  lakes  have the
highest proportion of contaminated  insects in their  diets (Nyholm            fl
pers. comm.; Eriksson et al. 1980).  Similar  findings  of  decreased           |
egg size and weight were found for  the eastern kingbird  (Tyrannus
tyrannus) in the Killarney area  of  central Ontario (Blancher 1982).           n
Although severe abnormalities in shell formation were  not evident in         •
the eggs examined in this preliminary  study,  egg porosity as measured
by the rate of water loss over the  incubation period was  negatively
correlated with pH.                                                           •

Elevated mercury levels have been found in fish in lakes  with low pH
in central Ontario (Suns et al.  1980).  In the Bohuslan  area of              •
Sweden, elevated levels of mercury  were found in eggs  of  goldeneye           |
(Bucephala clangula) (Eriksson et al.  1980b).   Raccoons  (Procyon
lotor) from the Muskoka area of  Ontario support liver  mercury levels         M
of 4.5 ppm, a concentration five times greater than  specimens from an        •
area with nonacidified waters (Wren et al. 1980).   Because neither of
these areas receives point source inputs  of mercury, the  sources are
believed to be leached from the  watershed by  acids or  mobilized from         •
sediments.  Methylation of mercury  has been related  to the process of        •
acidification and the formation  of  methyl mercury, a stable  and
soluble form which readily bioaccumulates, is believed to be favoured
at low pH (Fagerstrom and Jernelov  1972).
I
Results of a preliminary study  of metal  accumulation in the tissues          ^
of moose (Alces alces) have established  an age  dependent increase            •
in cadmium for tissues collected from 38 moose  and 56 roe deer in            ™
Sweden (Frank et al.  1981; Mattson  et al. 1981).   Aimer et al. (1978)
reported a 10-fold increase in  levels of cadmium  in acidified lakes          I
on the Swedish west coast  compared  with  those  in  nonacidified lakes          •
in the same region.   Cadmium may be accumulated in large concentra-
tions by some terrestrial  and aquatic plants  (Anderson and Nilsson           M
1974; Hutchinson and  Czyrska  1975), and  therefore, metal contamina-          •
tion of wildlife feeding on these plants may  be an indirect effect of
acidic deposition.                                                            ^

A summary of potential effects  on selected species of birds and              ™
mammals dependent upon the aquatic  ecosystem  for  their food and
habitat is presented  in Table 3-24.  This summary is based solely            •
on feeding habits as  research on the impacts  of acidification on             •
vegetation structure  and productivity relating to wildlife habitat
is at a preliminary stage.                                                    •


3.8     CONCERNS FOR  IRREVERSIBLE EFFECTS                                    _

3.8.1   Loss of Genetically Unique  Fish  Stocks                               "

Loss of fish populations with specific gene characteristics from             •
lakes and rivers may  be an irreversible  process.   Over several               |
thousand generations, most species  appear to  have evolved discrete
                                                                              I

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3.8.2   Depletion of Acid Neutralizing  Capacity
3.9   ATMOSPHERIC  SULPHATE  LOADINGS  AND THEIR RELATIONSHIP TO
      AQUATIC ECOSYSTEMS
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stocks adapted to similar, yet discrete  and  specific,  habitats
(Loftus 1976).  The basic unit of  a  stock  is the  gene  pool,  which             —
is composed of a naturally sustained,  genetically variable  group of           •
individuals, adapted through evolution to  specific lake  conditions.           *
Surface water acidification is a stress  that may  reduce  genetic
variability in populations of native fishes  in sensitive areas.  As           •
an example, Beamish and Harvey (1972)  documented  the loss of gene             |
pools of fish in acidified lakes in  Ontario.  The Ontario Ministry of
Natural Resources has attributed the extinction of lake  trout                 •
(Salvelinus namaycush) in 27 lakes in the  Sudbury-Temagami  area to            •
acidification (Olver pers. comm.).

A naturally evolved complex of stocks appears essential  to  utilize            •
fully the productive capacity of waters.   Therefore, it  is  important          •
to recognize and preserve stocks (Haines 1981c; Loftus 1976; Ryman
and Stahl 1981).
I
Loss of discrete stocks may  inhibit  effective  re-establishment of
naturally reproducing populations  in waters  undergoing rehabilitation          m
and affect future opportunities  for  fisheries  management.                       •
I
Evidence seems to be conflicting  as  to whether  the  geochemical
alteration of watersheds due  to acidic input  should be  viewed as               •
irreversible, and, if  so, on  what scale.   Irreversibility can be               |
viewed most strictly as a failure to recover  over geologic time; but,
for natural resource systems,  an  incomplete  recovery to a prestressed          _
or undamaged state over a few decades, for all  practical purposes,              •
may be regarded as irreversible.

Although irreversible  reduction in acid  neutralizing capacity of               K
lakes and watersheds is one of the potential  effects of acidic                 •
deposition, our present information base  is  insufficient to determine
its probability in impacted areas.                                              •


3.8.3   Soil Cation and Nutrient  Depletion                                      _

The loss of soil cations, particularly Ca^+  and Mg2+, which can
lead to decreases in soil fertility (Overrein et al. 1980), is
another potentially irreversible  consequence  of watershed titration.           •
However, the extent to which  these cation losses represent a                   m
significant depletion  of total available  material  is unknown.
                                                                                I
The previous  sections  have  discussed chemical and biological changes           •
observed  in some  surface  water  systems,  including pH depression and
                                                                                I

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                                                                   3-147
associated effects over long-term,  annual,  seasonal  and event-related
time series.  Most of  the  results  are  consistent  with the explanation
that they result from  acidity  associated  with the 804 2~ and NC>3~
ions originating from  atmospheric  deposition.   This  section will
consider the significance  of these levels of  chemical alterations,
with a comparision of  the  annual deposition that  could be associated
with acidification of  the  most  sensitive  streams  and lakes.  This
analysis requires consideration, not only of  trends  in surface water
and precipitation pH and sulphate  concentration,  but also of the
frequency and severity of  brief periods during which much of the
response to the total  acidic loading rate from runoff events is
expressed.

Emphasis has been placed on deriving as much  information as possible
from comparisons of observed water quality  and biological effects in
areas of varying deposition.   These empirical observations integrate
many "unknowns" regarding  soil water interactions which are impli-
citly taken into account by empirical  comparisons.  Loading rates
estimated from conceptual  models of aquatic systems  are compared to
the empirical observations.  Such  empirical approaches to support
environmental management are common.   For example, flood structure
designs can be based on empirical  relationships between discharge,
precipitation and physical characteristics  of  the watershed (Chow
1964).  Vollenweider and Dillon (1974) used an empirical modeling
approach to set phosphorus loading criteria for eutrophication
control in lakes and reservoirs, and these  have proven effective.

The following are the  principal findings  presented in previous
sections important in  evaluating aquatic  effects  related to measured
acidic deposition:

1.   Precipitation over most of eastern North America has hydrogen
     ion concentrations up to  100  times those  expected for distilled
     water in equilibrium with  atmospheric  carbon dioxide.

2.   Large quantities  of sulphate  and  nitrate  ions are deposited with
     ff1" ions in precipitation  in eastern  North America.

3.   Lakes in eastern  North America with  low  alkalinities are
     receiving elevated acid loadings.  Such  lakes,  and their
     associated streams, may suffer low pH  and elevated metal
     concentrations for short  periods  of  time, particularly during
     snowmelt and other periods of  heavy  runoff.

4.   Stressed fish populations have been  observed in lakes that
     experience short-term low pH  and  elevated metal concentrations.
     Mortalities of adult  fish have been  observed in one study lake
     experiencing these conditions.

5.   There are numerous examples of streams and lakes in Canada and
     the United States that have experienced  and  are probably now
     experiencing depletion of alkalinity.  Fish  populations that

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3-148
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     survive short-term low pH  conditions,  will eventually be lost if
     alkalinity is depleted and pH values  fall below critical levels
     causing successive reproductive  failure.   Long-term acidifica-           m
     tion has caused losses of  fish populations in some lakes and             •
     streams.

                                                                               I
3.9.1   The Relative Significance  of  Sulphur and Nitrogen Deposition          •
        to Acidification of Surface Waters

Results presented in the previous  sections  have shown that four major         |
ions of concern in acidic  precipitation,  (H+,  NH^"1", N(>3~
and SO^- have some potential for  altering  lake and stream water              g|
acidity.  Soil and plant interactions with  nitrate ions allow nitric          •
acid to be largely assimilated  by  the terrestrial portion of the
watershed, except during periods of heavy  runoff (Section 3.2.2)
(McLean 1981).  In contrast, in many  regions with poorly developed            •
soils, that are limited in ability to neutralize acid, biological             9
uptake of sulphate is  small in  comparison  to the mass balance of
sulphur (Harvey et al.  1981).   Christophersen and Wright (1980)
reported that the sulphur  export from a watershed in Norway was
essentially the same as the total  input over the period November 1971
to October 1978.  In a number of areas studied, where there exist no          _
significant terrestrial sources or sinks of sulphur, SO^" is a               •
conservative ion whose  export to surface waters is directly related
to deposition in precipitation.

There are additional aspects to the issue  of the dominant anion               •
associated with the acidification  of  surface waters.  These include:

     1)   the relative magnitude of  S0^~  and NC>3~ in the rain and            f
          snow inputs,  their variation during the year, and long-term
          trends;                                                              M

     2)   the relative magnitude of  the biological interactions of            *
          both anions  in watersheds,  as they are affected by
          biological activity at different  seasons and by changes in          B
          biomass over long periods;                                           •

     3)   the production  of alkalinity in terrestrial and aquatic             •
          systems when NC>3 is assimilated  by plants; and                      •

     4)   the contact  time of precipitation inputs with the water-            ^
          shed.                                                                •

Data presented in map  form in Section 2 and other data presented by
Galloway et al.  (1980g),  McLean (1981) and by Harvey et al.  (1981)            •
indicate that acidic sulphur  inputs exceed acidic nitrogen inputs             V
over eastern North America on an annual basis.  The net yield of
these anions to  streams and lakes  is  predominantly SO^" on an annual         •
basis (Harvey et al.  1981).  Because  nitrate reaches surface waters           •
in small amounts relative to  its loadings  on an annual basis and does
            I

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                                                                   3-149
not accumulate in surface waters,  its  influence  on long-term surface
water acidification is  less  than  that  of  sulphate.

Further evidence that nitrate  deposition  is  not  principally respons-
ible for long term surface water  acidification is given in
Table 3-25.  Data for 21 headwater streams  in  the Muskoka-Haliburton
area of Ontario with a  range of mean annual  pH values from 4.08 to
6.18 show that as acidity increases, the  relative importance of NOg
declines.  The acid (H+) concentration exceeds the N(>3~ concentration
on a chemical equivalents basis for annual  pH  values of  5.5 or less,
so that lower pH values cannot be explained  by the presence of nitric
acid.  The E+/SO^~ ratios are also given for  the same streams
(Table 3-25).  At lower pH values, H+/S042"  ratios increase.
The ratio is always less than  one which indicates that the acid
concentration can be explained by the  presence of sulphuric acid.
The SO^~/fiO^~ ratios range  from  14 to 337 with  a median value of
170, demonstrating the  dominance  of 8642- over NOg" in surface waters
in the Muskoka-Haliburton region  (Jeffries  et  al. 1979; Scheider
et al. 1979c; and ongoing studies by Ontario Ministry of the
Environment).

Nitrate may be important on  an episodic basis  by adding to the pH
depression caused by sulphate. At Sagamore  Lake, New York, nitrate
concentrations in the lake outflow increased during spring pH
depression, while sulphate concentrations did  not increase (Galloway
et al. 1980g).  Sulphate concentrations still  exceeded nitrate
concentrations on an equivalent basis,  even  during spring runoff.

Uptake of nitrate ions  by algae and aquatic  plants results in the
production of alkalinity in  surface waters  (Goldman and Brewer 1980).
This has been shown to  occur in one of the  study lakes at Muskoka-
Haliburton.  Reported increases in lake pH  from  5.1 to 6.6 over the
summer were associated  with  decreases  in  nitrate concentrations by
photosynthetic processes, and  this was given as  the explanation for
the pH increases (Harvey et  al. 1981).

The evidence available,  and  the published interpretations of that
evidence (Harvey et al.  1981;  Overrein et al.  1980), lead to the
conclusion that, for surface water systems,  increases in acidity are
the result of dilute solutions of strong  acids reaching these waters.
Further, Harvey et al.  (1981)  following extensive analysis of
Canadian data and Overrein et  al. (1980)  following extensive research
in Scandinavia conclude  that most of the  acidity is due to the
changes observed in 804^" concentration attributable to sulphate and
sulphuric acid deposition (Harvey et al.  1981;  Overrein et al. 1980).
Both sulphuric and nitric acid contribute acidity to surface waters
during periods associated with pH depressions  and fish stress.
However, there is no strong  evidence at present  for anticipating any
appreciable reduction in long-term lake or  stream acidification from
a reduction in nitrate  inputs. In contrast, it  is important to note
there is a strong correlation  between  between  sulphate deposition and
surface water concentrations to suggest that a reduction in sulphate

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TABLE 3-25.
                                                                   3-150
MEAN AND RANGE OF pH VALUES, MEAN H+/N03  , H+/S042

AND S042~/N03~ RATIOS (calculated as ueq/L) FOR  21

HEADWATER STREAMS IN MUSKOKA-HALIBURTON,  ONTARIO 1976-

1980   [Data is from an ongoing  study, methods and  study

area as described in Jeffries et al. (1979) and  Scheider

et al. (1979b)]
Stream
Dickie 11
Red Chalk 2
Dickie 5
Dickie 6
Dickie 10
Chub 2
Dickie 8
Harp 6A
Harp 5
Chub 1
Harp 3
Harp 6
Red Chalk 1
Red Chalk 3
Harp 3A
Red Chalk 4
Jerry 3
Jerry 4
Harp 4
Blue Chalk 1
Jerry 1
Mean
PH
4.08
4.30
4.34
4.35
4.59
4.82
5.03
5.19
5.34
5.41
5.64
5.77
5.81
5.95
5.95
5.96
5.98
6.07
6.08
6.16
6.18
Range
pH
3.53-5.61
3.68-4.81
3.71-4.76
3.74-5.05
3.92-5.10
4.12-6.08
4.04-5.87
4.34-6.39
4.66-6.60
4.48-6.61
4.89-6.39
5.20-6.90
5.19-6.69
5.17-6.65
5.30-7.30
5.28-6.71
5.27-6.67
5.49-6.55
5.29-6.90
5.71-6.62
5.58-6.74
H+/N03
(yeq/L)
93.60
60.00
58.30
60.20
25.90
23.90
12.60
9.57
2.49
5.49
1.05
0.83
1.74
0.21
0.29
0.24
0.51
0.46
0.15
0.67
0.04
H+/SO|~
(yeq/L)
0.457
0.188
0.318
0.297
0.119
0.071
0.049
0.028
0.017
0.019
0.009
0.007
0.009
0.006
0.004
0.006
0.004
0.003
0.003
0.003
0.003
SO|~/N03
(ueq/L)
245
265
233
247
170
236
284
337
145
232
156
130
174
34
100
37
134
118
57
198
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                                                                   3-151
loading to watersheds would  reduce  the  sulphate  concentrations and
associated acidification  of  surface waters.
3.9.2   Data and Methods  for Associating  Deposition Rates with
        Aquatic Effects*

The evidence available  on the  effects  of  acidic deposition on aquatic
resources indicates that  present  loadings  rates are in excess of the
ability of watersheds to  reduce  the  acidity  for some lakes in some
areas.  This section will explore the  association between loading
levels of acids or sulphates and  negative  effects on the aquatic
environment.  In the following analysis,  it  is  implied that sulphate
deposition can be used  as  a surrogate  for  the acidifying potential of
precipitation.

The use of sulphate in  precipitation as a surrogate for the acidi-
fying potential of deposition  should not  be  interpreted to mean that
wet sulphate is the only  substance potentially  damaging to aquatic
systems.  It is recognized that  dry  deposition  of sulphate and SC>2,
and wet and dry nitrates  contribute  to the concentrations of acids.
Sulphate in precipitation is reliably  measured  and therefore, is used
here as a surrogate for the total sulphur  deposition because dry
deposition cannot be measured  accurately.  Similarly,  this surrogate
does not reflect the contribution of nitrate to acidity of precipi-
tation.

Surface water quality alterations fall into  two categories:

     1)   short-term pH depressions  during snowmelt or heavy rains,
          and

     2)   long-term reductions in alkalinity, with corresponding low
          pH values in  surface waters  throughout the year.

The length of time it takes for  a lake to  become acidic (alkalinity
reduced to zero or less)  and the  rate  of  change of water quality are
among the least well-defined aspects of the  acidification phenomenon.
To date, the evidence available,  based on  sediment cores taken from
several areas (Section  6.3.4), suggests that acidification has
occurred and is occurring  on the  scale of  decades.
* It is the view of the U.S. members of the Work  Group  that  the
  reliability of wet sulphate deposition  values  is  uncertain and
  therefore, any attempt to use them for  analysis must  be  done with
  great care.  Examination of the data shows  that:   (1) limited
  deposition data are available, and (2)  annual variability  in wet
  sulphate deposition values can be large.

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                                                                  3-152
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Before the alkalinity of a lake or  stream  is  totally  depleted,  it is
very likely that the system experiences  short-term pH depressions
during periods of high runoff.  Large  temporal  fluctuations  in  pH            •
levels may represent a transition phase  in the  process of                     •
acidification.

The phenomenon of short-term pH declines is  probably  more  common than        |
long-term reductions in alkalinity  (in terms  of numbers of  lakes and
rivers affected in North America).   The  chemistry  of  these  events is         ^
fairly well defined.  The biological consequences  of  these  events are        •
known to be severe in some cases, but  the  relationship between
short-term pH depressions and effects  on aquatic biota are  not  fully
understood.                                                                   •

"In the second stage, the bicarbonate  buffer  is lost  during longer
periods and severe pH fluctuations  occur resulting in stress,                 •
reproductive inhibition and episodic mortalities in fish populations         |
(transition lakes)" (Henriksen 1980).  Damage  to fish  and other  biota
as a result of short-term exposures to low pH and  associated high            _
metal concentrations has been demonstrated to occur in both                  •
laboratory and field studies (Section  3.7).   Thus, summertime  or             ™
annual pH has questionable value for determining effects on organisms
of H+ or metals over a few days.  The  timing  magnitude and  duration          I
of short-term increases in H+, associated  with  spring melt  and                V
storm events must, therefore, be included  in  an evaluation  of
critical loading rate and episodic  response  relationships  for  streams        •
and lakes.                                                                    •

In summary, the short-term acute exposure  or  "shock"  effects                 —
(including responses to aluminum) can  take place in two to  four days         •
of exposure, with pH decreases in the  order  of  0.5-1.5 units;   and           •
these shock exposures can be expected  to occur  in  waters with a broad
range of pH above the level at which chronic  effects  occur.                   B

The second category, long-term acidification, has  altered a large
number of lakes in North America, but  the  percentage  of lakes  and            a|
rivers with mean annual alkalinity  of  zero or less remains  small.            •
The biological responses to long-term  acidification are, however,
more clearly defined and generally  more  severe  than for short-term pH
declines.                                                                     •

The acidity and chemical composition of  aquatic environments are
affected by:  (1) the acid neutralizing  capacity of the basin;                •
(2) the geologic and morphologic characteristics of the basin;  and           •,
(3) the acidity of the precipitation.  Biological  processes (e.g.,
production and decomposition) also  have  an effect  on acidity.   Models        •
used to simulate the geochemical processes and  aquatic ecosystem             •
effects are not fully developed or  validated  at this  time.
Development and application of detailed  models  will require detailed
information on basin geology, hydrology,  and biotic interactions.            •
These are unlikely to be available  soon  for  widespread application.          •
Therefore, at present, the relationships between acidic deposition
                                                                               I

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                                                                  3-153
and aquatic effects can be determined only  in  a  general  way.   Some
data and phenomenological models  exist  that relate the behaviour of
lakes and streams to acid loading.  These empirical  observations and
models are discussed below.
3.9.2.1   Empirical Observations


Observed sulphate loadings and corresponding  chemical  and  biological
observations for a series of study areas  in North America  and
Scandinavia are available.


The information in this section is drawn  from a number of  study areas
within eastern North America which are  located on the  Precambrian
Shield or on weathering resistant bedrocks.   The surface water
studies have been initiated for several reasons,  have  started at
different times and are operated by  different agencies.  However,
each project contributes information relevant to the acidification
problem by comparison of results among  and within the  studies
themselves.  In general, each project involves some highly detailed
work on a small number of watersheds and  surface waters  and less
detailed work on a larger study set.  Within  a given study area,  the
surface waters and watersheds are usually chosen to cover  as wide a
range of water quality and geology as is  available.


The study area descriptions will give some appreciation  for the
extent of the data base used in the  empirical derivation of
      loading versus chemical and biological  effects.
     SASKATCHEWAN SHIELD LAKES


     More than 300 lakes in Northern  Saskatchewan's  Shield and Fringe
     Shield regions have been sampled to assess  the  sensitivity of
     lakes.
       Deposition         Annual Precipitation          Annual Runoff
     (kg S042-/ha.yr)            (m)                        (m)
           5a 1980               0.357                   .100 - .200b




     a   CANSAP Measurement.


     b   Fisheries and Environment Canada  1978.

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                                                              3-154
 Observed Characteristics
 EXPERIMENTAL LAKES AREA, ONTARIO
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 1.  Alkalinity = -18.20 + 0.92 (Ca + Mg) (n=281,r=0.97)
    Liaw (1982) indicating that the bicarbonate and Ca + Mg are
    related by a 1:1 relationship and sulphate contributes very
    little to the total ion balance.                                      •

 2.  pH values range from 5.56 to 8.2, 39%  <7.0 (Liaw 1982).
I

I
 The Experimental Lakes Area is situated in northwestern Ontario
 on Precambrian shield granite.  Approximately one-half the area
 of Canada is Precambrian Shield.  Within the study area there
 are about 1,000 lakes, of which 46 lakes in 17 drainage basins           •
 have been set aside solely for experimental research.  The               •
 inflows and outflow of Rawson Lake (a control lake) are
 calibrated as well as 14 other watersheds.  The project was
 initiated in 1969 and is continuing a wide range of whole-lake           •
 chemical manipulations including the acidification of lakes with         •
 monitoring of chemical and biological parameters including fish
 population studies.  The results from this multi-faceted project         •
 are published in many scientific journals including two special          •
 issues of the Canadian Journal of Fisheries and Aquatic Sciences
 devoted entirely to the Experimental Lakes Area (1971,                   ^
 Volume 28, Number 2 and 1980, Volume 37, Number 3).                      I
                                                                          I
  Deposition                                Annual       Annual
(kg S042~/ha.yr) Fraction      Time      Precipitation   Runoff
 	  	     Period          (m)	     (m)             •

    9.07a          bulk        1972         0.69a        0.297a
   10.8a           bulk        1973         0.73a        0.354a           g
    5.9b           wet         1980         0.51b        0.223a           |

                                                         0.234a
                                                         0.15d            •

 Sum of Cations for 31 lakes     217 yeq/L _+  25  (Standard
                                                 Deviation)
 I
 a  Schindler et al. 1976; see also Figure  3-16.                          •
 b  Barrie and Sirois 1982.                                               |
 c  CANSAP measurement.
 "  Fisheries and Environment Canada  1978.                                •
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                                                             3-155
Observed Characteristics


1.   No long term acidification  or  biological  effects  observed
     in ten years of study  (Schindler  pers.  comm;  Can.  J.  Fish.
     Aquat. Sci. 37(3); Can.  J.  Fish.  Res. Board  28(2)).


2.   Sulphate export from the watersheds  is  about  equal to the
     measured wet deposition  (Schindler et al.  1976).


3.   Lake alkalinity distributions  for lakes in the  Rainy  River
     district have fewer low  alkalinity values  than  four other
     Precambrian Shield areas in Ontario  (Dillon  1982).


4.   Lake pH values for a 109 lake  survey ranged  from  4.8  to 7.4
     and averaged 6.5  (Beamish et al.  1976).


5.   Lake sulphate concentrations ranged  from  about  one-half to
     about equal to the bicarbonate  concentrations (Beamish
     et al. 1976, Dillon 1982).


6.   Filamentous algae are  common in July and  August but do not
     dominate the algal population  (Stockner and  Armstrong 1971)
ALGOMA, ONTARIO


The Algoma region of Ontario  is  an  area  of  862,000 ha in
northcentral Ontario.  From a chemical survey  of  about 85
lakes, Kelso et al. (1982) report results from 75 headwater,
nondystrophic lakes with watersheds undisturbed by recent
logging, fire or human settlement.  Sampling was  done in 1979-80
and included physical parameters, lake chemistry  and
phytoplankton analyses on the entire  lake set  with benthic
invertebrate, sediment and fish  tissue analyses done  on subsets
of the 75 lakes.


The Turkey Lakes Project, situated  within the  Algoma  region,  is
an ongoing calibrated watershed  study of 5  lakes  and  20 water-
sheds, plus the outlet of the entire  Turkey Lakes watershed
basin.  Initiated in 1980, intensive  chemical,  hydrological and
biological studies are in progress  including monitoring of
precipitation, air quality, forest  effects, ground and soil
water, stream and lake chemistry.

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                                                                  3-156
                                        calculated from ion concen-
                                        tration data from Kelso et al.
                                        (1982)  and precipitation data
                                        from Barrie and Sirois (1982)
   Barrie and Sirois  1982.
   Fisheries and Environment  Canada  1978.
     Observed Characteristics
                                                                              I
                                                                              I
  Deposition      Fraction                   Annual        Annual             •
(kg S042~/ha.yr)               Time       Precipitation     Runoff
	  	    Period          (m)	      (m)               •

25 APN Turkey       wet        1981           0.8a           0.50b
Lakes Station,                                                                _
(Barrie, pers.                                                                •
comm.)

28                             1976

22                             1977

32                             1978

23                             1979                                            _
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Sum of Cations for 75 lakes     285  yeq/L _+  125  (Standard  Deviation)

                              =™====™=      I
                                                                              I
     1.   pH depression  in  streams  during spring runoff up to 2.1 pH         •
          units with minimum  values as  low as 5.0 in streams with
          summer  alkalinities less  than 400 peq/L (Keller and Gale
          1982).                                                              •

     2.   Excess  sulphate  runoff  is elevated about five times over
          the remote areas  of northwestern Ontario and Labrador              •
          (Thompson and  Button 1982).   Sulphate export from watersheds       |
          exceeds wet  deposition  indicating possible dry deposition of
          sulphate.                                                           •

     3.   Of 75 headwater  lakes  surveyed, six had pH values of 5.3 or
          less and the lowest value was 4.8 (Kelso et al. 1982).

     4.   Sulphate ions  are the  dominant anions (i.e., exceed                •
          bicarbonate) in  lakes  below  pHs of about 6.5 (Kelso et al.
          1982).                                                              •

     5.   In a survey  of 31 headwater  lakes (1.6-110 ha), the number
          of lakes devoid  of  the  8  fish species reported in the area         _
          was observed to  increase  with decreasing alkalinity.  The          •
          relationship between the  presence of fish and pH in these          ™
          same lakes was weaker  although a greater proportion of
                                                                              I

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                                                             3-157
     lakes of pH  <5.5 were  fishless  than  lakes  of pH > 5.5
     (Kelso et al.  1982).  These  observations  are consistent
     with the hypothesis that  the  biota  in the surveyed  lakes
     have been adversely affected  by  changes  in lake chemistry
     but do not necessarily  indicate  causality (Kelso et  al.
     1982).

6.   Aluminum and lead levels  in  75 headwater  lakes in Algoma
     were elevated  in lakes  of  lower  alkalinity; mean total
     aluminum levels of 53 yg/L was slightly  greater than
     aluminum levels in Muskoka-Haliburton waters (Scheider et
     al. 1979a) and intermediate  between concentrations  found in
     severely affected and slightly affected  systems in  Canada
     and Norway (Kelso et al.  1982).
MUSKOKA-HALIBURTON ONTARIO

The study area in Muskoka and Haliburton  counties  of
southcentral Ontario encompasses  an  area  of  about  490,000
hectares within which are its 8 intensive study lakes  and 32
calibrated watersheds,  some  of which have been calibrated since
1976.  The watersheds vary in water  quality  and from  low to high
pH.  Twenty other lakes have been monitored  on a seasonal basis
for a varying number of years.  Many concurrent chemical and
biological studies are  ongoing on the calibrated lakes as
summarized in Harvey et al.  (1981).   The  results of these
studies have been reported in approximately  thirty publications
in the primary scientific literature.

Studies of precipitation, deposition,  air quality,  soils,
groundwater, forests and precipitation  throughfall are all being
carried out.  A stream  acidification experiment was started in
1982.

Studies of pH effects on fish and fish  populations have been
intensified since 1979  by Harold  Harvey of the University of
Toronto.

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Deposition Fraction
(kg S042-/ha.yr)























Sum
a
b
c
d



31 bulk


32 bulk


23 wet


29 wet

37 bulk

31 bulk
35 bulk
42 bulk
38 bulk

Annual
Precipitation
On)
0.8a
0.8a
1.2a
of Cations in Surface
Barrie and Sirois 1982.
Dillon et al. 1980.


Time Period

Aug76-Jul77


Aug77-Jul78


Aug76-Jul77


Aug77-Jul78

Jun76-May80
(Mean)
Jun76-May77
Jun77-May78
Jun78-May79
Jun79-May80

Annual
Runoff
(»>

0.45C
Waters 150-300


Fisheries and Environment Canada 1978.
Ontario Ministry of Environment, ongoing




3-158

Reference

Scheider et al.
1979a

Scheider et al.
1979a

Scheider et al.
1979a; Harvey
et al. 1981
Scheider et al.
1979a; Harvey
et al. 1981
Scheider & Dillon
1982
Unpublished4
Unpublished4
Unpublished4
Unpublished4





yeq/Lb


studies .


1
1
1
1





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1

1



1
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1

1


1
1

1
1
1

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                                                             3-159
Observed Characteristics


1.   Severe pH depressions in  streams  and  lakes  with values as
     low as 4.1 recorded  (Jeffries  et  al.  1979).


2,   Sulphate concentrations in lakes  average  about  equal  to the
     bicarbonate concentrations (Dillon  et  al.  1980).


3.   Manganese concentrations  are elevated  to  about  50 yg/L
     compared to about 3 yg/L  at the ELA station (Dillon et al.
     1980).


4.   Aluminum concentrations (50 yg/L) are  elevated  over values
     at ELA (Dillon et al. 1980).


5.   Clear Lake, for which there are historical  records, has
     declined in alkalinity from 33 yeq/L  in  1967  (Schindler and
     Nighswander 1970) to between 2 and  15  yeq/L in  1977 (Dillon
     et al. 1978), a reduction in alkalinity  of  greater than
     50%.


6.   Mercury concentrations are higher in  fish from  lakes  with
     low pH than from higher pH lakes  (Suns 1982).


7.   Unusually dense and extensive masses  of  filamentous algae
     proliferate in the littoral zones of many lakes with  pH
     values of 4.5-5.5 (Stokes 1981).


8.   Chrysochromulina breviturrita, an odour  causing alga  has
     reached densities that have reduced the  recreational  use of
     lakes for periods of time during  the  summer (Nicholls
     et al. 1981).  The species dominance  appears  to be a  recent
     phenomenon (within the past decade).   This  alga has been
     shown to increase with decreasing pH  in  lake  acidification
     experiments (Schindler and Turner 1982).


9.   Elemental composition of  fish  bones reported  by Fraser and
     Harvey (1982) showed the  centrum  calcium  was  reduced  in
     white suckers from lakes  of pH 5.08 (King)  and  5.36
     (Crosson) compared to lakes of higher  pH  in the same  area.


10.  The white sucker population in Crosson Lake (pH 5.1)  showed
     a truncated age composition compared with the age
     composition of the less acidic Red  Chalk  (pH 6.3) and Harp
     (pH 6.3) lakes (Harvey 1980).


11.  Adult pumpkinseeds (Lepomis gibbosus)  and frogs have  been
     killed around the edges of Plastic  Lake during  spring melt
     and acidification is the  suspected  cause.   Inlet  streams
     had pH values as low as 3.85 (Harvey and  Lee  1981).

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                                                             3-160
LAURENTIDE PARK, QUEBEC

Humid Alpine Lower Boreal Regions
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Elevated dome dominating the surrounding  plateau.   Elevation
varies from 500 to 1200 m asl with  summit elevations  of  1100            M
to 1200 m.  It is comparable to the entire Laurentian plateau,           •
although here there are very few  lakes  and the  drainage  pattern
is characterized by deep dissecting river valleys  such as  the
Jacques Cartier.                                                         •

The frost-free season is generally  80 days or  less with  a
growing season of about 140 days.   Average annual  rainfall,  one         •
of the most abundant in Quebec, ranges  between  1200 and                  p
1600 mm.

On the upper slopes and summits,  85% of the surface is covered           •
with glacial till of which two-thirds is  less  than 1  m deep,
while the other 15% consists of exposed bedrock (gneiss).
Low-lying areas are, for the most part,  blanketed  by  sandy              •
fluvio-glacial outwash deposits.  A few organic deposits exist           •
and are generally shallow, digotrophic  and treed.   Ferro-humic
podzols characterize the well-drained soils with little  or no
ortstein to be found on excessively to  well-drained sand soils.
I
The region, as defined by Thibault  (1980),  confirms  early work          _
completed by Jurdant and others  (1968,  1972).   The  limits               I
include all areas above 518 m.   Jurdant  (1968)  and  Lafond and           *
Ladouceur (1968) characterized a distinct  peripheral-band in the
central upland plateaus covered  by  balsam  fir  and black spruce          •
moss forests and occasionally white  birch  stands.  Forest               •
regeneration after cutting or fire,  is  dominated by white birch
rather than trembling aspen.  The central  plateau supports a            •
black spruce moss forest cover,  but  after  cutting,  regenerates          •
and develops into a balsam fir Hylocomium,  Oxalis forest (Lafond
1968).                                                                   _

The more exposed summits in the  region  such as  Mount Blie in the        *
Malbaie watershed, support a scattered  alpine  cover dominated by
a heath, moss, and sedge complex and occasionally lichens.              B

Humid Lower Boreal Region

This region, the Laurential foothills,  is  found between 47°30'          •
and 50°00' N latitude and 67° and 75° W longitude.   Mountainous
topography characterizes the region.                                    _

Average growing season is about  150 days with  a total annual            ™
rainfall between 900 to 1000 mm. Due to altitudinal variations,
local climate conditions vary within the region. Lower                 •
altitudes, especially in the southern sectors  are not as cold or        |
as wet as conditions on the higher  plateau, a  difference of
200-300 degree days and an average  rainfall 200-300 mm.                 •
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                                                             3-161
Near the foothills, crystalline Precambrian  bedrock underlies
the region.  Hillsides are generally  covered by a thin (less
than 1 m) layer of till, with  deeper  deposits near the base and
scattered deposits on  the upper slopes  and summits.
Fluvio-glacial deposits characterize  the  valley floors of the
region.  Ferro-humic and humo-ferric  podzols are the dominant
soil formations.

Rowe (1972), Jurdant et al.  (1972) and  work  completed using
provincial cover maps  (MER-Ministe're  d'Energie et des Resources)
were used to define the region.   The  limits  as defined by
Thibault (1980) and Jurdant  et al. (1972)  regroup regions
considered by Jurdant  as part  of  a large  balsam fir-white birch
forest domaine.  This  domaine  is  characterized by a semi-dense
forest cover (60% crown closure nature,  tree height greater than
21 m) of balsam fir and black  spruce  associated with white birch
and an absence of jack pine.

Rowe's forest region and the MER  information confirmed the
region's limits.  Mesic hillside  conditions  support balsam
fir-black spruce mass  as well  as  black  spruce-balsam fir mass
forest covers with white birch and white  spruce associations.
Pure black spruce stands preferred either  dry sites or poorly
drained hollows.  White birch  and to  a  lesser extent trembling
aspen associated with  black  spruce, balsam fir and white spruce
characterize the regeneration.

Except for a few isolated areas,  the  meridional sugar maple,
yellow birch, red maple, red pine, black  ash and American elm
are not to be found in the region.

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                                                            3-162
Deposition       Fraction   Time Period
(kg S042-/ha.yr)
                           Reference
    40
    30/6 mo
    10/6 mo
    35
wet      Apr79-Mar80
wet      Apr79-0ct79
wet      Nov79-Mar80
wet          1980
    22.2
wet    28Sep81-27Sep82
Interpolated* from
Glass and Brydges
1982


Interpolated* from
Glass and Brydges
1982


Interpolated* from
Glass and Brydges
1982


Thompson and
Hutton 1982;
interpolated from
Barrie and Sirois
1982


Grimard 1982
                Annual
             Precipitation
                  (m)


                 1.14a
                  Annual
                  Runoff
                   (m)


                    0.95a
a  Ferland and Gagnon 1974.


*  Interpolations from existing deposition  isopleth  maps  as  a
   basis for estimating deposition values can  be  in  error.
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                                                             3-163
Major Cations in Peq/L
Ca
Mg
Na
K
Cond
Average
114.8
54.1
37.3
8.3
22.5
Standard Deviation
57.6
23.9
12.5
3.7
8.7
Observed Characteristics


1.   The surface water  pH is  higher  than the precipitation pH.
     The pH of  152 lakes sampled  in  the  last week of March 1981
     and the first of April varied between 4.7 and 6.6 with an
     average of 5.9  (Richard  1982).


2.   The average content of sulphate  in  the lakes is of the
     order of 80 yeq/L  (Bobe"e et  al.  1982; Richard 1982) and it
     is higher  or equal to bicarbonate.


3.   The highest sulphate concentrations in lakes in Quebec and
     the greatest alkalinity  differences were observed in the
     southwest.  The lake water concentrations of sulphate and
     the alkalinity deficits  decrease  to the north and east
     (Bob€e et  al. 1982).


4.   There is a significant correlation  (r = 0.76, p ^ 0.001)
     between pH and total aluminum of  the 152 lakes of Richard
     (1982).


5.   The Laurentide Park area is  found in hydrographic regions
     05 and 06  (Figure  3-13).  Sulphate  vs. £ [Ca] + [Mg]  -
     [alk] for  these two hydrographic  regions is  found in Figure
     3-14.


6.   Compared to the pH of 1938-41,  there is a greater
     proportion of the  lakes  sampled  1979-80 in the classes of
     pH 4.40-5.09, 5.10-5.79  and  6.50-7.19 amongst 5 pH classes
     (Jones et  al. 1980).  Lakes  in  the  two lowest pH classes
     showed reductions  in pH;  the higher pH class increased
     because of road salt and nutrient additions.  The decline
     in surface water pH tended to occur in the southern part of
     the park.


7.   In lakes continuously open to fishing for nine years prior
     to 1982, average annual  angling yield, angling effort, and
     mean weight of fish caught in years 1978-81  were not
     significantly related to  lake pH.   Management policies
     within the Park provide  for  closure of a lake to fishing

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                                                             3-164
     and 1.2 times higher  in  the  population  of  the  three more
     acidic group of lakes comparatively  to  the  three  non-acidic
     group of lakes (Moreau et  al.  1982).
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     when angling success is reduced below  projected  levels.
     The 44 lakes which were closed to  fishing  over  the  nine
     year period included 43.5% of the  most acidic lakes                 •
     (Group 1, mean pH 5.2); as compared with 36.9% of Group  2           •
     lakes (mean pH 5.9) and 17.5% of the Group 3 lakes  (mean
     pH 6.4).  Although a direct  cause-and-effect relationship
     between fish productivity and pH has not been established,
     the greater number of closures in  the  more acidic lakes
     suggests a lower productivity in these waters (Richard              •
     1982).                                                               •

8.   The concentrations of manganese, zinc  and  strontium in the
     opercula of Salvelinus fontinalis  are  respectively  1.6,  1.3         •
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NOVA SCOTIA

The Nova Scotian River Study  by Watt  et  al.  (1983)  encompassed
the approximately 500 km long Atlantic  coast of  Nova Scotia
which is underlain by granite on about  one-half  of  the mainland.         B
This study of 23 rivers which historically supported salmon              •
fisheries reports results of  monthly  monitorings from June 1980
to May 1981, with certain rivers studied as  long as 10 years.             •
An historical comparison of five of these  rivers with data               •
collected in 1954-55 (Thomas  1960) pH,  alkalinity,  and major ion
concentration data was made.  Fisheries  data for the past 45             _
years was available for 22 of the  rivers and Watt et al.  (1983)          •
related angling success to current water chemistry  and                   ™
geological factors.  Within Kejimkujik  National  Park, central
Nova Scotia, an ongoing study involves  three calibrated lakes.           I
Kerekes (1980) reported results for these  lakes  for the                  •
June 1978 - May 1979 period.  From this  study a  chemical  budget
is available for the Mersey River  (the  outflow of Kejimkujik             •
Lake), which is included in the fisheries  data set  of Watt               •
et al. (1983).
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                                                             3-165
Deposition       Fraction    Time Period
(kg S042-/ha.yr)
                                           Location
    44
    22
    19

    22-29
    22
    17
    27
    32
    31
    18.12

    13.18
    29.01
    21.27
    22.50
              total
              wet
              wet excess
Jun78-May79
              wet and      1977-79
              dry excess
                             1981
                             1980
                             1980
                             1979
                             1978
                          Feb78-Dec80

                          Nov77-Dec80
                          Oct77-Nov79
                          May78-Dec80
                          Oct77-Mar80
Kejimkujik,
Kerekes (1980)
                 Interpolated*
                 from Figure 3,
                 Underwood (1981)

                 Kejimkujik3
                 Kejimkujikb
                 Truroc
                 Truroc
                 Truroc
                 East River
                 St. Marysd
                 Cobequidd
                 Bridgetown^
                 New Rossd
                 Kemptvilled
                Annual                   Annual
             Precipitation               Runoff
                  (m)                      (m)

                1.2e 1978                   1 mf
                1.6e 1979
                1.2e 1980
                1.40 June 1978 - May 1979
                1.46^ long-term average

Sum of Cations  for 41 lakes and rivers  59 _+  17  ueq/L
                                    (Standard Deviation)
a
b
c
d
e
f
Barrie pers. comm.
Barrie et al. 1982.
Truro CANSAP received a fair rating in  the  siting
assessment (Vet and Reid  1982) and the  station  is  being
moved (Barrie pers. comm.).
Underwood 1981 and Underwood pers. comm.
Barrie and Sirois 1982.
Fisheries and Environment Canada  1978.

Interpolations from existing deposition isopleth maps  as  a
basis for estimating deposition values  can  be in error.

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                                                             3-166
Observed Characteristics
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1.   Precipitation pH is generally  lower  than  the  pH of  the              •
     runoff water.  High runoff is  associated  with the  lowest  pH        •
     values in river waters.  The lowest  mean  monthly values  in
     rivers generally occur in winter  (Watt  et al.  1983).                •

2.   Sulphate is the dominant anion in three study lakes of
     pH 5.4, 4.8 and 4.5 (Kerekes 1980) and  was  highest  in the          _
     two coloured lakes with lowest pH.                                  •

3.   Excess sulphate export from the watersheds  are elevated
     above those of remote areas by a  factor of  about 4                  •
     (Thompson and Button 1982) and sulphate export exceeds  the         •
     measured wet deposition indicating possible dry
     deposition.                                                         •

4.   pH data are available for four rivers  (corrected for  flow)
     and 1980-81 values are less than  1954-55  by 0.24 to 0.79            _
     units.  The current bicarbonate concentrations are  lower            •
     and sulphate and aluminum concentrations  are  higher than            ™
     historical values (Watt et al. 1983).

5.   Two rivers (St. Mary's and Medway) had  the  lowest  pH  values        •
     and highest excess sulphate loads in 1973.  Similar changes
     in pH and excess sulphate were noted for  two  Newfoundland          •
     rivers (see Figure 3-30).                                           |

6.   Long-term (five years or greater) records for pH,  calcium          —
     and sulphate from eleven rivers in Atlantic Canada were             •
     fitted by time series models.  Five  of  eight  sensitive              *
     rivers decreased in pH and the other three  did not  change,
     while none of four insensitive rivers  decreased.                   B
     Relationships between trends in pH and  Calcium and  sulphate        8
     indicate that, conceptual models  applied  satisfactorily  for
     pH and in only a limited number of cases  for  calcium  and
     sulphate (Clair and Whitfield  1983).

7.   Salmon catch data for 22 rivers which have  not been                 _
     affected by watershed changes  or  salmon stocking,  have  been        •
     recorded from 1937 through 1980.  As a  group  (n =  10),              •
     rivers in the pH range 4.6 - 5.0  have  reduced salmon  stocks
     as reflected by a significant  decline  in  angling catches
     over this time.  Collectively, rivers with current  pH
     values >5.0 do not show any significant trend in salmon
     catch over the past 45 years (Watt et  al. 1983).  The              •
     absence or reduced abundance of Atlantic  salmon in 17              •
     rivers was corroborated by electrofishing surveys  in
     1980-82 (Watt et al. 1983).
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                                                             3-167
8.   Diatom assemblages in four Halifax  study  lakes  shifted
     toward more acid tolerant species between 1971  and 1980
     (Vaughan et al. 1982).
BOUNDARY WATERS CANOE AREA AND VOYAGEURS  NATIONAL PARK,
MINNESOTA

The Boundary Waters Canoe Area Wilderness (BWCA), a wilderness
unit within the Superior National Forest  (Minnesota) and located
along 176 km of the Minnesota-Ontario  border.   The area  varies
from 16 to 48 km in width.   Over  1,900 km of  streams,  portages,
and foot trails connect the  hundreds of pristine, island-studded
lakes that make up approximately  one-third of  the total  area.

Most of the BWCA is included within the Rainy  Lake basin,  except
for the eastern section, which is part of the  Lake Superior
watershed.  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 (Glass and Loucks
1980).

Filson Creek watershed is approximately 13 km  southeast  of Ely,
Minnesota.  Filson Creek drains 25.2 km^  and  flows north and
west to the Kawishiwi River.  Included in the  watershed  are
Omaday and Bogberry Lakes and one tributary, designated  South
Filson Creek for this study.  South Filson has a 6.3 km^
drainage area and no significant  lakes.

About 60% of Filson Creek watershed is covered by mixed  upland
forest, 30% by wetlands and  lakes, and the remainder by  planted
or natural stands of pine.   Wetlands surround  the lakes.

The precambrian bedrock is mostly troctolite  (a pyroxene-poor,
calcic gabbro) and other igneous  rocks of the  Duluth Complex.
The northern 10% of the watershed is underlain by the Giants
Range granite.  A mineralized zone along  the contact between the
granite and the Duluth Complex contains copper and nickel
sulfide minerals.  The watershed  has no carbonate rocks.
Bedrock is at the land surface in about 10% of the watershed.

Most of the watershed is covered  by drift generally less than
1 m thick.  Its mineral composition reflects the underlying
bedrock types.  The total thickness of drift and peat under the
wetlands can exceed 15 m.  The peat in most of the wetlands is
fibric, herbaceous, and partly decomposed (sapric) below about
0.75 m (Seigel 1981).

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                                                            3-168
Deposition Fraction
(kg S042-/ha.yr)
10-15 wet
13 wet
1 . 6 snow
17 bulk
17.2 wet
Time Period
1976-78
1981
1978
(snow season)
Nov76-0ct77
1980
Reference
Glass and Loucks
1980
NADP 1981-83
(Marcel site)
Glass 1980
Siegel 1981
NADP 1981-83
    16.6
    14.8
wet       Apr78-May79
Wet       Apr78-May79
(Marcell site)


Total NE Minn.,
Eisenreich et al,
1978


Heiskary et al.
1982 (Hovland
site)
Observed Characteristics


1.   No known chemical or biological effects in lakes  (Glass
     1980; Glass and Loucks 1980).


2.   Most of BWCA lakes surveyed have pH values <6.0 and  36.5%
     had CSI  >3 (Glass 1980; Glass and Loucks 1980).


3.   Of the 290 sites sampled 50.5% had alkalinity values
     between 40-199 ueq/L no lakes had alkalinity values  less
     than 40 yeq/L (Glass 1982; Glass and Loucks 1980).


4.   Filson Creek watershed retained 10.6 kg S042~/ha.yr
     of 17 kg S042~/ha.yr bulk (Siegel 1981)


5.   S042~ increased from 2 to 14 mg/L and  [H+] from pH
     values of 6.6 to 5.5 during snowmelt (Siegel 1981).
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                                                             3-169
NORTHERN WISCONSIN

Northern Wisconsin  is  a  region  in which a collapsing glacial
mass left deep  outwash sands  and  coarse tills interspersed with
ice-blocks.  The  study area encompasses portions  of seven
counties in the Upper  Wisconsin River  Basin.   Water covers 17%
of the area.  The area has had  a  30% increase in  population over
the last decade, much  of which  has occurred along lakeshores.
Although only 3%  of  the  total land area is developed,
approximately 40% of the lake shoreline is in residential land
use.

About 90% of the  land  surface in  the region is now forested.  A
century ago the upland vegetation was  dominated by white pine,
hardwoods and hemlock, but most of it  was removed during logging
and subsequent  burning in the late 1800s and  early 1900s.
Regrowth of aspen,  birch, mixed hardwoods and a few conifers has
taken place now, much  of it since 1920.  Black spruce is common
on the wet, peat  areas.  The  sands and sandy  loams in the
surface layers  have  produced mostly acid soils (commonly pH
4-5), with low  cation  exchange  capacities (10 meq/100 g) and low
base saturation (10-30%).  The  upland  soils are primarily sands
and sand loams  with  peatland  soils in  the depressions.   Total
concentrations  of calcium and magnesium in these  soils  are
typically 1-2 meq/100  g.

The igneous and metamorphic bedrock underlying these northern
Wisconsin counties  is  part of a southern extension of the
Precambrian Canadian Shield.  The principal bedrock type is
granite, with lesser amount of  diorite, schist, gneiss,
quartzite, slate  and greenstone.   The  bedrock is  overlain by the
glacial drift,  the most  recent  of which was deposited during the
Wisconsin glaciation.  Drift  thickness ranges between 10 and
70 m with an average slightly greater  than 30 m.   The drift is
low in calcareous material, calcareous pebbles are found only in
the deeper, older drift.  Essentially  all groundwater
contributions to  lakes and streams follows a  path through the
glacial drift.  Because most of the lakes occur in pitted
glacial outwash or  end moraines,  they  are generally shallow,
averaging about 10 m in maximum depth  and rarely  exceeding 30 m.
Consequently, virtually  all of  the lakes in this  study  area are
situated well above bedrock, encased in thick glacial deposits.

The recent pH of  the rainfall has averaged 4.6 annually compared
with an estimated 5.6  in the middle 1950s.  The climate is cool
and wet, with mean July  temperatures of 19°C  and  January
temperatures of -11°C.  The lakes commonly are ice-covered from
late November to  late  April (Schnoor et al. 1982).

-------
                                                            3-170
                                              (Trout Lake)

   17            wet (71 cm)     1980         NADP 1981-83
                                              (Trout Lake)

   16            wet (84 cm)     1981         NADP 1981-83
   22            bulk            1981         Becker et al.
                                              1982
            Precipitation           Runoff
                 (m)                 (m)

                 .80                    .30
I
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Deposition       Fraction   Time Period       Reference                 •
(kg S042-/ha.yr)                                                        |


   17            wet (68 cm)     1981         NADP 1981-83              I
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                                              (Spooner)                 •
I
               Annual               Annual                              •
I

I
Observed Characteristics

1.   Median alkalinity for 117 seepage lakes sampled was 39
     yeq/L.  Conductivity and colour for the same  lakes was 21          I
     yS/cm and 8 Pt units (Eilers et al. 1982).  For 409 total          •
     sites, 25.4% had alkalinities <40 yeq/L and 22.7% had
     alkalinities between 40 and 199 yeq/L (Glass  1982).                •

2.   Two separate comparisons of present chemistry with the 500
     Wisconsin lake survey of Birge and Juday  (1925-41) have            _
     found that most lakes have significantly  higher pH,                I
     alkalinity and conductivity (Bowser et al. 1982; Schnoor et        "
     al. 1982).  Approximately 20% of lakes sampled had pH
     declines but the differences were not statistically                •
     significant.                                                       •

3.   Hydrologic type appears to control alkalinity.  Median             •
     values of pH (6.4) alkalinity (39 yeq/L)  and  conductivity          •
     (21 ymohs) were found in seepage lakes (no defined inlet or
     outlet) (Eilers et al. 1982; Schnoor et al. 1982).                 _
                                                                         I

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                                                             3-171
ADIRONDACK MOUNTAINS  OF  NEW YORK

"As a result of extensive  glacial  activity,  the Adirondack
region of northeastern New York State contains a vast and varied
ponded water resource.   The most recent  count adapted from a
1979 inventory of  the Adirondack ecological  zone (Pfeiffer 1979)
reveals that there  are approximately 2,877 individual lakes and
ponds, encompassing some 282,154 surface acres.  The New York
State portion of Lake Champlain, 97,000  acres, is purposely
excluded from this  summary since its low elevation waters are
not considered to  be  representative  of the Adirondack uplands.
Average size of ponded waters  included in this inventory
approaches 98 acres and  ranges  from  those of less than one acre
to 28,000 acre Lake George."   (Pfeiffer  and  Festa 1980)

The Integrated Lake-Watershed  Acidification  Study (ILWAS)
selected three forested  watershed  areas  (Panther, Woods and
Sagamore) in the Adirondack Park region  of New York for field
investigation.  The watershed  areas  contain  terrestrial and
aquatic ecosystems  having  physical,  chemical and biological
characteristics which distinguish  one area from another.  Lake
outlets are the hydrologic terminal  points of all three
watersheds.  The study watersheds  are within 30 km of each
other.  Runoff in  Panther  and  Woods  watersheds drains directly
to the lakes without  extensive  steam development.  Sagamore Lake
receives the majority of its inflow  through  a drainage system of
bogs and streams.   All watersheds  contain mixtures of coniferous
and deciduous vegetation.

Panther Lake sits  on  thick till rather than  bedrock.  The
stratigraphy of the till is typically, from  top to bottom, sand,
sandy till, silty  till,  and clay till overlying bedrock.  The
till in Woods Lake  basin is primarily sandy  till with an average
depth of three metres.   Panther Lake basin has two till units, a
sandy unit and a clay-rich unit; the two units together may be
60 m deep in places.  Sagamore  Lake  basin has four units - a
loose sandy unit, a more compact sandy unit, a silt-rich unit,
and a clay-rich till.  A thick sand  deposit  greater than 30 m
deep, at the site of  a glacial  meltwater channel, is present
near the inlet to  Sagamore Lake.

High runoff periods typically  occur  during snowmelt.  A winter
thaw has been observed in  January  and February.  A larger spring
melt occurs in March  and April.  During  the  summer and fall,
occasional storms may also generate  high runoff.

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Deposition
(kg S042-/ha.yr)

26.4
29
34-37


39-43
40.03

5.38

39.40

6.19

32.92

5.71










Fraction

wet
wet
bulk


bulk
wet

dry

wet

dry

wet

dry










Time Annual
Period Precipitation
(m)
1981 1.02
1980
1965-78


1965-78
Jun78-May79 1.25

Jun78-May79

Jun78-May79 1.21

Jun78-May79

Jun78-May79 .98

Jun78-May79








3-172

Reference

NADP 1981-83
(Huntington site)
NADP 1981-83
(Huntington site)
Peters et al.
1981 (Canton
site)
(Hinckley site)
Johannes et al .
1981
(Wood ' s Lake -
ILWAS)
Johannes et al .
1981
(Panther Lake -
ILWAS)
Johannes et al .
1981
(Sagamore Lake -
ILWAS)







1
1
I

1
1
_
•

1

1




1

1

•


1
1
1
1
1
1

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                                                             3-173
Summary of 13 Years (1965-1978) Precipitation  Data (Mean + S.D.)
(Peters et al. 1981)
             Precipitation
Site            (cm/yr)          SO^2"  (ueq/L)     N(>3~ (yeq/L)
Canton          94 _+  8          0.104 Hh  0.057     0.033 + 0.034


Hinckley       129 +  52         0.084 +  0.039     0.027 + 0.025


8042~ concentration increased by  1-4%/yr, while  H+ has
remained unchanged.


     has increased by 4-13%/yr.


     and S042~ loads  have increased  [% slopes:   12-15% (N03~)
and 0.5-0.7% (S042~)  for the Canton  and  Hinckley sites,
respectively] due partially to an  increase  in  the amount of
precipitation.



Observed Characteristics


1.   In the East Branch of the Sacandaga River,  S042~
     concentrations exceed HC03~ concentrations.   USGS
     monitoring of the river from  1965 to 1978 indicate an
     increase in N03~ (4 peq/L.yr),  a decrease in
     S042~ (4 peq/L.yr), and a decrease  in  alkalinity (83
     peq/L.yr) (Peters et al. 1981).


2.   In a 1975 survey of 214 Adirondack  lakes at  high
     elevations, pH ranged from 4.3  to 7.4.  Fifty-two percent
     of the lakes had pH  <5.0; 7% pH 5.5-6.0  (Schofield
     1976c).


3.   For a subset of  40 of these 214 lakes,  historic  data on pH
     and fish populations are available  from the  1930s.   Over
     this period, the number of lakes with  pH  <5.0 increased
     from 3 (out of 40) to 19.  Likewise the number of lakes
     without fish increased from 4 to 22.   In both surveys,  none
     of the lakes with pH  <5.0 had  fish.


4.   For 138 Adirondack lakes, a comparison  of color-metric pH
     measurements for the 1970s vs.  1930s indicated a general
     decrease in pH (Pfeiffer and Festa  1980).


5.   pH depressions in streams during spring snowmelt and
     periods of heavy rainfall have  been observed (Driscoll  et
     al. 1980;  Galloway et al. 1980b).

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                                                             3-174
THE HUBBARD BROOK ECOSYSTEM, NEW HAMPSHIRE
I
I
6.   Based on a comparison between lakes in  the Adirondack
     region and within a given lake or  stream monitored  over
     time for a one- or two-year period, elevated  aluminum               •
     concentrations have been demonstrated to be associated with         •
     low pH (Driscoll et al. 1980; Schofield 1976).

7.   Current status of fish populations (presence/absence) in             |
     Adirondack lakes and streams is clearly correlated  with pH
     level.  The occurrence of fish is  reduced particularly at            •
     pH levels below 5.0 (Colquhoun et  al. 1980; Pfeiffer  and             I
     Festa 1980; Schofield 1976).  In the  1975 survey  of 214              •
     high elevation lakes, in 82% of the lakes with  pH < 5.0 no
     fish were collected.  For lakes with  pH >5.0,  about  11%             I
     had no fish collected (Schofield 1976b).                             •

8.   The New York Department of Environmental Conservation               •
     reported (based on available data) that 180 lakes have lost         |
     their fish populations (Pfeiffer and  Festa 1980).  Although
     no alternative explanations for this  loss of  fish are               _
     readily apparent, historic records are  not adequate to               I
     definitely establish acidic deposition  as the cause.                 *

9.   Survival of brook trout stocked into  Adirondack waters was
     inversely correlated (p < 0.01) with  elevated aluminum
     concentrations and low pH (Schofield  and Trojnar  1980).
I

I
The Hubbard Brook Experimental Forest  (HBEF) was  established  in          •
1955 by the United States Forest  Service  as  the principal                 •
research area for the management  of watersheds in New England.
The name of the area is derived from the  major drainage  stream           B
in the valley, Hubbard Brook.  Hubbard Brook flows generally              B
from west to east for about  13 km until it joins  with the
Pemigewasset River, which ultimately forms the Merrimack River           •
and discharges into the Atlantic  Ocean.   Water from more than 20         I
tributaries enters Hubbard Brook  along its course.  Mirror Lake,
a small oligotrophic lake, discharges  into Hubbard Brook at the
lower end of the valley.  The HBEF is  located within the White           B
Mountain National Forest  of  north central New Hampshire.                 B
Although the climate varies  with  altitude, it is  classified as
humid continental with short, cool summers and long, cold                 •
winters.  The climate may be characterized by:  (1) change-              |
ability of the weather; (2)  a large range in both daily  and
annual temperatures; and  (3) equable distribution of                     •
precipitation. HBEF lies  in  the heart  of  the middle latitudes            I
and the majority of the air  masses therefore flow from west to
east.  During the winter  months these  are northwesterlies  and
during the summer the air generally flows from the southwest.            B
Therefore, the air affecting HBEF is predominantly continental.          B
However, during the autumn and winter, as the colder polar air
                                                                          I

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                                                             3-175
moves south, cyclonic disturbances  periodically move up the east
coast of the United  States  providing  an occasional source of
maritime air.  The mean  air temperature in July is 19°C and in
January is -9°C.  A  continuous  snowpack develops each winter to
a depth of about  1.5m.   Occasionally,  mild temperatures in
midwinter partly  or  wholly  melt  the snowpack.   A significant
microclimatologic feature of  this area  is  that  even the
uppermost layer of the forest soils usually remains unfrozen
during the coldest months because of  the thick  humus layer and a
deep snow cover.

The HBEF covers an area  of  3,076 ha and ranges  in altitude from
229 to 1,015 m.   The experimental watershed ecosystems range in
size from 12 to 43 ha and in  altitude from 500  to 800 m.  These
headwater watersheds are  all  steep  (average slope of 20-30%) and
face south. The experimental  watersheds have relatively distinct
topographic divides. The  height  of  the  land surrounding each
watershed ecosystem  and  the area have been determined from
ground surveys and aerial photography.

The geologic substrate,  outcrops of bedrock and stoney till, in
the Hubbard Brook Valley was  exposed  some  12,000-13,000 years
ago when the glacial ice  sheet  retreated northward.  Bedrock is
derived from highly metamorphosed sedimentary rocks of the
Littleton formation  and  the granitic  rocks of the Kinsman
formation.  The bedrock  of  watersheds 1-6  is the Litleton
formation, which  in  this  area is made of highly metamorphosed
and deformed mudstones and  sandstones.   It is medium to coarse
grained and consists of  quartz,  plagioclase, and biotite with
lesser amounts of sillimanite.   Much  of the area of the
experimental watersheds  is  covered  with glacial till derived
locally from the  Littleton  formation.   The geologic substrate is
considered watertight and losses of water  by deep seepage are
minimal.

Soils are mostly  well-drained spodosols (haplorthods) of sandy
loam texture, with a thick  (3-15 cm)  organic layer at the
surface.  Most precipitation  infiltrates into the soil at all
times and there is very  little overland flow (Pierce 1967).
This is because the  soil  is very porous, the surface topography
is very rough (pit and mound, mostly  from  wind-thrown trees),
and normally there is little  soil frost.

Soil depths are highly variable  but average about 0.5 m from
surface to bedrock or till.   Soil on  the ridges may consist of a
thin accumulation of organic  matter resting directly on the
bedrock.  In some places, impermeable pan  layers at depths of
about 0.6 m restrict vertical water movement and root
development.  The soils  are acid (pH  £  4.5) and generally
infertile.

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                                                             3-176
The vegetation of the HBEF  is part  of  the  northern  hardwood
ecosystem, an extensive  forest  type that  extends  with variations
for Nova Scotia to the western  Lake Superior  region and
southward along the Blue Ridge  Mountains.   Classification of
mature forest stands as northern hardwood  ecosystems rests on a
loosely defined combination of  deciduous  and  coniferous species
that may occur as deciduous  or  mixed deciduous-evergreen
stands.
Deposition
(kg S042~/ha.yr) Fraction
36.4

22

38.4 + 2.5
33.7
30.0
41.6
42.0
46.7
31.2
29.3
34.6
33.0
43.4
52.8
wet

wet

bulk
bulk
bulk
bulk
bulk
bulk
bulk
bulk
bulk
bulk
bulk
bulk
Time Annual
Period Precipitation Reference
(m)
1981

1980

1964-74
Jun63-May64
Jun64-May65
Jun64-May65
Jun64-May65
Jun64-May65
Jun64-May65
Jun64-May65
Jun64-May65
Jun64-May65
1973-74
1973-74
1.50 NADP 1981-83
(Hubbard Brook)
.87 NADP 1981-83
(Hubbard Brook)
1.30 Likens et al. 1977a
Likens et al. 1977a










Observed Characteristics


1 . The external and  internal  generation of  H"1" exerts nearly
   equal roles in driving  the weathering reactions.   Input of
   H+ is mainly in the  form of  H2S04  and HN03 (Likens et
   al. 1977a).


2. Average streamwater  pH  ~ 5.   During  snowmelt events pH
   depressions of 1.0 to 2.0  units  have been reported (Likens et
   al. 1977a).


3. The Hubbard Brook ecosystem  accumulated  hydrogen, nitrate and
   ammonium ions over the  period 1963-74.  Over the  same period
   there was a net loss of SO^- (Likens et al. 1977a).
4. Ca2+ and SO^- dominated  the  streamwater chemistry
   at the HBEF.  SO^" was more  than 4 times as abundant
   as the next most  abundant anion which was N03~ (Likens
   et al. 1977a).
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                                                             3-177
5. Elevated levels of Al are found  in  the  headwater  portions of
   streams in the HBEF.  These  levels  are  2-29  times above
   levels in downstream waters.  This  effect  was  attributed to
   leaching of Al hydroride compounds  from soils  by  acidic
   deposition (N.M. Johnson 1979).
MAINE AND NEW ENGLAND


The 97 lakes sampled by Norton  et  al.  (1981a)  ranged in pH from
4.25 to 6.99 (median = 6.40), in elevation from 12 to 1307 m
(median = 154 m), surface area  from  <0.1  to  1098 ha (median =
56 ha), Secchi disc transparency from  2.5  to >5.0 m (median =
6.3 m), and water colour from 0 to 110 Pt  units (median = 8 Pt
units).  The bedrock of the  study  area was noncalcareous and
mostly granitic.  As a result,  the lake waters  were of  low
alkalinity (0-360 yeq/L, CaC03; median =  64)  and specific
conductance (0-68 ymhos/cm at 25°C; median =29).   The
watersheds were  almost completely  forested; very little cutting
had occurred in  the few decades prior  to  sampling.  Many of the
lowland lakes (fJjOO m) had cottages along  their shores  and
access roads in  their watersheds;  the  high elevation lakes were
pristine and accessible only on foot.   In  summary, the  lakes
were small to medium size, ologotrophic to mesotrophic  with
moderately to very transparent  water,  low  to  moderate
concentrations of humic solutes, and low  alkalinity and
conductance, and with moderately disturbed to  pristine
watersheds. Haines and Akielaszek  (1982)  sampled a similar set
of 226 headwater lakes and streams in  the  other New England
states, including Maine.
Deposition
(kg S
ha.

28.
25.
24.
17.

18

36.
22
38.4+2

35

04-2-/
yr)

0
31
80
22



4

.5



Fraction



wet
wet
wet
wet

wet

wet
wet
bulk
(129.5 cm)
wet

Time
Period


1981
1981
1981
1981

1980

1981
1980
1963-74
Annual
Precipi-
tation
(m)
1.10
.87
1.15
1.10



1.50
.87
1.30



Reference


NADP
NADP
NADP
NADP

NADP

NADP
NADP


1981-83
1981-83
1981-83
1981-83

1981-83

1981-83
1981-83
Likens et al


(Acadia site)
(Bridgton site)
(Caribou site)
(Greenville
site)
(Greenville
site)
(Hubbard Brook)
(Hubbard Brook)
. 1976, 1980
(Hubbard Brook)
1981

.74

NADP

1981-83

(Bennington VI
site)

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                                                                  3-178
     Observed Characteristics
SUMMARY OF EMPIRICAL OBSERVATIONS
                      (kg S042~/ha.yr)
NORTHERN              5 wet  (1980)               No  chemical  effects
SASKATCHEWAN
                       17 bulk  (1977)
                                                                         I
                                                                         I
     1. Lakewater pH declines based on  comparisons  with  historical             •
        information (Davis et al.  1978) where 85% of  94  lakes  studied         |
        (Norton et al. 1981 and 64% of  95 lakes  studied  (Haines  and
        Akielaszek 1982) were found to  have  lower pHs.                         •

     2. Loss of alkalinity from lakewater in the New  England states
        averaging about 98 )jeq/L for  56 lakes for which  there  was
        historical information (Haines  and Akielaszek 1982).                   I

     3. Paleolimnological confirmation  of pH declines in lakes (Davis
        et al. 1982).  Cores from  New England acidic  clear water              •
        lakes (pH less than 5.5) with undisturbed drainage basins  (5          |
        of the 30 lake samples taken  over at least  the last 50 years)
        show declines in sediment  concentrations of Zn,  Ca, Mg and Mn         «
        starting as early as about 1880 suggesting  increased leaching         •
        of sediment delutus prior  to  entry into  the lakes (Davis et
        al. 1982; Kahl et al. 1982) or  reduced sedimentation rate.

     4. Accelerated cation leaching from watersheds (Kahl and  Norton          •
        1982).

     5. Lakes of pH <5 are distributed  throughout a range in                   |
        elevation from 10 to 1000  m.  High elevation  lakes (>600 m)
        tend to have low pH and alkalinity.  All but  two lakes having         _
        pH <5.5 were also less than 20  ha in surface  area.                     I
        Alkalinity and pH also increased with stream  order (Haines             ^
        and Akielaszek 1982).  Of  226 lakes and  streams  sampled  25%
        had alkalinity 120 Veq/L,  41% were 1100  Meq/L and 50%  were             •
  1200 Ueq/L (Haines and Akielaszek  1982).


                                                                         I


                         SUMMARY

Location           Deposition                Summary  Effects              •
                                                                        I
ELA, ONTARIO           5.9 wet  (1980)             No  effect                      I
                       9 and  11 bulk (1972-73)                                  •

MINNESOTA              10-15 wet  (NovSO)          No  effect                      •
                                                                               I

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                                                                  3-179
NORTHERN WISCONSIN

ALGOMA, ONTARIO
NOVA SCOTIA
MAINE
HUBBARD BROOK,
NEW HAMPSHIRE
MUSKOKA-HALIBURTON
16-17 wet (1981)

24.7 wet (1981)
22 wet (1981) APN
(Kejimkujik)
17 wet (1980) APN
(Kejimkujik)
22.5 wet (1977-80)
(CANSAP-Kemptville)
13.2-32 (various years)
(CANSAP - various
 N.S. sites)

17-28 wet (1981)
36 wet (1981)
22 wet (1980)
33-53 bulk (1963-74)
23-29 wet (1976-78)
31-42 bulk
No effect

pH depression 2.1 pH
units
Elevated excess
sulphate relative to
region not receiving
acidic deposition
More lakes of low pH
than expected
Relationship between
fish and alkalinity

Loss of Atlantic
salmon populations
(historic record).

Historic record of
decreased pH in
river
Evidence of slight pH
decrease in lakes
(historic records)
No effects on
Atlantic salmon
No evidence of
effects on fish in
inland lakes

Spring pH depressions
No long term change
in stream or lake pH
1963-present

pH depressions
Fish kill associated
with pH depression in
one lake
Algal composition
related to pH

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                                                                  3-180
LAURENTIDE PARK,
QUEBEC
22.2-40 wet (1977-80)
ADIRONDACKS
32-40 wet (1978-79)
29 wet (1980)
34-37 bulk (1965-78)
Indications of
decrease in pH in
some lakes,
especially in
southern region of
park (increases in
some lakes,
especially along
roads); indication of
decline in angling
success in lower pH
lakes; pH depression
in lakes in spring
(Moreau et al. 1982)
and lower pH in lakes
in spring than summer
(Bob€e et al. 1982)

Evidence of pH
declines and loss of
fish populations over
time
     Detailed studies of watersheds  have  been  carried out in
     sensitive regions  of North  America and  Scandinavia under a range
     of sulphate deposition  rates.   The results  of  watershed studies
     conducted in North America  are  described  below.

     For those regions  currently experiencing  sulphate in
     precipitation  loading rates of  ^17 kg/ha.yr there have been no
     observed detrimental chemical or  biological effects.

     For regions currently experiencing between  20  and 30 kg/ha.yr
     sulphate in precipitation there is evidence of chemical
     alteration and  acidification.   In Nova  Scotia  rivers, historical
     records of salmon  population reductions as  documented by 40
     years of catch  records  have occurred as well as  reductions in
     stream pH.  In  Maine there  is evidence  of pH declines over time
     and loss of alkalinity  from surface  waters. In  Muskoka-
     Haliburton there is historical  evidence of  loss  of alkalinity
     for one lake.   There is documentation of  pH depressions in a
     number of lakes and streams. Fish kills  were  observed during
     spring melt in  one lake.  In the  Algoma region there are
     elevated sulphate  and aluminum  levels in  some  headwater lakes.

     For regions currently experiencing  loading  ^30 kg/ha.yr there
     are documented  long-term chemical and/or  biological effects and
     short-term chemical effects in  sensitive  surface waters.
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                                                                  3-181
     In Quebec, sulphate concentrations  in  surface  waters decrease
     towards the east  and  north  in  parallel with the deposition
     pattern.  Sulphate concentrations are  equal to or greater than
     the bicarbonate concentration  in  lakes in the  south west part of
     the Province.

     In the Adirondack Mountains  of  New  York,  comparison of data from
     the 1930s with recent  surveys  has shown that more lakes have
     been acidified.   Fish populations have been lost from 180 lakes.
     Elevated aluminum concentrations  in surface waters have been
     associated with low pH and  survival of stocked trout is reduced
     by the almuninum.

     In the Hubbard Brook  study  area in  New Hampshire there is pH
     depression in streams  during snowmelt  of  1  to  2 units.  Elevated
     levels of aluminum were  observed  in headwater  streams.
3.9.2.2   Short-Term  or Episodic  Effects

While current and historical  survey  data may  imply long-term trends,
the samples usually represent  only one  or  a few measurements at
any one location and  are usually  collected  only during the summer.
This limited sampling period  provides no record of pH and other
chemical changes which take place in relation to seasonal cycles or
major weather events.  If  short-term changes  in water chemistry
coincide with sensitive periods in the  life cycle of  fish,
significant mortality and  reduced reproduction can occur.

Severe pH depressions in streams  and small  lakes due  to snowmelt have
been documented in a  number of  locales  (e.g., Kahl and Norton 1982;
Schofield 1973).  The depression  may be as  much as 1-2 pH units.
Much of the metal content  of  the  snowpack  is  also released in early
melting stages.  Thus critical  hydrogen ion and trace metal levels
may be reached temporarily, even  in  waters  with relatively high
summer pH values.  Leaching of  metals from  soils and  sediments may be
especially severe during this  period, resulting in pulses of high
concentrations of potentially  toxic  metals  (e.g., Al   > several
hundred ppb [Kahl and Norton  1982; Schofield  and Trojnar 1980]).

The question has often been raised,  "How long does it take before the
lakes become acidic?"  The previous  sections  have indicated relation-
ships for lakes and streams which have  already been acidified.
However, the rate of  change is  one of the  least well-defined aspects
of the acidification  phenomenon.  The rate-of-change  questions become
less relevant in light of  evidence that current acid  loadings are
causing damage to fisheries and other biota due to short-term
exposures to low pH and associated high metal concentrations, as
reviewed earlier in this report.

The pH of lakes or streams tends  to  fluctuate considerably during the
year, and average annual pH is  a  composite  of these patterns.  Thus,

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                                                                  3-182
I
organisms which may respond to extreme  concentrations  of  H+ or
metals over a few days.  This, plus  the known  significance  of  brief          •
acute exposure (Spry et al. 1981), suggests  that  the magnitude and            I
duration of short-term increases  in  H+, associated  with a defined
"flushing event", could be used for  further  evaluating critical dose/
response relationships in stream  ecosystems, and  lakes.                       •

Research on brook trout and white sucker by  Baker (1981), Baker and
Schofield (1980), on Atlantic salmon by Daye (1980) and Daye and             •
Garside (1975, 1977, 1980), and related research  by Beamish and              J
Harvey (1972), Beamish (1974a, 1974b, 1976), and  Harvey (1975, 1979,
1980) has provided a broad understanding of  the response  of several          _
pH-sensitive fish species to both long-term  and short-term  elevated          •
H  and aluminum exposures.  Mortalities have been documented for
chronic pH depression, and effects on egg viability, hatching  success
and adult survival for short-interval acute  H+ and  aluminum                  •
exposures are reasonably well known  (Baker and Schofield  1980).              I

Among the experimentally-based relationships developed by Daye,              •
Garside, Baker and Schofield is a recurring  pattern (Loucks et al.            •
1981):

     1)   the short-term acute exposure, or  "shock", effects,                 •
          including responses to  aluminum, can take place in two to          ™
          four days of exposure,  with as little change as 0.5  to 1.5
          units of the pH scale;  and                                         H

     2)   these shock exposures can  be  expected to  occur  in waters
          with a broad range of pH above the level  at  which chronic          •
          effects occur.                                                      •

Stream water chemistry studies from  a number of locations
(Table 3-26) show short-term pH depressions  during  snowmelt and storm        •
events (e.g., 1.0 unit on the Shavers Fork River  in West  Virginia            B
[Dunshie 1979]) and from 1.0 to 2.0  units in two  watersheds being
studied in the Adirondacks (Galloway et al.  1980b). A third lake            •
studied by Galloway et al. (1980b) at the Adirondack site had  a mean          |
annual pH of about 4.8 and shows  no  pH  depression during  flushing
event.  Likens et al. (1977a) reported  pH depressions  of  1.0 to 2.0          ^
units for Hubbard Brook, New Hampshire.  Outside  the regions with            •
snow accumulation, the maximum pH decline during  a  flushing event
appears to occur during major rainfall  events  following a rain free
period (Dunshie 1979).                                                       fl

Sulphate loadings associated with observed short-term  pH  declines and
resulting biological effects are  summarized  in Table 3-26.   In the            •
ELA, Ontario, annual loadings of  sulphate in precipitation  of  about          |
10 kg S042~/ha.yr have generally  resulted in pH declines  of
only 0.2-0.3 units and no apparent biological  effects. Depressions          _
in pH of 0.3-1.0 units have been  observed in northern  Minnesota              •
streams receiving approximately 14 kg S042-/ha.yr.  However,
                                                                             I

                                                                             I

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                                                                                            3-183
TABLE 3-26.  PERIODIC pH DEPRESSIONS OBSERVED IN STREAMS AND LAKES WITH DIFFERENT SULPHATE LOADINGS AND
             CORRESPONDING BIOLOGICAL EFFECTS.  SURFACE WATER ALKALINITIES IN THESE AREAS ARE GENERALLY
             LESS THAN 200 yEQ/L.
Location






(kg
Annual
Sulphate
Loading
S042~/ha.yr
Lowest
PH
Observed

Largest
Between
pH
Difference
Spring pH
Observed Biological Effect


and summer or
by wet deposition)
w i nter
val ues

Tovdal R. Norway
L. Timmevatten Sweden
(1970)


Sweden (1972)
Hubbard Brook
Experimental Forest


Panther L.  ILWAS
Project New York
40
40
40
           pH shock suspected but no field
           measurements taken during the
           fish kill
4.2
4.3
0.8
1.1
     Harvey et a 1. 1982
     Mills pers. comm.
     Keller and Gale 1982
     Siege) 1981
     Church and Galloway 1983
                                    Fish kilI  (sea trout)3
Wild population of minnows
have disappeared*3


Caged sea trout and minnows
experienced 68$ and 59%
mortality6


No biological studies
                                                 No biological  data available;
                                                 fish population 1st from one
                                                 lakeJ
Muskoka-Hal i burton 30 4.1 1.1
Ontario (4 streams)
( lake outflows) 30 4.8 1.3
Plastic Lake 30 4.0 1 .7
Ontario Inlet
Outlet 30 5.0 0.7
Shavers Fork W. Virginia 30 5.6 0.9
(stream)
Algoma 5.0 2.1
Fi Ison Creek, 14 5.5 0.3-1
Northern Minnesota
Experimental Lakes 10 4.5 has been 0.2-0.3
Area Ontario observed generally
above 5
Evidence of fish population
damage in areas lakes0 and
actual algae species^
100? mortality of caged
rainbow trout'
13? mortality of caged
rainbow trout^
Conditions caused by heavy
rain; no biological studies6
No biological studies11
No biological studies'
No apparent biological
effects
a Braekke 1976
b Hultberg 1977
c Harvey 1980
d Nichol Is et al . 1981
e riiinchia 1Q7Q

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                                                                  3-184
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the lowest pH reading recorded is  5.8 and no  biological  studies  have
been conducted.

Galloway and Dillon (1982) have examined  the  relative  importance of           •
sulphuric and nitric acids in causing alkalinity (and  pH)  reduction
during snowmelt and conclude that  a major portion of  the reduction in
alkalinity during snowmelt was attributable to  nitric  acid.   Although         •
                                                                               •
      itself showed little variation  during  snowmelt,  its
continued large presence in the  stream was responsible for the
alkalinity reduction in an indirect manner,  namely by  causing                 •
long-term alkalinity reductions  (as opposed  to  episodic).  Thus,  the          |
episodic reduction of alkalinity due  to  NOg" is added  to the
long-term reduction in alkalinity due to SO^".  Jeffries et                  jm
al. (1981) demonstrated that in  Muskoka-Haliburton the increase in            •
hydrogen ion concentration in  several streams during snowmelt was due
to increases in both N(>3~ and  SO^".


3.9.2.3   Sensitivity Mapping  and Extrapolation to Other Areas of
          Eastern Canada                                                       J|

TERRESTRIAL

In order to identify the magnitude of the surface water acidification         •
problem our ability to extrapolate the results  of the  detailed
watershed study areas to the remainder of eastern North America must
be determined.  Within eastern North  America are hundreds of                  •
thousands of lakes and streams and it is clearly impractical to               •
establish detailed or regional hydrochemical monitoring for them all.
However, there is an urgent need to determine if the watershed study          fij
areas currently being monitored  are anomalous in terms of their               |
geochemical characteristics or if, in fact,  they are representative
of conditions occurring over large areas of  eastern North America.

An early approach to this problem in  Canada  was to consider all of            ™
the Precambrian Shield as "sensitive" and then  assume  any study area
located anywhere on the Shield would  be  representative of over 75% of         •
eastern Canada (Altshuller and McBean 1979). This approach implied           |
that the Canadian Shield was a single granitic  plate and not, as is
the case, a number of complex  geological provinces composed of a              «m
variety of rock types (including marble) and covered,  in places, by           •
unconsolidated material of varying texture and  carbonate content
(Section 3.5).  Areas outside  the Shield, where hydrochemical changes
have occurred (e.g., the Maritime Provinces), also exhibit a range of         9
soil and bedrock conditions.                                                   ™

A major drawback to more detailed analyses and  extrapolation has been         •
the lack of the analyses of information  on surficial and bedrock              j|
geological conditions for all  of eastern North  America, in a regional
but detailed form.  This has recently been alleviated  for Canada with         M
bedrock sensitivity mapping of Shilts et al. (1981) which has been            •
incorporated into the bedrock-soil mapping composite of Lucas and
                                                                               I

                                                                               1

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                                                                  3-185
Cowell (1982).  This mapping  is discussed  in  more detail in
Section 3.5.  In order  to  determine  the  representativeness of three
of the detailed watershed  study areas,  (Algoma,  Muskoka-Haliburton
and southwest Nova  Scotia), the 65 classes of soil and bedrock
characteristics mapped  by  Lucas and  Cowell (1982) will be utilized.

The basis for extrapolation is the 1:1,000,000 scale map shown in
Figure 3-9  (in map  folio).  This mapping represents the most detailed
compendium  of soil  and  bedrock characteristics yet assembled for all
of eastern  Canada.  Extrapolation has been carried out by reviewing
the kinds of soil and bedrock terrains which  form the geochemical
templates of three  of the  watershed  study  areas  and then determining
how representative  these areas are in eastern Canada.

The 65 classes of terrain  characteristics  are listed in Tables 3-27
and 3-28.   Each class is identified  according to a two or three
character alpha-numeric code  which is defined in Table 3-8.
Table 3-27  lists the area  and percent cover of each class north and
south of 52°N latitude  for each province.  [Figure 3-9 shows only the
areas south of 52°N.]   Table  3-28 summarizes  the area and percent
cover of each class for all of eastern Canada.   This table indicates
that 54% of eastern Canada is composed of  bedrock types in
combination with soil types which have a low  potential to reduce
acidity.  These are predominately noncalcareous  sands and sandy tills
overlaying  granitic-type bedrock.  Within  the area south of 52°N, 51%
or 911,089  km^ is considered  as having a low  potential to reduce
acidity of  atmospheric  deposition prior  to entering surface waters.
Terrain Characteristics of Three  Specific  Study Areas

Terrain classes are based on bedrock  geology,  percent  bedrock
exposed, soil depth and soil texture  or  depth  to carbonate
(Table 3-8; Section 3.5).  Table  3-29 shows  the terrain classes for
watersheds within which the study lakes  and  rivers  occur.   These
results have been obtained by directly overlaying the  watershed areas
for Algoma, Muskoka-Haliburton and Nova  Scotia onto Figure 3-9.

By far the greatest proportion of each area  is composed of terrain
classes interpreted as having a low potential  to reduce the acidity
of atmospheric deposition (69 to  98%).   The  most complex area and the
one with the greatest range of terrain conditions is Algoma which has
up to 69% has a low potential to  reduce  acidity, 25% interpreted as
having a moderate potential, almost 5% with  a  high  potential to
reduce acidity and less than 1% organic  terrain (which has not been
interpreted).

Two low potential terrain classes dominate in  each  area.  In Algoma
and Muskoka-Haliburton these are  the  L3  (41.79% and 59.42%,
respectively) and the L4c (21.05% and 32.25%,  respectively) classes;
in Nova Scotia these are the L4b  (53.15%)  and  L4c (27.11%) classes.

-------
3-186
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                                                                                        3-187
TABLE 3-28.  SUMMARY OF TERRAIN TYPES  AND POTENTIAL TO REDUCE ACIDITY FOR ALL OF EASTERN

             CANADA
Terrain Types
(Potential to
Reduce Acidity)
Hla
Hlb
Hie
Hie
Hlf
Hlg
H1h
Hli
Hlj
H2a
H2b
H3a
H3b
H3c
Total
High
Potential
Mia
Mic
Mid
Mlf
Ml i
Mlj
Mln
Mlo
Mlp
Mlq
Mir
Mis
Mlt
South of
(area =

km2
43,632
65,690
8,105
1,004
109
7,989
5,305
8,959
1,405
1,283
3,237
15,933
61,555
83,914

308,390

86

20





174
48
3,956

698
52'N Latitude
1,779,436 km2)

% of Zone
2.45
3.71
0.46
0.06
0.00
0.45
0.30
0.50
0.08
0.07
0.18
0.90
3.46
4.72

17.33

<0.01

<0.01





0.01
<0.01
0.22

0.04
North of
(area = 1

km2
35,258








3,034
2,230
4,634
3,915
17,506

66,577

7,018
83
5,523
9,615
2,325
489
1,038
3,114
566

10,389
374
1,520
52 °N Latitude
,357,595 km2)

% of Zone
2.60








0.22
0.16
0.34
0.29
1.29

4.90

0.52
0.01
0.41
0.71
0.17
0.04
0.08
0.23
0.04

0.77
0.03
0.11
Total for
(area =

km2
78,890
65,960
8,105
1,004
109
7,989
5,305
8,959
1,405
4,317
5,467
20,567
65,470
101,420

374,967

7,104
83
5,543
9,615
2,325
489
1,038
3,114
740
48
14,345
374
2,218
Eastern Canada
3,137,031 km2)

% of
Eastern Canada
2.51
2.10
0.26
0.03
< 0.01
0.25
0.17
0.29
0.08
0.14
0.17
0.66
2.09
3.23

11.95

0.23
< 0.01
0.18
0.31
0.07
0.02
0.03
0.10
0.02
<0.01
0.46
0.01
0.07

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                                                                                     3-188
TABLE 3-28.  CONTINUED
Terrain Types
(Potential to
Reduce Acidity)
M1u
Mlv
M2a
M2b
M3
M4a
M4b
M4c
M5
M6a
M6b
M7a
M7b
M7c
Total
Moderate
Potential
Lib
Lie
Lid
Lie
L2a
L2b
L3
L4a
L4b
L4c
L4d
Total
Low
Potential
South of 52'N Latitude North of 52'N Latitude Total for Eastern Canada
(area = 1,779,436 km2) (area = 1,357,595 km2) (area = 3,137,031 km2)
km2


82
982
13,662
1,564
117,987
9,382
7,749
10,104
32,237
18,023
83,473
46,831

345,058


143
5,064
914
705
2,110
369,467
11,226
109,262
386,090
21

911,089

% of Zone km2


<0.01
0.06
0.77
0.09
6.63
0.53
0.44
0.57
1.81
1.01
4.58
2.63

19.39


0.01
0.28
0.05
0.04
0.12
20.76
0.63
6.14
21.70
< 0.01

51,20

415
14


46,726
13,670
84,180

6,027
4,051
19,060
17,523
22,933
17,973

274,626

3,322
6,395
75,736
9,491
46,755
40
157,723
4,369
52,247
290,162


788,920

% of
% of Zone km Eastern Canada
0.03
0.01


3.44
1.01
6.20

0.44
0.30
1.40
1.29
1.69
1.32

20.23

0.24
0.47
5.58
0.70
3.44
<0.01
11.62
0.32
3.85
21.37


58.11

415
14
82
982
60,388
15,234
202, 167
9,382
13,776
14,155
51,297
35,546
104,406
64,804

619,684

3,322
6,538
80,800
10,405
47,460
2,150
527,190
15,595
161,509
676,252
21

1,700,009

0.01
< 0.01
< 0.01
0.03
1.93
0.49
6.44
0.30
0.44
0.45
1.64
1.13
3.33
2.07

19.76

0.11
0.21
2.58
0.33
1.51
0.07
16.80
0.50
5.15
21.55
<0.01

54.19

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TABLE 3-28.  CONTINUED
Terrain Types
(Potential to
Reduce Acidity)
Ola
Olb
Olc
Old
02a
02c
02d
03a
03c
03d
Total
Organic
Terrain
South of
(area =

km2
51,349
15,799
40,598
106,519
34

170
48
55
327

214,899

52'N Latitude
1,779,436 km2)

% of Zone
2.89
0.89
2.28
5.99
<0.01

0.01
<0.01
<0.01
0.02

12.08

North of
(area =

km2
154,399
24,627
12,351
35,681

207
207




227,472

52*N Latitude
1,357,595 km2)

% of Zone
11.37
1.81
0.91
2.63

0.02
0.02




16.76

Total for
(area =

km2
205,748
40,426
52,949
142,200
34
207
377
48
55
327

442,371

Eastern Canada
3,137,031 km2)

% of
Eastern Canada
6.56
1.29
1.70
4.53
< 0.01
< 0.01
0.01
0.01
< 0.01
0.01

14.10


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TABLE 3-29.

Terrain
Class
L2b
L3
L4a
L4b
L4c
Total L
M4b
M7a
M7b
M7c
Total M
Hlb
Hlc
Hli
Total H
Ola
Olc
Old
Total 0
Study Area






TERRAIN CHARACTERISTICS OF WATERSHEDS
STUDY AREAS OF EASTERN CANADA
Algoma Muskoka-Haliburton
km2 % km2 %
116.1 6.52
3,380.7 41.79 1,058.1 59.42
283.9 3.51
225.8 2.79
1,703.2 21.05 574.2 32.25
5,593.6 69.14 1,748.4 98.19
1,838.7 22.73
109.7 1.36
25.8 0.32
116.1 1.44 19.4 1.09
2,090.3 25.85 19.4 1.09
45.2 0.56
264.5 3.27
77.4 0.96
387.1 4.79
12.9 0.16
6.5 0.08 12.9 0.72
19.4 0.24 12.9 0.72
8,090.4 1,780.7





3-190
CONTAINING THE DETAILED

Southwest Nova Scotia
km2 %
154.8 1.36
6,045.2 53.15
3,083.9 27.11
9,283.9 81.62
1,419.4 12.48
1,419.4 12.48



509.7 4.48
161.3 1.42
671.0 5.90
11,374.3





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                                                                  3-191
It is assumed that these classes  represent  the  terrestrial
geochemical template  for the  three  study  areas.   The other "low"
potential classes are very minor  in these watersheds and one would
expect little or no effect of  acidic deposition in basins dominated
by "moderate" and "high" potential  templates.

In the Muskoka-Haliburton watersheds,  nine  of  the lakes  and
associated tributary  streams which  have been monitored closely occur
entirely within the L3 class.   Detailed lake basin mapping by
Jeffries and Snyder (1983) for 6  of the lakes  indicate that this L3
class is predominately composed of  their  "Minor Till Plain" and "Thin
Till" classes overlaying gneiss bedrock.  These  two surficial types
represent between 84.3 and 94.0%  of the basins  of Red Chalk, Blue
Chalk, Chub, Dickie,  Harp and  Jerry lakes.

The three dominant terrain classes  in these study areas  (L3, L4b and
L4c) are composed of  the following:   (1)  L3 -  shallow sands and
acidic type rocks (granite, gneiss,  quartzite  or other alkalic rocks)
which outcrop in 0-49% of the  map area;   (2)  L4b - deep sands
overlaying ultramafic, serpentine and noncalcareous sedimentary rocks
outcropping in 0-49%  of the unit; and  (3)   L4c  - deep sands
overlaying bedrock similar to  L3.  These  classes represent dominant
conditions in a map area.  At  this  scale  of mapping (1:1,000,000)
other subdominant conditions  probabl}  occur.  However, the evidence
from more detailed mapping at  Muskoka-Haliburton,  as described above,
indicates that the descriptions are representative.  It  should be
noted further that the term "sands"  refers  to  the matrix texture; the
deposit it represents is most  commonly a  till or glacial-fluvial
outwash which include larger  sized  fragments.
Results of Terrain Extrapolation

Table 3-27 provides the basis of extrapolation  by  province  and
Table 3-28 for all of eastern Canada.   Terrain  classes  L3,  L4b and
L4c, which represent the major geochemical  templates  for  the
watershed study areas, are  three of  the four most  common  terrestrial
types.  In eastern Canada,  they cover  17%  (527,190 km2),  5%
(161,509 km2) and 22% (676,252 km2)  respectively (Table 3-28).
They represent over 80% of  the sensitive terrain types  in Eastern
Canada.  Other classes which cover significant  areas  but  are  not
represented in the study areas are H3c  (deep clay  overlying granitic
rocks), Ola (organic deposits overlying carbonate  rocks), Old
(organic deposits overlying granitic rocks), and L2d  (shallow sand
overlying granitic rocks with 50-74% outcropping).

Approximately one-fifth of  eastern Canada  (690,117  km2) currently
receives loadings of about  20 kg/ha.yr  or more  of  SO^2" in
precipitation in 1980.  Within this  loading zone terrain  classes  L3,
L4b and L4c cover 18% (127,237 km2), 6% (40,222 km2)  and  22%
(153,545 km2) respectively.  In total,  the  three terrain  types
cover 46.52% of eastern Canada within the  20 kg/ha.yr,  or higher,

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                                                                  3-192
AQUATIC
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loading of SO    in precipitation.  This  is  an  area  of
321,004 km2 (125,192 mi2) which  represents 99%  of  all  those  areas
with the lowest potential to reduce acidity  within this  loading zone.          fl
These areas occur primarily on the Grenville Province  of the                  I
Precambrian Shield in southern Quebec and Ontario  as well as in the
Appalachian Region of New Brunswick and Nova Scotia  (Figure  3-9).             •

These results indicate that over one-half of eastern Canada, is
representative of terrain characteristics (Table  3-8)  under  which
aquatic acidification effects have been observed.                              •

From these results, it is concluded that  terrain  characteristics
in the three watershed study areas are correlated  with measured               ft
acidification effects, especially as expressed  by  alkalinity                  0
measurements.  These three study areas are not  anomalous but are
representative of larger portions of Eastern Canada  as defined by             mm
these terrain characteristics.                                                 •
1

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As shown in the previous  section  the  bedrock and  surficial geology of
the study areas are  typical  of  large  areas  of eastern Canada.
However specific watersheds  with  varying  glacial  deposits (kame,
spillway, till, etc.) rock component  hardness (i.e.,  resistance to           ^
weathering) and varying hydrological  characteristics  result in               W
surface waters of varying alkalinity  and  total cation concentrations
within each study area.

Hydrochemical data from the  Muskoka-Haliburton area of Ontario also          ml
compares closely with mapped terrain  conditions.   Average annual and
spring T.I.P. alkalinity  values for 9 lakes within the Muskoka-              •
Haliburton study area are all lower than  71yeq/L (Table 3-30).  Five        jj
of these lakes are considered very  sensitive on the basis of their
alkalinity regime (<40 peq/L).  The basins  of all 9 lakes are                _
composed primarily of shallow to  deep (<2 m) sandy tills overlaying          •
gneiss (class L3 and L4c).   In  addition there is  a close correlation
between terrain class and alkalinity  regime for a population of 141
lakes sampled throughout  Haliburton County  and Muskoka District.             M
Table 3-31 shows the occurrences  of lake  alkalinities grouped by             v
sensitivity classes, in each of the mapped  terrain types.  There is
clearly a strong relationship with  77.5%  of the lowest alkalinity            J|
lakes (0-39.9 and 40-199.9 yeq/L) occurring in terrain classes L3 and        J
L4c.  It is not possible, at present, to  extrapolate the results of
Table 3-31 to all the areas  of  eastern Canada mapped  in these two            —
terrain classes.                                                              I

Further support for  the representativeness  of the study areas is
drawn from the water quality data.  Figures 3-49 and 3-50 show the           4|
distribution of lake alkalinities for a  series of geographical areas         •
on sensitive and moderately  sensitive terrain.  The data are taken
                                                                              I

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                                                                  3-193
TABLE 3-30.  AVERAGE ANNUAL OR SPRING TOTAL  INFLECTION  POINT
             ALKALINITIES FOR NINE LAKES  IN  THE  MUSKOKA-HALIBURTON
             WATERSHED STUDY AREA (data from Ontario Ministry  of
             Environment)
    Lake
Time of Record
      Alkalinity
   mg/L        yeq/L
  Harp
  Dickie
  Chub
  Red Chalk
  Blue Chalk
  Jerry
  Plastic
  Heney
  Crosson
    1979-80
    1979-80
    1979-80
    1979-80
    1979-80
    1979-80
   Spring/79
   Spring/79
   Spring/80
   3.32
   0.762
   0.798
   3.15
   3.53
   3.31
0.62 +; 0.5
0.34 +_ 0.5
0.49 + 0.5
   66.4
   15.24
   35.96
   63.0
   70.6
   66.2
12.4 H- 10.0
 6.4 + 10.0
 9.8 + 10.0

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TABLE 3-31.
                                                                  3-194
 DISTRIBUTION OF 141 LAKE ALKALINITIES, GROUP BY
 SENSITIVITY CLASSES, IN VARIOUS TERRAIN TYPES OCCURRING
 IN HALIBURTON COUNTY AND MUSKOKA DISTRICT, ONTARIO
Terrain
Class
L3
L4C
L2d
L2b
Hlc
Hli
M4b
M7c
Old
Map
Area
(km2)
4283.9
1645.2
206.5
141.9
109.7
51.6
25.8
45.2
25.8
Alkalinity
0-39.9 40-199.9
34 (24.1) 61 (43.4)
5 (3.5) 9 (6.4)
3 (2.1) 3 (2.1)
4 (2.8) 3 (2.1)
2 (1.4)




Classes (yeq/L)
200-499.9 500
3 (2.1) 6 (4.4)
7 (4.9)



1 (0.7)



Total
6535.6   46 (32.5)
78 (55.4)   11 (7.7)
6 (4.4)
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       M
       M
       _ra
       O
       >>
       +••
       'c
       O
       03
       0
       0)
       JC
       ca
100

 80

 60

 40

 20

  0-


100


 80

 60

 40-

 20

  0


100

 80

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  0

100

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 60

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  0

100

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  0

100

 80

 60

 40

 20

  0
                  <0 ^0-39^^40-199 200-499
>500
                                                                         3-195



                                                    BRUCE AND GREY COUNTIES

                                                       n=10
                  <0 ' 0-39.9  40-199 200-4991  >500
                  <0 ' 0-39.9  40-199  200-499  >500
                  <0  0-39.9  40-199 200-499  >500
                  <0  '0-39.9  40-199 200-4991  >500
                                                    HALIBURTON COUNTY

                                                       n=197
        MUSKOKA DISTRICT

          n=159
        KENORA DISTRICT

         (S. of 51° Lat.)
                                                    RAINY RIVER DISTRICT

                                                       n=99
Figure 3-49.
                                                    ALGOMA DISTRICT

                                                       n=449
      <0   0-39.9 40-199 200-499  >500

             Alkalinity (peq/L)

     Distribution of  alkalinity values for  lakes in  six
     regions  on Ontario.

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3-196
         o
        •H

         tO
        4J

        <§

        4-1
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         C
         O
         CO
         CU
    0>    co
    ^    CU
   O   3
         C
        •H
         to

        M-l
         o

         o
         CO   •
        •H  ^-N
        •a  eg
            tX5
         
         >  -H
        •H
        4-"  C
         to  o
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         3  i-l
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        in
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                                                                  3-197
from Table 3-12.  The  percentage  distribution  of  lake alkalinities
are similar  in all  areas  and  contrast  strongly with the alkalinities
of 10 lakes  in Bruce and  Grey Counties  which are  located on
calcareous till  in  southern Ontario  (nonsensitive terrain).

While the alkalinity distributions are  similar,  there are some
important differences.  The distributions  for  Haliburton, Muskoka,
and Algoma have  already been  altered in that there is a greater
number of lakes  with low  alkalinity  than in  the Kenora or Rainy River
Districts or in  background areas  such  as Northern Saskatchewan.
Dillon (1982) further  demonstrated the  differences in alkalinity
values for lakes in the areas of  higher sulphate  deposition (Muskoka-
Haliburton and Parry Sound) by plotting the  cumulative distributions
(Figure 3-50).   It  is  accepted that  alkalinity distributions are
already influenced  by  acid loadings  in  some  areas and to reflect
natural conditions  the distributions should  be shifted to the right
as plotted in Figures  3-49.

Within each  study area, the number of  lakes  for which detailed data
are available is small relative to the  total number of lakes.
Therefore, it is important to show that the  intensive study lakes and
rivers themselves are  representative of the  surface waters of the
sensitive areas.  There are a total  of  18  calibrated study lakes at
ELA (1), Algoma  (5), Muskoka-Haliburton (8), Quebec (1) and Nova
Scotia (3).  The current  alkalinities  show 2 less than 0 peq/L, 7 in
the 0-40 yeq/L range and  9 in the 40-200 yeq/L range.  Lakes above
200 are not  subjected  to  intensive studies since  acidification
effects are minimal.   In  addition, Ontario has extensive information
on five calibrated  lake studies near the point sources in Sudbury
which is used to contrast effects of local sources and long range
transport.   Of the  22  rivers  in Nova Scotia  used  in analysis of
salmon catch data,  current alkalinities range  from less than zero
(acidic) to  173  yeq/L  (Figure 3-47).

The study lakes  and streams are located in areas  with terrain
characteristics  and have  alkalinity  values similar to other sensitive
areas in Canada.  Therefore,  the  effects observed in the study lakes
and rivers in response to specific loading rates  should be similar in
other water bodies  in  these sensitive areas.  Similarly, loading
rates protective of these study lakes  should be protective of other
sensitive waterbodies.

Possible Magnitude  of Effects

The Canadian members of the Work  Group  have  concluded that an
indication of the extent  of the current water  quality effects may be
derived for all  of Ontario using  the information  presented in
Section 3.6.1.   The Precambrian area east  of Algoma contains some
50,000 lakes (Cox 1978).  The distribution of  alkalinity values for
lakes in districts  within the 20  kg/ha.yr  wet  SO^~ deposition
isopleth (from Table 3-12) indicates that  about 20% or about 10,000
lakes have alkalinity values  and  acid loadings that are combining to

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                                                                  3-198
3.9.3   Use of Acidification Models
 I
 I
currently cause pH depression  to  values  (less  than 5.5)  likely to be
causing biological damage.

Cox (1978) has indicated that  the lake counts  underestimate the               •
number of lakes with surface areas less  than one  hectare by as much
as a factor of three so the 50,000 and 10,000  numbers  are both
underestimates.
 I

 1
The data for the 57 headwater streams  in Muskoka-Haliburton show that
65% experience minimum pH values less  than 5.5  and  26%  have minimum
pH values less than 4.5 (Figure 3-21).  Although  the  total  number of
miles of streams within the 20 kg/ha.yr wet SO^- deposition
isopleth is not known and quantitative extrapolations are not                «
possible, it is clear that many miles  of stream water must  also              •
currently experience pH depressions  to levels that  can  potentially
cause biological damage.

There is a larger area of lakes underlain by Precambrian rock in             V
Quebec and the Maritime provinces where the acid  loadings are at
least as much as those at Algoma.  While specific lake  count data are        •
not available, it is likely that many  thousands of  lakes are                 ||
currently receiving acidic deposition.

In both Ontario and Quebec many more thousands  of lakes are slightly         •
less sensitive to acidic deposition  and may experience  biological            *
damage in the future if the acid deposition continues.

   _
Precambrian areas of eastern North America is measured  in the tens of
thousands with even more sensitive to  effects in  the  future.                 •

The U.S. members of the Work Group believe the  statements in this
section cannot be supported by the facts.  The  combined analysis of          _
lake survey data, terrestrial mapping  data and  deposition data is an         •
interesting methodology.  Pending validation, the U.S.  members have          ™
too many concerns about the influence  of uncontrolled variables to
consider its use more than speculative.  One  important  variable is           I
the level of dry deposition from local sources  which  can affect the          •
representativeness of the survey lakes.  Other  factors  which may
determine the overall neutralizing capacity of  a  watershed  system in         •
addition to terrain class include elevation,  hydrologic routing time,        \l
lake morphometry and vegetative cover.  We therefore  cannot support
the conclusions in this section in the absence  of further                    _
methodological validation.                                                    •
I
A number of process-oriented  (mechanistic)  models  have been developed
(or are under  active  development)  that  simulate in detail the flow           •
of acidic precipitation  through  terrestrial systems and the resulting        •
chemical response  of  surface  waters.   These models have the potential
                                                                              I

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                                                                  3-199
to predict stream and  lake  responses  (e.g.,  pH depressions) to
episodic events, but most of  them  are not  suitable  for predictions of
long-term ecosystem responses.  Examples of  these process-oriented
models include the ILWAS model  (Chen  et al.  1982),  the Birkenes model
(Christophersen et al.  1982), and  the trickel-down  model (Schnoor
et al. 1982).  Each of  these  models has achieved some success in
relating short-term variations  in  water chemistry of  small drainage
basins to hydrology and chemistry  of  precipitation.  These models,
while calibrated for specific watersheds have  not been validated on a
temporal or spatial scale that  permits their general  application with
significant confidence.

More global modeling efforts, such as those  of Hough  et al. (1982),
and USFWS (1982) have  formulated detailed  mechanistic submodels but
have not developed them to  the  level  of working codes.  Thus,
prediction of the dynamic response at the  aquatic regime to the
atmospheric loading remains to  be  achieved at  this  time.  However,
several efforts towards development of empirical or semi-empirical
steady state models relating  aquatic  chemistry to the atmospheric
loading stress have advanced  to the point  that response estimates are
possible within the limits  of assumptions  of the models.

Three important general points must be made  about these models.
First, validation (especially for  surface  waters in North America)
remains to be achieved.  Second, each of these models is based upon
individual, specific sets of  asumptions regarding their application.
Application of these models is  therefore limited by the degree to
which these assumptions are met.   Third, these models are not dynamic
and therefore, determination  of the rates  of reaction between
sulphate deposition and lake water pH based  on the  models is not
possible.  The models  rely  on steady  state conditions.  With these
important points in mind, potential use of these models for
quantitative estimates of the relationship of  SO^- deposition
to lake pH is discussed below.

The earliest empirical acidification  model was developed by Aimer
et al. (1978) and modified by Dickson (1980, 1982), who related lake
pH and excess SO^" load (concentration of excess SO^" multiplied by
annual runoff) for arbitrary  classifications or groupings of Swedish
lakes.  Since this relationship is, in effect  incorporated by
Henriksen (1979, 1980,  1982)  in his model, it  will  not be discussed
in detail here.
3.9.3.1   The "Predictor Nomograph"  of Henriksen

Henriksen (1979, 1980) has studied atmospheric  and  edaphic  influences
on the chemistry of oligotrophic lakes in  Scandinavia  and has
developed empirical formulations relating  these influences  to
acidification.  He has derived an acidification "indicator," a
quantitative acidification "estimator," and an  acidification

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                                                                  3-200
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"predictor nomograph" (Henriksen  1979,  1980).  Of  these  formulations,
only the "predictor nomograph" is intended for use as  a  predictive
tool.                                                                        •

Henriksen (1980) developed his "predictor nomograph" of  freshwater
acidification based on the hypothesis that "acidified  waters  are  the         M
result of a large scale acid base titration."  He  compared  the               •
concentration of "Ca* + Mg*" with lakewater 804* concentrations
(* indicates "excess concentration" —  that above  contributions from
seasalts) in the pH range 5.2-5.4 and 4.6-4.8 using data from 719           •
lakes in southern Norway (Wright and Snekvik  1978) and obtained              ™
"highly significant" linear correlations.  The line for  the pH range
5.2-5.4 agreed very well with a theoretical titration  nomograph of           l|
bicarbonate concentration vs. (H+ added), assuming that  bicarbonate          j|
concentration is directly proportional  to (Ca* + Mg*)  concentration
and that (H+ added) is proportional to  804* concentration.  The              _
line for the pH range 4.6-4.8 did not agree with such  a  theoretical          •
bicarbonate titration nomograph, but Henriksen (1980)  argued  that his
deviation was readily explained by the  effects of  dissolved aluminum
leached from soils.  To complete his predictor nomograph, Henriksen          I
(1980) added a Ca* concentration axis parallel to  the  (Ca*  +  Mg*)           I
axis and a precipitation pH axis parallel to  the 804*  axis
(Figure 3-51).  The former was derived  from correlations of Ca*              •
concentrations and (Ca* + Mg*) in lake  waters; the latter was derived        •
by combining: (1) a correlation of 864*  concentration  in lake water
to 804* concentration in precipitation,  and (2) a  correlation of             ^
864* concentration in precipitation to  H+ concentration  in                   V
precipitation.  Henriksen (1982) added  an axis of  864* in                   •
precipitation parallel to the axis of 804* in lakewater  based on
his 1980 regression.                                                         •

Henriksen (1979, 1980) derived his predictor  nomograph for  pristine,
oligotrophic lakes in areas with granitic or  siliceous bedrock types         •
and thin podsolic soils.  In these lakes that have been  receiving           •
acidic deposition, 864^" is the major anion.  Prior to the
advent of acidic deposition, Ca2+ and HC03~ were the dominant               _
ions in these lakes.  Lakes used to develop the relationships had low        fl
concentration of organic acids.   The lakes ranged  in area from               '
0.1 to 30 km2 and in 90% of the lakes the Ca+2 concentration
was less than 80 yeq/L.  None of  the lakes was on  a major river              H
(i.e., had very large watersheds) (Wright and Snekvik  1978).                 I

Henriksen (1980) verified the predictor nomograph  with an independent        •
data set from an October 1974 survey of 155 Norwegian  lakes (Wright          •
and Henriksen 1978).  These lakes ranged in area from  0.25  to
1.0 km2, occurred at the head of  undisturbed  watershed drainage
basins, and constituted 5% or more of their watersheds (Wright and           •
Henriksen 1978).  Henriksen (1980) found that for  over 85%  of the           ™
lakes, the nomograph correctly predicted a pH "grouping" (pH<4.7 —
"acid lakes", 4.7  pH <5.3 — "transition lakes",  pH>5.3  —               •
"bicarbonate lakes").  He also found that the nomograph  was valid for        |
18 "large lakes" in southern Norway.
                                                                             I

                                                                             I

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| 3-201
1
1
• 300-


™ § 200-
3-
^H **
I *<»
+
§*«
0
_ 100-
1
vv

1
0J
250-

200-

3 150-
"17
CD
3-
*«"
0 100-



50-

0-




&''
X
X
X
X
/ 1
X ft,.1 x
HCOo- Lakes xx ^xx
O ' Vx"
X ^^
X^ x-
^/^ ^^

.X ^x^
/ ^^ Acid Lakes
>x ^^
//^
////^
1 1 1 1 1 1 1 1 1 1 1
0 100 200
• SO4* in Lakewater, fyieq/L)
i i i i i i i i i i i i i i
10 50 100
SO4* in Precipitation, fyieq/L)
1

i i i i i i i i
7.0 5.0 4.7 4.5 4.4 4.3 4.2 4.1 4.(
_ pH of Precipitation
1
• Figure 3-51. Nomograph to predict the pH of lakes given the sum of
^ nonmarine calcium and magnesium concentrations (or
nonmarine calcium concentration only) and the nonmarine
• sulphate concentrations in lake water (or the
• weighted-average hydrogen ion concentration in
precipitation) (Henriksen 1982).
1
1

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                                                                  3-202
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Henriksen (1980) concluded  that  the nomograph could  successfully
predict lake pH changes  in  response to  changes in the pH of the
precipitation of the particular  composition  for that area and,  if the       m
titration process of lake acidification is  reversible, the nomograph        •
could be used to indicate the amount  of decrease in  precipitation
acidity necessary to restore acid  lakes to  bicarbonate lakes.               _

A number of assumptions  and cautions  pertain to the  use of the               ™
predictor nomograph.  One assumption  initially inherent in the
predictor nomograph was  that increases  or decreases  in the acidity of       4
precipitation do not affect the  rate  of leaching of  Ca^+ or                 |
Mg2+ from soils.  As Henriksen  (1980) noted, this is a matter of
debate (e.g., see Aimer  et  al.  1978;  Dillon  et al.  1979) and a               m
question that "certainly deserves  further attention."  If, for               •
example, increased acidity  of precipitation  does cause increased
cation leaching from soils  (instead of  decreased lake pH), then the
titration hypothesis on  which the  nomograph  is based is violated and        •
extrapolations from the  precipitation pH axis will  be incorrect.            ™

Henriksen (1982) has performed  further  research on  this particular          4
problem.  Using data from lakes  in Norway,  Sweden,  Canada, and  the          41
U.S., he:  (1) compared  historic and  recent  concentrations of
(Ca* +Mg*), and (2) evaluated  ranges of (Ca* + Mg*) concentrations         •
in lakes in similar geologic settings over  a gradient of acidic             •
deposition.  In some cases  he found that (Ca* + Mg*) concentrations
increased in conjunction with higher  levels  of acidic deposition.  In
other cases he found no  such concurrent increases.   For the data he         V
examined the maximum value  of a  "base cation increase factor" for the       •
lake waters would be about  0.4  yeq (Ca* + Mg*)/yeq  804* (Henriksen
1982).  Thus, estimates  of  the  effect of changes in  acidic deposition       •
on the chemistry of lake waters  still require knowledge of the  degree       |
of increase of base cation  concentrations,  ranging  from 0 ueq
(Ca* + Mg*)/yeq 804* to  roughly 0.4 yeq (Ca* + Mg*)/yeq 804*.               •
This applied to certain  lakes in Sweden, Norway, and North America          •
where there was enough historical  information to make an estimate.
However, he does state (p.38, Henriksen 1982) for Lake
Rishagerodvatten, Sweden, the factor  was 0.63, and  the Birkenes model       •
(Christophersen et al. 1982) predicts an increase factor of about           •
0.55. Dickson (1980) showed increases greater than  0.4 for some
Swedish west coast lakes.                                                    •

The increase factor represents  possible responses of the watershed
system to acidic deposition.  It reflects the geologic and hydrologic       ^
sensitivity of the system.  The lowest  limit of the increase factor         •
is zero, which refers to a  system  with  little base  exchange capacity        *
in the organic soil, quartz (Si02) sands for the mineral soil,
and/or a lake in which precipitation  does not flow through soils.           •
Perfect seepage lakes without any  drainage  area other than lake area        V
would qualify as systems with near-zero increase factors based  on the
lack of flow through neutralizing  soils. The maximum upper limit           •
would be a watershed with calcareous  soils  or bedrock which would           |
serve as a perfect buffer and yield an  increase factor of 1.0 yeq
(Ca + Mg)/peq 8042~.                                                         _
                                                                             I

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1
                                                                  3-203
The leaching of aluminosilicate minerals  in  response  to  hydrogen ion
attack has been studied  in  the laboratory.   Wollast  (1967)  found a
dissolution increase factor of 0.33  initially  with respect  to
hydrogen ion attack in 5% K-feldspar solutions.   Furrer  and Stumm
(1982) found a 0.4 increase factor in the dissolution of A^C^.
The factors that control a watershed's neutralizing  capacity,  and
hence the cation increase factor, are not well known  and are
critical.

A second caution noted by Henriksen  (1980) is  that the predictor
nomograph should not be  applied to waters containing  high
concentrations of organic acids.  Not only may the organic  acids
affect lake pH in a manner  independent of precipitation  acidity, but
also ionic Ca^+ and Mg^+ may  be overestimated  inasmuch as analyses
for these ions include Ca^+ and Mg^+ bound to  organics
(Henriksen 1980).  A final  point  to  note  is  that  the  derivation  and
verification of this model  is based  upon  the premise  that the
observed data represent  steady state conditions,  both for
concentrations and pH in deposition, and  concentrations  and pH in
lake water.

A key question is whether the "predictor  nomograph"  is applicable to
sensitive lakes in northeastern North America. Relationships between
Ca* and (Ca* + Mg*) and  between concentrations of these  cations  and
80^* may be different in regions  of  varying  geochemistry in North
America.  Furthermore, the  empirical relationship between SO^* in
lake waters and 804* in  precipitation (as well as the relationship
between SO^* in precipitation and pH of precipitation) may  vary  in
different geographical regions.   Therefore,  for more  accurate
predictions it would be  appropriate  to develop region-specific
regression relationships and  predictor nomographs like Henriksen's
from data bases for the  regions of interest.  Such studies  would be a
useful extension of Henriksen's model and should  be  pursued.

Church and Galloway (1983)  examined  data  from  two small  oligotrophic
headwater lakes in the Adirondacks and found,  using  only the (Ca* +
Mg*) and lake water (SO^*)  axes,  that the nomograph  correctly
predicted the pH for all 66 measurements  in  a  "bicarbonate  lake" and
71% of 78 measurements for  an "acid-transition lake". However,  they
also found that the relationship  between  the precipitation  pH axis
and lake water (864*) axis  for the Adirondacks differs
significantly from the relationship  for southern  Norway.  This is
possibly due to the different contributions  of nitric and sulphuric
acids to precipitation acidity or to the  presence of  other  cations in
precipitation in the two geographic  regions.  The variation of nitric
and sulphuric acid contribution to acidity of  precipitation has  been
further shown by Barrie  (1982).   Because  as  shown in  Section 3.9.1,
nitrate has only minor influences on long-term acidity of the aquatic
regime in comparison with sulphate,  only  the relationships  to
sulphate loading are considered in this section.   For water pH values
less than 4.7, the presence of aluminum or of  other  buffering
apparently becomes important  as shown by  Henriksen (1980, 1982)  and

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                                                                  3-204
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may affect regression lines.  However, we are more  concerned  with the
"transition" sector of the Henriksen  nomograph.

Raines and Akielaszek (1982) examined data  from  122 New  England  lakes        •
in relation to the predictor nomograph.  The nomograph correctly
predicted 6 of 7 lakes in the pH range <4.7 but  incorrectly predicted        flj
that 19 other lakes with higher pH values fell in this grouping.  The        £
nomograph correctly predicted 5 of 14 lakes that fell in the  pH  range
4.7 - 5.3 but incorrectly predicted that 32 lakes not in this range           M
had such pH values.  Of the 101 lakes in the pH  range >5.3, the               •
nomograph correctly predicted 60%.

For those New England lakes the nomograph predicted the  pH of acidic         •
lakes correctly but frequently predicted lower pH values than were           •
actually observed in higher pH lakes.  These differences may  occur
because the relationships of calcium, magnesium, and sulphate are            M
different in New England than they are in Norway, where  the model was        •
developed.  Application of the predictor nomograph  in New England
should be based on empirical relationships  that  exist in this region.        —
Presently the relationship between lake sulphate concentration and           m
atmospheric sulphate deposition has not been established for  this            ™
region.

Keeping in mind the important limitations and assumptions inherent in        ||
its use, we have attempted an application of this approach to
estimating the effects of SO^" deposition  on the chemistry of               M
lakes in northeastern North America.  Numerous lakes in  Norway have           •
calcium concentrations less than 50 yeq/L,  and Bobe"e et  al. (1982)
found that 7.5% (15) of 199 lakes sampled on the Precambrian  Shield
of the Province of Quebec had calcium concentrations less than               •
50 yeq/L.  Raines and Akielaszek found that 11%  (25) of  226 lakes and        ™
streams in New England had calcium concentrations less than 50 yeq/L.
This indicates that such a limit would include all  except the more           M
sensitive waters.  From the regressions given by Henriksen on:               |
(1) the relationship of both (Ca* + Mg*) vs. alkalinity  and (Ca*) vs.
alkalinity I and thus (Ca*) vs. (Ca*  + Mg*)I (Henriksen  1980), and           -mt
(2) the relationship of strong acidity to 804* and  (Ca*  + Mg*)I               •
both with and without increased leaching of base cations (Henriksen
1982)1, we can roughly estimate a 804* concentration that yields a
pH of 5.3 in surface waters having initial  Ca* concentrations of             •
50 ueq/L.  Using the regression given by Henriksen  (1980) on  the             w
relationship of lake 804* concentration to  804*  concentration in
precipitation and assuming an annual  rainfall of 100 cm, we can  then         fl
estimate loading rates consistent with maintenance  of a  pH of 5.3 or         ||
greater (pH 5.3 is the upper limit of Henriksen's transition  zone).
The results of such calculations and  the regression equations used           •
are given in Table 3-32.  Estimated loading values  of wet sulphate           •
deposition that will maintain lakewater pH  at values 2:5.3 range  from
approximately 26 kg/ha.yr (assuming no increased leaching of  base
cations) to approximately 43 kg/ha.yr (assuming  leaching of base             •
cations of 0.4 times the change in excess sulphate  concentration (see        •
Henriksen 1980) and an initial lake 804* concentration of
0 yeq/L).                                                                     •
                                                                              I

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TABLE 3-32.
                                                                  3-205
             CALCULATION OF WET SULPHATE LOADINGS CONSISTENT WITH pH  5.3
             OR GREATER IN LAKES WITH INITIAL CALCIUM  CONCENTRATION OF
             50 yeq/L OR GREATER (Regressions are from Henriksen [1980,
             1982])


All Units (yeq/L)
(except where noted)
Ca*i
(Ca* + Mg*)i
(Ca* + Mg*)
(so4*)w p
(S04*)
(S04*)£ (kg/ha. yr)

No Leaching
of Base
Cations
50
70
70
81
53
26
Condition
Leaching
(according
.4
50
70
128
146
87
43

of Base Cations
to Eqn (4) below)
.2 .1
50 50
70 70
121 114
138 130
83 78
41 39
Ca*i
(Ca* + Mg*)±

(Ca* + Mg*)p

(so4*)w

(S04*)p

(so*)L
                          concentration of excess  sulphate  in  lake
                          water prior to "acidification"  (i.e.,
                          initial S04* concentration)
                          initial excess calcium concentration
                          initial sum of excess calcium plus excess
                          magnesium concentrations
                          predicted sum of excess  calcium plus excess
                          magnesium concentration
                          final concentration of excess sulphate  in
                          lake water
                          concentration of excess  sulphate  in
                          precipitation
                          areal wet sulphate loading assuming
                          annual rainfall of 100 cm
                   Equations Used in Calculations

                        = 1.32 (Ca*)± + 4.3 (adapted from
                          Henriksen 1980)
                        = [1.01 (Ca* + Mg*) + 1.81/0.9  (assuming no
                          leaching of base cations; Henriksen  1982)
                        = [1.01 (Ca* + Mg*)p +  1.8J/0.9  (assuming
                          maximal leaching of base cations; Henriksen
                          1982)
                        = (Ca* + Mg*)± + 0.4 (  S04*)w (Henriksen 1982)
                        = (Ca* + Mg*)i + 0.4 (S04*w -
(1)  (Ca* + Mg*)±

(2)  (S04*)w

(3)  (S04*)w
(4)  (Ca* + Mg*)
(5)  (Ca* + Mg*)p

Substituting Equation 5 into Equation 3 and solving for  (S04*)w yields
(6)  (S04*)w
(7)  (S04*)
(8)  (S04*)£
                        = 2.04 (Ca* + Mg*)± + 3.64 - 0.82 (S04*)i
                        = KS04*)  + 191/1.9 (Henriksen  1980)
                        = (S04*) /2 (assuming 100 cm annual rainfall)

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                                                                  3-206
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3.9.3.2   Cation Denudation Rate Model  (CDR)

Thompson (1982) developed a model relating  the  pH of  a  river to the          •
atmospheric loading of excess  sulphate  and  the  rate  of  cations from
a watershed via runoff (the Cation  Denudation Rate or CDR).   This
model is designed to apply to  areas with  acid-resistant bedrock,             fl
till, and soils and relatively unbuffered surface waters.                     V

In most fresh waters the sum of base cations (Ca+2,  Mg+2,  Na+, K+)            •
closely approximates the sum of anions  HC03~ and  SO^"  after                 •
correction for seasalt or road salt contributions.  Thompson (1982)
noted that if excess sulphate  concentration is  plotted  against the            ^
sum of the cation concentrations, a series  of lines  can be generated,        •
each line representing constant bicarbonate concentration.  If the            ™
partial pressure of CC>2 (Pco2) ^n tne surface water  in
question is constant, then each line also represents  constant pH.            •
This model may be applied to either rivers  or lakes  (Thompson 1982;          fl
Thompson and Hutton 1982).  If a runoff value of  1 m/yr is assumed
and the concentrations of terms in  the  axes of  Figure 3-52 are               ^
multiplied by this value, the  axes  become loading rates, and the             •
figure becomes a plot of cation denudation  rate (CDR, meq/m^.yr)
versus the discharge rate of excess sulphate (Thompson  1982).  If all
the atmospheric sulphate deposited  on the watershed  is  contained in          •
runoff and if we assume that all non-seasalt sulphate comes  from             W
atmospheric loading, then the  abscissa  is equivalent  to atmospheric
loading of acid sulphate.  Note that if wind-blown dust has
neutralized some of the sulphuric acid  in atmospheric deposition, the
loaing terms in Figure 3-52 must be corrected for these neutral
salts.  Thus, according to the model, if  CDR, runoff, excess sulphate        _
load, and Pc02 are known, mean pH can be  estimated.                           •

An example of how model calculations are made is  given  below.  If the
rate of excess SO^" loading is less than the CDR by 20 meq/m^.yr            •
(i.e., the HCC>3~ residual equals 20 meq/m2.yr), the  model estimates          •
that the resultant runoff water (assuming a yield of 1  m/yr) will
have a mean pH of 5.6 (Figure  3-52). As  the rate of excess                  •
504^" loading approaches the CDR, the runoff water will approach a           f
pH of 5.1 (at which HC03~ alkalinity is totally exhausted).   Data
for very soft water rivers in  Nova  Scotia and Newfoundland that have         _
mean runoff rates near 1 m/yr  are shown in  Figure 3-52.  These rivers        •
have a total CDR ranging from  55 to 200 meq/m^.yr.  In 1973 at               *
least three of these rivers received SO^"  loads  exceeding
their CDR and had median pH values  less than 5.1.                            M

At first glance the CDR model  appears to  be quite similar to the
predictor nomograph of Henriksen.   The  CDR  model  is  developed                •
strictly from consideration of charge balance,  however, whereas the          •
predictor nomograph is strongly dependent on empirical  observations.
Thompson (1982) explicitly assumes  that CDR is  independent of acid           —
loading; that it varies only with discharge.  The recent data review         •
by Henriksen (1982) shows that CDR  cannot be considered to be                ™
I
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                                                  3-207
CO
                                                    r2.5
                                            PC02=10
                                            RUNOFF = 1m/yr
                               100
200
                   ACID LOAD  or EXCESS SO4
                  (meq/m2. yr)   (|aeq/L)
                                                 2-
 Figure 3-52.  The model plot - pH predicted for consideration of the
           sum of cations and sulphate (modified from Thompson
           1982).

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                                                                  3-208
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constant in all cases.  Thompson  et  al.  (1980)  compared  data from
between 1954-55 and  1973 for very soft  water  rivers  in southern Nova
Scotia.  They found  a lower pH and higher  excess  804^"                        •
concentrations in the most recent  data  but  did  not  find  significant           |
changes in major cation loads.

A way in which the CDR model is similar to  Henriksen's predictor              •
nomograph is that it does not apply  in  situations where  organic acids
strongly influence pH.  The CDR differs, however, in that  it does not
consider the possible effects of  buffers other  than  bicarbonate.              •
Also, PCOZ roust be known to  estimate  pH  with  the  CDR model.
As is commonly known, Pcc-2 varies  significantly in surface
waters.                                                                        A

Raines and Akielaszek (1982) applied  the CDR  model to data  from 122
New England lakes.  The CDR  model  gave better results than  the                •
predictor nomograph (discussed  above).   Predicted pH agreed very well         •
with measured pH at values <_6.3.   However,  this model also  predicted
lower pH than was measured for  many lakes with pH >6.3.

As discussed above, estimates of the  relationship between sulphate            H
deposition rates and surface water pH may be  made.  As an example,
the Roseway River, Nova Scotia  (Figure 3-53)  has  a CDR of                     •
56 meq/m^.yr.  If all of the assumptions noted above hold and if              •
the acidification process is reversible,  then a reduction of the
sulphate loading rate to 40  meq/m^.yr (20 kg  SC>42-/ha.yr)
might be expected to return  the river to an annual pH of  roughly 5.3.         •
A significant problem exists with  such a prediction.  The Roseway
River has strongly coloured  waters, as do the Mersey and  Medway
Rivers (also shown in Figure 3-53).   As  Thompson  (1982) notes, the pH         II
values of these rivers "have been  thought to  be dominated by                  •
naturally- occurring organic acids."   Thompson (1982) feels that
"their low pHs can be explained quite well  on the basis of  simple             •
inorganic chemistry."  No chemical data  (e.g., Gran titrations for            •
weak and strong acids) were  presented to confirm  this. If  the pH
values of these rivers were  controlled by naturally-occurring organic         _
acids, reduction of excess sulphate deposition would not  result in            •
the increases in stream water pH predicted.                                   ™

Figure 3-54 and Table 3-33 were calculated  based  on the Thompson              •
(1982) model.  If 80 yeq/L of cation  concentration (roughly                   f
equivalent to 50 ueq/L Ca2+  as  used in Table  3-33) is used  as a
criteria for basin sensitivity  to  acidification,  maintenance of the           m
basin water to a mean pH  >5.3 should  be  possible  with sulphate                •
loadings of 35 kg S042~/ha.yr given a runoff  of 100 cm/yr.
Other combinations of sulphate  deposition and runoff are  shown on
Table 3-33.  It should be noted that  any retention of sulphate within         •
the watersheds or increased  leaching  of  base  cations would  violate            9
assumptions in the model, causing  the above loading estimates to be
too low.                                                                       •
                                                                               I

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                                                                     3-209
            200
         CT
         0)

        §

        rr
        Q

        <•>  150
            100
                  RIVER    CDR   EXCESS SO42~  MEDIAN pH

                  Wallace    203
                  Meteghan  129
                  Le Have    126
                  Pipers Mote  101
                  St. Mary's  100
                  Tusket    75
                  N£.Pond   71
                  Medway   71
                  Mersey    66
                  Roseway  56
                                             	O 4.3
Figure  3-53.
                             50          100          150

                                    Excess   SO4    meq/m2- yr
Cation Denudation Rate Model  applied to rivers  of  Nova
Scotia and  Newfoundland (Thompson 1982).

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                                                                        3-210
                                                                                    I
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2  400

CO
CO
£  360
3
0
C
C
o
**
CO
l_
•frrf
c
0)
o
c
o
o

c
o
4~
CO
o
                to maintain Aquatic Regime at:


         __	  pH 5.3, i.e., HCOg  = 10jjeq/l_


          	pH 5.8, i.e., HCO   = 32jueq/|_
   320
                                                                 Runoff

                                                                 30 cm/yr
TJ
0

o 280
CD
i_
i_
O

3 240
£ 200

3
CO
o 160

«
•S   120  -
    80




    40



     0
                    8
12
16    20
24    28
32
36
40    44
                        Excess Sulphate    (kg SCL2 /ha - yr)
      Figure 3-54.
                    Relation of excess sulphate and cation concentration

                    for pH 5.3 and 5.8 for basin runoff of 30, 50 and

                    100 cm/yr.  The model was developed for an area with

                    100 cm runoff.  It has not been corroborated for areas

                    with lower runoff (derived by the Work Group from

                    Thompson 1982).
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                                                                               3-211
              TABLE  3-33.    ACIDIFICATION SENSITIVITY OF SURFACE WATERS RELATED TO

                            SULPHATE LOADING FOR TWO pH OBJECTIVES AND THREE RUNOFF
                            Thompson (1982)]
Cation
Concentration

( jjeq/L) pH Objective
300 5.3
5.8
200 5.3
5.8
100 5.3
5.8
50 5.3
5.8
Runoff (cm/yr)

30
44
40
28
25
13
10
6
3

50
50
50
47
42
22
17
10
5

100
50
50
50
50
45
34
20
9
•                          VALUES [derived by the Working Group from CDR model,


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             The model was  developed  for  an area with 100 cm runoff.  It has not
             been  corroborated  for  areas  with lower runoff.

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                                                                  3-212
3.9.3.3   Summary
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The application of two simplified models  to  the  problem of  relating           •
wet deposition of sulphate to lake pH has  been discussed in this               •
section.  Before any environmental or water  quality model can be  used
to make estimates with specified confidence  of future  conditions  in a         •
particular geographic region, the applicability  of that model for             •
that region and conditions must be verified.  This process  of
verification is just beginning for Henriksen's predictor nomograph            M
and CDR model to northeastern North America.  Until such verification         •
(and perhaps, model adaptation) is achieved,  quantitative predictions
based on these models must be viewed with  caution.
                                                                               I
3.9.4   Summary of Empirical Observation  and Modelling


to normal or altered fluxes in  the  hydrologic  regime; the regional
responses in lake chemistry; the  basin  characteristic which influence         ^
sensitivity to acidification; evidence  of  changes  or  trends in                •
surface water quality in sensitive  regions; evidences of  alteration           ™
of biological components;  and finally,  the methodologies  which are
available to assist in estimation of  target loadings  by atmospheric           B
deposition which would be  consistent  with protection  of the ecosystem         •
to a degree acceptable to  society.  Because environmental concerns
are of rather recent recognition  and  those which have been recognized         M
are most often related to  more  intense  urban contamination, long term         •
records of verified significance  are  available in  only  a  few cases
from which firm conclusions can be  drawn  relating  to  acidification of
remote ecosystems.  A deterministic knowledge  of the  inter-                   •
relationships of the bio-hydrogeochemical  system and  of its responses         ™
to altered precipitation chemistry  is not  yet  available,  therefore
rendering precise predictive modelling  of  system responses, as yet,           fl|
unattainable.  These limitations  have been thoroughly reviewed in             I
recent summaries of the Associate Committee on Scientific Criteria
for Environmental Quality, National Research Council  of Canada                m
(Harvey et al. 1981) and by the Committee  on the Atmosphere and the           I
Biosphere, Board on Agriculture and Renewable  Resources Commission on
Natural Resources (NAS 1981) and  are  further detailed in  this report.
However, these learned summaries  of present knowledge have all                •
indicated strong evidence  of significant  ecosystem deterioration due          9
to past and present levels of acid  precipitation loading  and thus
indicate the urgent need to use this  present knowledge  to arrive at           A
best estimates of levels of acid  loadings which can be  tolerated.             |

While this chapter has considered only  the aquatic portions of the            «
ecosystem, it would appear that because of the interactions with              •
other components, protection of the aquatic regime would, to a
large degree, result in protection  of the total environment.  This
sub-section therefore, reviewed the information and methodologies             •
presented earlier with respect  to their utility in producing                  •
estimates of loading/response relationships.
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                                                                  3-213
As developed in previous  sections,  acidification of aquatic regimes
can be related to  proton  (H+)  loading,  concentration of IT1", i.e.,
of precipitation,  or  to the  constituents  of  the loading which
determine  the acidity (i.e.,  the  major  ionic species).  The
anthropogenic loadings add  to  and interact with the natural
components  to an extent that  also influences the factors available
for effective control.  Evans  et  al.  (1981), after reviewing the
extensive  evidence of dose  response acidification relationships and
considering the empirical model approach  of  Henriksen (1980) have
proposed that "an  annual  volume weighted  H+  concentration of 25
yeq/L (pH  4.6) in  precipitation appears to be a critical threshold."

These authors have reached  their  conclusions through the basic
consideration of H+ exchange  in the reaction processes and through
general empirical  observations of dose  response in sensitive regimes.
However, as reviewed  in earlier sections,  the biosystem response and
ability to assimilate nitrate, ammonia  or  sulphate (the primary
acidifying  ions of precipitation) differ  and therefore the acidifying
potentials of these ions  differ.   In  addition,  Stensland (1979) and
Barrie (1981) have shown  that  the ionic concentrations of
precipitation over eastern  North  America  varies as to relative
contribution to its acidity in both space  and time.  Thus the H+
concentration cannot  be considered  to have a unique relation to the
acidity controlling ions  nor  has  it a unique relation in its dose
response in the bio-hydrogeosystem.  Thus, neither H+ concentration
of precipitation nor  H+ loading rates form acceptable criteria for
target loadings in relation to protection of aquatic ecosystems from
acidification.

Henricksen  (1980)  has argued  that surface water acidification can be
accounted  for as the  titration of bicarbonate waters and replacement
of bicarbonate by  sulphate  in  the ionic charge balance.  He found
good empirical agreement  between  sulphate  loadings and observed
acidification in widely diverse areas without consideration of any
nitrogen species.   His relationship to  precipitation pH, as cited by
Evans et al. (1981),  was  empirical  and  based upon Norwegian
precipitation and  was not an  integral part of the argument.  It
should be  stressed here,  that  while Henricksen's model has a basis in
chemical equilibrium,  as  shown by Thompson (1982), it is in fact a
"phenomenological"  model  which derives  from  actual dose response
observations.

A range of  sulphate loading vs bio-geo-system responses observed in
eastern North America are summarized  in Table 3-26 and Summary Table
(p. 3-178).  This  includes  several  cases  relating to episodic event
pH changes.  While the number of  cases  are small and statistical
significance cannot be assigned,  the  identified cases of surface
water acidification and observed  biosystem effects all fall within
regions of  sulphate deposition of greater  than 17 kg S042-/ha.yr.
There appear to have  been no  reported cases  of identified
acidification which cannot  be  related to  organic sources in areas of
less than  this level  of sulphate  deposition.

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                                                                  3-214
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The Canadian members of the Work Group consider  that  this  evidence,
often circumstantial but not inconsistent with theory, leads  to the
approach best able to provide estimates of  target  loadings of                 •
sulphate in relation to surface water acidification.  It  is well               gj
recognized that this estimate is of limited accuracy  in terms of
predicted ecosystem response and must surely  be  subject to later              ^
re-evaluation as more information  is developed from scientific study.          •
The empirical observations presented in Table 3-26 and Summary                *
Table (p. 3-178) immediately suggest a target loading of  sulphate
which could be accepted but is only poorly  defined in terms of                •
geosystem parameters.  The Henricksen-Thompson model  permits  a                I
quantification of the target loadings in  terms of  the geochemical
                                   r)~i-     Q I
Jbasin sensitivity parameter CDR (Ca*  + Mg^  ) as  an  approximation or         •
unaltered alkalinity as suggested  in Section  3.9.3 and further                •
developed in this section.  As pointed out  by Henricksen  (1980) this
model will have, perhaps, significant errors  below the titration end          —
point for alkalinity due to other  buffers but should  apply with               •
sufficient accuracy for estimates  of the loadings  of  sulphate which            ™
would control the aquatic regime acidity above this transition pH.
The CDR serves as the basic geosystem sensitivity  criteria in this            •
model and thereby links the basin  hydrology and  the sulphate  loading          fl
to sensitivity to acidification.   CDR and cation concentrations are
related through the hydrological runoff.                                       M

Information derived from the Thompson (1982)  model may, within
the limitations cited, be used to  estimate  target  loadings of                 ^
sulphate (Figure 3-54 and Table 3-33).  Thus  if  200 yeg/L of  cation            •
concentration (also unaltered—at/cai-inity; is  used  as  a criteria for            ™
basin sensitivity to acidification, protection of  the basin water to
a mean pH of 5.3 would be indicated for sulphate loadings                     fl
47.5 kg S0^2~/ha.yr if runoff of 50 cm/yr occurred.   For  a                    m
30 cm/yr runoff the protection would only tolerate a  loading  of
28 kg SO42~/ha.yr.  Thus the criteria of  200  yeg/L total                       M
cations or unaltered alkalinity is a reasonable  choice of threshold            •
of sensitivity to acidification over much of  eastern  North America
where runoff may be near 50 cm and sulphate loadings  exceed
40 kg S042~/ha.yr (see Figure 2-6b).                                           •

A target loading of 15-20 kg SO^2~/ha.yr  would,  by this model,
serve to maintain surface water pH greater  than  5.3 on an annual              H
basis for basins having cation concentrations of 200  yeg/L or greater         ^
even in areas of low runoff.  More sensitive  basins in low runoff
areas could not tolerate this level of loading and maintain a pH              m
greater than 5.3.                                                              •

The estimates of dose-response relationships  presented here do not
account for the episodic events discussed earlier  which may,  in some          •
ecosystems, be cause for more concern than  that  based on  the  mean             ™
acidity.  The estimates do not consider any time response and must
therefore be limited to steady state conditions. Rate of  response of          •
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                                                                  3-215
any basin to changes  in  precipitation loading,  either quantity or
quality, must relate  in  general  to  the water residence time.   Other
factors such as  ionic migrations in the soils are not considered.
Thus no response rates or  equilibrium times  are implied,  in any
sense, by these  loading  estimates.

In the watershed studies summarized above, sulphate in precipitation
was used as a surrogate  for  total acid loading.  Sulphate in
precipitation is reliably  measured.   It is recognized that dry
deposition of sulphate and sulphur  dioxide,  and the wet and dry
deposition of nitrogen oxides,  nitric acid,  particulate nitrate and
ammonia, as well as other  compounds also contribute to acidic
deposition.  Based on documented effects, wet and dry deposition of
sulphur compounds dominate in long-term acidification.

Based on the results  of  the  empirical studies,  interpretation of
long-term water quality  data, studies of sediment cores and models
that have been reviewed, we  conclude that acidic deposition has
caused long-term and  short-term  acidification of sensitive surface
waters in Canada and  the U.S.   The  work group also believes on the
basis of our understanding of the acidification process that
reductions from present  levels  of total sulphur deposition in some
areas would reduce further damage to sensitive  surface waters and
would lead to eventual recovery  of  those waters that have already
been altered chemically  or biologically (Loss of genetic stock would
not be reversible.)

The U.S. members conclude  on the basis of modelling and empirical
studies that reductions  in pH, loss  of alkalinity,  and associated
biological changes have  occurred in areas receiving acidic
deposition, but cause and  effects relationships have often not been
clearly established.  The  relative  contributions of acidic inputs
from the atmosphere,  land  use changes,  and natural  terrestrial
processes are not known.   The key terrestrial processes which provide
acidity to the aquatic systems and/or ameliorate atmospheric  acidic
inputs are neither known nor quantified.  The key chemical and
biological processes  which interact  in aquatic  ecosystems to
determine the chemical environment  are not known or quantified.
Based on this status  of  the  scientific knowledge,  the U.S. Working
Group concludes that  it  is not  now  possible  to  derive quantitative
load ing/effects relationships.
3.10    CRITICAL RESEARCH  TOPICS

The following topic areas  represent  issues  in  which there  are major
information gaps, and which should be  addressed  by  research programs,
in both the U.S. and Canada,  at the  earliest possible  date.

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                                                                  3-216
3.10.1  Element Fluxes and Geochemical Alterations  of Watersheds
                                                                              I
                                                                              I
Three areas of research are needed here, all requiring  relatively            •
intensive study of both terrestrial  (geochemical) and aquatic                 B
(hydrologic) components, mostly focused around  calibrated watersheds
of comparable research design and intensive data quality assurance.           —
                                                                              •
                                                                              B
1.   The four ions of primary concern regarding acidification  are
     hydrogen, ammonium, sulphate, and nitrate.   Each  ion  reacts
     differently with the soil matrix and vegetation.   It  is
     necessary, therefore, to define , in specific terms , the fate  and
     effect on surface water acidification of hydrogen, ammonium,
     sulphate and nitrate ions originating as atmospheric  input.              m

     Comparison of results from calibrated watersheds  with different
     soil and vegetation conditions  is urgently needed. This  report
     indicates that priority may have to be given to sulphur                  B
     emissions control, drawing heavily on evidence  that nitrogen             9
     deposition does not contribute  significantly to long-term
     surface water acidification, even though it  contributes to
     precipitation acidity and pH depression during  snowmelt or
     runoff events.  The long-term necessity for  a sulphur control
     priority needs to be established beyond doubt,  as soon as               M
     possible, in order to minimize  the risk of making costly  errors          B
     in a control program.
                                                                             I
                                                                              I
2.   Acidic deposition results in mobilization  of metals,  such  as             B
     aluminum, iron, zinc and manganese, from the soil particles in          B
     watersheds.  Further work is needed to define  the amounts  and
     species of metals leached from watersheds  and  their biological
     consequences.

3.   There is evidence that groundwater is being acidified,  and that          M
     metal concentrations are elevated, in areas where snowmelt gains         B
     direct access to sandy subsoils with low acid  neutralizing
     capacity.  The effect may be seasonal, with pH values recovering
     during the summer, as neutralization slowly takes place.                 B
     Further surveys are needed to establish the extent and                   B
     characteristics of groundwater modification over time and  across
     geographical gradients in acid loadings.                                 •


3.10.2  Alterations of Surface Water Quality                                  •

Two major areas of information needs have been  identified  in the
extent and periodicity of surface water quality effects:

1.   The geographical extent of surface water acidification  is  not            B
     yet fully documented in North America.  Obvious data  gaps  exist
     in the central, southern and western U.S.  and  in parts  of                •
     Canada.  In addition, reliable data on time-trends in water             £
     quality appear to be sparse throughout North America, although
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                                                                  3-217
     some data have not yet been evaluated.  Much of the new data
     needed can be obtained as part of the long-term monitoring
     program described below.  The critical need is to begin long-
     term water quality measurements, in a carefully selected  range
     of aquatic environments, as soon as possible.

2.   One of the most common manifestations of acidic deposition
     observed in eastern North America is periodic pH depression in
     streams and lakes, due to snowmelt or heavy rain.   Since
     periodic low pH is a current problem for biological resources,
     and likely to remain so until acid deposition is reduced, the
     quantitative relationship between acid deposition and  short-
     period pH depression should be determined for a broad  spectrum
     of aquatic environments.  A dose-response relationship for
     episodic acute exposures to H+ and aluminum will be a  major
     element in defining acceptable acid loadings.
3.10.3  Alteration of Biotic Components

Effects on the biological components of aquatic ecosystems  are known
only partially.  Five research topics are identified:

1.   It is essential that the biological responses  to various water
     chemistry changes induced by acidic deposition, be  evaluated  in
     considerable detail to define dose-response  relationships
     further.  Studies of dose-response relationships in aquatic
     ecosystems should include surveys of phytoplankton,  macro-
     phytes, zooplankton, benthos and amphibians.   Several  species
     among these groups are quite sensitive to changes in pH.

     Of particular importance to the dose-response  relationship is
     quantification of response data from indigenous species which
     may be vulnerable to low pH or elevated aluminum, and  the pH at
     which effects are expressed.  Special attention needs  to be
     given to determining the pH at which species unique to certain
     areas are harmed and begin to show some failure in  reproduction.
     In addition, community-level attributes of aquatic  systems are
     likely to be sensitive to acid-induced stresses, but are
     difficult to determine; nevertheless, they should be understood
     fully.  These include plankton species composition,  predator-
     prey relationships, and trophic-state modification  of  lakes due
     to altered nutrient cycles.

2.   Damage to fish populations is of particular  concern because the
     loss of fish breaks a major link of the water/terrestrial food
     chain.  Sport fishing is an important industry in most of the
     areas affected by acidic precipitation and reduction in fish
     supply could have serious economic consequences.  Mechanisms by
     which low pH and high metal concentrations affect fish should be
     studied to improve general understanding of  the toxicity
     phenomenon and to improve the ability to predict future effects

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                                                                  3-218
and if so, whether there has been any reduction  in  spawning
success for fish species in those tributaries.
                                                                        I
                                                                        I
     if acidic deposition continues.  Fish sensitivity  to H+ and
     metal ions should be determined, by direct bioassay, at
     different stages in the life cycle, concentrating  on                    fl
     reproduction and recruitment.  Behavioural or physiological             •
     changes (e.g., blood ion levels) known to be affected  by
     sublethal acid and metal concentrations should also be                  •
     evaluated.  Long-term monitoring should include fish population         •
     data, as well as other measures of biological productivity.

3.   Further study is needed to define the biological effects and            •
     tolerances for periodic pH depression in streams and lakes.             •
     Current work should be extended , to include the Great  Lakes
     tributaries draining Precambrian areas.  All such  potentially           B
     sensitive areas in the U.S. and Canada should be surveyed, to           |
     determine whether low pH and high metal concentrations occur,
                                                                             •
                                                                             •
Mercury concentrations in fish and other wildlife may  be
increased by the acidification process and/or by increased
atmospheric emissions.  Increased effort should be placed on
measuring existing mercury concentrations and time trends
throughout the wildlife food chain, as a function of lake and
stream pH values.  Laboratory and field studies are needed  to
establish the biological significance of various mercury
concentrations in indigenous species of fish, birds and                 •
mammals.                                                                I
                                                                             I
5.   When aquatic and/or terrestrial productivity  is  affected,  the
     effect is often evidenced through the entire  food  chain.   Thus,         •
     there is reason to believe that acidification will have  an             •
     adverse effect upon food availability to the  higher trophic
     levels of the food chain, including aquatic birdlife and               •
     mammals.  The long-term effects of habitat damage  on the               |
     populations of wildfowl and other wildlife should  be better
     defined, and the losses of habitat should be  quantified.                •


3.10.4  Irreversible Impacts

1.   Geochemical and hydrologic principles suggest that the processes        W
     of sulphate accumulations, and associated acidification  of soils
     and surface waters, represent a large-scale titration of               •
     available acid neutralizing capacity.  There  is  evidence that           f|
     the capacity of watersheds to provide neutralization of  acids
     may become depleted, over long periods.  Therefore,  further work        _
     is needed to define the rate of acidification of surface waters,        •
     develop predictive models to quantify watershed  capacity to
     neutralize acid over the long term, and to anticipate recovery
     following abatement.                                                    •
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                                                                  3-219
     The studies should include measurements on  the  rates  of
     acidification of lake and stream  sediments.   The  results  of  such
     studies are needed to assist  in setting acid  loading  tolerances
     which will be protective of  the aquatic environment  in the long
     term.
3.10.5  Target Loadings and Model Validation

Much uncertainty remains as to  the quantification  of  sulphate
deposition level ("target loadings") consistent  with  no  further
significant degradation of natural resources.  Two  areas  of  research
are needed:

1.   Several relationships, based on field  environmental  data,  have
     been used to develop descriptive and predictive  models  of  the
     acidification process.  Dickson's  relationship,  the  Henriksen
     nomograph, and the episodic receptor/dose relation,  appear to be
     potentially useful empirical models which warrant comparative
     analysis with similar background data  bases.   Efforts should be
     made to conduct additional validation  of existing and emerging
     model descriptions of the  process  of acidification.

2.   Relatively detailed simulation models  of the  acidification
     process, and its effects,  are being developed  by several
     research groups.  These should be  evaluated,  using watershed
     data bases from a number of intensive  study sites in sensitive
     areas, as identified in this report.   If important  data are
     presently missing at these sites,  they should  be added  to  the
     measurement program, or if certain summaries  are not being made,
     these should be added.  The need is to have the  most complete,
     quantitative long-term dose-response models evaluated fully and
     compared with the more empirical field relationships now in use.
     In support of this validation process, every  effort  should be
     made to maximize the use of existing information from all
     sources.

Reasonable validation of both types of  models will  require
considerable new research.  Study areas for evaluating atmospheric
transport models (see Work Group II report) and  loading  predictors
should coincide with detailed studies of sensitive  receptor  areas.
Locations which already have some data, and which  should  be
considered, include:

          Experimental Lakes Area                -  Ontario
          Boundary Waters Canoe Area Wilderness  - Minnesota
          Algoma Area Watershed Study            - Ontario
          Dorset-Haliburton Study Area           - Ontario
          ILWAS Project                          - New York
          Laurentide Park (Lac Laflamme)         -  Quebec
          Kejimkujik Park                        - Nova Scotia
          Hubbard Brook                          - New Hampshire

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                                                                  3-220
          Northern Highlands Lakes               -  Wisconsin
          Coweeta                                -  North Carolina
          Andrews                                -  Washington
          North Cascades                         -  Washington
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3.10.5.1   Long-Term Data Collection  and Monitoring                           •

The present limited ability of  the  scientific  community  to  assess
critically the extent of impacts  from elevated acidity  in                    H
precipitation, and from other components of  atmospheric  deposition,           |
is a consequence of few reliable  baseline  observations  on sensitive
aquatic environments.  This lack  of systematic data  arises,                   •
primarily, because many studies and monitoring programs  were planned         •
to define the influences of local anthropogenic development  and are,
therefore located near these influences.   Because  acidification is of
greatest importance in remote areas unaffected by  local  discharges,           •
very few areas exist with any long-term baseline information.                ™

Filling this information gap as quickly as possible  should  be a              B
priority in both the U.S. and Canada.   This  information  is  needed so         |
that positive, definitive analyses  of  ecosystem response to  the
changes in atmospheric deposition can be carried out, with extensive         M
verifications.  Unless a monitoring program  is in  place  and  providing        •
a documented time-series of system  properties, there will be no
significant capacity to quantify  the  results  of either  emission
reductions or increases.                                                      •

While a variety of data needs have  been implicit throughout  the
aquatic effects section, certain  classes of  long-term measurements
are needed at selected sites.   Included are  the following four:

1.   Since a major component of aquatic research is  the  calibrated           «
     watershed, long-term studies of  these systems should be                 •
     intensified with the general objective  of improving the
     estimates of rates of changes  in water  quality  and  biological
     effects relative to acid loadings (i.e.,  dose-response                   •
     relationships), improving  the  understanding of  the  relative             ••
     influence of sulphur and nitrogen loading; and  establishing
     better measures of lake sensitivity,  so  that  the present and
     potential extent of the problem  can be  more clearly defined.

2.   Analyses should be undertaken  of  all  available  baseline studies,        •
     including regional monitoring  of  surface  water  quality,                 •
     plankton, fauna, soil, and vegetation records.

3.   Criteria for selection of  streams and lakes for new monitoring           •
     of water quality and biota should include factors  related to            •
     alkanity sources, lake morphometry, watershed morphometry,
     groundwater inputs, vegetation cover  (i.e., age of  forest and           •
     community structure), surface  water chemistry,  groundwater              £
     chemistry, and type of biotic  community (cold water, warm water
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                                                                  3-221
     etc.).  The regions and lakes chosen  for analysis  should  range
     from very sensitive, through moderately sensitive,  to  "tolerant"
     (reference lakes), although a geographic grid  of comparable
     sites should also be developed.  Data collected  should include
     chemical and biological parameters  identified  as susceptible  to
     change.


4.   Experimental manipulations should be  carried out,  using adjacent
     watersheds with small lakes.  Watershed-level  experiments  should
     include "simulated acid precipitation" additions of  ff1",
     SO^-, NH^, N03~, etc., so that long-term  recovery, following
     termination of acid additions, can  be  investigated.

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                                                                 3-222
     1974.  Effects of acidification  on  Swedish  lakes.   Ambio
     3:30-36.
              1982.  Effects on  fish  of metals  associated  with
                                                                              I
                                                                              I
3.11   REFERENCES

Abrahamsen, G.  1980.  Effects of  acid  precipitation on soil  and              •
     forest.  4.  Leaching of plant nutrients.   In Proc.  Int.  Conf.           •
     Ecological Impact of Acid Precipitation,  eds.  D.  Drablos  and
     A. Tollan, p.  196.  SNSF - Project,  Sandefjord,  Norway,  1980.

Abrahamsen, G.; Horntvedt, R.; and Tveite,  B.   1977.   Impacts  of acid         •
     precipitation  on coniferous forest ecosystems.   Water, Air, Soil
     Pollut. 8:57-73.                                                         •

Ahern, A., and Leclerc, J.   1981.  Etude  comparative de trois  modeles
     de prevision de la sensibilite" des milieux lacustres:  Le               M
     nomogramme de  prevision du pH d'Henriksen (1980),  1'indice de            •
     staruation calcique de Conroy (1974) et la prevision
     d'alcalinite future d'Hesslein (1979).  Final  Report,
     Bio-conseil Inc., Quebec, P.Q.                                           •

Aimer, B.; Dickson, W.; Ekstrom, C.;  and  Hornstrom,  E.   1978.   Sulfur
     pollution and  the aquatic ecosystem.   In  Sulfur in the                   •
     environment.   Part II.  Ecological impacts,  ed.  J.O. Nriagu,             |
     pp. 273-311.   New York:  John Wiley  and Sons.
Aimer, B.; Dickson, W.; Ekstrom,  E.;  Hornstrom,  E.;  and  Miller,  U.            •
     1 Q~7 /•   "C*-C-C rt rt +-j-i nf .-tA-iJ'i-P-ixin-t--; mn  «. «  Or-rn J -i rt T-»  1 .nlv A n    A *n W-i A                 ^™



                                                                              I
Altschuller, A.P.,  and McBean, G.A.   1979.   The  LRTAP problem in
     North America; a preliminary  overview.   U.S.-Canada Research
     Consultation Group  on  the Long-Range Transport  of Air                   •
     Pollutants, Atmospheric Environment Service,  Environment Canada,         •
     Downsview, Ont.

Andersson, A.,  and  Nilsson, K.O.   1974.  Influence of lime and soil          •
     pH on Cd availability  to plants.  Ambio 3:198-200.                       *

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Watt, W.D.; Scott, D.; and Ray, S.   1979.  Acidification and  other
     chemical changes in Halifax County lakes after  21 years.
     Limnol. Oceanogr. 24:1154-1161.                                           jL

Watt, W.D.; Scott, D; and White, W.J.  1983.  Evidence of acidifi-
     cation in some Nova Scotia rivers and of impact on Atlantic              •
     salmon, Salmo salar.  Can. J. Fish. Aquat. Sci.  (in press)                £

Wetzel, R.G.  1975.  Limnology.  Philadelphia:  Saunders Co.                    £
                                                                               I
Wiederholm, T., and Eriksson, L.  1977.  Benthos of  an acid lake.
     Oikos 29:261-267.

Wiklander, L.  1973/74.  The acidification of soil by acid                     W
     precipitation.  Grundforbattring  26:155-164.

Wilson, C.V.  1971.  Le climat du Qu€bec, atlas climatique.   Service           |
     de la M£t£orologie, Ministere de  1'Environnement, Quebec, P.Q.
     pp. 74.                                                                   _

Wilson, D.E.  1979.  The influence of  humic compounds on titrimetric
     determinations of total inorganic carbon in freshwater.
     Arch. Hydrobiol. 87:379                                                   •

Wiltshire, J.F., and Machell, J.R.   1981.  A study of acidification
     in sixteen lakes in mainland Nova Scotia and southern New                •
     Brunswick.  Preliminary Report, Environmental Protection                •
     Service, Atlantic Region, Environment Canada, Halifax, N.S.

Wollast, R.  1967.  Kinetics of the  alteration  of K-feldspar  in               M
     buffered solutions at low temperatures.  Geochim. et Cosmochim.          ^
     Acta.  31:635-648.

Wren, C.;  MacCrimmon, H.; Frank, R.;  and  Suda, P.   1980.  Total and          I
     methylmercury levels in wild mammals  from  the Precambrian Shield
     area of  south-central Ontario,  Canada.   Bull.   Environ.  Contam.
     Toxicol. 25:100-105.
1

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      Verh.  Int.  Verein.  Limnol. 20:765-775.

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      contaminated  lake near  Sudbury,  Ontario;  1973-1977.  Water,  Air,
      Soil Pollut.  11:43-55.

Yan,  N.D.,  and Miller, G.E.  1982.  Characterization  of lakes near
      Sudbury, Ontario.   In Studies of lakes and watersheds  near
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      pp. 127-137.

	.  1978.   Phytoplankton  of  an acidic  lake  and its  responses
      to experimental alterations  of pH.  Environ. Conserv.  5:93-100.

Yan,  N.D.,  and Strus,  R.   1980.   Crustacean  zooplankton communities
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     SECTION 4

TERRESTRIAL IMPACTS

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                                                                  4-1
                              SECTION 4
                         TERRESTRIAL IMPACTS
4.1   INTRODUCTION

A number of air pollutants generated  by  various  sources  cross
international, state and provincial boundaries.   The  main pollutants
which are potentially harmful to  terrestrial  ecosystems  are  oxides  of
sulphur (SOX), oxides of nitrogen (NOX),  particulates,  and secondary
products, such as oxidants and acidic deposition.   There are also
smaller amounts of heavy metals,  several  of which have  potentially
toxic significance after accumulation.

Sulphur dioxide (802) is emitted  at phytotoxic  concentrations  by a
large number of mainly anthropogenic  sources, including  power  plants
and smelters.  Most of this S02 is deposited  in  dry forms near the
sources, though some is transformed chemically  in the atmosphere to
other sulphur compounds.  A moderate  amount of  S02 remains widely
distributed in the atmosphere.  In areas  remote  from  sources,  the
concentration of S02 near the ground  is  close to background  levels,
and not likely to cause adverse direct effects.   However, S02  is
transformed in the atmosphere through a  series  of  reactions  into
sulphuric acid (H2S04) thus contributing to the  formation of the
secondary pollutant, acidic deposition.   Similarly, NOX gives  rise
to nitric acid (HN03) and are likewise precursors of  acidic
deposition.  Ozone (03) is also an indirectly emitted secondary
pollutant formed in the atmosphere in the presence of sunlight, after
chemical transformations of nitrogen  dioxide  and reactive
hydrocarbons.

In summary, acidic deposition and ozone,  although secondary in
nature, are usually considered to be  long-range  transported  pollut-
ants as they frequently occur in  relatively high concentrations at
distances hundreds of kilometres  from the source of their primary
precursors.  Because ozone is a strong oxidizer, oxidative decay
usually is rapid in polluted atmospheres  and  therefore  decreases in
concentration during late afternoon and  evening  as sunlight  intensity
decreases.  However, ozone can persist overnight in rural areas or  at
altitudes where there are low concentrations  of  reactive components
(Jacobson in press).

Improved understanding is needed  of the  ecological effects of  the
phytotoxic primary and secondary  pollutants on  terrestrial eco-
systems.  Field observations and  laboratory studies have provided
detailed descriptions of the visible  injury symptom syndrome produced
by ozone.  Several review articles and chapters  have  provided
excellent descriptions of these symptoms  (Brandt and  Heck 1968;
Hill et al. 1970; USEPA 1978a).   Field studies  including the use of
field chambers (Heagle et al. 1973; Thompson  and Taylor 1966)  and
those with plots located in a natural ozone gradient  have

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                                                                  4-2
                                                                             I
                                                                             I
demonstrated that chronic ozone exposures suppress growth and reduce
yield, often in the presence of little or no visible injury  symptoms.
A more detailed description of the response of plants to acute and            •
chronic exposures to ozone is presented elsewhere (NAS  1977).                 •

It has been more difficult to determine the adverse or  beneficial             •
effects of acidic deposition on plant communities.  Although                 |
simulated rainfall experiments have produced some direct effects on
plants exposed to higher than normal hydrogen ion (H+)  loadings,              ^
direct effects have not been documented conclusively in the  field for         •
vegetation exposed to ambient precipitation (Jacobson 1980).
However, some studies have demonstrated the direct effects of acidic
deposition on soils (Cronan et al. 1978; Dickson 1978).                       A

Indirect effects of acidic deposition (i.e., acting through  soil,
other organisms) and its implications are even less well known.               •
Increases in acidic deposition could result in accelerated changes in         •
the natural evolution of soils, leading to alterations  in soil
fertility over the long term.  These changes in soil chemistry could          ^
have detrimental implications for long-term sustained forest                 I
productivity, and also must be considered in association with aquatic         ™
sensitivity.

This section on terrestrial effects of transboundary air pollutants           0
is presented in four parts: (1) effects on vegetation;  (2) effects on
wildlife; (3) effects on soil; and (4) sensitivity assessment.  Where         M
possible, the information on acidic deposition and combinations of            •
these pollutants has been partitioned and further subdivided into
agricultural crop and forest effects.


4.2     EFFECTS ON VEGETATION
                                                                              I

                                                                              I
4.2.1   Sulphur Dioxide (S02)

4.2.1.1 Introduction

Sulphur dioxide is an air pollutant of concern  to  vegetation  having
most often been recognized for inducing direct  foliar effects to
plants growing proximal to major point sources  of  emission.   The              •
phytotoxicity of this gas has been studied  extensively  around                V
long-term sources such as Sudbury, Ontario  (Dreisinger  and McGovern
1970; Linzon 1971) and the districts of Fox Creek  and West                    •
Whitecourt, Alberta, (Legge et al. 1976).   Controlled long-term              •
exposure studies have recently been completed as part of  the  Montana
Grasslands Studies (Lee et al. 1978; Preston  1979).  This pollutant           _
has also been considered of great importance  to the  vegetation within        •
the heavily industrialized areas of Great Britain  (Cowling and Koziol        *
1978) and central Europe (Guderian 1977).

Sulphur dioxide is not found on a regional  basis at  concentrations            ^
sufficient to cause direct injury to most plant species.  Long-term,
                                                                              I
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                                                                  4-3
low-dose studies have demonstrated direct effects  to  lichen
communities (Hawksworth  1971) and indirect  effects to several  plant
species (Keller  1978, 1980; Laurence  1978).  Likewise effects  may
result from lower doses  of pollutants  in combination  with special
reference to 03  and S0£  in mixtures (Heagle  and  Johnston 1979;
Reinert and Nelson 1980).  Several reviews  of  the  effects of  SC>2  on
vegetation are available (Guderian 1977; Jacobson  and Hill 1970;
Linzon 1978; Rennie and  Halstead  1977;  Treshow 1970;  USEPA 1973,

1978b).
4.2.1.2  Regional Doses  of  S02


As presented in Table  2-3 of  Section  2  (Rasmussen et  al.  1975),
estimates of global background  concentrations  of  SC>2  in gaseous
form should be expected  within  a  range  of  approximately
0.5-5.0 yg/m3 (0.0002-0.002 ppm S02 at  STP) with  expected
residency times of these concentrations  to  last from  one  to  five
days.  Regional S02 emissions are shown  in  Figure 4-1.


Mueller et al. (1980)  reported  on atmospheric  pollutant data
collected during the period August 1977  -  October 1978  for an area
covering much of the eastern half of  the United States  (Figure 4-2).
Monthly 1-hr averages  varied  from 5-40 yg/m3 (0.002-0.015 ppm
802).  The highest annual average SC>2 concentrations  occurred
along the Ohio River Valley; averages ranged from 0.019-0.029 ppm
S(>2.  The maximal 1-hr concentrations were  from 0.11-0.19 ppm S02
and occurred in the same area during  October 1978.  Hourly deposition
values of 1.5-2.3 ppm  S02 are common  near  large emission  sources
(USEPA 1978a).


In the northeast alone,  anthropogenic sources  exceed  all  others by a
factor of 12.5.  Within  this  region,  S02 levels annually  average
16 yg/m3 (0.006 ppm S02) (Shinn and Lynn 1979) which  is several
times that recorded in pristine areas.   Therefore,  it is  reasonable
to assume that at the  present time concentrations  of  S02  seldom
reach direct foliar injury  thresholds for vegetation  growing in
forested areas or in areas  of significant agricultural  production.
Duchelle and Skelly (1981)  reported S02  concentration ranges of
0.001-0.002 ppm/hr S02 during the summer seasons  of 1979  and 1980
within the Shenandoah  National  Park in Virginia and did not  consider
this pollutant of importance  to vegetation  in  the area.


Distribution of even these  low  doses  of  SC>2 (and  N02) over the
major portion of eastern United States corresponds well with known
ozone occurrences (USEPA 1978b).
4.2.1.3  S02 Effects to Agricultural Crops


There are several possible responses to S02 and  related  sulphur
compounds: (1) fertilizer effects appearing as increased  growth  and

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                                                                            4-4
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                                                                       >10,000
                                                                       1000.1-10,000
                                                                    x3 100.1-1000.0
                                                                    &x
                                                                    :-:+\ 10-100.0
                                                              (ANNUAL EMISSIONS IN g/s)

                                                              200     0     200     400
0 1
    2  3  4 5  6  7  8  9  10 11 12  13 14 15 16 17 18 19  20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39
    Figure 4-1.    Magnitude  and distribution of  sulphur dioxide
                    (802) emissions in  eastern North America.   Data from
                    SURE II  data base and Environment Canada  (Environment
                    Canada 1981d).
1

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                                                                           4-5
                                  SO2(ppm)

                                  Aug. 1977
                                Jan./Feb. 1978
                                  SO2 (ppm)

                                  Jul. 1978
SO2 (ppm)
Oct. 1977
                                                                   1978
 SO2 (ppm)

 Oct. 1978
Figure 4-2.    Geographic  distribution  of monthly arithmetic means for
                S02  (Mueller et  al. 1980).

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                                                                  4-6
acids and proteins.  The rate  of entry  is  particularly  important  to
determining toxicity.  Plants  have  an inherent,  and  apparently
                                                                              I
                                                                              1
yields; (2) no detectable responses;  (3)  injury manifested  as  growth
and yield reductions without visible  symptom  expressions  on the
foliage or with very mild foliar symptoms  that would  be difficult  to         •
perceive as air pollution incited without  the presence of a control          •
set of plants grown in pollution-free  conditions;  (4)  injury
exhibited as chronic or acute  symptoms  on  foliage  with or without             •
associated reductions in growth and yield;  and  (5)  death  of plants           £
and plant communities.

Sulphur.dioxide passively enters plants via stomata as part of normal        •
gas exchange during photosynthesis.  Many  factors  govern  stomatal             •
opening and closing including  light,  relative humidity, CC>2
concentration and water stress.  Sulphur  dioxide uptake and ingress          ft
may also be limited according  to plant  genetics, previous exposure to        V)
SC>2 (Jensen and Kozlowski 1975) and subsequent  biochemical  and/or
physiological alterations within exposed  plants.   Sulphur dioxide  has        •
been shown to increase or decrease stomatal resistance and  this may          •
directly affect potential for  the photosynthetic performance
(Hallgren 1978).  Based on  the available  literature,  it is  difficult
to assess the relationship  of  SC>2-induced  biochemical and/or                 I
physiological changes at the cellular  level in  relation to  subsequent        •
effects on photosynthetic activity or  resultant  growth and  yield.
Sulphur dioxide, upon absorption  is  further  oxidized  to 863 and
50^2- ancj subsequently is  incorporated  into  S-containing amino
                                                               » *-  A- A


species dependent, capacity  to  absorb,  detoxify,  and  metabolically           ™
incorporate SC>2 and some plants may  absorb low concentrations of
S02 over long time periods without injury.                                    •

Atmospheric S02 can have beneficial  effects  to agronomic vegetation
(Noggle and Jones  1979).   Sulphur is one  of  the elements required for        •
plant growth and Coleman (1966) reported  that  crop  deficiencies of S         •
have been occurring with increasing  frequency  throughout the world.
Several studies using SC>2  as  a  nutrient supply for  S  requirements            •
of plants have been accomplished  under  varying degrees  of soil-              •
sulphur availability (Cowling et  al. 1973; Faller 1970; Noggle and           *
Jones 1979).  The  results  of  these and  other studies  leave little
doubt that application of  S  as  a  nutrient via  SC>2 fumigation of              •
plants grown on borderline or S-deficient soils will  lead to                 V
increased productivity.

The interpretation of studies demonstrating  such beneficial effects          •
must be evaluated  in light of their  single influence  to one crop.
Long-term natural  ecosystem  studies  showing  similar positive effects         —
for the entire ecosystem have not been  accomplished.   Since these            •
agronomic and natural ecosystems  are often physically proximal to one        ~
another, further research  is  needed  on  the potential  influence of S
compounds to each  singly and  collectively.                                    •
                                                                              I

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                                                                  4-7
Acute foliar in j ury occurs following high-dose  exposures  and  the
rapid absorption of a toxic  dose  of SC>2  results at  first  in
marginal and interveinal areas having a  dark-green,  watersoaked
appearance.  After desiccation and bleaching  of tissues,  the  affected
areas become light ivory to  white in most  broadleaf  plants.  Some
species show darker colours  (brown or red), but there  is  characteris-
tically an exact line of demarcation between  symptomatic  and  asympto-
matic portions of leaf  tissues.   Bifacial  necrosis  is  common.  In
monocotyledons (e.g., corn,  grasses) foliar injury  occurs at  the  tips
and in strips along the veins (Malhotra  and Blauel  1980;  USEPA
1976).

Plant injury that is visible but  does not  involve  collapse and
necrosis of tissues is  termed chronic injury.   This  type  of visible
injury is usually the result of variable fumigations consisting of
both short-term, high-concentration or long-term,  low-concentration
exposures to
In broadleaf plants,  chronic  injury  is  usually  expressed in tissues
found between the veins, with various forms  of  chlorosis predomi-
nating.  Chlorotic spots or chlorotic mottle may persist following
exposure or may subside and disappear following pollutant  removal or
as a result of changing environmental conditions (Jacobson and Hill
1970).

The presence of acute or chronic  foliar injury  is not  necessarily
associated with growth or yield effects.  Furthermore,  when present,
the degree of foliar  injury may not  always be a reliable indicator of
subsequent growth or yield effects.  The uniformity  of  exposure to
even the low doses of 862 experienced by crops  growing  under field
conditions presents difficulty in measuring  'treatment1  effects due
to the lack of a set  of control (nonpollutant exposed)  plants.
Artificial systems must therefore be used under more controlled
laboratory and field  situations.  The more ubiquitous  exposure to
known phytotoxic concentrations of 03 must also be recognized and
singly evaluated.

Yield effects in the absence  of foliar  symptoms have been reported
for soybeans by Sprugel et al. (1980) and Reinert and Weber (1980)
under field conditions using  a zonal air pollution delivery system
and using chamber exposures.  Both reports,  however, used  doses more
typical of point sources of emission and would  therefore not be
considered comparable to regional conditions of exposure.   No studies
consider all the potential variables that can effect plant response.
This is not a possibility for a single  study and is  especially true
for field studies (which are  most relevant)  where many  environmental
variables cannot be controlled.  From the data  available,  we can
conclude that growth and yield effects  are not  necessarily related to
foliar injury.  Depending upon the plant affected, the  environmental
conditions, and the pollutant exposure  conditions, one  may observe
yield effects without injury, injury without yield effects or more
direct correlations between injury and  yield.

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                                                                  4-8
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The primary focus of dose-response  studies  should  be  to  develop
useful generalizations of the relationship  between meaningful
parameters of plant response and measurable  indices of exposure dose.          •
The relationship between exposure dose  and  the  amount  of pollutant             I
entering the plant may be significantly influenced by  environmental
factors controlling the rate of pollutant  flux  into plant leaf                _
tissues (see Figure 4-3).  The dose  of  862 must be considered  in              •
relation to known concentrations under  field conditions  since  both             *
the regionally expected dose and the  phytotoxicity of  S02 are
comparatively low (e.g., ozone dose  and phytotoxicity  are relatively          4
high).                                                                         •

The role of short-term fluctuations  in  S02 may  be  of  particular               m
importance in areas proximal to point sources of SC>2  (Mclaughlin              V
and Lee 1974).  Here concentrations  may fluctuate  widely during
exposure and damage to vegetation may be closely associated  with
short-term averages (1 hr) or even  peak concentrations.   McLaughlin           •
et al. (1979) studied the effects of  varying the peak  to mean  S02             ™
concentration ratio on kidney beans  in  short-term  (3  hr) exposures  to
SC>2.  They found that increasing the  peakrmean  ratio  from 1.0                  B
(steady state exposure at 0.5 ppm for 3 hr)  to  2.0 (3  hr exposure             |
with  peak = 1.0 ppm) did not alter  post fumigation photosynthetic
depression.  However, further increasing the ratio to  6.0 (1 hr               _
exposure with peak =2.0 ppm) tripled the  post  fumigation                     •
photosynthetic depression.  Total dose  delivered in the  three
exposures was 1.5, 1.8, and 1.1 ppm respectively.   Clearly the
quantity of S02 to which the plants  are exposed may have a very               I
different effective potential as the  kinetics of the  exposure  are             ^
changed.

Data  on S02 effects on plant growth and yield in most  cases  provide           f
the most relevant basis for studying  dose-response relationships.  As
a whole-plant measurement, plant productivity is an integrative               ^
parameter which considers the net effect of  multiple  factors over             •
time.  Productivity data are presently  available for  a wide  range of          ™
species under a broad range of experimental  conditions.   Because
results would not be expected to be  closely comparable across  these           •
sometimes divergent experimental techniques, data  have been  tabulated          flj
separately for only controlled field exposures  (Tables 4-la  and
4-lb).                                                                         •

Relatively few crops of economic importance have been studied  under
field conditions utilizing various  field exposure  systems.  Of the             ^
seven "studies" reviewed in Tables  4-la and  4-lb,  dose exposure to             •
induce a yield effect was 0.09 ppm  S02  for  4.2  hr average                     ^
fumigation period on 18 days scattered  from July 19 through  August  27
of the soybean growing season (Sprugel  et  al.  1980).   Five studies             •
indicated no effect following various exposure  regimes,  and  one study         |
(Neely and Wilhour pers. comm.) reported increased yields (27% and
8%) of winter wheat cv. Yamhill following  exposure dose  of 0.03 and           ^
0.06  ppm S02 for 24 hr/day for the  entire  growing season,                     •
respectively.
                                                                               I

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                                                              4-9
                                POLLUTANT
                              CONCENTRATION
      NUMBER OF
      EXPOSURES
CLIMATIC FACTORS

 EDAPHIC FACTORS

  BIOTIC FACTORS
PLANT RECEPTOR
                           MECHANISM OF ACTION
 DURATION OF
'EACH EXPOSURE

-GENETIC MAKEUP

 STAGE OF PLANT
 DEVELOPMENT
                                  EFFECTS
                      ACUTE
   CHRONIC     SUBTLE
    Figure  4-3.   Conceptual model of the factors  involved  in air
                 pollution effects (dose-response) on vegetation
                 (Heck and Brandt 1977).

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4-10





















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                                                                  4-12
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I
Tables 4-la and 4-lb also  reviewed  a large  number of studies which
were conducted using various  greenhouse  or  exposure chamber
techniques and exposure  of  agronomic or  horticultural crop plants.            f|
Conclusions indicated difficulty  in determining the significance of           |
results of such studies  in  relation to  actual similar fumigations
under field conditions.  Doses used for  exposure treatments were              m
usually considered to be in excess  of expected doses for ambient              I
field exposures.  Acute  foliar effects have not been reported in
long-term studies using  less  than 0.15 ppm  S02 for 24 hr/day for 7
days.                                                                          •

In greenhouse experiments  conducted in England using ryegrasses,
yield losses were measured  following long-term exposure to low levels         fl
of SC>2.  In one study (Bell and Clough  1973), perennial ryegrass              |
experienced a 52% reduction in dry  weight after exposure to a mean
concentration of 0.067 ppm S02 over a 26~wk period.  At the end of            M
the study the plants were  smaller and chlorotic in comparison to the          H
control plants exposed to  air that  was  purified by both activated
charcoal and an absolute filter.  In the other study (Crittenden and
Read 1978), shoot dryweight of Italian  ryegrass was reduced by 30 to          •
40% after 8-10 wk of exposure to  0.02 to 0.03 ppm S02, and was                •
reduced about 10% after  5-wk  exposure to air containing 0.004 to 0.02
ppm S02«  The Italian ryegrass plants did not display visible                 •
symptoms of air pollution  injury  in either  the exposure chamber or            |
the control filtered air chamber.

In spite of differences  due to exposure  regimes, techniques, and              •
species, certain generalizations  can be  made with respect to average
and outer-limit responses  of  the  plants  under study.  These have been
made in the form of correlations  of yield response with total                 •
exposure dose in part-per-million hours  (ppmh).  The latter data were         W
calculated as the product  of  exposure time  and SC>2 concentration
and transformed to log values.  For experiments employing controlled          •
exposures under field conditions  (Tables 4-la and b), data are                ^
graphed in Figure 4-4 (McLaughlin 1980). For the 36 data points
shown, exposure dose ranged from  0.24 to 259 ppmh.  No effects on             —
yield were detected in any  of the six studies at doses _>_ 6 ppmh.              •
Yield losses occurred in 26 cases at levels ^_ 6 ppmh, while no
effects and positive effects  were noted  in  two cases each at levels
_> 6 ppmh.  A linear regression of yield  on  dose for all studies               •
reporting yield losses showed strong positive correlation (r = 0.75)          •
of yield with dose and took the form:

                 Yield loss = -13.6 + 23.8  (log dose)                         |
                         r2 = 0.53  (Significance = >_ 0.001)

This correlation excludes  four data points, two with no effects and           •
two with positive responses.  All were  studies with wheat reported by         *
Neely and Wilhour (pers. comm.).  Data  from studies reporting no
effect or a positive effect are however all plotted in Figure 4-4.            fl

Calculation of the phytotoxic potential  for regional scale S02
exposures involves many  assumptions regarding toxic and nontoxic               m
                                                                                I

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                                                                4-13
           REGRESSION  LINE:
           % YIELD LOSS —13.6 + 23.8 (LOG DOSE)
           r2*0.53  P>F< 0.001
           22 DATA POINTS
                                   I
                                               I
                    0.1
                                1.0            10.0

                              EXPOSURE DOSE(ppmh)
100.0
Figure 4-4.
            Regression of yield response vs. transformed dose
            (ppnh) for controlled exposures using field chambers
            (zero and positive effects excluded from regression
            analysis) (after McLaughlin 1980).

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                                                                  4-14
4.2.1.4  S02 Effects to Forest Vegetation
I
I
components of the total dose  to which vegetation  is  exposed.
Obviously not all, but probably most exposures  to S(>2  on a  regional
scale are below levels producing phytotoxic  reactions.   An  important           H
aspect of evaluating the likelihood that plants will be  negatively            |
influenced by S02 exposures is the determination  of  what components
within a plant's total exposure history are  phytotoxic.   Mclaughlin            M
(1980) recently examined USEPA (1978b) data  on  regional  S02 concen-            •
tration averages.  Using the  assumption that only the  upper 10% of
all S02 exposure days would have S02 concentrations  high enough
to cause stress to vegetation, and that only daylight  exposure                 •
(8 hr/day) during the active  growing season  (6  mo/yr)  would be                 •
effective, he calculated that the average  potentially  phytotoxic dose
within designated air quality control regions would  range from  0.9            •
ppmh (Region IX) to 5.5. ppmh (Region VIII).  Maximum  doses (highest           Jf
reporting stations within regions) ranged  from  2.6 ppmh  to  27 ppmh,
thus pointing once again to the potential  injury  to  vegetation  grown           ^
within smaller areas of high  S02 point source emissions.                       •
I
The effects of S02 on broadleaf  tree  species  and  similar  types  of
native vegetation closely resemble  those  as described  for agronomic           •
crops.                                                                         •

In conifers, acute injury on  foliage  usually  appears  as  a bright              —
orange red tip necrosis on  the current-year needles,  often with a              •
sharp line of demarcation between the injured tips and the normally           •
green bases.  Occasionally, the  injury may occur  as bands at  the tip,
middle, or base of the needles (Linzon 1972).                                 A

Recently incurred injury is light coloured but  later  bright orange or
red colours are typical for the  banded areas  and  tips.  As needle              M
tips die, they become brittle and break or whole  needles  drop from            I
the tree.  Pine needles are most sensitive to S02 during  the  period
of rapid needle elongation  but injury may also  occur  on  mature
needles (Davis 1972).                                                          •

Chronic effects of S02 in conifers  are generally  first expressed on
older needles (Linzon 1966).  Chlorosis of tissues starting at  the            •
tips progresses down the needle  towards the base  (i.e.,  symptoms              ||
progress from the oldest to youngest  tissues).  Advanced  symptoms  may
follow, involving reddening of affected tissues.   Continued chronic           M
injury to perennial foliage of coniferous trees results  in premature          •
needle abscission, reduced  radial and volume  growth,  and  early  death
of the trees (Linzon 1978).

Forest trees vary considerably in their sensitivity to S02 doses              W
and Jones et al. (1973) evaluated the response  of numerous species
growing near point sources  in southeastern U.S. (Table 4-2).   Visible
symptom expression only occurred on the most  sensitive species  at
 I

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                                                                  4-15
TABLE 4-2.  SULPHUR DIOXIDE CONCENTRATION CAUSING VISIBLE  INJURY  TO
            VARIOUS SENSITIVITY GROUPING OF VEGETATION3  (Jones  et
            al. 1973)
Maximum Sensitivity grouping
average
concentration Sensitive Intermediate Resistant
(ppm S02) (ppm S02) (ppm SC^)
Peak 1.0-1.5
1 hr 0.5-1.0
3 hr 0.3-0.6
Ragweeds
Legumes
Blackberry
Southern pines
Red and black oaks
White ash
Sumacs
1.5-2.0 2.0
1.0-2.0 2.0
0.6-0.8 8.0
Maples White oaks
Locust Potato
Sweetgum Upland cotton
Cherry Corn
Elms Dogwood
Tuliptree Peach
Many crop
and garden
species
a Based on observations over a 20-year period of visible injury
  occuring on over 120 species growing in the vicinities of coal-
  fired plants in the southeastern United States.

-------
                                                                  4-16
I
I
doses of 0.30 ppm/3 hr thus once again pointing to the smaller area
of source influence on direct foliar injury.  Dreisinger and McGovern
(1970) indicated a somewhat similar injury threshold  (i.e., 0.26 ppm          •
S02/4 hr) for visible foliar injury to the most sensitive vegetation          I
to S02, but doses were still above ambient concentrations as
expected on a regional basis.                                                 •

A few major investigations of the effects of  S02 on tree species
growing under natural conditions have been reported (Dreisinger  1965;         ^
Dreisinger and McGovern 1970; Linzon  1971, 1978).  These reports             •
indicated that a pollution (802) gradient existed within the                  ™
designated study area near Sudbury, Ontario,  and effects correlated
well with this gradient.  Chronic effects on  forest growth were               fl
prominent where S02 air concentrations during the growing season              |
averaged 0.017 ppm S02, and were only slight  in areas receiving
0.008 ppm S02 (Linzon 1978).  In Czechoslovakia, Materna et al.               m
(1969) reported the occurrence of moderate chronic injury to foliage          •
of spruce trees at Celna, under the influence of an average annual
concentration of S02 at 0.019 ppm.                                            ^

Table 4-3 summarizes the results of tree studies that have utilized           •
artificial exposure chamber systems under laboratory  conditions.
Only two studies (exposures) used doses close to ambient concentra-           •
tions (Houston 1974); however, the use of selected clones of known            ^j
sensitivity to S02 hinders further field speculation  from this
study.  The remainder of the studies presented in Table 4-3 have used         M
doses above expected occasional exposures under field conditions.             •
Concentrations of 0.25 ppm S02 for 2 hr were  required to induce
slight injury to several pine species (Berry  1971), but overall
trends for increasing foliar injury do not follow increasing dose for         •
conifers per se.  Smith and Davis (1978) exposed several conifers             W
(pine, spruce, fir and Douglas fir) to doses  of 1.0 ppm S02 for  4
hr or 2.0 ppm S02 for 2 hr and only pines developed necrotic tips             •
at the 2.0 ppm dose.  Likewise, Keller (1980) found only trends  in            f
reduced photosynthesis in Norway spruce at S02 doses  of 0.05 ppm
S02 for 10 wk exposure with significant effects noted at 0.10 and             M
0.20 ppm S02 over the same period.                                            •


4.2.1.5  S02 Effects to Natural Ecosystems                                    I

Ecosystems are basically energy processing systems whose components
have evolved together over a long period of time.  They are composed          •
of living organisms together with their physical environmental                •
conditions.  Ecosystems respond to environmental changes or perturba-
tions only through the response of the organisms of which they are
composed (Smith 1980).  The living (biotic) and nonliving (abiotic)           •
units are linked together by functional interdependence.  Processes           •
necessary for the existence of all life, the  flow of  energy and
cycling of nutrients are based on relationships that  exist among the          •
organisms within the system (Billings 1978; Odum 1971; Smith 1980).           |
Because of these relationships, unique attributes emerge when
                                                                               I

                                                                               I

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                                                                  4-24
I
I
ecosystems are studied that are not observable when individuals,
populations or communities are studied.

Natural ecosystems are seldom, if ever, exposed  to a single air               «•
pollutant.  Therefore, the responses observed under ambient
conditions cannot conclusively be attributed to  a single  substance            •
such as sulphur dioxide alone.  Consideration of low SC>2  doses on a           |
regional basis presents even further difficulties in discerning
effects induced by this pollutant.                                            .

Questions relating how sulphur deposition from anthropogenic
emissions is incorporated and distributed by aquatic and  terrestrial
ecosystems is not fully resolved.  The issue is  critical  since                •
ecosystems subject to excess nutrients or toxic  materials do not              •
commonly distribute them uniformly throughout the system  but rather
preferentially sequester them in specific pools  or compartments.  In          m
addition, sulphur dioxide as a gas can cause injury to  the vegetative         •
components of specific and local ecosystems so that energy flow and
the cycling of other nutrients as well as sulphur may be  disrupted if         ^
the pollutant is at sufficient concentrations.                                •

Specific studies of the more detailed effects of SC>2 on natural
systems have been conducted proximal to point sources of  high  862             B
emissions and include studies in the vicinity of the Kaybob gas               V
plants (Fox Creek, Alberta) (Winner et al.  1978)5 West Whitecourt gas
plant (Whitecourt, Alberta) (Legge et al. 1976)  and the Sudbury,              •
Ontario smelter district (Dreisinger and McGovern  1970; Linzon 1971).         •
Additionally, a series of designed studies  using ariticial sources of
S02 have been conducted in the Montana grasslands  (Preston 1979).

The results of these studies, particularly  the West Whitecourt and            •
Montana grasslands studies, document the usefulness of  addressing
ecosystem level responses to S02 from a multidisciplinary approach            •
incorporating investigations of physiology, autecology, synecology,           |
geochemistry, meteorology and modelling.  The results confirm  that
producers are sensitive to direct S02 effects as evidenced by                 mm
S02~associated changes in cell biochemistry, physiology,  growth,              I
development, survival, fecundity, and community  composition.   Such
responses are not unexpected.  An equally important point of
agreement among the different research efforts is the potential for           •
ecological modification resulting from either direct S02  effects on           •
nonproducer species or direct changes in habitat parameters, which in
turn affect an organism's performance.  Changes  in biogeochemistry,           •
particularly in the soil compartment, are notably responsive to               •
low-dose S02 exposures.  A major conclusion of the Montana
grasslands studies indicated that at S02 levels  above 0.02 ppm (52            _
yg/nH), induced changes occur in the performance of producers,                •
consumers, and decomposers.  Many of the responses are  individually           *
small, but collectively over time they gradually modified the
structure and function of the grasslands.   The significance of these          B
changes to the long-term persistence of the ecosystem remains                 |
controversial (Preston 1979).
                                                                               I

                                                                               I

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                                                                  4-25
Direct effects of SC>2 on individuals within  natural  plant
communities are most noted within  the  lichens.   Sulphur  pollution not
only has caused the depletion  of lichen  vegetation in certain areas,
but also has resulted in changes in the  distribution of  different
species (Hawksworth et al. 1973).  Epiphytic lichen  communities have
been mapped within several regions of  North  America.   In a rural area
of Ohio surrounding a coal-consuming power station (emitting 1025
tons S02/day), the distribution of two corticolose lichens,
Parmelia caperata and I>. ruderta,  was  markedly  affected  by elevated
S02 levels (Showman 1975).   In regions experiencing  an annual S02
average exceeding 0.020 ppm, both  species were  absent.   The
distribution of more resistant lichens was not  noticeably  affected
until S02 levels exceeded 0.025 ppm (annual  average).  Somewhat
lower levels were projected  by LeBlanc and Rao  (1973)  to effect the
ability of sensitive lichen  species to survive  and reproduce; acute
and chronic symptoms of S02  toxicity in  epiphytic lichens  occurred
when annual averages of SC>2  exceeded 0.03 and 0.006-0.03 ppm
respectively.


The network of biotic-abiotic  interactions,  which is characteristic
of managed and natural ecosystems, leads to  the hypothesis that S02
effects on producers must have repercussions to other  trophic levels.
Demonstration of such responses, however, is difficult experimen-

tally, and an accurate assessment  of the specific importance of S02
in eliciting these responses is complicated  by  the often complex
relationships between producers, consumers,  and decomposers.


More subtle effects may occur  in areas of low S02 (0.05  ppm annual
average) deposition by shifts  in soil  microfloral populations thus
further influencing plant rhizopheres  leading to subsequent  ecosystem
alterations (Legge et al. 1976; Wainwright 1979).


Induced changes in natural ecosystems  should not be  evaluated on a
positive or negative basis.  Change as induced  by anthropogenic
sources of 862 must be considered  as an  alteration of  natural
processes.  For example, natural ecosystems  evolved  on sulphur-
deficient soils have done so within the  imposed constraints  per se.
Although atmospherically derived sulphur may not be  sufficient  to
cause injury, the prolonged  input  of sulphur may relax the
constraints of a limited sulphur supply  thereby inducing shifts in
species composition.
4.2.2   Ozone (03)


Ozone air pollution injury was first  reported  by  Richards  et  al.
(1958) and during the subsequent years  a diverse  array  of  visible
injury symptoms was described on a wide variety of  crop, ornamental
and native vegetation.  Numerous review chapters  and  journal  articles
contain detailed descriptions of these  symptoms (Brandt and Heck
1968; Hill et al. 1970; NAS  1977; USEPA 1978a).   Characteristics of
the injury symptoms and extent of injury are influenced by climatic

-------
                                                                 4-26
4.2.2.1   03 Effects to Agricultural Crops
I
I
and edaphic conditions, genetic variability, characteristics of  the
pollutant dose, and by interactions between the pollutant and other           _
air pollutants or other environmental factors  (NAS  1977).  Injury             •
symptoms described by the various researchers  have  included:                  ™
bleaching, bifacial necrosis, general chlorosis,  chlorotic mottling,
chlorotic streaking, topical necrosis such as  "fleck" and "stipple,"          I
and pigmented leaf tissue (Hill et al.  1970; NAS  1977; USEPA 1978a).          •
In addition to the development of visible injury  symptoms, exposure
to atmospheric ozone can:  (1) suppress photosynthesis;  (2) stimulate         •
respiration; (3) inhibit carbohydrate transport;  (4) change membrane          •
properties; (5) alter metabolite concentrations;  (6) alter symbiotic
associations; and (7) alter host-parasite interactions.                       —

Prior to 1970 most 03 research dealt with observed  foliar symptoms            •
resulting from acute (short-term), artificially controlled,
dose-response studies.  In the 1970s, the research  approach shifted           •
toward chronic (long-term) studies providing a more realistic                 |
estimate of natural plant response.  The results  of several such
studies are summarized in Table 4-4.  These studies formed the                M
foundation for quantification of dose-response relationships that             •
provided a more realistic basis for the assessment  of losses under
field conditions.  A number of assessment techniques (e.g., open-top
chambers, protective sprays) were utilized in  several major studies           •
designed to pursue this objective.                                            V

The National Crop Loss Assessment Network (NCLAN)  (Heck  et al.  1982)          •
utilized open-top chambers and controlled 03 concentrations.  Its             f
purpose was to provide standardized crop dose-response data which
could be utilized in the development of reliable  regional scale  loss          m
assessment calculations.                                                      •
I
Foliar responses of crops  to artificial 63  exposure  have  been well
documented and used in the development of species  and  varietal               •
sensitivity listings and the preparation of predictive dose-response         £
curves (Larsen and Heck 1976;  Linzon  et al. 1975).   However,  these
data may not be reliable for estimating the total  effect  on crop              _
productivity (e.g., yield, quality).  Most  information now indicates         •
that the severity of foliar symptoms  is not a  reliable index  of crop         ™
growth or yield effects (Reinert  1980) as there  is uneven competition
among several sinks that receive  photosynthate.  Also,  compensatory           H
responses to ozone can produce  rapid  recovery  from injury (Jacobson           |
in press).  Studies with soybeans (Tingey et al.  1973), tomatoes
(Oshima et al. 1975) and alfalfa  (Tingey and Reinert 1975) all               M
support this concept.  The exceptions to this  general  finding are            •
cases where the harvested  product is  the foliage  and where foliar
injury development coincides with the rapid growth of  the harvested
product (Linzon et al. 1975).                                                 •
                                                                              I

                                                                              I

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                                                                                 4-27


















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                                                                  4-31
Although the adverse effects of 03 exposure on  crop  yield  or
productivity have not been as extensively documented as  has been the
case with foliar injury, there are nevertheless numerous reports on
this topic.  Any assessment of yield or quality parameters under
field conditions is complicated by the ubiquity of ozone exposure,
the effect of meteorological variables on ozone distribution  within
crop canopies, and the difficulty in establishing ozone-free  control
plots.  Numerous biotic (pathogen, genetics) and abiotic factors
(i.e., RH, light, and soil moisture) within the environment must also
be taken into account.  These difficulties have been partially
overcome by recent progress which has been made in the development  of
field assessment techniques for plant growth and productivity
(Reinert 1980).  These include open-top field chambers,  pollutant
exclusion methods, open-air fumigations, ambient air pollutant
gradients and chemical protectants.

Experimental studies with field grown crops have demonstrated yield
reductions in a large number of ozone-sensitive crops:   beans
(Heggestad et al. 1980), potatoes (Heggestad 1973),  grapes  (Thompson
et al. 1969), corn (Heagle et al. 1972) and others (Heggestad 1980;
Jacobson in press; Reinert 1975).  In general the studies  have shown
that decreased yield of susceptible species occurs with  average ozone
concentrations of between 0.05 and 0.1 ppm for  6-8 hr/day  during the
growing season (Heck et al. 1977).  In a 5-yr study  in Maryland
(1972-79), typical yield reductions were 4, 9,  10, 17 and  20%
respectively for field grown (open-top chambers) snap beans,  sweet
corn, potatoes, tomatoes and soybeans (Heggestad 1980).

The first report from the NCLAN project (Heck et al. 1982) appears  to
provide good agreement with earlier dose-yield  response  data  (Heagle
and Heck 1980) and with yield losses in the various  crops  as  follows:
soybean 10%, peanut 14-17%, a single turnip 7%, head lettuce  53-56%
and red kidney bean 2%.  The yield reductions were equated with
seasonal 7 hr/day mean 03 concentrations of 0.06-0.07 ppm  compared
to the 0.025 control value.  In the earlier study (Heagle  and Heck
1980) employing open-top chambers with 03 dispensing capabilities,
an annual U.S. crop loss estimate assuming a seasonal 7  hr/day mean
03 concentation of 0.06 ppm in all crop production areas was
calculated at $3.02 billion (5.6% of the national production).  In  a
subsequent manuscript Heck (1981) pointed out that it is a weak
assumption that crops in all parts of the United States  are in a
sensitive state during much of the growing season and the  values
should be reduced by 50%.  This would bring the estimate of 63 crop
losses in the U.S. to between $1 billion and $2 billion  or 2-4% of
total production assuming all areas were at concentrations of 0.12
ppm for 1 hr.  As most sections of the country  are above the  current
standard, the national losses are probably higher than the above
values (Heck 1981).

There are limitations in assessing 63 impact on crop species,  in
that a majority of presently operating 03 monitors in both the U.S.
and Canada are in urban locations.  They therefore may not represent

-------
                                                                  4-32
I
I
levels to which rural vegetation is exposed.   However,  some  indica-
tion of the occurrence of 03 in rural areas along  the U.S./Canada
border is given in Table 4-5.  The Ontario rural data (Table 4-6)             I
have been summarized to provide some indication of the  potential  for         •
adverse crop effects (growing season daytime  basis)  and can  be
compared directly with the 03 data (Table 4-7) for urban locations            •
in the National Air Pollution Surveillance Network (NAPS) in Ontario,         |
Quebec and New Brunswick.

It is apparent from these urban and rural data that  the southern              •
portion of the Province of Ontario is most adversely affected by
ozone in Eastern Canada.  This finding  is corroborated  by numerous
reports of ozone-related crop injuries  in this area  (Cole and Katz            •
1966; Curtis et al. 1975; Hofstra et al. 1978; Ormrod et al. 1980)            •
and by the absence of any documented injurious effects  to sensitive
agronomic or forest species in Quebec or the  Maritime provinces.
I
In Ontario the first indication of  transboundary  ozone  movement
across Lake Erie was documented (Mukammal  1960) following  extensive           •
work on the relationship between the incidence of weather  fleck  on           •
tobacco and meteorological conditions associated  with the  buildup of
ozone.  Since then a number of large-scale meteorological  investi-
gations (Anlauf et al.  1975; Yap and Chung 1977)  have documented             •
these early findings and have shown that high ozone  levels generally          •
are associated with regional southerly  air flows  which  have passed
over numerous urban and industrialized  areas of the  U.S. and which,           •
as they move across the lower Great Lakes, undergo rapid dispersion           •
as they encounter unstable conditions near the northern shore of Lake
Erie.  Contributing to  these influx patterns are  the more  localized           _
downwind urban effects which can add to the already  high background           •
levels.                                                                       ™

In an effort to estimate the severity and  extent  of  plant  injury or           B
yield loss resulting from exposure  to ambient ozone  in  southern               |
Ontario, a summary has been prepared for all major crop species  on
the basis of documented research reports of yield or productivity            •
losses in Ontario or the northeastern U.S. and on unpublished                •
documents by government agencies or university departments working
under assessment mandates or research contracts.  On the basis of
these findings and 1980 economic values it is estimated that the             •
average annual loss for ozone-sensitive Ontario crops based on 1980           •
economic values is in excess of $20 million (Pearson 1982).  An
example of the types of work which  were considered in the  assessment          •
of crop loss is shown for one of the most  sensitive  species, white           |
bean.

In 1961, bronzing and rusting of white  bean foliage  was reported             •
(Clark and Wensley 1961) throughout southwestern  Ontario and the
resultant defoliation and pod abortion  was estimated to have resulted
in a loss of approximately 600 pounds of beans per acre (45% yield           •
loss) in severely affected fields.  Following extensive field work in        •
1965 and 1967 the disorder was found to be associated with the
                                                                              I

                                                                              I

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                                                                  4-33
TABLE 4-5.  THE NUMBER OF TIMES IN  1980 and  1981 THAT OZONE
            CONCENTRATIONS EXCEEDED THE USEPA  STANDARD  OF  0.12  ppm
            ALONG THE U.S./CANADA BORDER3
Station
Allen Park
Detroit
Detroit
Essexville
Livonia
Macomb Co .
Marquette Co.
Port Huron
Port Huron
Southfield
Warren
Lake Co .
St. Louis Co.
Berlin
Amherst
Erie Co.
Essex Co.
Monroe Co.
Niagara Co.
Niagara Falls
Rochester
Wayne Co .
Berea
Cleveland
Conneaut
Elyria
Elyria
Painesville
Toledo
Toledo
Westlake
Burlington
Burlington
State
MI
MI
MI
MI
MI
MI
MI
MI
MI
MI
MI
MI
MI
NH
NY
NY
NY
NY
NY
NY
NY
NY
OH
OH
OH
OH
OH
OH
OH
OH
OH
VT
VT
1980
1
2
6
1
1
6
0
5
-
0
0
0
-
-
0
-
5
1
5
2
1
2
0
0
1
0
2
1
0
3
0
0
0
1981
1
0
4
-
1
6
0
7
7
0
0
0
0
0
0
1
7
0
1
0
1
1
1
0
2
-
1
-
5
2
0
0
0
   Only data from the U.S. counties  touching  the  international
   boundary were used.  Data were  compiled  by Rambo  and Patent
   (pers. comm.).  SAROAD data base  covers  all  of calendar  year 1980,
   but only includes January to  September of  1981.

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4-34



















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                                                                  4-38
4.2.2.2  03 Effects to Forest Vegetation
I
I
occurrence of elevated levels of atmospheric ozone pollution  (Weaver
and Jackson 1968).  The symptoms first appear sometime between               «
flowering and normal senescence, a critical period in the development        •
of yield potential.  They appear as a bronze-coloured necrotic
stipple which, as it becomes more severe, results in premature  leaf
drop and reduced seed set.                                                   •

In an effort to assess and compare the annual severity of ozone
injury on sensitive white beans, Ontario government personnel have           •
conducted visual assessment surveys throughout  the major production          •
areas in southern and southwestern Ontario since  1971.  These studies
ruled out any varietal resistance and confirmed that the bronzing            _
disorder was widespread throughout all the bean production areas             •
(Pearson 1980).                                                              •

Studies utilizing chemical protectants against  ozone injury have             fl
helped to provide information on the economic relevance of the               ||
bronzing disorder in Ontario.   In one case a 13% yield increase was
associated with the reduction in bronzing severity (Curtis et al.            M
1975), while in another study,  yield increases  of up to 36% (27%             •
yield reduction) were realized  (Hofstra et al.  1978).

In 1977 and 1978 yield increases with antioxidant protection  were not        •
as high (Toivonen et al. 1980)  due to climatic  problems.  The overall        •
response in these years was 16% and 4% increase in yield respectively
due to antioxidant protection.  On the basis of these values  and
considering the uniformity of cultivar sensitivity, the average
annual loss for this crop was estimated at 12%  (Pearson 1982).
I

I
As in the case of agricultural crops, economic  evaluation  of  the            I
effect of pollutants on forest productivity  is  ultimately  contingent        •
upon the establishment of dose-response  relationships.   Consideration
must be given to pollutant loadings  and  then quantitative  measure of        •
growth-suppression or yield-depression.                                      •

There are different considerations in evaluating  the effects  of  03          _
and acidic deposition on forest  trees than for  agricultural crops.          •
Most forest tree species are  long-lived,  perennial  plants  that are          ™
not subjected to fertilization,  soil amendments,  cultivation,
extensive pest control or other  cultural  practices  that  agricultural        •
crops receive.  Their size also  precludes pollutant  exclusion               |
(chambers) studies or protective sprays  limiting  the assessment  of
growth or productivity losses to visual  observations of  growth              «
characteristics.  This must then be  related  to  ozone dose  information       •
(i.e., pollution gradients) where available.

In general, many tree species indigenous  to  North America  are               •
classified as susceptible to  03  damage    (Davis and Wilhour  1976;           '
Skelly 1980).  Direct injury  to  tree foliage by 03  has  been
                                                                             I

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                                                                  4-39
demonstrated repeatedly  in  experiment  situations  (Table 4-4),  and in
nature as well.  Concentrations  of  03,  at  least  in some forested
areas, are sufficient  to  cause injury  (Miller  and McBride 1975;
Skelly 1980).  These effects  of  03   can alter  the productivity,
successional patterns, and  species  composition of forests (Smith
1980) and enhance activity  of insect pests and some diseases
(Woodwell 1970).


The current status concerning 03~induced effects  on Temperate  and
Mediterranean forest tree species,  communities and ecosystems  has
been summarized  (Skelly  1980).   It  is  possible that primary
productivity, energy resource flow  patterns, biogeochemical patterns
and species successional  patterns may  all  be challenged by oxidant
air pollution.
4.2.3   Acidic Deposition


Various types of injury listed below may  result  from direct  exposure
of plants to acidic deposition (Cowling  1979;  Cowling and Dochinger
1980; Tamm and Cowling 1977):


            1) Damage to protective surface  structure such as
               cuticle;


            2) Interference with normal functions  of guard cells;


            3) Poisoning of plant cells,  after diffusion  of  acidic
               substances through stomata or cuticle;


            4) Disturbance of normal metabolism  or  growth processes,
               without necrosis of plant  cells;


            5) Alteration of leaf- and root-exudation processes;


            6) Interference with reproductive  processes;


            7) Synergistic interaction with  other  environmental
               stress factors;


            8) Accelerated leaching of substances  from foliar
               organs;


            9) Increased susceptibility to drought  and other
               environmental stress factors;


           10) Alteration of symbiotic associations;  and


           11) Alteration of host-parasite interactions.


In contrast to results with 63, experimental studies  with simulated
acidic deposition have produced both positive and negative results

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                                                                  4-40
4.2.3.1  Acidic Deposition Effects  to  Agricultural  Crops
I
I
(Jacobson 1980; Shriner  1978).   Increases and  decreases  in  yield,  as
well as no significant effects,  have  been found.   These  results
depend upon concentrations of acids,  plant  species  and cultivars,             I
pattern and timing of rain applications, and soil,  environmental,  and        I
cultural conditions (Irving and  Miller  1980; Lee  et al.  1980).   Each
species may thus have unique patterns of physiological and  genetic           •
responses to the potentially beneficial and detrimental  components of        I
acidic deposition.
                                                                              I
Experimental studies with plants  grown  under  controlled  (or                  I
semicontrolled) conditions have demonstrated  that  visible  foliar             •
symptoms can be produced on certain  crops,  when  pH of  applied
simulated rain is 3.5 or less  (Table 4-8).  Field-grown  plants may be        •
less susceptible to the development  of  foliar symptoms than plants           I
grown under controlled or semicontrolled  conditions (Jacobson 1980;
Shriner  1978).  Further, as with  03  and SC>2,  foliar symptoms may             _
not correlate closely with yield  reductions (Lee et al.  1980).               •
However, recent evidence suggests that  generalizations concerning            •
effects  on crops from experiments with  03 alone  or with  acidic
deposition alone, may underestimate  the interactive effects of               •
sequential exposures to these  two pollutants  (Jacobson et  al. 1980).          |
Further  research is needed to  determine if  acidic  deposition enhances
the likelihood of actual yield reductions in  areas also  experiencing          H
repeated exposures to elevated concentrations of 03.                          I

In studies with soils and in studies on aquatic  systems  focus has
often been on relationships with  mean annual  deposition  rates.               •
Characteristics of individual  rain events may have greater                   •
significance in producing direct  effects  on agricultural crops than
average  annual rates.  Although annual  pH values of rain are as low          •
as 4.0 in eastern North America,  concentrations  of H+  ions (and              |
30^2- an(j N03~ ions) may be ten times greater than average
during individual events.  The one (or  several)  most acidic event(s)          •
of a growing season may have greater significance  for  production of          •
direct effects on annual crops than  average deposition rates.

The potential for crop damage  in  the field from  acidic deposition is          I
further  amplified substantially by agricultural  practices.  Economic          •
constraints in any given area  and year  tend to result  in the exposure
of extensive areas of a given  crop in a relatively uniform state of          •
plant development.  The onset  of  the cycle of flowering  physiology,          •
pollen dispersal and fertilization,  and photosynthetic partitioning,
could all be potentially susceptible to extensive  damage over vast
areas.                                                                        •

To evaluate the economic cost  of  acidic deposition on  agricultural
crops, answers to several questions  are needed.  Which crops are             •
actually benefited by components  of  acidic deposition?  Which crops          |
are most susceptible to reductions in yield by exposure  to acidic
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TABLE 4-8.  REPRESENTATIVE TOLERANCE LIMITS OF SELECTED PLANTS TO SIMULATED ACID
            PRECIPITATION3
Plant Species
Birch
Wi 1 low herb
Scots pine
Mosses
Lichens
Sunflower, bean
Hardwoods
Rad i sh
Beet
Carrot
Mustard greens
Sp i nach
Swiss chard
Tobacco
Lettuce
Cau 1 i f 1 ower
Brocco 1 i
Cabbage
Brocco 1 i
Potatoes
Potatoes
Alfalfa
Kidney beans
Oak
Conifer seed 1 ings
Mosses
Chrysanthemums
Juniper
Yel low birch
Pol lutant
Concentration
pH 2.0 - 2.5
pH 3.0
pH 4.0
pH 2.7
pH 2.5
pH 3.5
pH 4.0
pH 4.0
pH 3.5
pH 3.5


pH 3.0
pH 3.0
pH 3.0
pH 3.5
pH 3.5
pH 3.2
pH 2.0
pH 2.0 - 3.0
pH 3.0
pH 4.0+
pH 2.3 - 3.0
Species
Effect
Foliar lesions

Reduced N
fixation rate
Fol iar damage
Fol iar damage
Fol iar damage
Fo 1 iar damage
Reduced yield
Foliar damage
and reduced
marketabi 1 ity
Fol iar damage



Reduced yield
Fol iar damage
reduced yield
Increased yield
Fol iar damage
Increased yield
Inhibition of
parasitic organisms
Fol iar damage
Desiccation, death
Fo 1 i ar damage
and increased
phosphate uptake
Growth decreased
Fo 1 i ar damage
Reference
Abrahamsen et al . 1976

Denni son et al . 1976
Evans et al . 1977
Haines and Waide 1980
Lee et al . 1980











Shriner 1976
Strifler and Kuehn 1976
Teigen et al . 1976
Tukey 1980
Wood and Bormann 1976
  The average precipitation pH in eastern North America is currently greater than
  or equal  to pH 4.0.   Individual  storm events may have episodes where the pH drops
  into the range of pH 3.0 to 4.0.

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                                                                  4-42
4.2.3.2  Acidic Deposition Effects  to  Forest  Vegetation
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deposition?  Unfortunately, only preliminary indications are  avail-
able in response to these questions  (Lee et al.  1980).  Accordingly,
the dose-response function needs to  be provided  with many more                 I
quantitative dose descriptions that  relate to yield effects under             B
actual growing conditions.  Information on the influence of other
parameters on these dose-response functions also needs  to be                   •
provided.  These factors include patterns of rainfall occurring  as             |
they interact with stage of crop development, soil nutrient and  water
supplies, and deposition of particulate matter from the atmosphere.            _
Further clarification also is needed of the possible modifying                 •
influence of NC>3~ and S0^~ as nutrients in leaf tissue in response            ™
to acidic rainfall events.  Finally, the critical factors determining
plant susceptibility, expressed as yield reductions, need further             I
definition to enhance extrapolation  from a few of the most economi-            |
cally important crop species and cultivars to describe  the response
of the entire ecosystem.                                                       •

When this information is provided, it may then be possible to make
reasonable and reliable estimates of the economic impact of acidic
deposition on agricultural productivity.                                       I
I
Effects of acidic deposition on  forest  trees  involves  several
considerations differing  from  those  relating  to  agricultural  crops.            K
Trees are perennial plants with  long lifetimes.   Thus,  there  is               •
greater concern with  the  cumulative  impact  or repeated  exposures to
acidic deposition.  Furthermore,  forests  are  usually in areas where
soil nutrient supplies are limited,  and are generally  not  supplied            I
with fertilizers or lime.  Forests present  large surface areas for            I
interception of gaseous and particulate pollutants  from the atmos-
phere, and these substances eventually  move to the  soil.  Finally,            •
the composition of precipitation as  it  passes through  the  forest              f
system, the properties of soil,  and  characteristics of  streams and
lakes in watersheds are partially affected  by the nature,  age, and            •
condition of forests.  Consequently, the  effect  of  acidic  deposition          •
on forests could also have important secondary impacts  which  are              ™
initiated by direct effects on trees.

The historic pattern  of forest growth as  revealed in the growth               •
rings may show "direct" evidence of  the effects  of  acidic  deposition.
Based on substantial  analysis  of growth rings of Scots  pine and               •
Norway spruce trees that  grow  in spatially-intermixed  "more                   I
susceptible" and "less susceptible"  regions in south Sweden,  Jonsson
and Sundberg (1972) concluded  that "acidification cannot be excluded
as a possible cause of the poorer growth  development,  and  may be              •
expected to have had  an unfavourable effect on growth  within  the more         •
susceptible regions."  This is a controversial study because  other
Scandinavian researchers  have  not been  able to uncover  similar                •
trends.  For example, in  a large study  in Norway, Strand (1980) was            |
unable to "find definite  evidence that  acidic deposition has  had an
                                                                               I

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                                                                  4-43
effect on  the growth of  the  trees".   Studies of a similar type in
North America have  been  limited in scope.   Cogbill (1976), having
examined historic patterns of  growth rings in two forest stands (one
a beech-birch-maple woods  in New Hampshire and the other a spruce
woods in Tennessee) observed that "no regional, synchronized decrease
in radial  increment was  evident in the two mature stands studied."
However, Johnson et al.  (1981)  noted both  an abnormal decrease in
growth of  pitch pine on  the  New Jersey pine barrens, and a strong
statistical  relationship between stream pH (an index of precipitation
pH) and growth.  The relationship of these findings to other possible
incitants  (i.e., disease,  insects,  ozone)  should be more fully
explored.

Experimental evidence from studies  of the  action of simulated acidic
deposition on tree  parts does  indicate that under regimes of high
acid dosing, direct damage (i.e., foliar lesions) can be produced
(Table 4-8).

A potential  impact  of acidic deposition may occur indirectly through
the soil and may become  involved in  the complex natural circulation
of elements  upon which forest  vegetation depends, (i.e., the nutrient
or biogeochemical cycle).  Rodin and Bazilevich (1967) describe this
cycle of elements as "the  uptake of  elements from the soil and the
atmosphere by living organisms,  biosynthesis involving the formation
of new complex compounds,  and  the return of elements to the soil and
atmosphere with the annual return of part  of the organic matter or
with the death of the organisms."  Interrelationships in the cycle
are such that a change in  one  part  of the  system, if not counter-
acted, could ultimately  produce changes throughout.

Generally, forests  are relegated to  soils  which are of low fertility
or, for some other  reason, unsuited  for agricultural use.  In
contrast to  agricultural practice,  amendments (i.e., fertilizers or
lime) are  rarely used in forestry practice.

Deficiencies of nitrogen (N) are common in forests of the temperate
and boreal regions.   Appreciable responses to N-fertilizer have been
reported frequently,  particularly for conifers on upland sites in
both the acidic deposition zone of  eastern Canada (Foster and
Morrison 1981), and in Scandinavia  (Malm and Holler 1975; Moller
1972) .  In a small  number  of fertilizer field trials carried out with
conifers in  Canadian forests,  phosphorus (P), potassium (K), calcium
(Ca) or magnesium (Mg) fertilizers  did appear to elicit responses,
though only when demand  for  N  was first met (Foster and Morrison
1981; Morrison et al.  1977a,b).

Growth of  red pine  and other conifers has  been shown to be limited by
K and Mg deficiency in restricted areas of New York State (Heiberg
and White  1951; Leaf 1968, 1970;  Stone 1953), and Quebec (Gagnon
1965; Lafond 1958;  Swan  1962).

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                                                                  4-44
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The generally-held association of  base-rich  with more fertile soils
and base-poor with less  fertile  soils  (well-demonstrated in agricul-
tural situations) has been investigated  with forest  species and soils          •
in only a limited number of  instances.   Pawluk and Arneman (1961)              I
associated better growth of  jack pine  on sites in Minnesota and
Wisconsin with several soil  factors  which could be considered acidic
deposition sensitive, including  cation exchange capacity (CEC),                I
exchangeable K and percent base  saturation.   Also, in northern                 B
Ontario Chrosciewicz  (1963)  associated better growth of  jack pine
with soils rich in basic minerals  (and presumably richer in
exchangeable bases).  Hoyle  and Mader  (1964) noted a high degree of
correlation between Ca content in  foliage and height growth of red
pine in western Massachusetts.   Lowry  (1972) across  a wide range of            mm
sites in eastern Canada  noted with black spruce relationships between          H
site index and foliage content (including N, P, Ca,  and  to a lesser
extent Mg concentrations).

Studies of forest soils  (Lea et  al.  1979) indicate that  Ca and Mg              •
levels can be leached following  applications of acidic deposition
simulants.  Leaching  of  these elements from  forest soils, as a result
of high S04   mobility (Mellitor and Raynal  1981), may lead to
a chronic decrease in nutrient status  of certain soils.

Since nutrient availability  is a significant growth-limiting factor            •
for many forest ecosystems,  the  concern  is that acidic deposition              *
will interfere with uptake and cycling of various elements.  First,
acidic deposition may promote increased  leaching of  essential foliar           I
constituents (e.g., K, Ca and Mg)  as a function of both acid-                  •
related surface disintegration and mass  exchange by HT1" ions.

Both wet and dry deposition  undergo  chemical alteration directly on            •
the surface of the leaves and  indirectly within the cellular tissue.
The nature of the leachate or throughfall depends upon plant                   _
characteristics such  as  tree species,  leaf morphology, stand                   I
characteristics (e.g., age and stocking), and site conditions                  •
(e.g., precipitation  rate, distribution  and  chemical composition).
Input/output analyses and element  budgets with particular reference            H
to acidic deposition, have been  described by various authors (Lakhani          |
and Miller 1980; Mayer and Ulrich  1980;  Tukey 1980).  Generalizations
are difficult, because of the wide range of  environmental (i.e.,               •
soil, water, and climate) conditions.                                           I

Not all elements are  leached equally and although all plant parts can
be leached, young leaves are less  suceptible to leaching than mature           •
foliage (Tukey 1980).  Some  elements (e.g.,  K) leach readily from              •
both living and dead  parts,  while  others (e.g., Ca) leach more
slowly.                                                                         •

Some researchers have found  that throughfall from deciduous forests
exhibit increased pH  and higher  Ca and Mg concentrations when                  •
compared  to the incident precipitation.   In other instances the                I
opposite has been found. In studies of  two  hardwood species (i.e. ,
                                                                                 I

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                                                                  4-45
sugar maple and red alder),  little  difference  in throughfall
chemistry was  reported  (Lee  and Weber  1980).   Stemflow from birch
species shows  increased acidity,  relative  to  the incident  precipita-
tion (Abrahamsen et al. 1977).  Beneath  coniferous canopies, through-
fall pH generally decreases  relative to  precipitation in open areas
even though concentrations of  Ca  and Mg  as  well  as many other
dissolved ions may increase  (Horntvedt and  Joranger 1976).   This ion
enrichment is  due to  both washout of dry deposits and canopy
leaching.  It  has been  reported that 90% and  70% of the H+ in
precipitation  was retained in  the forest canopy  in New Hampshire
northern hardwood (Hornbeck  et al.  1977) and  Washington Douglas-fir
(Cole and Johnson 1977) forests,  respectively.   Leaching of low
molecular weight organic acids from the  canopy may decrease the pH of
throughfall (Hoffman  et al.  1980).

Spruce canopies may filter dry pollutants  from the atmosphere better
than deciduous canopies.  This cleansing action  is partially
attributed to  the presence of  spruce needles  throughout the winter,
during which S02 is dissolved  in  water films  adhering to their
surfaces.  Subsequent removal  of  these deposits  accounts for part of
the difference in chemical composition of  the  throughfall.

In summary, several processes  may be affected  when rainfall passes
through a forest canopy.  Substances residing  on and in foliage are
removed.  These processes occur with both  acidic and nonacidic
deposition.  Certain  elements  are leached more rapidly than others,
especially when rainfall is  acidic.  There  are also differences
between species and stages of  leaf  development in rates of  leaching.
Leaching results in a marked change in the  chemistry of precipitation
before it reaches the soil.  Dry  deposits  removed from leaf surfaces
and substances lost from foliar tissues  may neutralize or  enhance
acidity and the concentration  of  inorganic  substances may  increase
considerably.  More rapid transfer  of elements to the soil  provides
opportunities  for enhanced uptake and recycling  by trees.   Moreover,
soil processes may also be affected by these  deposits.  Several
pathways exist by which changes to  precipitation occurring  in the
forest canopy  can affect the chemistry of water  transported through
the terrestrial ecosystem and  into  streams  and lakes.  These are
discussed further in  other sections of this report.

Acidic deposition may affect health and/or  productivity of  forest or
other vegetation through indirect channels, or through effects on
nutrition.  Research  efforts are just beginning  to evaluate the
possible role  of acidic deposition  in the predisposition of trees to
disease infection and insect attacks.  Further,  the behaviour of
plant litter and soil-occurring facultative saprobes,  which may
exhibit plant  pathogenic tendencies under acidification, requires
evaluation.

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                                                                  4-46
4.2.4   Pollutant Combinations
I
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For much of the northeast and midwest  sections  of  the United States             •
where acidic rainfall events and  low dose  SC>2 trends have been                  |
recorded, ozone air pollution also  occurs  on a  concomitant basis.

Sulphur dioxide, NOX, and particulate  emissions may be of "local"               •
importance to vegetation, but mesoscale  background concentrations of
these pollutants are well below known  thresholds for inducement of
direct vegetation effects.  From  these background  concentrations,               •
long-term accumulation by plants  of sulphates and  nitrates and the              •
related potentially beneficial or detrimental effects are poorly
defined.                                                                         •

Extrapolation from results of single pollutant  effects on vegetation
under ambient field conditions must be approached  with caution.                 ^
Reactions in pollutant combinations may  be additive (sum of effects),           I
less than additive (antagonistic),  or  more than additive                        ™
(synergistic).  In addition to pollutant combinations under
controlled conditions, the interaction of  constantly changing                   •
environmental factors and fluctuating  pollutant doses must be further           •
evaluated before a conclusive statement  of the  importance of such
interactions can be made.  Reinert  (1975)  and Reinert et al. (1975)
have prepared the most recent reviews  of this area of investigation.
I
4.2.4.1  S02 - 03 Effects                                                       I

The most frequently  occurring  pollutant  combination of significance
to plant life must be  considered  as  03 and S02•   However, few                  I
studies have utilized  doses  which would  be considered as even close            |
to ambient except as they  pertain to areas affected by point sources
of emission of S02-  Studies using combinations  of 03 and S(>2                  •
are presented in Table 4-9.  As indicated, only  the study of Houston           •
(1974) used doses of SC>2 approaching regional expected averages.
He used mixtures of  S02 and  03 in doses  to simulate actual field
conditions and reported that even the lowest concentrations of 03              fl
(0.05 ppm) and S02 (0.05 ppm)  for 6  hr in mixture caused more                  H
serious damage than  that resulting from  either pollutant alone at
similar concentrations.  Studies  by Tingey et al. (1971a,b, 1973),             •
Tingey and Reinert (1975), and Neely et  al. (1977) used doses                  |
reasonably expected  in smaller areas such as the Ohio Valley (Mueller
et al. 1980).  Doses used  in other studies used  less realistic doses           _
for either S02 or 03 and the results are of little value in                    •
estimating field effects on  a  regional basis.                                  —

A recent study by Reich et al. (1982) utilized a linear gradient               •
field exposure system  of S02 and  63 over soybeans exposed during               •
pod fill.  Low dose  exposure combinations averaged S02 at 0.040 ppm
and 03 at 0.034 ppm  for 5.5  hr per day for 12 days.  Yield                     •
                                                                                I

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4-47








































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                                                                  4-50
4.2.4.3  S02 - 03 - Acidic Deposition Effects
I
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expressed as dry mass/seed was 9% less than that  of  plants  exposed  to
ambient air; higher doses reduced yield by 10% and  15%.                       _


4.2.4.2  S02 - N02 Effects

The possibility of adverse effects occurring on plant  life  due  to  the         |
interaction between atmospheric  S02 and N02 needs consideration.
Tingey et al. (1971a) demonstrated experimentally that a  gaseous              m
mixture of 0.10 ppm S02 and 0.10 ppm N02 caused synergistic                  •
effects with more than 5% leaf injury being induced  on 5  of 6 plant
species treated in 4-hr exposure periods.  The symptoms of  injury
produced by a mixture of S02 and N02 can resemble those caused  by             •
ozone which may make diagnoses in the field difficult.                        *
I
The currently available literature  concerning  the  interactive  effects         _
of acidic deposition and gaseous  air  pollutants  on terrestrial               •
vegetation is extremely limited,  consisting  of only three  separate           ™
studies.  Shriner  (1978) examined the interaction  of acidic
deposition and S02 or 03 on  red kidney bean  (Phaseolus  vulgaris)              M
under greenhouse conditions.  Treatments with  simulated rain at pH           •
4.0 and multiple 63 exposures resulted in  a  significant reduction
in foliage dry weight.  Simulated precipitation  and sulphur  dioxide          m
in combination did not affect either  photosynthesis or  biomass               •
production.  Troiano et al.  (1981)  exposed two cultivars of  soybean
to ambient photochemical oxidant  and  simulated rain at  pH 4.0, 3.4,          _
and 2.8 in a field chamber system.  The interactive effects  of               •
oxidant and acidic deposition were  inconclusive  with seed  germination         ™
being greater in plants grown in  the  absence of  oxidant at each
acidity level.  Irving and Miller (1980) also  examined  the response          4
of field-grown soybeans to simulated  acidic  deposition  at  pH 5.3  and         P
3.1 in combination with sulphur dioxide and  ambient ozone  concentra-
tions.  No interactive effects of acid treatments  with  S02 on                 m
soybean yield occurred.  However, sulphur  dioxide  alone resulted  in a         •
substantial yield  reduction.

Changes in such things as soil chemical properties nutrient                   •
recycling resulting from acidic deposition do  not  occur rapidly.              •
After more than a  decade of  research  in Scandinavia, the observed
changes in chemical properties of forest soils that can be attributed         M
to acidic deposition still remain undetermined  (Overrein et  al.               |
1980).  It is therefore unlikely  that interactive  effects  of acidic
deposition and gaseous pollutants on  plants  involving changes  in  soil         ^
properties will become evident within a single growing  season.               I

A physical and chemical potential exists for interaction of  various
forms of wet fall  and dry fall (including  gases  and trace  metals) at,         •
on, or within leaf surfaces.  However, very  few  studies have                 •
addressed these interactions and  the  significance  of the observed
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phenomena remain inconclusive  (Fuzzi  1978;  Gravenhorst et al.  1978;
Penkett et al. 1979).
4.3   EFFECTS OF ACIDIC DEPOSITION  ON TERRESTRIAL WILDLIFE

Although direct effects of  acidic deposition are not likely,
terrestrial wildlife may be  indirectly affected  in three ways:
(1) contamination by heavy  metals mobilized under acidic conditions;
(2) loss of essential nutritional components from food;  and (3)
reduction in food resources.

While the sensitivity of organisms  such as  plankton and  fish to
metals released in  acid waters  has  been established (Baker and
Schofield 1980; Marshall et  al.  1981;  Muniz and  Leivestad 1980),
the potential for accumulation  and  subsequent effects on terrestrial
animals is less well understood.  Metal contamination and reduced
size of roe deer (Capreolus  capreolus) antlers from an industrialized
area of Poland has  been reported recently (Jop 1979; Sawicka-Kapusta
1978).  Acidification and sulphurization of roe  deer browse
(Sawicka-Kapusta 1978) was  suggested  as the cause of the high metal
levels (Jop 1979).  Such a  means of contamination has been
demonstrated in southeastern Denmark  where  cadmium and copper in
epiphytic lichens and mosses were compared  with  those from
northwestern Denmark (Gydesen et al.  1981).  Epiphytes from the
southeastern areas  of Denmark which received elevated metal
deposition in bulk  precipitation showed metal levels 1.5 times
higher on average.  The same trend  was found in  the kidneys of  cattle
feeding in these areas.  While  direct deposition to plant surfaces
may be partially responsible, plant uptake  of some metals such  as
cadmium increases as soil pH decreases (Andersson and Nilsson 1974),
and high plant metal content is  another route of contamination.  In
Sweden, moose (Alces alces)  closer  to sources of anthropogenic
sulphur supported higher tissue  levels of cadmium and the body  burden
increased with age  (Frank et al. 1981; Mattson et al.  1981).  The
mechanism of contamination  was  not  explored and  could be via
terrestrial or aquatic vegetation.

The availability of essential elements in wildlife nutrition may be
affected by sulphur deposition  and  soil pH.  Selenium, for example,
is an essential element for  vertebrates (Stadtman 1977).  Selenium
deficient conditions lead to degeneration of major body organs  such
as the liver, kidney and heart  (Harr  1978;  Schwarz and Foltz 1957).
Most importantly from the viewpoint of ranchers, muscular dystrophy
(known as white muscle disease)  has been caused  by selenium
deficiency and reported in  sheep, cattle,  swine  and horses (Harr
1978; Hidiroglou et al. 1965; Muth  et al.  1958).  The occurrence of
white muscle disease in North American livestock is correlated  to the
concentration of selenium in forage (Allaway and Hodgson 1964).
Lameness and poor growth and reproduction in domestic animals have
resulted from selenium-deficient diets (Harr 1978).  In poultry,
edema (abnormal excess accumulation of fluid in  connective tissue or

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4-52
                                                                               I
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body cavities) has been  related  to  selenium deficiency (Harr 1978;
Patterson et al. 1957).

Many of the soils in the temperate  region  of  eastern North America              •
are low in selenium and  hence  produce  forages which contain low
selenium concentrations, frequently less  than the 0.1 ppm minimum              •
level for animal health  (Kubota  et  al.  1967;  Levesque 1974; Winter              •
and Gupta 1979).  Although  selenium deficiencies  in livestock have
been associated with forages grown  on  soils naturally low in                   _
selenium, many incidences of deficiency have  been attributed to the            V
high agricultural use  of sulphate  fertilizers (Allaway 1970; Davies            9
and Watkinson 1966).   Calves reared on  hay grown  in Kapuskasing,
Ontario, developed muscular dystrophy  due  to  selenium deficient                I
conditions in the soil there (Lessard  et  al.  1968).                            flj

Due to the correlation between soil selenium levels and concentra-              M
tions in plants grown  on these soils (Muth and Allaway 1963), there            w
is evidence that wildlife forage plants are similarly selenium
deficient.  This was the finding in a  study of moose browse plants  in
Alaska (Kubota et al.  1970).   Moreover, selenium  deficiency symptoms           M
have been reported for several wildlife species,  (e.g., the prong-              IP
horn; Antelocapra americana) (Stoszek  et  al.  1978).  Mountain goats
(Oreamnos americanus)  from  an  area  where  selenium levels in forage
are low and where white  muscle disease  occurs in  livestock, revealed
symptoms of white muscle disease upon  being stressed by handling
(Herbert and Cowan 1971).   It  is suggested that the symptoms in wild           —
populations may well be  masked by predation (Herbert and Cowan 1971).          •
The net effect of selenium  deficiency  diseases in wildlife would be            ™
an increased susceptibility to predation  as well  as reduced
productivity and survival of young.                                            •

Recent increases in anthropogenic  sulphur  emissions have caused
concern regarding the  influence  on selenium availability in                    •
vegetation.  Selenium  concentrations in plants in heavily industrial-          •
ized Denmark have decreased over the past  decades (Gissel-Nielsen
1975). Experimental applications of S02 and SO/   to plants                    ,—
and soils have demonstrated that selenium levels  are depressed by              •
both the presence of sulphur and reduced  soil pH  (Shaw 1981a,b).               ™
Because excessive sulphur and  sulphate cause uptake of selenium to be
reduced in plants (Davies and  Watkinson 1966; Gissel-Nielsen 1973;              fi
Shaw 1981a), the impact  in  areas of low selenium soils could be                |
substantial.  Furthermore,  the solubility of selenium declines with
pH, rendering selenium less available  to  be taken up by plants in              M
acid soils (Geering et al.  1968; Johnson 1975).                                |

Sulphur and its  compounds have a further depressing effect upon
selenium in the  animal itself.  Excessive sulphur in the diet can              •
lead to increased elimination  of selenium from the body (Harr 1978),           •
compounding deficiency conditions.
              9
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Other essential elements in animal nutrition  such  as  calcium,
magnesium and sodium are similarly released from soils  upon acidifi-
cation (Abrahamsen  1980; Rorison  1980;  Stuanes  1980).   Accordingly,
such elements will  be less available  for  uptake by plants,  resulting
in lowered concentrations in plant tissues (Beeson 1941).   Soil
acidification similarly causes  leaching of phosphorous  which,  if
reflected in the vegetation (Rorison  1980), could  have  significant
effects on wildlife nutrition.  Lucas and Davis (1961)  summarize  the
influence of pH on  the availability of  12 plant nutrients.

Aside from nutrient content, the  availability of food resources may
decline due to acidic deposition  affecting the entire food  web
including wildlife.  For example, caribou (Rangifer sp.) may be
affected due to the sensitivity of lichens to sulphur and acid
compounds (Lechowicz 1981; Puckett 1980;  Sundstrom and  Hallgren
1973).  The importance of lichens in  the  winter diet  of Canadian
caribou herds is well documented  (Kelsall 1960, 1968; Thompson and
McCourt 1981).  Thompson and McCourt  (1981) reported  that 67% of  the
diet of the Porcupine Caribou Herd of the Yukon consists of lichens.
The George River caribou herd of  Nouveau  Quebec and Labrador is the
largest in North America (Juniper 1979; Juniper and Mercer  1979;
Mallory 1980) and may rely heavily on the carrying capacity of their
winter range.  Much of this area  lies in  the  zone  of  acidic
deposition (Figure  8-lb).  Exposure of  the primary caribou  lichen
(Cladina stellaris) to simulated  acidic deposition with pH  4.0,
reduced maximum photosynthesis  by 27% and slowed recovery from
dormancy after wetting by 14% (Lechowicz  1981).  These  results
suggest that acidic deposition  reduces  the growth  and productivity of
this lichen (Lechowicz 1981).   The significance of reduced  lichen
productivity to the population  dynamics of these caribou herds is
uncertain, because  the degree to  which  they are food-limited is
unknown.

Another example of  potential food loss  involves herbaceous  ground
cover.  Trees have  tap roots in deep  soil layers that are less
susceptible to acidification, while plants draw their moisture and
nutrients from the upper layers of soil making them more exposed  to
the effects of acidic deposition  (Clark and Fischer 1981).
Application of sulphuric acid in  quantities corresponding to
100 kg/ha.yr killed much of the ground  vegetation  consisting mainly
of mosses, lichens, and a species of  dwarf shrub (Tamm  et al.  1977).
Therefore animals which feed on such  vegetation may be  affected by
food loss.
4.4   EFFECTS ON SOIL

Soils vary widely with respect  to  their  properties  (i.e.,  physical,
biological, chemical and mineralogical),  support  different
vegetation communities, are subjected  to  different  cultural
practices, are situated in different climatic  zones,  and are  exposed

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                                                                  4-54
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to a broad spectrum of acid loadings making  it  difficult  to
generalize from findings indicated  in  this report.   Further,  there
are various offsetting mechanisms,  influencing  effects  of increased         •
precipitation acidity which vary with  soil properties,  vegetation           •
types, climatic regimes and cultural practices.  Water  moves  through
soils by uniform capillarity and gravitational  processes.  Also,             A
considerable moisture flow may be directed overland  or  may be               <|
channelized in the soil in root channels  reducing  the opportunity for
equilibration.  A high stone content can  concentrate leaching effects       ~
to a smaller soil volume than in nonstony soils.   Thus, theoretical         •
calculations have to take into account  particular  ir± situ character-        ™
istics.

In the discussion which follows, the documented and  hypothesized             9
effects of acidic deposition on soils  are described  under the
following headings:                                                          •

1.  Effects on Soil pH and Acidity.

2.  Impact on Mobile Anion Availability,  Base Leaching, and Cation          V
    Availability.                                                            ™

3.  Influence on Soil Biota and Decomposition/Mineralization                 fl
    Activities.                                                              I

4.  Influence on Phosphorus Availability.                                   <^fl

5.  Effects on Trace Element and Heavy Metal Mobilization and
    Toxicity.                                                                —

                                                                             I
4.4.1  Effects on Soil pH and Acidity


acidifying sulphate fertilizers brings about appreciable  soil
acidification, along with other changes in soil chemical  and                 •
biological properties (Glass et al.  1980).   The more striking of             •
these changes are reductions in exchangeable bases,  increases in
soluble aluminum and manganese levels,  shifts in  optimum conditions         ^
for bacteria and mycorrhizal fungi,  and reductions in soil micro-           •
faunal populations.  Some of these  undesirable  changes  have  also  been       •
shown to occur in the proximity of  strong point emitters  of  sulphur
dioxide (Freedman and Hutchinson 1980;  Nyborg et  al. 1976; Strojan          •
1978), so concern is well-founded that the range  of  soil  changes             |
outlined in Table 4-10 could occur  to  a greater or lesser extent  over
more widespread geographical areas.                                          M
                                                                             I
The process of soil acidification primarily  involves the replacement
of exchangeable basic cations (Ca,  Mg,  K, Na, NH^"1")  by  H+ and,
at lower pH ranges, Al^"*" ions.  The chemistry of  soil acidification         •
is relatively well understood, at least in states  other than  strong         •
                                                                              I

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                                                                  4-55
TABLE 4-10.   ACIDITY RELATED REACTIONS  INFLUENCING AVAILABILITY

              OF SEVERAL ELEMENTS
       Element(s)                      Type of Reaction
            N                 Chiefly biological -
                              biochemical; nitrifying  bacteria
                              decline with declining pH,  thus
                              ammoniacal-N predominates  over
                              nitrate-N;  reduces mineralization.


            P                 Phosphate  fixation reactions.


       K, Ca, Mg              Chiefly mass displacement  of
                              absorbed bases by H  and Al^+ ions.


         Fe, Mn               Chiefly dissolution of hydroxides
                              in acid solution; organic  status,
                              redox important particularly for Fe.


           Al                 pH regulated solubility  of  Al-oxy
                              and hydroxy compounds.

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                                                                  4-56
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acid as described by Jenny (1961), Wiklander  (1973/74,  1975,  1980a),
Bolt and Bruggenwert (1978), Bache (1980), and Nilsson  (1980).   In
the most strongly acid soils, there is evidence  that  aluminum becomes        •
very mobile without there being any associated notable  change in pH         ™
(Cronan and Schofield 1979; Norton et al.  1981;  Ouellet 1981;  Ulrich
et al. 1980).  The common range of pH for  soils  in  humid regions is         fl
about pH 5.0 to 7.0, with the preferred  range for cultivated  soils          ||
being pH 6.0 to 7.0.  Many forested soils, particularly under
coniferous cover, fall within the range  pH 4.5-5.5  in the  mineral           •
horizons, with surface organic layers commonly exhibiting  pHs in the         •
range 3.5 to 4.5.

The numbers of field situations where investigators have been able to        M
compare present with former soil pH values are extremely limited.           9
However, Linzon and Temple (1980) report a lowering of  soil  pH in the
brunizolics, but not podzols, of south-central Ontario  after  18 years        ft
of pollutant deposition.  Ulrich (1980b) and  his colleagues  (Ulrich         \|
et al. 1980) working in the more heavily polluted parts of central
Germany report a long-term fluctuation of  pH  in  the surface  humus           —
under beech and spruce.  The pH values do  not show  a  steady  decline,         Tm
but rather show cyclic variation between 4.2  and 3.8.  This  parallels        ™
deacidification and acidification phases alternating  between  cooler,
moister summers and warmer, drier ones.  From 1969  to 1980 under            M
beech, and from 1973 to 1980 under spruce, there were substantial           •
increases in the amounts of soil aluminum  mobilized.  These  increases
were associated with the continued entrapment and deposition  of acid          •
sulphate pollutant.                                                          •

Various field and laboratory experiments of a simulation nature have          _
also been set up to examine the effects  of acidic deposition  on soil         fl
acidity.  Results indicate that artificial acidic deposition  at pH<4         ™
can lead to measurable decreases in soil pH (Abrahamsen et al.  1976;
Bjor and Teigen 1980; Stuanes 1980).  For  example,  simulated  acidic         4
deposition inputs of pH 4.0 and below to spruce  podzol  soils  in             ^
Norway caused soil acidification of the  0, A, and B horizons
(Abrahamsen et al. 1976).  In some cases,  the soil  pH depression over        
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pH, 4.9), carbonic  acid  contributed  approximately twice as much H"1"
to the soil as did  precipitation.  However,  a drop in pH to 4.0
(about 30 times more  acid  than  normal)  occurs in the most heavily
impacted areas of eastern  North America (Cogbill and Likens 1974) and
results in H+ inputs  far in  excess of  that  produced by carbonic
acid.  In the more  acid  soils having a  pH of less than 5.5 (e.g.,
podzols developed under  coniferous forests), organic acids contribute
significantly to natural soil acidification.  It is not as yet known
what role anthropogenic  acidification  will  have in these ecosystems.
Presumably, extremely acid soils will  experience the least change in
pH, but changes in  the ionic make-up of the  soil colloidal complex
and ionic mobility  may take  place.

Sollins et al. (1980)  proposed  a comprehensive scheme for calculating
H+ ion budgets in forest ecosystems, based  upon measured mass
balances of cations and  anions  within  the nutrient cycles.
Andersson et al. (1980b) used this model to  obtain H+ ion budgets
for forest ecosystems  in Sweden, West  Germany, and Oregon.  In the
heavily impacted Soiling site in West  Germany, their analysis shows
that atmospheric H+ ion  inputs  are small (approximately 10%)
compared to net internal flows.  Ulrich (1980b), using essentially
the same approach,  stressed  input-output balances to assess the
long-term net acidification  of  soils caused  by internal compensations
of H+ production and  consumption and uptake  and mineralization
processes.  He also pointed  out  important spatial considerations
within the soil profile.  For example,  ammonium mineralization that
consumes hydrogen ions might occur in  litter layers while ammonium
that produces hydrogen ions  may occur  in mineral soil layers at the
same time.  Some indication  of  orders  of magnitude of H"1" ion
contribution by softwood versus  hardwood forest and their
relationship to anthropogenic loading,  were  provided (Ulrich 1980b).
Total H+ ion input  was determined as about  ca 0.81 keq/ha, of which
0.79 keq/ha was considered man-made.  A beech canopy generated an
additional ca 0.58  keq/ha  and a spruce  canopy, an additional 2.28
keq/ha.  This evidence suggests  that as mean pH of rainfall declines
below pH 4, its contribution to  the  H+  ion  balance is not
insignificant even  in comparison to  spruce  forest H+ ion
production.  Thus,  the process  of podzolization is hastened.

As noted earlier, the  adverse effect of soil acidification results
chiefly from the influence of changed  pH on  other processes (e.g.,
soil biochemical reactions and  N availability, organic matter
turnover, mobilization of  trace  elements, and transformation of clay
minerals) .
4.4.2   Impact on Mobile Anion Availability  and  Base Leaching

Acidification and soil impoverishment  involves the  displacement of
basic cations (i.e., K, Ca, Mg,  Na)  from  exchange surfaces,  their
replacement by H"1" and Al^+ ions,  and the  establishment  of  new
exchange/solution equilibria  (Wiklander 1973/74).  Under natural

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1
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conditions, two sets of processes  seem  to  be  involved:  (1)  there are
exchange processes whereby H"1" ions  displace base  cations  from the             _
exchange surface, and (2) there are  the processes  whereby the                 •
exchanged ions are transported within the  soil  column under the                ™
influence of mobile anions (Johnson  and Cole  1976, 1977).

                                                                    _
capacity or CEC and the relative degree of saturation of  the CEC with
bases or base saturation).   In humid regions,  the  total permanent and         m
pH dependant CEC of a productive soil under cultivation might range           I
from 15 to 30 meq/100 g.  In the surface horizons  this  might be
higher and in the subsoil it may be  lower.  To  illustrate this,  in
coniferous podzols the CEC of the  humus layer may  be high while                I
beneath it values decrease abruptly  with depth.   It is  presumed  that          Qi
the loss, particularly of those base cations  of nutritive value
(chiefly K, Ca, and Mg), could be  accelerated under acidic
deposition, with attendant adverse  impacts on  forest growth.
I
Various "simulated acidic deposition"  leaching  experiments  are                »
described in the literature  (Abrahamsen  et  al.  1976;  Abrahamsen and           M
Stuanes 1980; Lee and Weber  1980; Morrison  1981;  Overrein 1972;                *
Roberts et al. 1980; Singh et  al . 1980).  In  some controlled
irrigation experiments, Ca and Mg appear  to be  the  most  affected and          •
K the least affected (Abrahamsen  1980; Hovland  et al.  1980;  Ogner             •
and Teigen 1981; Wood and Bormann 1976).  To  some extent,  this may
reflect the relative amounts of  these  cations on  soil  exchange sites,          •
but the rate of increase in  K  depletion  seems to  be consistently              •
below that for Ca or Mg under  acid  irrigation as  well  (Abrahamsen
1980; Ogner and Teigen 1981; Wood and  Bormann 1976).   The relative            ^
lack of response in K may also be due  to  the  greater  plant                     fl
requirements for K, as opposed to Ca or  Mg, and possibly also to              ~
fixation of K in 2:1 clays.
 9
In some cases, the accelerated  cation  leaching  has  led to net
depletion of available cations  in  the  rooting zone.   Significant
reductions of base saturation percentage  were noted  in the 0 and A            •
horizons in Norwegian spruce podzol  soils,  following applications of          •
simulated acidic deposition with a pH  of  3.0 or lower (Abrahamsen
1980).                                                                         ^

Soil acidification and decreases in  base  saturation  do not always             ™
occur concurrently.  Under natural soil acidification by humic acids,
production of humus increases CEC, but does not increase the cation           B
content (Konova 1966).  Soil pH and  base  saturation  will thus                 |
decrease without a corresponding reduction  in exchangeable base
content (Ulrich 1980a).   Similarly,  with  anthropogenic acidification,         •
soil pH and base saturation may decrease, with  no corresponding net           I
nutrient loss.  This occurs if  the soil is  actively  adsorbing both
H+ and SO^-, which would increase CEC over time (Johnson and
Cole  1977).  In addition, decreases  in  base  saturation and pH in              •
soils subjected to  leaching  losses  of base  cations can be offset to           ™
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                                                                  4-59
some extent by  acid-induced  increases in soil weathering (Johnson
1980).

Much of  the potential  impact of atmospheric deposition stems from the
input of  the mobile  S0^~ anion to soils.   Whereas the mobility
of bicarbonate  or  organic anions may be severely limited in many acid
or clay-rich northern  soils, SO^" anions  may be very mobile in
these same soils.  It  has been shown that  atmospheric H2S04
inputs overwhelm natural  leaching processes,  in some New Hampshire
Spodosols, causing perhaps a threefold increase in the natural rate
of cation denudation,  and marked increases in the leaching of soluble
inorganic Al. In New Hampshire subalpine coniferous soils, anthro-
pogenic  504^" anions supplied 76% of the electrical charge
balance  of the  leaching  solution, while A1.3+ and H+ were the
dominant  cations in  solution (Cronan 1980; Cronan et al. 1978; Cronan
and Schofield 1979).  In  contrast, some soils (chiefly those rich in
Fe- and Al-sesquioxides)  exhibit a substantial capacity to adsorb
S0^~, and thus demonstrate  a considerable initial resistance
to base  leaching by  anthropogenic ^864 (Johnson and Cole 1977;
Johnson  and Henderson  1979;  Morrison 1981; Roberts et al. 1980; Singh
et al. 1980).   This  generally implies that the effect of acidic
deposition on soil cation leaching is highly dependent upon the
mobility  of the anion  associated with the  acid, whether it be
864^", N03~, or an organic anion (Cronan 1980; Johnson and
Cole 1980; Seip 1980).  This is due to the requirement for charge
balance  in the  soil  solution, a necessary  condition that precludes
the leaching of cations without associated mobile anions.  Soils low
in free  Fe and Al, or  high in organic matter (the latter appears to
block sulphate  adsorption sites, [Johnson  et  al. 1979, 1980]) are
therefore generally  susceptible to leaching by H2S04 (e.g.,
Cronan et al. 1978).  Where  SO,2- adsorption does occur, (e.g.,
in the highly weathered soils of Tennessee),  S accumulation could
initially be beneficial in three ways:  (1) prevent cation leaching
by H2S04  by immobilization of the 804^" anion; (2) create
new cation exchange  sites; and (3) release OH~ from adsorption
surfaces  (Johnson  et al.  1981).   It follows,  however, that once
804^" exchange  sites become  fully occupied, cation leaching
could commence.  On  Walker Branch Watershed,  48% of total S to input
accumulates in  the soil,  whereas only 13%  accumulates in vegetation
(Johnson  and Henderson 1979;  Shriner and Henderson 1978).  Along the
same lines, one might  expect the N03  in acidic deposition to
contribute to net  cation  leaching only in  those systems where
N03~ is mobile.  Because  of  the N-limited  status of many forests,
most N03  tends to be  assimilated by plants during the growing
season,  thereby not  contributing to cation leaching.

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                                                                  4-60
4.4.3   Influence of Soil Biota and Decomposition/Mineralization
        Activities
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It has been postulated that atmospheric deposition  of  strong  acids
may adversely affect soil biota and decomposition activities  either
directly through soil acidification or indirectly through  trace                 tt
metal mobilization and toxicity.  Laboratory  experiments and                    •
observations on soils in close proximity  to pollutant  sources provide
information on changes which occur in soil biota, as a result of               —
increased acidic deposition.  Observations indicate decreases in                j
total numbers of soil bacteria and actinomycetes, and  some  relative             ™
increase in presence of fungi; although,  under  conditions  of  very
high loading, fungi have been reported less abundant.   Generally,               H
total numbers of enchytraeids have not been affected (except  under             £
extreme conditions), though differential  species responses  have been
reported (Abrahamsen et al. 1976, 1977; Alexander 1980; Baath et al.           *
1980).                                                                         '|

The available evidence on the effect of acidity on  organic  matter
breakdown and soil respiration is not conclusive (Rippon 1980; Tamm            ^B>
et al. 1977).  However, decomposition experiments suggest  that acidic           ™
deposition may retard organic matter decomposition. Studies  (Baath
et al. 1979, 1980; Francis et al. 1980; Lohm  1980;  Tamm et  al. 1976)           ft
have noted decreased decomposition or carbon  mineralization in soils           ||
and litter exposed to artificial acidic deposition  inputs  at  pHs
below 3.5 to 3.0.  Meanwhile, other studies have shown little or no             ^
effect (Abrahamsen 1980; Hovland et al. 1980).  Clearly, the  results           •
are partly dependent on soil type and severity  of the  simulated                 ™
acidic deposition treatment.

In some soils, there are indications that acidic deposition may  alter           •
humic/fulvic acid dynamics.  While moderate acidity may aggregate
humic acid particles, it may lead to dissolution and mobilization  of           •
fulvic acids.  In soils like Podzols, which contain appreciable                 •
quantities of fulvic acid, substantial losses could occur  in  moderate
acidic leaching.

Besides carbon cycling, there is concern  that acidic deposition may             *
have adverse effects on N cycling patterns and  processes.   In this
case, there are actually two potential sides  to the issue:  (1)  the             •
possibility that acidic deposition may decrease N mineralization and           |
availability, and (2) the possibility that atmospheric inputs of
anthropogenic N compounds may provide a fertilizer  effect  by  increas-           M
ing the amount of available nitrogen.  Tamm (1976)  predicted  short-             •
term increases in N availability and tree growth, due  to net  N losses
from ecosystems.  In Germany, Ulrich et al. (1980)  resampled  soils              ^
over a 13-year period and showed significant  accumulations  of N-poor           •
organic matter in the forest floor of a 120-year old beech forest.              w
This was interpreted as a condition which could lead to internal H+
ion production, immobilization of N, and  mobilization  of soluble                •
Al3+.  other studies, by Francis et al. (1980)  and  Alexander                    £
(1980) show ammonification and nitrification  may decrease  markedly  in
                                                                                I

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                                                                  4-61
soils exposed to artificial  rain  at  pHs  approaching 3.0.   However,
several studies have demonstrated  increased N  availability,  at least
during the initial stages of H2S04 input  (Abrahamsen 1980;  Ogner
and Teigen 1981; Roberts et  al.  1980), and  this  has produced minor
growth increases in situations where N is limiting (Abrahamsen 1980;
Tamm and Wiklander 1980; Tveite  and  Abrahamsen 1980).   Whether this
increase in N availability is due  to change in microbial  activity, or
to the acid catalyzed hydrolysis  of  labile  soil  N, is  unknown as yet.
Norwegian studies show  that  both  N availability  and N03~  leaching
were stimulated by H2S04 inputs-.   This strongly  suggests  that
contrary to earlier predictions  (Tamm 1976), nitrification can be
stimulated by acid inputs as well.   This  has definite  negative
long-term implications  for forest  N  and  cation status,  if NC>3~
production exceeds plant uptake,  resulting  in  net ecosystem N and
cation loss.
4.4.4   Influences on Availability  of  Phosphorus

Like N, phosphorus (P)  is  an  essential element  for plant life.  In
soil, P occurs in both  inorganic  and organic  compounds.   It is
utilized from the soil  solution by  plants  chiefly, though not
entirely, as the (inorganic)  orthophosphate anion.  For  perennial
plants, including trees, P is  assimilated  through the intermediary
mechanism of a mycorrhizal  root association (Bowen 1973; Fogel 1980;
Hayman 1980).  The availability of  P to plants  is determined to a
large extent by the ionic  form in which it is present.  In soil
solutions of low pH, available P  is present largely as H2P04";
as pH increases, HP042~ predominates.   In  strongly acid  soils,
H2P04~ ions may react with soluble  Mn, Al  and Fe compounds and
be mostly precipitated  as  the  insoluble and nonavailable metal
hydroxyphosphate (Hsu and  Jackson 1960).   Also,  under conditions of
increasing acidity, H2P04~ tends  to react  with  the insoluble
oxides of Fe, Al and Mn, and  in more weathered  soils it  may become
fixed on silicate clays, through  the process  of  anion exchange.
4.4.5   Effects on Trace Element  and  Heavy Metal Mobilization and
        Toxicity

A further effect of  acidic  deposition or  increased soil acidification
is an increased solubilization  of heavy metals  in the soil system.
This can arise from  the increased solubilization of metals that are
already present in mostly insoluble  or nontoxic forms or it may arise
from metals being deposited along with an acidifying pollutant.
Thus, at low concentrations naturally present Mn and Fe serve as
essential nutrient elements for the  growth of higher plants and
except in alkaline or  calcareous  soils are usually present in
adequate available amounts.  However, at  high  concentrations these
metals and Al can cause nutritional  imbalance and growth impairment.
Different plant species vary in their susceptibility to heavy metals,

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                                                                  4-62
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an example being Al.  Barley,  sugar  beet,  corn and  alfalfa are very
sensitive, whereas ericaceous  shrubs and  conifers  appear much more
tolerant.  Soil characteristics  also affect  tolerance/susceptibility           fl
including soil pH, Ntfy"1" compared  with NC>3~ nutrition,  Al-exclusion             V
processes, Ca and P status, and  organic-Al complexation (Foy et al.
1978).  Striking examples  of the  effect  of soil pH  on  the solubility           *
of Mn and Al are given in  Glass  et al. (1980),  concentrations rising           •
very rapidly in each  suite of  soils  when  pH  values  moved from 5 to

                                                                                1
In acid forest soils  that  support highly  productive forest in eastern          •
Canada it is not unusual to have  a pH gradient down the profile of
from 3.0 to 4.6.  Associated with such values  are  exchangeable Ca              A
values falling from 2.0 to 0.15  meq/lOOg  and exchangeable Al values            "p
falling from 7.0 to 0.40 meq/lOOg (Anonymous 1979). Of a very much
wider Ca/Al ratio, however, is the Soiling soil profile in Germany             «
described by Ulrich et al. (1971), where  exchangeable  Ca and Al                •
concentrations are respectively  0.2  and 4.7  meq/lOOg,  and where
Gb'ttsche's beech studies in the  acidification  year  of  1969 are
plotted to reveal the remarkable  correlation between the seasonal              •
increase in soluble soil Al concentrations and the  dramatic increase           w
in fine-root mortality (Ulrich 1980b).  Indeed, this correlation and
other studies have encouraged  Ulrich (1981)  to advance his ecosystem           •
hypothesis explaining the  widespread "die-back" of  fir in Europe.              «
Fine roots are killed by high  soil Al concentrations or high Al/Ca
ratios with a subsequent invasion of the  damaged tree  tissues by rot           ^
fungi.  There is evidence  to indicate that increased amounts of                •
aluminum can be mobilized  in the soil and passed on to water bodies            *
(Abrahamsen et al. 1976; Cronan  and  Schofield  1979).  It is not clear
whether the allegedly toxic concentrations present  in  the                      •
loess-derived forest  soils of  central Germany  can  also be expected to          •
arise in the glacial  till-derived soils  of Scandinavia or
northeastern North America (Tyler 1981).
 1
Soil acidification  in  environments  where  there is also appreciable
deposition of heavy metals  is  the  second  area of concern.   Heavy               ^
metals arise from various industrial  activities, including fuel                •
combustion (Hansen  and Fisher  1980; Watanabe et al.  1980).  The scale          *
of emissions and airborne transportation  has caused  increasing
attention to be directed  to the  amounts of different elements being            I
deposited in remote rural areas.   Thus, at the Soiling site in                 m
central Germany, for an open-site  wet deposition of  23.8 kg of
sulphur per hectare per year,  there is an accompanying 10  kg of                •
nitrogen, 10.4 kg of calcium,  1.9  kg  of magnesium and 1.1  kg of                •
aluminum (Ulrich 1980b).  In south-central Ontario recent  comparable
figures are 10 kg for  S,  6  kg  for  N,  5 kg for Ca, and 0.7  kg for Mg            -
(Scheider et al. 1979).   For the  same locality figures for elements            •
more commonly understood  as "heavy" are 0.46 kg for  aluminum, 0.54 kg          ™
for iron, 0.095 kg  for zinc, 0.132 kg for lead, 0.033 kg for copper
and  0.022 kg for nickel  (Jeffries  and Snyder 1981).  These authors            4|
also point to the much higher  deposition  rates near  smelters where             £
cumulative levels of heavy  metals  in  the  soils have  exercised
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                                                                  4-63
pronounced toxic effects upon the vegetation  (Hutchinson and Whitby
1974, 1976).  However,  there is  danger  in  extrapolating  from such
heavily polluted local  situations onto  the more  diffuse  regional
scale without taking  into  account the different  parameters.
Nevertheless, if the  Soiling site is taken as  exemplifying the more
diffuse rural situation, Heinrichs  and  Mayer  (1977,  1980) found that
the beech and spruce  forests act as filters for  atmospheric
substances.  Some elements  (e.g., sulphur, lead,  mercury, bismuth and
thallium) are largely accumulated in the upper part  of the soil
profile but  the complex biogeochemical  picture that  emerges  suggests
that far more needs to  be  known  in  other locations on  the fate of
deposited metals having potentially significant  physiological and
toxicological roles (Andersson et al. 1980a;  Bradley et  al.  1981;
Smith and Siccama 1981).   There  is  a rapidly  expanding literature
focusing on  the soil  behaviour of heavy metals derived from  town
wastes (Leeper 1978)  and much of this related  to  pH-dependent
considerations (Hatton  and  Pickering 1980; McBride and Blasiak
1979) and metal-organic compound complexes (Bloom et al. 1979;
Marinsky et  al. 1980; McBride 1980) should be  applicable to  the
acidic deposition problem.

The dissolution and mobilization of many other trace metals  in soils
is also affected by acidic  deposition and  decreasing soil pH.  Recent
studies in the Adirondack  Mountains of  New York  have determined from
acidic leaching experiments on native bedrock  that this  process is an
important contributor of Cu, Pb, and Hg in addition  to Al (Fuhs
et al. 1981).  The trace metals  Cu, Pb, Hg, Cd,  and  Zn were  leached
rapidly upon exposure to acid while Al  and other  major metals were
leached more gradually.  Leaching of soils and bedrock by long-term
acidic deposition has resulted in soil  impoverishment  for metals such as
Mn and Zn in New Zealand (Norton et al. 1981).

Other studies have demonstrated  accumulations  of  trace metals in
soils.  Norton et al. (1980) found  Pb and chemically similar metals
accumulating in soils while Al and Mn were being  leached. Leaching
occurred in  the upper soil  horizons resulting  in  potential
impoverishment for shallow  rooted plants.  Deeper rooted plants, on
the other hand, are subjected to potentially  toxic concentrations of
dissolved metals.  Tyler (1978) also showed that  Pb  is not readily
leached from surface soils  by acidic deposition inputs.   Although the
solubility of this element  increases with decreasing pH, most soils
contain sufficient organic  matter to tie up the  Pb as insoluble
organic - Pb complexes  in  the soil matrix.  Mobility and transport
within the soil horizons and direct atmospheric deposition is
responsible  for the accumulation of metals in  the soil.   For example,
concentrations of Cu and Ni increased in soils with  proximity to the
Sudbury, Ontario smelter (Heale  1980).  Studies of metal deposition
in the Walker Branch Watershed in Tennessee,  found that  soils
efficiently  retained Pb, Cd, and Cu, and less  readily accumulated Cr,
Mn, Zn, and Hg (Andren  et  al. 1975).  McColl  (1980), however, found
that the concentrations of  Mn, Fe,  Cu,  and Zn  were all greater in

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                                                                  4-64
soil solutions than in acidic deposition  falling  in  Berkeley,
California.
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In restricted areas, vegetation may  be  stunted  or  absent  due  to
toxicity of metals such as Ni  (Foy et al.  1978).   In  a  well-known
study on serpentine-derived  soils  in Czechoslovakia,  Nevmec (1954)             M
attributed the failure of pine plantations  and  various  hardwood               •
species to excessive levels  of Ni , Cr,  and  Co.   Plantation failure
was considerably reduced by  fertilization with  lime and diabase dust.
Around Sudbury, Canada, Ni and Cu  added  from  atmospheric  deposition          "W
from smelters are maintained in acidified soils  in concentrations             •
sufficiently high to be toxic  to vegetation (Hutchinson and Whitby
1974, 1976).  Thus, any possibility  of mobilization of  trace  metals          1^
through decreasing soil pH by  acidic deposition has implications for         ^
forest productivity.  Accumulations  of  trace  metals from  atmospheric
deposition can contribute to this  problem.
                                                                               £
4.5   SENSITIVITY ASSESSMENT

Several sets of sensitivity criteria  have  been  proposed  and  used to           M
define geographical regions most  susceptible  to acidic deposition
effects (Johnson and Olson in press).  Each set of  criteria  is  based          ft
upon a different philosophy and  is  aimed at different  target                  £
organisms or ecosystems  (e.g., forests, fish, soil,  bedrock, aquatic
ecosystems).  Those directed toward aquatic effects  have emphasized           «
bedrock geology (Hendrey et al.  1980;  Norton  1980)  or  bedrock geology         •
and soils in combination (Cowell  et al. 1981; Glass  et al.  1982; see          ™
Section 3.5).  Those directed toward  terrestrial effects have
emphasized cation exchange capacity and base  saturation  (Klopatek             •
et al. 1980; McFee 1980a,b; Wang  and  Coote 1981).                              •

Terrestrial sensitivity  has been  defined in terms  of forest                    Ife
productivity (Cowell et  al. 1981; Table 4-11) and  in terms  of soil            ||
acidification (Wiklander 1973/74, 1980b; Table  4-12).  In both cases
effects in the soil body were emphasized.   Cowell  et al. (1981)              ^
regarded low pH soils as the most sensitive based  on the assumption          ^m
that these already had the smallest reserve of  nutrient  cations.              *
Thus, any additional loss of forest nutrient  cations,  however small,
would be significant to  forest productivity in  acid  soil systems              •
(even though these soils were less  sensitive  to acidification).  This         *i
sensitivity assessment concentrated on the upper 25  cm of the soil
profile where, at least  in boreal ecosystems, nutrient cycling is             •
most efficient.  Acid soils are  known to actively adsorb SO^",               •
hence reduce cation mobilization, and are  considered less sensitive
than nonsulphate-adsorbing soils  (Johnson  and Cole 1977; Singh et al.         ^
1980).  This contrasts with the  sensitivity concept  suggested by              •
Wiklander (1973/74, 1980b) whereby  noncalcareous,  moderately acid             *
sandy soils (pH 5-6) with low cation  exchange capacities are
considered most sensitive.  Wiklander (1973/74, 1980b) derived these          I
criteria from laboratory studies  in which  he  found that  the  cation            9
displacing efficiency of H+ was  greatly diminished as base
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4-65












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                                                                  4-67
saturation and pH decreased.  Thus,  for a given H+  input, very  acid
soils will yield fewer cations and are classed as less  sensitive  than
moderately acid soils.  Moderately acid soils with  low  cation
exchange capacity (i.e.,  less buffering by exchange sites) will
experience more rapid pH-change  than very acid soils with the same
exchange capacity.  This  concept  of  assessing soil  acidification
potential, in which the most sensitive soils are those  experiencing
the greatest change in their inherent properties, is specifically a
soil sensitivity evaluation.  No  cause-effect relationships with
vegetative or aquatic systems are specified.
4.5.1   Terrestrial Sensitivity Interpretations

Acidic deposition may cause increases as well as  decreases  in  forest
productivity (Abrahamsen  1980; Cowling and Dochinger  1980).  The  net
effect on forest growth depends upon a number of  site specific
factors such as nutrient  status and amount and composition  of
atmospheric acid input.   In cases where nutrient  cations  are abundant
and S or N are deficient, moderate inputs of acid may actually
increase forest growth.   At the other extreme, acidic deposition  in
sufficient amounts may reduce productivity on sites with  adequate
N and S but deficient in  cations.  Other detrimental  effects to
forest productivity include changes in soil, microorganisms and Al
toxicity.  These effects  are increased (Ulrich et al. 1980) with
increased acidification.  However, there is insufficient  empirical
evidence establishing cause-effect linkages between forest
productivity and acidic deposition.  It is not certain which
ecosystem factors are most significant with respect to forest  systems
and thus it is not presently possible to map forest productivity
sensitivity at any scale.

Sensitivity assessment for this section, therefore, will  concentrate
on soil characteristics and how pH, CEC and sulphate  adsorption
properties hypothetically relate  to different effects. Terrestrial
ecosystem effects to be considered are:  loss of  base cations, soil
acidification and Al solubilization.  Table 4-13  and  Figures 4-5  and
4-6 depict hypothetical sensitivities (Johnson and Olson  in press).
For nonsulphate-adsorbing soils (Figure 4-5), it  is assumed that  each
equivalent of incoming H+ causes  the leaching of  an equivalent of
some cation (including H+ or Al^+) through the forest soil.

Case 1.   For soils with  pH  >6,  H+-base cation exchange  is likely
to be nearly 100% efficient (Wiklander 1973/74, 1980b), and thus
soils are very "sensitive" to base cation loss (Figure 4-5a).  If the
soil with pH  >6 has a high CEC (i.e., a large reserve of
exchangeable cations and  hence a  large buffering  capacity), it will
take a very long time for a given acid input to acidify it.  This is
depicted by the width of  the CEC box in Figure 4-5a.   Thus,  such  a
soil is thought to have low sensitivity to acidification  and Al
mobilization.

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4-68

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               pH
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                   >7

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SOIL 5

     4

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   pH
Figure 4-5.
                   NONSULPHATE-ADSORBING SOILS

              (a)   CATION  EXCHANGE CAPACITY
                            HIGH
                                                    2H+
                      100
              %BASE
             SATURATION
                                                                804"
                                           CATION
                                           EXCHANGE
                                                   BASE
                                                  CATIONS


                          (b)  CATION  EXCHANGE  CAPACITY


                                        HIGH
                                                  SO?"
                      100
                          % BASE
                         SATURATION
                       0
                                  LOW
                                  •4—»>
                          H+AI3+
                          CATIONS;
                         V/////
                                           CATION
                                           EXCHANGE
                                                  H+,AI3+
                                                   BASE
                                                  CATIONS

                          (c)  CATION   EXCHANGE  CAPACITY


                                                    2H+
                     100
              % BASE
             SATURATION

H+.AI34"
LOW


//////A///
                         BASE
                         CATIONS
                                                      CATION
                                                      EXCHANGE
                                    H+AI3 +
                                    BASE
                                   CATIONS
                                                    V
                                                              4-69
                                                           INPUT
                                                                      SOIL
                                                                      INTERACTIONS
                                                           OUTPUT
                                                                804"  INPUT
                                                                       SOIL
                                                                       INTERACTIONS
                                                    SO?"   OUTPUT
                                                    So|"   INPUT
                                                                      SOIL
                                                                      INTERACTIONS
                                                                     OUTPUT
                         Effects on base cation loss,  soil  acidification and
                         Al->+ solubilization for nonsulphate-adsorbing soils
                         having (a) moderate to high pH ( >6), (b) moderate pH
                         (5-6) and  (c) low pH ( <5) (Johnson and Olson in
                         press).

-------
                                                                  4-70
                                                                                I
                                                                                1
Case 2.   If the soil with pH  >6  has  a  low CEC (area depicted to the
right of the dashed  line  in  the  CEC  box  in Figure 4-5a),  it will take
less time to deplete the  exchangeable  cation reserves and,  therefore,          •
a low-moderate rating is  arbitrarily assigned to acidification and Al          f
mobilization in soils to  differentiate it  from case 1.  As  in case 1,
H+-cation exchange is nearly 100%  complete,  so that soils are                  ^
"sensitive" to base  cation loss.                                                •

Case 3.   If a soil  has pH 5-6  (i.e.,  a  moderate base saturation),
H+-cation exchange will be nearly  as complete as in cases 1 and 2              •
while cation reserves (at a  given  CEC) will be lower (Figure 4-5b).            H
For the high CEC case, a  moderate  rating is assigned to acidification
and Al mobilization  in terrestrial ecosystems.  As in cases 1 and 2,           •
soils are "sensitive" to  base cation loss.                                      V

Case 4.   In this case, the  total  reserves  of base cations  are low             _
yet H+-cation exchange is nearly 100%  efficient (Figure 4-5b) and              I
thus the soil is highly sensitive  to base  cation loss and                      ™
acidification.  Once base cations  are  depleted and the soil is
acidified, Al may become  mobilized;  thus,  a moderate rating is                 I
assigned to soil Al mobilization.                                               •

Case 5.   In soils with pH   <5  (i.e.,  low  base saturation), H^-base            •
cation exchange is less efficient  and  therefore soils are only                 'M
moderately sensitive to base cation  loss but have a low sensitivity
to further acidification  (Figure 4-5c).   Such a soil may be sensitive
to Al mobilization given  sufficiently  high acid inputs, however.  In           w
the high CEC case, a moderate sensitivity  is assigned to Al                    P
mobilization in soils.
                                                                                1
Case b.   In this case,  the  soil  is  acid  and has low CEC (Figure
4-5c), making it only moderately  sensitive  to base cation loss but
highly sensitive to Al mobilization.   These soils have only a low              •
sensitivity to further acidification.                                           •

In sulphate-adsorbing soils,  leaching  of  H"*", Al^+, and base
cations is inhibited for the  reasons described previously.  The                •
degree of sulphate adsorption is  dependent  to some extent on pH                9
(Harward and Reisenauer  1966)  as  well  as  on inherent soil properties
such as organic matter and Fe- and Al-oxide content.  Sulphate is              1|
more strongly adsorbed in most acid  soils.   Soils having a pH  >6              |
would not be expected to exhibit  high  sulphate adsorption properties
(cases 7 and 8;  Table 4-13).   High Fe- and  Al-sesquioxide content              ^
required for sulphate adsorption  would not  be characteristic of these          •
soils.  Also, any soils  having high  CEC (cases 9 and 11;  Table 4-13)           *
would not be expected to adsorb sulphate  if the exchange capacity was
controlled primarily by  organic matter.  High organic matter content           •
tends to block the adsorption potential of  Fe and Al oxides (Johnson           •
and Henderson 1979;  Singh et  al.  1980).

Cases 9 to 12 are analogous  to cases 3 to 6, respectively, with                •
regard to pH and CEC.  Due to the sulphate  adsorption capacity of
                                                                                1

                                                                                I

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                                                                  4-71
soils in cases 9 to  12, however,  base  cation  leaching is  lower than
in analogous soils in  cases 3 to  6  (Figure  4-6).   However,  sulphate
adsorption prevents  H  transport  as well  as base  cation leaching
from soils in cases  9  to  12, and  the displacing efficiency  of H
for base cations is  less  of a factor in  soil  acidification.  Soils in
cases 9 to 12 are rated slightly  more  sensitive to Al solubilization
than their counterparts 3 to 6.

The preceding discussion  as well  as Table 4-13 and Figures  4-5 and
4-6 by no means represent a rigid set  of  criteria for site  sensiti-
vity to acidic deposition.  They  merely  represent a hypothetical
construct based upon a combination  of  known and previously  employed
sensitivity criteria.  These criteria  have  limitations and  are by no
means complete.  For instance, while considering  the sensitivity of
terrestrial and aquatic ecosystems  to  acidic  deposition effects, it is
important to realize that acids are produced  naturally within these
systems (Rosenqvist  1978).  The effects  of  atmospheric acid inputs
must be viewed as an addition to  natural, ongoing acidification and
leaching processes within soils due to carbonic acid formation,
organic acid formation, free cation uptake, and a variety of other
processes (Andersson et al. 1980b;  Sollins  et al. 1980; Ulrich 1980a).
Unfortunately, the data base for  including  natural acid formation
criteria into regional sensitivity  assessments is extremely limited.
Thus, previous sensitivity rating schemes,  by default, assume that
atmospheric inputs add significantly to  internal  acid production, an
assumption that is by  no  means universally  accepted (Rosenqvist
1978).

It is also important to distinguish between acidification and
elemental leaching when considering the  role  of natural acid
formation.  Carbonic acid is a major leaching agent in some forest
soils, yet it does not produce low  pH  (i.e.,  <5.0) solutions under
normal conditions (Johnson et al. 1977).  Organic acids may contribute
substantially to elemental leaching in forest soils undergoing
podzolization (Johnson et al. 1977), and  they can produce low pH
(i.e., <5.0) in unpolluted natural  waters as  well (Johnson  1981).
Also, because leaching is only one  of  several processes that affect
soil acidity (other  major factors being  humus build-up, plant cation
uptake, and mineral  weathering; Ulrich 1980a), the relative
contribution of atmospheric acidic  deposition to  elemental  leaching
may be quite different from the relative  contribution of  atmospheric
deposition to soil acidification.
4.5.2   Terrestrial Mapping  for Eastern  North America

The lack of empirical  data identifying cause-effect  linkages with
respect to impacts of  acidic deposition  on forest and agricultural
systems makes sensitivity mapping  difficult.   One must identify a
target process  (i.e.,  soil acidification,  Al  solubilization, cation
loss, etc.) and then make specific assumptions regarding ecosystem
interactions which result in a significant impact.  The mapping

-------
                                                             4-72
                                                              I
    >7
     6
 PH  5
     4
   3-4
    >7
     6
pH   5
     4
   3-4
        SULPHATE-ADSORBING  SOILS

   (a)   CATION  EXCHANGE  CAPACITY
                            ,Fe , Al OXIDES
                             2H +
                    r^y
          100
    %BASE
SATURATIONS
                                                   SO?"
                      ANION
                   ADSORPTION
                               CATION
                               EXCHANGE
                                     INPUT
                SOIL
                INTERACTIONS
                                     H+,AI3+
                                      BASE
                                     CATIONS
                               S04~
                                               OUTPUT
  (b)   CATION  EXCHANGE CAPACITY
                            •Fe , Al OXIDES
                HIGH
          100
   %BASE
SATURATION
                      0



H+,
LOW
r*
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                                     INTERACTIONS
BASE  CATION"
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                                     BASE
                                    CATIONS
                                         SO
                                            2-
                                     OUTPUT
Figure 4-6.
   Effects on base cation loss, soil acidification and
     Oj_
   Al   solubilization for sulphate-adsorbing soils
   having  (a) moderate pH (5-6) and (b) low pH (<5)
   (Johnson  and Olson in press).
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                                                                  4-73
framework and thus the maps  themselves  could  vary substantially
depending on these assumptions  and  on which processes  were targeted
(Table 4-13).  For this  report  mapping  is  concentrated on terrain
characteristics, especially  soil  chemistry (or its surrogate),  of
eastern North America rather than sensitivity per se.   It is hoped
these maps will provide  a useful  basis  for comparison  and for
eventual interpretations of  terrestrial sensitivities  once actual
impacts are documented.

Figures 4-7 and 3-9  (in  map  folio)  show terrain characteristics in
the Eastern United States and Eastern Canada,  respectively.   Although
an attempt was made  to compile  compatible  and comparable  maps,
differences in mapping criteria and  data quality exist between  and
within the two maps.  Specific  mapping  factors and data sources are
listed in Table 4-14.  The data availability  in some parts of eastern
Canada necessitated  map  production  at 1:1,000,000 to ensure adequate
representation.  The U.S. map,  produced from  the Geoecology Data Base
(Olsen et al. 1980)  is reproduced here  at  1:5,000,000.

Terrain characteristics  for  the United  States are mapped  as soil
chemical classes based on pH and  CEC.   These  classes can  be compared
back to Table 4-13 to interpret relative sensitivities to acidic
deposition for Al solubilization, cation loss and soil acidification.
The discussion which follows  deals  primarily  with potential for soil
acidification based  on the Wiklander (1973/74) concept of
sensitivity.  The limit  of Wisconsin glaciation is shown  on the map
as a basis for comparison between younger  soils of the north and
northeast and the older, more deeply weathered soils characteristic
of the south and southeast.

Bedrock geology has  been included in terrain  classes for  the
Canadian mapping because soils  in Canada,  especially throughout the
Precambrian Shield,  tend to  be  thin  and discontinuous.  In these
areas the bedrock forms a major substrate  for forest systems and
represents the only  "store"  of  nutrient cations.  Because of a  lack
of soil chemical data for soils outside limited agricultural areas in
Canada, soil texture and depth  to carbonate data have  been
substituted  (Table  4-14).   These are the  only surrogates available
for soil chemistry at the scale of  compilation (1:1,000,000).   It is
not possible, therefore, to  relate  the  terrain classes on the
Canadian map directly to the  soil property classes shown  in
Table 4-13.  However, some indirect  comparisons can be made  on  the
bases of soil order.
4.5.2.1  Eastern United States

The map showing various classes of  soil  characteristics  covering the
eastern 37 states (Figure 4-7) was  produced  at  Oak  Ridge National
Laboratory (Olson et al. 1982).  The analysis utilized various
national resource inventories to map soil  classes based  on  pH,  CEC,
Histosols and land use (Table 4-14).  County-level  data  from the
Geoecology Data Base (Olson et al.  1980) were used  in  the analysis to
provide a regional perspective and  understanding of soil

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                                                                  4-74
characteristics which can be evaluated  in  terms  of  the  potential  for
acidic deposition impacts on terrestrial ecosystems (Table  4-13).   As
more detailed data or new studies are completed,  the  resolution or
interpretation of the map may need  to be revised.
                                                                               I
                                                                               1
                                                                               I
Initially counties that were predominantly  ( > 50%)  urban  or                    ,»
agricultural were excluded from the  analysis.  Management and  land             •
use practices (e.g., liming, fertilizing) in  these  areas  would tend
to determine current soil nutrient/pH conditions.   The  1977  National
Resource Inventory (USDA 1978) was used  to  define land  in urban               •
built-up areas and transportation corridors.   The 1978  Census  of               •
Agriculture (USDC 1979) provided data on cropland.   This  resulted  in
1,648 of the 2,660 counties in the east  being  included  in the
analysis as containing predominantly forest,  range,  or  pasture.
                                                                               M
                                                                               •
Moderately acid soil  (pH  5-6) and  low CEC  were  used  to  identify soils          _
which would be most sensitive to acidification  (Wiklander 1973/74,              •
1980b).  Very acid soils  will yield  fewer  cations  and  thus,  are                *
classed as less sensitive than moderately  acid  soils (Wiklander
1973/74).  Moderately acid  soils with low  CEC (i.e., less buffering            I
by exchange sites) will experience more  rapid pH change than very              m
acid soils with the same  CEC (Table  4-13).   McFee  (1980a,b)  used
CEC only as a first reasonable approximation to site sensitivity.  He          •
used a CEC value of 6.2 meq/lOOg to  identify soils that would change           •
most quickly under the influence of  acidic deposition.   This
criterion was used to distinguish  between  "low  CEC soils" and "high            ^
CEC soils" (Table 4-9).   As noted  earlier,  however,  the interpre-              •
tation of soils sensitive to acidic  deposition  does  not account for            •
the relative significance of this  deposition compared  to internal
acid generation.  It  is not presently possible  to  classify soils as            •
to internal acid generation especially in  a regional-level analysis.           £

Counties covered by 50% or  more of soil  types with a surface pH of              ^
greater than 5.5 and  CEC  less than 6.2 were classified  as having a              •
high potential to undergo acidification from acidic  deposition.  In
addition, two other classes were defined which  may undergo
acidification but at  a slower rate with similar levels  of acidic               •
deposition.  Soils with a pH greater than  5.0 and  CEC  less than 6.2            9
constituted class 2.  Class 3 included soils with pH greater than 5.0
and CEC less than 9.0.                                                          •

Chemical and physical soil  characteristics employed  in the analysis
represent average values  for the A horizon (upper 20-25 cm)  for the            ^
82 great soil groups  occurring in  the eastern United States.  These            •
values were obtained  from published  literature  (Klopatek et  al.                ™
1980).  The great soil groups were combined to  estimate values for
the 195 soil mapping  units  that are  mapped (USGS 1970)  in the east.            fl
Although the exact proportions of  great soil groups  within map units           P
are not readily available,  the dominant great soil group was given  a
weighting factor of 0.66  to calculate average map unit  values.                 M
                                                                                I

                                                                                1

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                                                                  4-75
Proportions of soil mapping units within  counties were  estimated  from
the 1:7,500,000 scale soil map of the United States  (USGS  1970).

Sulphate adsorption capacity was also considered in  defining
sensitive soils.  Soils with sulphate adsorption capacity  prevent the
transport of cations by H2S04 (Johnson and Cole 1977) and  can
increase soil exchange capacity (Wiklander 1980a) thus  reducing the
sensitivity of such soils to acidification.  Because of  the relative
lack of empirical information on sulphate adsorption capacity, only
Ultisols are considered as sulphate-adsorbing soils  (Johnson et al.
1980).  Even the data on sulphate adsorption capacity of Ultisols are
limited in geographic extent.  Ultisols have lower pH and  higher  CEC
values than given above for defining soils sensitive to  acidic
deposition.  Therefore, sulphate adsorption does not appear on Figure
4-7 as part of the classification.  Soils other than Ultisols have
varying capacities to adsorb sulphate and this factor may  be
important in mediating the acidification  of a soil that would
otherwise appear sensitive.

Counties were used both to integrate the  various factors and to
display the results.  Although counties are generally uniform in  size
in the eastern United States, some of the larger counties  occur along
the U.S./Canada border in Maine and Minnesota.  All  the  factors
utilized a 50% criteria to classify counties.  Therefore,  significant
areas can exist within counties that differ from the final designated
classification.  Thus Figure 4-7 displays the broad  regional patterns
but evaluation of an individual county requires more detailed
analysis to determine the extent and coincidence of  the  various
factors within that county.

Six classes were used to characterize soils (Table 4-15),  with
agricultural/urban areas shown as blank on the map (Figure 4-7).
Classes 1 to 3 are specifically related to the increasing  potential
for soils to undergo acidification with acidic deposition. The other
three classes were included to provide additional information on
soils which could be used with alternate  hypothesis  of  soil
sensitivity or in better understanding acid inputs from  soils to
aquatic systems (Section 3.5).  Class 4 includes low pH  soils
(pH  <5.0) and Class 5 includes high pH soils (pH >  5.0) that also
have a high CEC (CEC >9.0).  Class 4 soils are those most  likely  to
experience Al mobilization and have the potential to transfer both
H+ or Al3+ ions to aquatic systems, given sufficient inputs of
acid.  Section 3.5 with Figure 3-10 provides additional  discussion on
the potential transfer of acid to aquatic systems.

Class 6 includes areas dominated by Histosols (peat  soils).  Although
these organic soils may not be sensitive  to further  acidification, it
is important to recognize them in the overall assessment of acidic
deposition impacts.  Class 6 is most informative when compared to
Figure 3-10 in Section 3.5 relative to acid inputs to aquatic
systems.  These and similar Canadian peatland areas  naturally

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4-76
I
TABLE 4-14. TERRESTRIAL FACTORS AND ASSOCIATED DATA BASES UTILIZED FOR
TERRAIN CHARACTERISTICS MAPPING IN EASTERN CANADA AND THE
EASTERN UNITED STATES
Terrestrial Factors/Surrogates
EASTERN UNITED STATES
1) Soil Chemistry
i) Mean soil order pH
( in distilled water) 	 	
ii) Mean soil order CEC 	
iii) Histisols (Organic soils) 	 	
2) Limit of Wisconsin Glaciation. 	 	



EASTERN CANADA
1) Soil Chemistry
Surrogates: i) Texture (sand, loam
or clay) - Northern
Ontario, Quebec,
the Maritimes and
Newfoundland/Labrador .
ii) Depth to Carbonate
(high, low or no
iii) Glacial Landforms -
northwestern Ontario..
iv) Organic Soils (>50%
of mapping unit) ......
2) Soil Depth - very shallow (approx. <25 cm),.
- shallow and deep C25 cm)
3) Bedrock Geology — lithology. ................


a All U.S. data sources listed have been compiled
Data Base (Olson et al. 1980).
Data Sources3
..Soil Map (USGS 1970)
..Soil Map (USGS 1970)
..Soil Map (USGS 1970)
..USGS 1970
..1977 National Resource
Inventory (USDA 1978)
. . 1978 Census of
Agriculture (USDC 1979)
. .Ecodistrict Data Base
(Environment Canada
1981a,b,c)
. .Ontario Land Inventory
(OMNR 1977)
..Pala and Boissonneau 1979
. .Ecodistricts (Environment
Canada 1981a,b,c)
..Ecodistricts (Environment
Canada 1981a,b,c) and
Ontario Land Inventory
(OMNR 1977)
..Shilts et al. 1981
. .Ecodistricts (Environment
Canada 1981a,b,c) and
Ontario Land Inventory
(OMNR 1977)
within the Geoecology
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

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TABLE 4-15.
                                                                   4-77
     SOIL CHEMICAL CLASSES AND AREAS DOMINATED BY HISTOSOLS IN
     THE EASTERN UNITED STATES AS MAPPED IN FIGURE 4-7
 Class
Acidification
  Potential
 No. of

Counties
Characteristics
   1         High           16


   2       Moderate         19


   3     Moderate-Low       45


   4         Low           849


   5         Low           700


   6         Low            13
                           Moderate pH (>5.5), lowest CEC (<6.2)


                           Moderate pH (>5.5), low CEC (<9.0)


                           Moderate pH (>5.0), low CEC (<9.0)


                           Low pH (>5.0)


                           Moderate pH (>5.0), high CEC (>9.0)


                           Histosols

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                                                                  4-78
Category I:   Organic Soils  (Histosols)
I
1
contribute acids of varying strength  to  lakes  and  streams  due to
high levels of organic acids.


4.5.2.2   Eastern Canada

The map of eastern Canada is  the  same  as that  used in Chapter 3                ||g
(Figure 3-9).  The reader is  referred  to Section 3.5.1.1 for  detail
regarding map compilation.                                                      ^

This map shows 62 classes of  terrain  characteristics  based on                  ™
combinations of soil depth, soil  texture (or depth to carbonate) and
bedrock sensitivity.  In the  previous  chapter  it was  used  to  define            fl
areas of varying potential to  reduce  the acidity of incoming                    f
precipitation prior to entering surface  waters.   In this section the
62 map classes are recombined  in  order to emphasize soil                       •
characteristics.  The classes  have  been  grouped  according  to  five              •
soil categories:  (1) organic  soils  (I);  (2) barren areas  (>75%
bedrock outcropping; II); (3)  sandy  soils (III);  (4)  loamy soils
(IV); and (5) clayey soils (V; Table  4-16).  These are correlated to           m
soil orders of the Canadian System  of  Soil Classification. They are           •
also subdivided on the basis  of underlying bedrock sensitivities.  It
is possible to break down these divisions further, such as by soil
depth (25 cm - 1 m and >1 m),  or  even  to recombine classes if some
other characteristic is preferred as  a basis for discrimination.
However, the grouping suggested in  Table 4-16  provides a framework             «
for summarizing soils of eastern  Canada  and discussing some aspects            •
of terrestrial sensitivity.
I
I
In Table 4-16, organic  soils  overlying  carbonate bedrock are
identified separately (IA) from  those overlying other rock types               A
(IB).  Category IB map  units  occur  over wide  areas of Ontario, Quebec          fl
and Labrador and in  small pockets  throughout  eastern Canada.  Organic
soils overlying carbonate strata is most common in the Hudson Bay              ^
Lowland of northern  Ontario and  northwestern  Quebec.                           •

The presence of limestones and dolomites beneath peat is significant
because local hydrological conditions influence peat development and           A
peatland chemistry.  More minerotrophic types of peatland ecosystems           9
occur where groundwater comes in contact with the substrate (Cowell
et al. 1979; Sjors 1963).  Consequently large portions of IA organic           •
soils have "fen" and "swamp"  type  ecosystems  which may have a                  •
groundwater pH well  in  excess of 5. This could be a significant
consideration with respect to the  impact of acidic deposition on such
terrain.  This is also  true for  IB  peatlands  (and other wetlands)              •
occurring on clay (northeastern  Ontario and southern Ontario).                 ™
Peatlands occurring  on  the Canadian Shield tend to be less
minerotrophic but local soil/groundwater conditions need to be
evaluated.
I

1

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                                                                  4-81
Category II:   Barren Areas

These are map units dominated  (^75%)  by  exposed bedrock.   Three
classes of barren  terrain  have  been  mapped  on  the basis of bedrock
lithology identified in Table  4-11 according to  "sensitivity".
Levels of sensitivity relate the  potential  or  capacity of  rock  types
to reduce acidity  of atmospheric  deposition as defined by  Lucas and
Cowell (1982).  Most of these  classes  in  eastern Canada lie above the
treeline and southern limit of  continuous permafrost.

Category III:   Sand or No Lime Soils

According to the Soil Map  of Canada  (Clayton et  al.  1977)  these areas
(IIIA to ITIC; Table 4-16) are  primarily  Humo-Ferric Podzols,
"Rockland" (  j^60% exposed bedrock)  and Dystric  Brunisols.  These
soil types have acidic surface  horizons (pH <5.5,  dominantly   <5)
and correlate most closely with cases  5 and 6  in Table 4-13.  They
are thus considered to have a  low sensitivity  to acidification, a
moderate sensitivity to base cation  loss  and a moderate to high
sensitivity with respect to Al  solubilization.   Soils  mapped as Mlq,
Mir, M4a and M4b (IIIB), and L2d  and L3 (IIIC) in Figure 3-9 are
probably the most  sensitive because  they  are the shallowest.
Category IIIA soils however overlie  calcareous bedrock.

Boreal and northern temperate  podzols  are characterized by the
accumulation of organic matter  and Fe-and Al-sesquioxides  (Stobbe
1968).  Although high Fe and Al content are properties known to
enhance sulphate adsorption (Johnson and  Cole  1977), high  organic
matter tends to block the  adsorption process (Johnson  and  Henderson
1979).  Low pH, high CEC podzols  in  eastern Canada  probably do  not
adsorb sulphate significantly  (Case  11; Table  4-13)  because their
CEC is controlled  primarily by  organic matter.   At  this time however,
there is very little empirical  evidence regarding the  sulphate
adsorption capacity of Canadian soils.

Category IV:   Loam or Low Lime Soils

Categories IVA to  IVC are  represented by loam/low lime soils of
varying depth and  overlie  different  bedrock types.   It is  not  certain
how these relate to the soil chemical classes  identified in Table
4-13.  They are mapped by  Clayton et al.  (1977)  as  primarily Podzolic
and Brunisolic (and as Rockland).  Based on the  interpretation  of
texture and depth  to carbonate  as surrogates for soil  chemistry,
these classes are  considered to exhibit the properties of  Cases 3 and
4 in Table 4-13 (moderate  pH).

Category V:   Clay or High Lime Soils

These soils (VA to VC) are interpreted as having low to moderate
sensitivity with respect to soil  acidification and Al
solubilization.  However,  sensitivity to base cation loss  is high.

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                                                                 4-82
    incidence of common diseases  and  insect  infestations  is likely
    to be affected by acidic deposition  and  ozone.
                                                                               I
                                                                               I
                                                                              I
These soils are primarily Gray Luvisols  and  Gleysols  (clay-rich
and/or under periodic or seasonal  flooding)  according to  the Soil Map
of Canada (Clayton et al. 1977).                                                •

Map units in Figure 3-9, as noted  earlier, are  based  on Ecodistrict
and Ontario Land Inventory polygons.   The  best  spatial resolution is
in Ontario, south of 52 °N latitude, where  Ontario  Land Inventory
(OMNR 1977) units were used.  Because  soil and  bedrock
characteristics are identified on  the  basis  of  dominance,  subdominant          •
characteristics are not shown on the map.  There  remains  a need for            •
much improved soil chemistry data  from nonagricultural areas in
eastern Canada.


4.6   RESEARCH NEEDS

The following list does not confer an  order  of  priority;  rather, the           f
ordering reflects the general progression  of the  foregoing chapter
from INTRODUCTION through SENSITIVITY  ASSESSMENT.                               m
                                                                                I
 1.  Improve resolution (spatial and temporal)  of  current  wet and dry          "
     deposition patterns in both the United  States and Canada.

2.  Improve projection of wet and dry deposition within  designated
    areas of United States and Canada.

3.  Improve information on capture and  fate of  dry  S  and N within            Q
    principal terrestrial ecosystem  types.

4.  Determine tree and crop species  exposed to  greatest  risk  of              •
    reduction in productivity by acidic deposition.   Determine plant         ~
    characteristics associated with  susceptibility/tolerance  to 03
    and acidic deposition.                                                    •

5.  Determine quantitative relationships  between dose-response
    acidic deposition and productivity  of trees and  crops.                   •
                                                                              I
6.  Determine extent to which dose-response relationships are
    altered by presence of 03, deposition of  particulates, soil              _
    nutrient and moisture supplies,  and pattern and  timing of                W
    precipitation events with respect to  stages of  plant develop-            ™
    ment.  Identify stages of vulnerability of  agricultural crops
    and/or forest vegetation, particularly to  episodic wet and/or            ft
    dry deposition.                                                           |

7.  Determine degree to which uptake of metals, particularly                  tm
    aluminum, is increased by exposure  to acidic deposition.                  •

8.  Determine the interaction of acid stress  with  other  abiotic and
    with biotic stresses on terrestrial plants. Determine whether           •
                                                                               I

                                                                               I

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                                                                 4-83
 9.   Develop a standardized biological indicator of acidic
     deposition, having known relationships to changes in
     productivity of trees and crops.


10.   Identify beneficial as well as injurious effects of various
     components of acid pollution, with particular reference  to rate
     relationships for principal terrestrial ecosystem types.
     Determine the effects of H4", SO^", and NC>3~, separately and
     combined, on forest nutrient status.  (This is a problem of
     quantifying benefits of SO^" and N03~ inputs vs.
     detriment of H+ deposition and net overall effect on forest
     ecosystems at current and projected input levels.)


11.   Based on actual field observations, quantify natural H+ ion
     production and consumption rates for the principal terrestrial
     ecosystem types, and the clear distinction of anthropogenic and
     natural H+ ion production.  Obtain more information on natural
     internal acid production and leaching for a variety of forest
     ecosystems.  (This must be used in a full, comprehensive
     analysis of acidic deposition effects on soil leaching of metal
     cations and transfer to aquatic ecosystems.)


12.   Determine sensitivity of aquatic and terrestrial components of
     headwater pond and lake ecosystems to acid loadings.


13.   Improve information, based on actual field observations  on a
     representative range of soil types, on impact of acidic
     deposition on sensitive biochemical and/or chemical processes,
     and generally identify soil types sensitive to various
     pollutants and pollutant combinations.


14.   Determine major factors affecting soil SO^" adsorption
     capacity, and how they vary among soil orders and/or major soil
     types.


15.   Based on actual field observation on a representative range of
     mainly natural soils, improve information on impact of acidic
     deposition on soil biota, soil mineralogy and soil organic
     matter.


16.   Improve understanding of relationships between forest
     productivity and acid sensitive properties of soils.


17.   Consider the long-term site impoverishment potential of
     continued acidic deposition, in the light of trends in forest
     management toward more rapid growth, shorter rotations and
     full-tree, or even whole-tree, harvesting.


18.   Improve system of mapping terrestrial sensitivity, hopefully
     incorporating existent data bases, to allow further
     identification of key sensitive areas.

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                                                                  4-84
I
I
19.  Improve soils information base, including also such factors as
     depth to carbonate and sulphate adsorption capacity,
     particularly in remote areas.                                            •

20.  Extended or "whole" ecosystem field studies of biological
     response to acidic deposition to understand the complex  trophic          •
     interactions amongst the organisms and the resulting  community           fj
     changes, particularly those affecting wildlife and the top
     carnivores in the food chain.                                            ^
                                                                              •
21.  Develop mitigative measures for correcting acidity impacts.              ™

22.  Determine the "threshold" or critical dosage of 03 required to           •
     produce injury and/or suppression of growth and yield under a            m
     variety of field conditions.

23.  Determine interactive response involving 03 and chemical                £
     additives (i.e., insecticides, fungicides, nematocides,  growth
     regulators).  When responses occur, identify physical and                ^
     chemical factors involved in the interactions.                           •

24.  Determine the diurnal pattern of 03 occurrence in the major
     agricultural and forested regions as a guide for field                   Aj
     fumigation studies and as a guide for calculation of  realistic           £
     dosages.
                                                                              I
4.7   CONCLUSIONS

1.  Field and laboratory studies with 03 that  indicate  reductions             m
    in yield may occur for various tree species and  such  crops  as             »
    beans, tobacco, potatoes, onions, radishes, grapes, soybeans and
    sweet corn.  During the growth season frequent exposures  to 03            A
    concentrations in excess of 0.1 ppm have produced up  to  20% yield         ||
    losses for susceptible species.

2.  Although simulated rainfall experiments have produced  some  direct         V
    effects on plants exposed to higher than normal  H+  concentra-             *
    tions, direct effects have not been documented conclusively in
    the field for vegetation exposed to ambient precipitation.                •

3.  Experiments with simulated acidic deposition and 03 have
    demonstrated greater plant growth reduction from the  two  together         A
    than would be expected from the results of their individual              •
    effects.

4.  Individual precipitation events which occur during  critical              H
    growth stages (e.g., during flowering or pollination)  offer              "
    amplified potential for damage to agricultural crops.
                                                                              I

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                                                                  4-85
5.  Direct effects of acidic deposition on soils have been shown  to
    increase 8042- movement and increase the rate of nutrient
    cation denudation.  However, some soils exhibit a substantial
    capacity to adsorb SO^j   and resist nutrient cation
    leaching.


6.  The terrestrial system's influence on the acid component of
    atmospheric deposition has important implications for the  aquatic
    ecosystem.


7.  Multifactor data bases have been employed, to develop maps of
    eastern North America which depict the sensitivity of various
    areas (down to the county level for the U.S. and Ecodistricts  in
    Canada) to impacts from acidic deposition.

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                                                                  4-86
4.8  REFERENCES
I
I
Abrahamsen, G.  1980.  Acid precipitation, plant nutrients  and  forest          •
     group.  In Proc. Int. Conf. Ecological  Impact  of Acid                     f
     Precipitation, eds. D. Drablos and A. Tollan,  pp. 58-63.
     SNSF-Project, Sandefjord, Norway, 1980.                                   M

Abrahamsen, G.; Horntvedt, R.; and Tveite, B.   1976.  Impacts of  acid
     precipitation on coniferous forest ecosystems.  In  Proc. First
     Int. Symp. Acid Precipitation and the Forest Ecosystem, eds.              M
     L.S. Dochinger and T.S.  Seliga,  pp.  991-1009.   USDA Forest               »
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	.  1977.  Impacts of acid precipitation on coniferous               |
     forest ecosystems.  Water, Air,  Soil Pollut. 8:57-73.

Abrahamsen, G., and Stuanes,  A.D.  1980.  Effects of simulated  rain            •
     on the effluent from  lysimeters  with acid, shallow  soil, rich in
     organic matter.  In Proc. Int. Conf. Ecological Impact of  Acid
     Precipitation, eds. D. Drablos and A. Tollan,  pp. 152-153.               •
     SNSF-Project, Sandefjord, Norway, 1980.                                   •

Alexander, M.  1980.  Effects of acidity  on  microorganisms  and                 •
     microbial processes in soil.  In Effects  of acid precipitation            f
     on terrestrial ecosystems, eds.  T.C. Hutchinson and M. Havas,
     pp. 363-374.  New York:  Plenum  Press.                                    ^

Allaway, W.H.  1970.  Sulphur-selenium relationships in  soils and             ™
     plants.  Sulphur Inst. J. 6(3):3-5.

                      _
     forage and pastures:  selenium in forages  as related to the
     geographic distribution  of muscular  dystrophy  in livestock.               M
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Andren, A.W.; Lindberg, S.E.; and Bate, L.C.   1975.  Atmospheric
     input and geochemical cycling of selected trace elements in               •
     Walker Branch Watershed.  Environmental Sciences Div.  Pub. No.            •
     728, Oak Ridge National  Laboratory,  Oak Ridge,  TN.

Andersson, A.M.;  Johnson,  A.H.; and Siccama, T.G.   1980a.  Levels of          ^
     lead, copper and zinc in the forest  floor in  the northeastern
     United States.  J. Environ. Qual. 9:293-296.                              M

Andersson, A.M.,  and Nilsson, K.O.   1974.   Influence of  lime and  soil          ~
     pH on K availability  to  plants.  Ambio  3(5):198-200.

Andersson, F.; Fagerstrom, T.; and Nilsson,  I.  1980b.   Forest                 V
     ecosystem responses to acid deposition  -  hydrogen ion budget and
     nitrogen/tree growth  model approaches.  In Effects  of acid               •
     precipitation on terrestrial ecosystems,  eds.  T.C.  Hutchinson            ^
     and M. Havas, pp.  319-334.  New  York:   Plenum Press.
                                                                               I

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                                                                  4-87
Anlauf, K.G.; Lusis, M.A.;  Wiebe,  H.A.;  and Stevens,  R.D.S.   1975.
     High  ozone  concentrations  measured  in the vicinity of Toronto,
     Canada.  Atmos. Environ.  9:1137-1139.


Anonymous.   1979.   Soils  and land  use in the central  New Brunswick
     Uplands and St. John River Valley.   Tour Guide published for the
     25th  Annual Meeting.   Cdn. Soc.  Soil Sci. , Fredericton,  N.B.
     11 pp.


Baath, E.;  Berg, B.; Lohm,  U.;  Lundgren, B.; Lundkvist, H.;
     Rosswall, T.;  Soderstrom,  B.; and Wiren, A.   1980.  Soil
     organisms and  litter decomposition  in a Scots pine forest -
     effects of  experimental acidification.  In Effects of acid
     precipitation  on  terrestrial  ecosystems, eds. T.C. Hutchinson
     and M. Havas,  pp.  375-380.New  York:Plenum Press.


Baath, E.;  Lundgren, B.;  and Soderstrom, B.  1979. Effects  of the
     artificial  acid rain on microbial activity and biomass.   Bull.
     Environ. Contam.  Toxicol.  23:737-740.


Bache, B.W.  1980.  The sensitivity of soils to acidification.  In
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     T.C.  Hutchinson and  M.  Havas, pp. 569-572.New  York:Plenum
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Baker, J.P., and Schofield,  C.L.   1980.   Aluminum toxicity to fish as
     related to  acid precipitation and Adirondack surface  water
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     Precipitation, eds.  D.  Drablos and  A. Tollan, pp.  292-293.
     SNSF-Project,  Sandefjord,  Norway, 1980.


Baule, H.,  and Fricker, C.   1970.   The fertilizer treatment  of forest
     trees.  Munich:   BLV-Verlag.


Beeson, K.C.  1941.  The  mineral composition of crops with particular
     reference to the  soils  in  which  they were grown.  A review and
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Bell, J.N.B., and Clough, W.S.   1973.  Depression of  yield in
     rye-grass exposed  to sulphur  dioxide.  Nature 241:47-49.


Berry, C.R.  1971.  Relative  sensitivity of red,  jack,  and white pine
     seedlings to ozone and  sulphur dioxide.  Phytopathology
     61:231-232.


	.  1974.  Age of  pine seedlings with primary  needles
     effects sensitivity  to ozone and  sulphur  dioxide.
     Phytopathology 64:207-209.


Billings, W.D.   1978.  Plants  and the  ecosystem,  3rd  edition.
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                                                                 4-88
Bjor, K., and Tiegen, 0.  1980.  Lysimeter experiment in greenhouse.
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Cogbill, C.V., and Likens, G.E.  1974.  Acid precipitation in the
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                                                                             I
     eds. D. Drab1os and A. Tollan, pp. 200-201.  SNSF-Project,              I
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                                                                             I
Bloom, P.R.; McBride, M.B.; and Weaver, R.M.  1979.  Aluminum organic
     matter in acid soils:  salt-extractable aluminum.  Soil Sci.
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Bolt, G.H., and Bruggenwert, M.G.M.  1978.  Soil chemistry;  basic           •
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Bowen, G.D.  1973.  Mineral nutrition of ectomycorrhizal.  In                fl
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Bradley, R.; Burt, A.J.; and Read, D.J.  1981.  Mycorrhizal infection        •
     and resistance to heavy metal toxicity in Calluna vulgaris.
     Nature 292:335-337.

Brandt, C.S., and Heck, W.W.  1968.  Effects of air pollutants on            •
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Carlson, R.W.  1979.  Reduction in the photosynthetic rate of Acer,          ^
     Quercus and Fraxinus species caused by sulphur dioxide and              •
     ozone.  Environ. Pollut. 18:159-170.                                    *

Chrosciewicz, A.  1963.  The effects of site on jack pine growth in          A
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                                                                              I
Clark, K., and Fischer, K.  1981.  Acid precipitation and wildlife.          ^
     C.W.S. Manuscript Report No. 43, Can. Wildl. Serv., Environment         •
     Canada, Ottawa, Ont.                                                    ™

Clayton, J.S.; Ehrlich, W.A.; Cann, D.B.; Day, J.H.; and                     •
     Marshall, I.E.  1977.  Soils of Canada.  Can. Dept. Agric.,             W
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Cogbill, C.V.  1976.  The effect of acid precipitation on tree  growth        •
     in eastern North America.  In. Proc. First Int. Symp. Acid
     Precipitation and the Forest Ecosystem, eds. L.S. Dochinger and
     T.S. Seliga, pp. 1027-1032.  USDA Forest Service Gen. Tech.             •
     Report NE-23, Columbus, OH.,  1976.

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                                                                  4-89
Cole, A.F.W., and Katz, M.   1966.  Summer ozone concentrations  in
     southern Ontario  in  relation  to photochemical  aspects  and
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Cole, D.W., and Johnson,  D.W.  1977.  Atmospheric  sulfate  additions
     and cation leaching  in  a Douglas fir ecosystem.  Water Resour.
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Coleman, R.  1966.  The importance of sulphur  as a plant nutrient  in

     world crop production.  Soil  Sci.  101:230-239.


Constantinidou, H.A.,  and Kozlowski, T.T.   1979a.   Effects  of  sulphur

     dioxide and ozone on Ulmus americana seedlings.  I. Visible
     injury and growth.   Can. J. Bot. 57:170-175.


             1979b.  Effects of sulphur dioxide and ozone  on Ulmus
     americana seedlings.  II.  Carbohydrates, proteins, and lipids.
     Can.  J. Bot. 57:176-184.


Cowell, D.W.; Lucas, A.E.; and Rubec, C.D.A.   1981.   The development
     of an ecological  sensitivity  rating for acid  precipitation
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     Environment Canada,  Ottawa, Ont. 42 pp.


Cowell, D.W.; Wickware, G.M.; and  Sims, R.A.   1979.   Ecological land
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Cowling, D.W.; Jones, L.H.P.; and  Lockyer,  D.R.  1973.  Increased
     yield through correction of sulphur deficiency  in  ryegrass
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Cowling, D.W.,  and Koziol, M.J.  1978.  Growth of  ryegrass  (Lolium
     perenne L.) exposed  to  S02.   I. Effects on photosynthesis  and
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Cowling, E.B.  1979.  Effects of acid precipitation  and atmospheric
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Cowling, E.B.,  and Dochinger, L.S.  1980.   Effects  of acidic
     precipitation on health and the productivity  of  forests.   In
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Craker, L.E.   1972.   Decline and recovery of petunia  flower
     development from ozone  stress.  Hortscience 7:484.

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                                                                 4-90
Curtis, L.R.; Edgington, L.V.; and Littlejohns, D.A.  1975.  Oxathin
     chemicals for control of bronzing of white beans.  Can. J. Plant
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Craker, L.E., and Feder, W.A.  1972.  Development of inf luorescence
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Crittenden, P.D., and Read, D.J.  1978.  The effect of air pollution
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Cronan, C.S.  1980.  Solution chemistry of a New Hampshire sub-alpine         _
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Cronan, C.S.; Reiners, W.A. ; Reynolds, R.C.; and Lang, G.E.   1978.
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Cronan, C.S., and Schofield, C.L.   1979.  Aluminum leaching  response          •
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                                                                              •
Davis, D.D.  1972.  Sulphur dioxide fumigation  of  soybeans:   effect
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Davis, D.D., and Wilhour, R.G.   1976.  Susceptibility of woody  plants         *
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Davies , E.B., and Watkinson, J.H.  1966.  Uptake of native  and                •
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Dennison, R. ; Caldwell, B.; Bormann, B.; Eldred , L. ; Swanberg,  C.;            ™
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Dodd, J.L.; Lauenroth, W.K.;  Heitschmidt,  R.K.;  and  Leetham,  J.W.
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Dreisinger, B.R.  1965.   Sulfur dioxide  levels  and the effects  of  the
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Dreisinger, B.R., and McGovern, P.C.   1970.   Monitoring atmospheric
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Duchelle, S.F.,  and Skelly, J.M.   1981.  Response of common milkweed
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Environment Canada.  1981a.   Ecodistrict maps and descriptions  for
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	.  1981b.  Les  ecodistricts  du  Quebec.  Lands Directorate,
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	.   1981c.  Ecodistrict maps and descriptions  for  Ontario.
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Reich, P.B.; Amundson, R.G.; and Lassoie, J.P.   1982.  Reduction  in            |
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                                                                                I

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Reinert, R.A.  1975.  Monitoring, detecting and effects  of  air
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             1980.  Assessment of crop productivity  after chronic
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Reinert, R.A.; Heagle, A.S.; and Heck, W.W.  1975.   Plant  response  to
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Reinert, R.A., and Nelson, P.V.  1980.  Sensitivity and growth  of
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Reinert, R.A., and Weber, D.E.  1980.  Ozone and  sulphur dioxide-
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Rennie, P.J., and Halstead, R.L.  1977.  The effects of sulphur on
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Richards, B.L.; Middleton, J.T.; and Hewitt, W.B.   1958.   Air
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Richards, N.R.; Hansen, J.A.; Worthy, W.E.J.; and Irvine,  D.E.  1979.
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     79-2, Guelph, Ontario.  178 pp.


Rippon, J.E.  1980.  Studies of acid rain on soils  and catchments.

     In Effects of acid precipitation on terrestrial ecosystems,  eds.
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Roberts, T.M.; Clarke, T.A.; Ineson, P.; and Gray,  T.R.  1980.
     Effects of sulphur deposition on litter decomposition and
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     acid precipitation on terrestrial ecosystems,  eds.
     T.C. Hutchinson and M. Havas, pp. 381-394.   New York:   Plenum
     Press.


Rodin, L.E., and Bazilevich, H.I.  1967.  Production and mineral

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     288 pp.

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Rorison, I.H.  1980.  The effects of soil acidity on nutrient
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                                                                               I
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Rosenqvist, I.Th.  1978.  Alternative sources for acidification  of             mm
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Sawicka-Kapusta, K.  1978.  Estimation of the contents of heavy
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Scheider, W.A.; Snydner, W.R.; and Clark, B.  1979.  Deposition  of             •
     nutrients and major ions by precipitation in south-central                |
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Schwarz, K., and Foltz, C.M.  1957.  Selenium as an  integral  part of           •
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Seip, H.M.  1980.  Acidification  of  freshwater  -  sources  and
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Shaw, G.G.  1981a.  The effect of S02  on  selenium concentrations  in           M
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Shilts, W.W.; Card, K.D.; Poole,  W.H.; and  Sanford,  B.V.   1981.               •
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Shinn, J.H., and Lynn, S.   1979.   Do man-made  sources affect  the
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                                                                               I

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Stone, E.L.  1953.  Magnesium deficiency of some northeastern pines.
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Stuanes, A.O.   1980.  Effects of acid precipitation on soil and               I
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Sundstrom, K.R. , and Hallgren, J.E.  1973.  Using lichens as                  •
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Tamm, C.O.  1976.  Acid precipitation:  biological effects  in  soil
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Tamm, C.O., and Wiklander, G.  1980.   Effects of artificial                   |
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Tamm, C.O.; Wiklander, G.; and Popovic, B.  1976.  Effects  of                 •
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Thompson,  D.C., and  McCourt, K.H.   1981.   Seasonal  diets of  the
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Tingey,  D.T.;  Heck,  W.W.;  and Reinert,  R.A.   1971a.   Effect  of low
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Tingey,  D.T.,  and Reinert,  R.A.  1975.   Effect  of ozone and  sulfur
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Tingey,  D.T.;  Reinert, R.A.; Dunning, J.A.;  and  Heck,  W.W.   1971b.
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Tingey,  D.T., Reinert,  R.A.; Wiekiff, C.;  and Heck,  W.W.  1973a.
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Toivonen, P.M.A.; Hofstra, G.;  and Wukasch,  T.   1980.   Assessment of
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Treshow, M.  1970.  Environment  and  plant  response.  Toronto:
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Tveite, B., and Abrahamsen, G.  1980.  Effects of artificial rain on          _
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Tyler, G.  1978.  Leaching rates of heavy metal ions in forest soil.          •
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Wainwright, M.  1979.  Microbial S-oxidation  in soils  exposed to
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Wang, C.,  and Coote, D.R.   1981.   Sensitivity classification  of
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Watanabe, A.; Lutz, E.J.; and Moghissi,  A.A.   1980.  Atmospheric
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Wiklander, L.  1973/74.  The acidification of  soil by  acid
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Wood, T., and Bormann, F.H.  1976.  Short-term  effects  of  a simulated
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     Forest Ecosystem, eds. L.S. Dochinger and  T.S. Seliga,
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     Toronto, Ont.
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      SECTION 5




HEALTH AND VISIBILITY

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                                                                  5-1
                             SECTION 5
                        HEALTH AND VISIBILITY
5.1   HEALTH

A complete assessment of the health  implications  of U.S./Canadian
transboundary air pollution would encompass  the full  range  of  current
pollution concerns, including photochemical  oxidants,  sulphur  and
nitrogen oxides, particulate matter, and associated toxic substances.
Although future phases may address these air quality  concerns  more
completely, this report will focus on potentially indirect  health
effects associated with the transboundary deposition  of acidifying
substances, with only a brief summary of information  on direct
inhalation of the above mentioned pollutants.

Available information gives little cause for concern  over direct
health effects from acidic deposition.  The  pH of acidic deposition
is generally well within the range normally  tolerated  by the  skin and
gastrointestinal tract.  Although high  levels of  SC^,  NOo,  and
acidic aerosols are reported in urban areas,  no studies have  been
found which suggest adverse effects  from dry deposition on  the skin.

Evidence does suggest, however, that inhalation of high levels of
such substances may produce respiratory and  other internal  disease
(NAS 1977a; USEPA 1980), and one early  epidemiological study  (Gorham
1958) even reported an inverse statistical association between
bronchitis mortality and the pH of winter precipitation in  Great
Britain.  In this case precipitation acidity was  probably an  index  of
acid precursor air quality, since a  plausible mechanism for causality
does not exist.

Evidence for the following potentially  indirect health effects
associated with acidic deposition is discussed below:
(1) contamination of edible fish by  toxic materials,  principally
mercury; (2) leaching and corrosion  of  watersheds and  storage  and
distribution systems, leading to elevated levels  of toxic elements;
and (3) prolonged direct contact with acidified water  in recreation
settings.  In addition, a brief assessment is given on direct
inhalation of common pollutant classes  (i.e., photochemical oxidants,
acidic aerosols and sulphur and nitrogen oxides)  that  can be
associated with acidic deposition.
5.1.1   Contamination of Edible Fish

Some evidence suggests that acidic deposition may  alter  the
biogeochemical cycle of metals, including mercury  (Brosset and
Svedung 1977; Jensen and Jernelov 1972;  Schindler  1980;  Tomlinson
1978).  Poorly buffered waters in areas  remote  from  any  point  source
of discharge of mercury have been found  to  contain fish  with elevated

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                                                                  5-2
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levels of mercury.  Scheider et al. (1979) found that the mercury
content of walleye from 21 Ontario lakes was significantly higher  for          _
lakes where alkalinity was less than  15 mg/L (as CaCOo), as  opposed            •
to lakes with higher alkalinities.  According to Tomlinson et  al.
(1979), fish from poorly buffered lakes and rivers  in Quebec,  New
Brunswick, Minnesota, New York, and Maine also  contain elevated                I
mercury.                                                                       I

The mechanisms by which acidic deposition might increase fish  mercury          •
content are not known, but most likely involve  both biological and            I
chemical processes.  The principal forms of mercury of interest  are
elemental (Hg°), dimethyl mercury  ((CHo^Hg), mercuric mercury                 _
(Hg  ), and monomethyl mercury (CH-jHg"*).   Jensen  and Jernelov                  I
(1972), and several other investigators, have shown that  inorganic             ™
mercury can be methylated in both  aquatic  and terrestrial ecosystems.
One hypothesis that attempts to explain the relationship  between  pH           •
and mercury, holds that monomethyl mercury formation is at low  pH             |
( <7), while dimethyl mercury forms  at higher pH  ( > 7) (Jensen  and
Jernelov 1972; Tomlinson et al. 1979).  Dimethyl  mercury  has a  high           «
vapour pressure, is relatively insoluble,  and is  thus largely                  •
released to the atmosphere.  Methyl  mercury uptake  by fish in lakes           *
having higher pH regimes would thus  be minimized.   According to this
hypothesis, lakes with lower pH produce proportionately larger                 I
amounts of monomethyl mercury, which is efficiently taken up by               I
biota.  The reduced availability of  young  fish  containing low mercury
levels, and increased foraging activity by larger predator fish,  both          ••
characteristic of acidified lakes, would then increase the                    •
bioaccumulation of methyl mercury  in larger fish.   Recent
experiments, however, found a very poor correlation between mono- and          —
dimethyl mercury versus pH, calling  this hypothesized mechanism into          •
question.                                                                      ™

The processes leading to increased mercury burdens  in  fish are  likely          •
to be more  complex, including considerations  like the  complexity  of           p
the food chain, redox conditions,  inorganic and organic  sequestering
agents, watershed to lake area ratio (Suns et al. 1980),  as well  as           *m
the rate of atmospheric mercury input.                                         •

Although natural sources appear to contribute the major  portion of
atmospheric mercury (NRC 1978), emissions  from  coal combustion  can be          I
of significance on a regional scale.  Lindberg  (1980)  collected air           •
samples from a plume of a major coal-fired generating  station  and
found that  the mercury emitted was predominantly  in the  elemental             •
vapour phase, with very little conversion  to  particles  as the                  J|
distance from the source increased.   Due  to the nature  of the Hg, his
findings support the theory  that  the majority  of  Hg emitted during            _
coal  combustion is deposited regionally rather  than locally.   Since           I
the Hg is in the vapour phase, the major  route  of removal is  thought          •
to be via precipitation scavenging,  which  should  theoretically
increase in efficiency as  the pH  of  the precipitation falls.   Using           •
calculations from Brosset  and Svedung (1977),  Tomlinson  (1978), and           |
Brouzes et  al.  (1977),  it  is hypothesized  that  acid-containing
                                                                                I

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                                                                  5-3
clouds and rains should  effectively  remove  methyl mercury from the
atmosphere.  The surface of  acidified  lakes should also be an
effective sink for  the dry deposition  of  methyl  mercury.  Once
removed, methyl mercury  would  then be  more  likely to stay in solution
in acidified waters.  This scenario  is shown in  Figure 5-1, which
illustrates the distribution of mercury in  waters of three different
acidities.  Again,  recent evidence suggests that the process is much
more complicated (Barton and Johnson 1980).  These authors could
detect no dimethyl  mercury in  air from measurements taken at several
locations in Ontario.  Although a clear association appears to exist
between mercury in  fish  and  acidity  of lakes,  the mechanism by which
this phenomenon might be explained remains  obscure.  Although the
extent to which acidic deposition may  have  contributed to
mobilization or retention of mercury in fish is  speculative, fish
that are harvested  from  these  lakes  present a potential health hazard
to humans.

Presently the mercury content  of fish  tested in  the affected areas is
usually less than the U.S. FDA recommended  levels of 0.50  yg/g.  If
the situation is not changed,  it would be prudent to assume that the
mercury content of  fish  will continue  to  rise as lake pH drops
(Figure 5-2).

Another important factor is  that the bioaccumulation of mercury is
related to the species'  trophic level.  The larger pisciverous fish
are known to have greater concentrations  of mercury in the tissues
than the planktivors (Philips  et al. 1980).  These fish are also the
most prized sport fish,  and  make up  the majority of the yearly catch
eaten.  Little research  has  been directed at mammals inhabiting areas
of elevated mercury levels.  One study by Wren et al. (1980) suggests
that terrestrial species have  a demethylating process, which can
reduce the amount of toxic organic mercury  in their bodies.

With respect to human health,  elevated levels of mercury can lead to
serious disorders.  The  severity of  these ailments is usually related
to the exposure level to mercury.  This type of  disorder has been
reviewed in the past by  many authors including Chang (1977).
Generally the blood-Hg level for threshold  effects lies somewhere
between 100 and 200 ng/mL in a normal  adult,  but the maximum
recommended blood Hg level for pregnant females  is 20 ng/mL (NRCC
1979).

Epidemiological studies  have been completed in Canada which
investigated the health  of populations, especially natives, that were
exposed to increased concentrations  of Hg in food and had as a
result, elevated blood and hair Hg levels (Rudy  1980).  For example,
Rudy (1980) documented some  mild neurological abnormalities in adult
Cree men and an association  between  reflexes in  young Cree boys and
the concentration of methyl  mercury  in their mothers' hair during
pregnancy.  Due to  the lack  of accurate exposure modelling and many
shortcomings, it would be premature  to regard this work as an example
of a long-range transport of air pollution  associated problem.

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                                                                       5-4
      (CH3)2Hg
              .1
Sphagnum
  LAKE pH

  Mercury
  Concentration
  In  Fish
 <5.0
No Fish
3.5- 6.5
7.5-8.0
                                                          CaCO-:
0.5 -5.0ppm(mg/l)     0.1 —1.0 ppm(mg/D
   Figure 5-1.    Varying effects of  lake pH on the distribution of
                  mercury in ecosystems  (Tomlinson 1978).
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         200
         180
         160
       O)

       O)
         140
       DC
       I-
       Z
       LU
       O
120
       O 100
       O
       O  80
       DC
       LU
       ^.

          60
          40
          20
                  4.0
                 5.0
5.5
  6.0

PH
                                                                    5-5
                                                    A = 0.63

                                                     p<0.05
6.5
7.0      7.5
Figure 5-2.   Mercury in yearling yellow  perch and epilimnetic  pH
              relationships (Suns et  al.  1980).

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                                                                  5-6
However, an appreciation of  the  potential  risk of long-term exposure
to elevated levels of Hg in  food should  be maintained and careful
monitoring of the situation  should  continue to avoid any further
deterioration in health.
                                                                                I
                                                                                I
                                                                                I
5.1.2   Contamination of Drinking  Water                                        •

Acidic deposition can increase  the concentration of toxic metals in
drinking water by:   (1) increasing the  deposition of metal in soluble          V
forms (e.g., mercury);  (2)  leaching of  metals  from the watershed and           9
from sediments; and  (3) acid  corrosion  of  materials used in
reservoirs and drinking water distribution systems.                            •

Again, no clear evidence of health effects arising from the
consumption of drinking water contaminated with metals from acidic             A
deposition are reported in  the  literature, but some potential                  •
problems are identified.  In  New York State water from the Hinkley
reservoir has become acidified  to  such  an  extent, that lead
concentrations in drinking water at the tap exceed the maximum levels          •
for human use (50 Pg/L) recommended by  the New York State Department           •
of Health (Turk and  Peters  1978).

Fuhs and Olsen (1979) investigated drinking water in the Adirondack            •
region of New York State.   They found high metal concentrationns at
several test sites.  At one home with a water  pH of 5.71, copper and           ^
lead levels reached  6.6 and 0.10 mg/L respectively in a water line             1
which had not been used overnight.  In  another home which had a water          ^
pH of 4.95, copper concentrations  of 2.3 mg/L  were recorded from a
flushed line.  Both  of  these  homes obtained their water from shallow           •
wells.  The corrosive nature  of the groundwater was estimated using            |
the Langelier Saturation Index.  The results indicate that a large
portion of the water in the area is corrosive.  From their study,              •
Fuhs and Olsen (1979) concluded that high  concentrations of metals              •
are present in homes with metal piping  especially if the lines are
used intermittently.

Taylor (1982) has recently  reported some of the data obtained from             ™
an examination of surface and groundwater  drinking water supplies in
New England.  Utilizing the calcium saturation index and the                   tt
aggressive index as  indicators  of  water quality, he concluded that              |
raw water supplies in the region were generally very corrosive.  In
addition, many of the watersheds tested had a  very limited capacity            im
to withstand further acid input without deteriorating further.  An              •
analysis of past water  quality  records  for the area is proposed to
determine what increment of the acidic  conditions may be attributed
to acidic deposition.                                                           fl

A recent study completed for  the Department of National Health and
Welfare (Meranger and Khan  1982),  measured the leaching rates of
metals from the plumbing systems of cottages in central Ontario on
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                                                                  5-7
acid-sensitive lakes.  In addition, samples of tap water  taken  from
flushed and unflushed systems were analyzed for  Cu,  Pb, Zn  and  Cd.

Results from the leaching study indicate that the maximum rate  of
leaching occurs during the first 2 hours of water residence in  the
system, although levels do rise for up to  10 days.   The maximum
concentration of metals observed in the study resulted  from 10-day
static samples.  Maximum values of 4.56 mg/L, 0.478  mg/L, 3.61  mg/L
and 0.0012 mg/L were recorded for Cu, Pb,  Zn and Cd  respectively.
The concentrations of all metals decreased after flushing but still
remained above source levels.  This indicates that the  concentration
of metals are related to the contact time  in the distribution
system.

The cottage survey consisted of obtaining  tap water  samples from
standing and flushed supply systems for metal analysis.   The median
values recorded for static samples were 0.067 mg/L Cu,  0.014 mg/L Pb,
0.219 mg/L Zn and 0.0002 mg/L Cd.  As anticipated, the  metal
concentrations in the water decreased by up to 80% following
flushing.  There was only one recorded instance  where a sample
slightly exceeded federal guidelines (0.053 mg/L Pb), and this  value
was obtained from a standing water supply.

Based on these preliminary data, no immediate threat to human health
is perceived.  Careful monitoring of the situation should continue to
document any significant alterations in metal levels that may occur
in the future.

Consumption of drinking water with a low pH from municipal  sources is
not a major issue.  The raw water utilized by the treatment plant is
adjusted to drinking water standards by the addition of appropriate
substances.  The only health concern related to  this matter is  to
ensure that no excessive accumulation of cations (e.g., Ca2+)
develops as a result of the neutralization process.

Groundwater may also become acidified in poorly  buffered  areas
(Cronan and Schofield 1979).  For example, in Sweden some well  water
became so acidified that substantial corrosion of household plumbing
occurred (Hultberg and Wenblad 1980).  An  occurrence of this kind
could lead to increased levels of such metals as aluminum,  zinc,
copper, lead and cadmium in drinking water.

Many wells in the Precambrian area of Ontario are located in
proximity to shallow bedrock, so the potential for acidification
exists.  The first field surveys were carried out in 1980 in the
Muskoka-Haliburton area.  A total of 85 groundwater  samples were
field-tested, and 28 samples were analyzed in the laboratory for
major ions and some trace metals.  Groundwater was sampled  in July
from shallow springs and wells from both bedrock and overburden
formations.  Eleven of the 85 samples had  pH values  less  than 6.0
with the lowest value being 5.2.  October  sampling of five  of the low
pH wells resulted in only one sample with  a pH value less than  6.0,

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                                                                 5-8
5.1.4   Recreational Activities  in Acidified  Water
                                                                              I
                                                                              I
suggesting that groundwater pH may fluctuate during the year.  The
lowest recorded pH of 5.2 was from a shallow well servicing a
permanent home near Bracebridge, Ontario.                                     4
                                                                              I
5.1.3   Drinking Water From Cisterns

Sharpe et al. (1980) provide significant information on the  effects
of deposition of lead and cadmium as well as acidic deposition  on             M
the quality of drinking water from cisterns in Clarion County,                V
Pennsylvania.  Wet and dry deposition of lead and  cadmium  resulted  in        ™
solutions which were in the same order of magnitude as recommended
United States drinking water limits (50 Ug/L and 10 Ug/L                      I
respectively).  Lead levels in tap water from cisterns were  much              ™
higher than those found in the source water; about 16% of  the
households sampled had tap water levels in excess  of the United              •
States drinking water standard.  The investigators concluded that  the        f
increase in tap water lead levels resulted from acid corrosion  of  the
lead soldered joints in the cistern and plumbing.  Thus, cistern              _
water users are at special risk in areas of high acidic deposition.           •

There is a time dependence for the initiation of adverse health
effects resulting from drinking water contaminated with metals  at,  or        •
approaching,  the concentrations listed in Table 5-1.   For  example,            V
brief episodic excursions of lead over the recommended standard
associated with snowmelt derived acidity in water  from small lakes  or        *|
streams, is not likely to be of major concern.  Longer or  continual          •
consumption of water containing lead levels 25 pg/L could  be of
concern (NAS  1977c), although the actual standard  for  drinking  water
lead levels in the United States and Canada is  50yg/L.                       •
                                                                               I
Due  to  the increased  atmospheric  fallout  of  acids,  poorly buffered
bodies  of water  have  shown a decline in pH.   Some of these lakes and         ,_
rivers  have  attained  acidity levels in excess of the federal                 •
guidelines for drinking water of  pH 6.5 (NHW 1980).  As a result of           *
this  situation,  attention has been focused on the safety of these
affected waters.   There is concern that recreational activities in           •
these waters (e.g. ,  swimming) may prove to be detrimental to human            •
health.

However, the rationale  for the federal pH standard, which was                ^
accepted by  most provinces in Canada, is  based on corrosion and
incrustation effects, not on health considerations.  Generally metal
corrosion may become  a  problem when the water pH falls below 6.5 and          ,1
scale build-up on supply systems  is usually encountered above pH 8.5.         «
If an organ  system was  susceptible to the effects of acidified water,
then it is felt  that  the eye would be the most likely candidate.              •
This  possibility is  rather remote at best.                                    |
                                                                               I

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                           5-9
             TABLE 5-1.    CANADIAN AND UNITED STATES DRINKING WATER
                          GUIDELINES FOR TOXIC METALS ( yg/L)
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Canadian       United States
_           Lead                                     50               50
V           Mercury                                   1                2
™           Cadmium                                   5               10
             Copper                                 1000             1000
•           Zinc                                   5000             5000
•           Arsenic                                  50               50
             Selenium                                 10               10

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                                                                  5-10
1
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Doull et al. (1980) states that  acid-induced  eye  damage is a function
of pH and the capacity  of  the  anion  in question to combine with              «
protein.  Therefore the clinical  findings  may vary depending on the          •
concentration and type  of  acid under consideration.  Exposures to            '
mixtures of acids would be even  more complicated  to assess.  With
hydrochloric acid virtually no clinically  significant effects are            M
present above pH 3 while some  discomfort was  evident between pH 4.5          •
and 3.5.  Doull et al.  (1980)  and Grant  (1974) reported that in
normal rabbit eyes, only acid  solutions  below pH  2.5 produced any            M
significant eye injury  and in  humans brief contact of solutions from         J
pH 7 to as low as pH 2  caused  no  damage.   However, the subjects did
complain of "an increasingly strong  stinging  sensation" as the acid          ^
level increased.                                                              •

Due to the lack of scientific  data on this issue, the Department of
National Health and Welfare (Canada) is  funding research into                •
investigating the effects  of acidified water  on the eye.  The water          W
used in this work will  be  obtained from some  of the most severely
affected lakes in central  Ontario to simulate the worst possible             4
conditions a person may be subjected to.   Results from this study            •
are anticipated in mid-1982.   A  preliminary study by Basu (1981) has
indicated that there are no ocular clinical effects produced by              ^
short-term exposures to lake water with pH values as low as 4.6.             I
Based on all of the above  information it would seem unlikely that any        ™
ocular exposure to the  mildly  acidic waters in affected regions would
produce any harmful health effects.   However, a final conclusive             •
statement on this matter should  be reserved until the results of the         |
Health and Welfare study are complete.


5.1.5   Direct Effects;  Inhalation  of Key Substances Related
        to Long Range Transport  of Air Pollutants

Although no direct health  effects were associated with acidic                B
deposition per se, deleterious effects have long  been attributed to
inhalation of high concentrations of several  important pollutant             ^
classes that were implicated as  precursors to acidic deposition.             £
These include ozone and other  photochemical oxidants, acidic aerosols
and other particulate matter,  and oxides  of sulphur and nitrogen.            A
The effects associated  with these pollutants  led  to the establish-           •
ment of minimum air quality standards for  each pollutant in both the
U.S. and Canada (Table  5-2).   Extensive reviews of the health effects
literature were recently conducted for these  pollutants (e.g., NAS           jl
1977a,b, 1978; USEPA 1978, 1980,  1981, 1982;  WHO  1979).  These               •
reviews generally support  the  notion that  attainment of the respec-
tive air quality standards will  protect public health.  The reader is        ||
referred to these documents for  a comprehensive assessment of the            J|
effects literature.  The discussion  below is  intended only as a brief
summary of some aspects of interest.                                         —
                                                                               I

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5-11
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                                                                  5-12
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Ozone is a secondary gaseous  pollutant,  formed  as  a result of
photochemical reactions  of  volatile  organic  chemicals and nitrogen
oxides.  Therefore, the  formation  and  transportation of  ozone is             V
limited by the production of  NOX and suitable environmental                  Q
conditions.

Ozone is a deep lung irritant,  capable of  causing  death  from                 •
pulmonary edema in serious  cases.  Sublethal exposures produce
substernal tightness, irritation of  mucous membranes, dry cough, and
headache.  Morphological and  biochemical changes in the  lung are also        9
observed following exposures  to low  levels of 03.   In addition,               ™
extrapulmonary effects were documented.  Changes in the  circulating
red cells of animals exposed  to ozone  were reported.   Since 03 is            I
unlikely to penetrate the pulmonary  mucosa,  the alterations are               f
suggested to arise as a  result  of  a  chain  reaction when  various  free
radicals are formed (Goldstein  1980).                                         •

The effects of ozone are influenced  by factors  other than
concentrations and length of  exposure  and  young animals  are more
susceptible.  Elevated temperatures,  increased  relative  humidity and         f
exercise all increase the toxicity of  03 (Doull et al. 1980).  As            9
with other toxicants, the individual health  of  a person  has an effect
on the results.  People  with  respiratory disease (e.g.,  asthma,               JM
emphysema or bronchitis) are  believed  to be  particulary  sensitive to         £
low-level exposures.

Ozone produces eye, nose and  throat  irritation  in  the 0.1 - 0.15 ppm         •
range (Ferris 1978), and the  America Lung  Association (1977) states          *
that significant health  effects are  found  when  ozone levels are above
0.37 ppm.  Goldsmith and Nadel  (1969)  found  consistent increases in          •
airway resistance after  1-hour  exposures of  1.0 ppm,  while other             •
researchers found similar results  with lower 03 concentrations and
longer exposure times (Kerr et  al.   1975;  Young et al. 1964).                •

There is some controversy surrounding  the  possible synergistic
properties of 03 in combination with other pollutants.   Although             ^
evidence was developed that suggested  ozone  has an enhanced toxicity         M
when combined with S0£ (Hazucha and  Bates  1975; NRC 1975), recent            ™
studies have found no clear support  for  such synergism (Bedi et  al.
1979; Kleinman et al. 1981).                                                  fi|

One theory gaining some  acceptance deals with exposures  to low
concentrations of ozone  over  several days.   Ozone  is thought to  have         •
a short-term cumulative  effect  above a threshold value (Folinsbee            •
et al. 1980).  In consecutive exposure studies  a decrease in
pulmonary function is maximized during day 2-3.  Additional exposures        ^
result in a return to pre-exposure values  or an improvement in               •
pulmonary response on day 4-5 (Farrell et  al. 1979; Hackney et al.           ™
1977).  These results also  support the notion that some  form of
adaptation or tolerance  is  developed following  repeated  exposures.           •
This tolerance, however, may  be of limited duration and  dependent on         |
peak concentration. All  of  these experiments have  dealt  only with
                                                                              1
                                                                              I

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short-term responses,  and  the  consequences  of  biological changes
resulting in  tolerance are not known.   Specifically, more data is
required on chronic  or long-term exposures  in  view of,animal studies
suggesting increased susceptibility to infection, morphological
abnormalities and extrapulmonary effects (USEPA 1978).

In summary, brief exposures to ozone can be linked to alterations in
pulmonary function.   At low levels, 03 produces eye, nose and
throat irritation.   Based  on the available  quantitative evidence, the
established air  quality standards appear to be protective of public
health.  Ozone levels  achieve  maximum  readings from April to July and
the annual mean  concentration  exceeds  maximum  acceptable levels at
several locations, predominantly in eastern Canada (see Tables 4-6,
4-7).  The ozone air quality standards are  also exceeded in a number
of northern U.S. cities (Table 4-5).

Nitrogen oxides, among the photochemical irritants, are primarily
derived from  internal  combustion engines, and  NO is rapidly converted
to M>2 in the atmosphere.   A recent national air pollution survey
(Environment  Canada  1979)  indicates that N0£ concentrations are
highest from  January to July,  but concentrations do not exceed
existing Canadian guidelines.   Nitrogen dioxide, like ozone, is a
deep lung irritant and can produce pulmonary edema in severe cases.
Both short- and  long-term  exposures to N0£  enhance susceptibility
to infections.   There  is some  evidence that elevated levels of N0£
will produce  an  increase in respiratory disease (Florey et al. 1979;
Guidotti 1978; Speizer et  al.  1980),  but presently it is not clear
whether transient peaks of N0£ or long-term exposure to low levels
are primarily responsible  for  these observations.  The  levels of
N02 in Canada are relatively low and unless further information
becomes available, current standards  seem adequate to protect human
health.

Sulphur oxides (S02)  and related particulates  are also  respiratory
irritants.  An important feature of sulphur oxides are  their ability
to interact with other pollutants to  form substances that vary in
their respiratory instancy potential.   The  most prominent response to
inhaled S0£ is bronchial constriction  leading  to increases in flow
resistance.   Healthy individuals begin to respond to S02 peaks of
about 5 ppm while sensitive  individuals may respond to  short-term
exposures of  less than 1 ppm (USEPA 1981).

Various sulphate forms  have  also been  associated with increases in
pulmonary disease and  some concern has been raised over statements
linking airborne sulphates to  human morbidity/mortality (Lave and
Seskin 1973).  This  and other  investigations were reviewed by the
subjects and  from ill-defined  groups  that may  have confounding
factors (e.g., smoking  habits  and health problems) and  may lack good
exposure estimates and  contain uncertainties with respect to
statistical models.   This  limits the use of these studies for
assessing health effects of  specific pollutants.  At best, they
provide qualitative  support  for the association of sulphur-
particulate pollution  with health effects (USEPA 1981).

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                                                                  5-14
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As with nitrogen oxides, the levels of  SC>2 asssociated with
transboundary transport between the U.S. and Canada  are  relatively
low, and current standards seem adequate to protect  human  health.             I
However, some concern has been expressed about  regional  transport  of         •
sulphur containing fine particles  including sulphuric acid,  sulphates
and associated substances.  The effects of general particulate  matter        •
and sulphur oxides were reviewed recently by Ware et al. (1981) and           •
Holland et al. (1979) and are the  subject of a  revised EPA criteria
document (USEPA 1981) and staff paper  (USEPA 1982).  These reviews           _
suggest that it would be inappropriate  to single out sulphates  as  the        •
only significant component of the  sulphur - particle complex.   Until         •
ongoing standard reviews and perhaps additional research is  con-
ducted, it appears that attainment and  maintenance of the  current             I
U.S. and Canadian standards for particulate matter would provide             |
reasonable public health protection.   The U.S.  is considering  the
possibility of new standards based on  particle  size.  No changes in           A
the maximum acceptable levels for  suspended particulate  matter are           •
anticipated in Canada.                                                        *

In summary, to the extent that transboundary transport  contributes           •
significantly to violations of the air  quality  standards listed in           0
Table 5-2 (an issue  for Work Group III to resolve),  the  matter should
be the subject of the bilateral discussions.                                  fij


5.1.6   Sensitive Areas and Populations at Risk - Health                     ,_

Certain areas are sensitive to acidic  deposition resulting in                 ™
contamination of fish and drinking water  supplies.   These  include
areas with poorly buffered lakes and streams (with a viable  fish             11
population), watersheds with unusual accumulations of metals in              •
sediments or soils,  areas which lack drinking water  treatment
facilities, and areas with substantial lead plumbing.                         m

Some populations are more susceptible  to environmental  insults than
others.  These populations include those  dependent on  fish from
acidified waters as  a major dietary staple, those with  elevated              •
mercury or lead blood levels from  other exposures, those dependent on        W
cisterns as a primary source of drinking water, and  women  of
childbearing age as  well  as  children.
1

1
5.1.7    Research  Needs

Due  to  the  common areas  of  interest between the health effects and
aquatic sections, there  are also similar gaps in data bases and
research requirements.   For example,  work is required in the                  •
following areas:                                                               •

1.    Acidic  deposition  appears  to increase the mobilization of               •
      metals  from soils  and the  leaching rates in water distribution          •
      systems.  Therefore,  data  is needed to further clarify the
                                                                               I

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      levels, species, and  temporal  variations  of  these  metals and

      their effects on biological  systems.


2.    A data base needs  to  be  developed  that  will  enable researchers
      to identify sensitive areas  and  receptors in order to predict
      which regions have a  greater risk  of  developing health related
      problems.


3.    There is an apparent  relationship  between declining water pH
      and increasing Hg  levels  in  the  food  chain.   Therefore,  more
      data related to their exposure levels and Hg content in various
      species is needed.


4.    More research is needed  to differentiate  the health effects
      resulting from short-term exposures and long-term  exposures to
      pollutants subjected  to  long range transport.


5.    Carefully designed and controlled  epidemiological  studies are
      necessary in order to relate exposure to  various air pollutants
      to the health of susceptible individuals  as  well as the  general
      population.


6.    The relative contributions of  transported air pollutants that
      contribute to acidic  deposition  should  be determined.  The
      levels of these pollutants should  be  compared to the National
      Ambient Air Quality Standards.
5.2   VISIBILITY


This discussion is largely  adapted  from  a  recent  EPA staff assessment

(USEPA 1982).  The effect of  transboundary pollution on visibility is
directly related to air quality,  rather  than  deposition.   The
particulate phase precursors  to acidic deposition (mostly sulphuric

acid aerosol and various ammonium sulphate aerosols)  as well  as  other
fine particles play a major role  in atmospheric visibility.
Available data suggest that nitrates  exist predominantly  in  the
vapour phase and are for the  most part of  little  consequence  to
visibility in eastern North America.  For  some isolated point
sources, however, NC>2 may produce visible  brown plumes  at distances
of 100 km from the source (Menlo  1980).
5.2.1   Categories and Extent of Perceived Effects


Impairment of visibility is perhaps  the most  noticeable  and  best

documented effect of particles  in  current North  American atmospheres.
It is often equated with "visual range" as measured  by airport
weather observers.  However, visibility in a  broader context relates
to visual perception of the environment and involves colour  and
contrast of viewed objects and  sky,  atmospheric  clarity,  and the
psychophysics of the eye-brain  system  (USEPA  1979).

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                                                                  5-16
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For present purposes, it is useful to classify pollution-derived
effects on visibility into two categories:   (1)  regional  haze,  and
(2) visible plumes.  The nature and extent of these  effects  are              I
determined largely by the distribution and characteristics of                 •
anthropogenic and natural particles and, to  a lesser extent, by
N02•  Salient features of both categories are outlined  below.                 •

Regional haze is relatively homogeneous, reduces visibility  in  every
direction from the observer, and  can occur on a  geographic scale              _
ranging from an urban area to multistate regions.   Increased haze            •
reduces contrast causing more distant objects to disappear.  Nearby          ™
objects can appear "flattened" and discoloured,  the  horizon  sky is
whitened, and scattered light is  perceived as a  gray or brown haze            B
(Charlson et al. 1978).  When urban light and haze  combine at night,         |
the contrast between the night sky and the stars is  reduced, markedly
limiting the number of stars visible in the  night sky (Leonard  et al.        •
1977).                                                                        |

The best available indication of  the extent  and  intensity of regional
haze with time is visibility (visual range)  data routinely measured          •
at airports and some other locations. Some uncertainties arise  from          "
the use of such data to characterize regional visibility; among them
are differences in target quality and observers  between sites  and at         jfl
the same site, representatives of the airport location, and  potential        j|
biases in measurement techniques. Analyses  of  airport  visibility
trends from 1948 to  1974 suggest  that visibility in the eastern U.S.         _
declined over that period, particularly during  the  summer months             •
(Husar et al. 1980; Trijonis et al.  1978b).  The analysis of                 *
visibility trends has recently been  extended for this report by Husar
and co-workers (Husar pers. comm.) to include Canadian  and U.S. data         •
through 1980.  Figure 5-3 presents the results  of the preliminary            •
analysis.  This figure represents extinction weighted airport
visibilities for about 300 U.S.  sites and  177 Canadian sites (94 in          •
eastern Canada).  Sites were selected on the basis  of a reasonably           •
continuous record.   The airport  data  reflect 5-year quarterly  means
of noon extinction,  (3.9/visibility)  from  1950  to 1980 exclusive of
readings with fog, precipitation  or  blowing  material.  Because  the           •
figure represents average extinction, the  estimated visibility  as            W
derived from the indicated scale  is  weighted to lower than actual
average visibility on fog/precipitation  free days.   These data  are           -M
quite  preliminary and subject  to  the  usual  caveats  regarding airport         l|
visibility trends.   The U.S. results  appear  consistent  with  other
published data.  The  lower density  and  variability  of Canadian sites         ^
make regional representations  presented  considerably less reliable.          •
Differences exist between  some  features  in the  figure and other              *
examinations of specific sites in Canada;  these may be  related  to
site or to different  treatment.   Until  further  examination of  the            I
Canadian data is completed,  the  results  should  be treated with               •
caution (Christe pers. comm.).

The figures show eastern visibility  is  substantially less than that          •
in the west.  The unusual  area  of persistent low visibility in
                                                                              1

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                                                           QTR 2
           QTR 3
                             1/km

                              0.18-0.24


                              0.24-0.30

                              0.30-0.36

                                > 0.36
                                                           QTR 4
                                                          ENA  0.24

                                                          EUS  0.26

                                                          SURE 0.27
Figure  5-3a.   Seasonal  and spatial distribution of long-term trends

               in extinction - weighted  airport visibilities for North
               America,  1950-54 (after Husar pers. comm.).

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          QTR 3
                            0.24-0.30

                            0.30-0.36

                              > 0.36
Figure 5-3b.   Seasonal and spatial distribution of long-term trends
               in extinction - weighted  airport visibilities for North
               America, 1960-64 (after Husar  pers. cornrn.)-
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\   o.
            QTR 3
            ENA  0.28

            BUS  0.32

            SURE 0.33
                                                       QTR 2
                                                         QTR 4
 Figure 5-3c.  Seasonal and spatial distribution of long-term trends
               in extinction - weighted  airport  visibilities for North
               America, 1970-74  (after Husar  pers.  comm.).

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                                                                  5-20
          QTR 3
                                                         ENA 0.26
                                                         EUS 0.30
                                                         SURE 0.31
Figure 5-3d.  Seasonal and  spatial  distribution of long-term trends
              in extinction - weighted airport visibilities for North
              America, 1976-80  (after Husar pers. comm.)»
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                                                                  5-21
northern most Canada has  not  been  explained,  but may be related to
very high humidity  and  the  presence of  ice crystals and, in
wintertime,  reduced daylight.   It  is unlikely to be related in any
substantial  way  to  anthropogenic sources.   Moreover, the number of
sites in this large region  is  quite limited,  and may not be truely
representative of precipitation/fog free days.

Consistent with  earlier U.S. work,  Figures 5-3a,b and c shows that
while visibility in some  urban areas improved or stayed the same from
1950-74, the occurrence of  episodic regional  haze appears to have
increased in the eastern  U.S.  and  portions of southern and eastern
Canada.  Summertime (Quarter  3)  trends  are most  pronounced in these
areas.  Since 1972, regional  visibility in eastern Canada (Figure
5-3d) and in both the east  and west of  the U.S.   apparently has
improved slightly but not to  pre-1960 levels  (Marians and Trijonis
1979; Sloane 1980). Whether  this  recent improvement is related to
more favourable  meteorology or reduced  regional  particle and sulphur
oxide emissions  is  not  known with  certainty,  but such reductions are
reflected in emissions  inventories  in both east  and west.

Regional differences in average  U.S. visibility  are illustrated in
Figures 5-4  a and b.  As  indicated  by suburban and nonurban airport
data, visibilities  in the east are  substantially lower than in most
of the west.  Some  of the differences between east and west may be
related to the lower regional  humidity  in  the west, but a more
important difference is the generally higher  regional particle
loading in the east.  Based on:   (1) long-term historical data in the
northeast from 1889 to  1950 (Husar  and  Holloway  1981);
(2) examination  of  airport  visibility trends  after deleting data
possibly influenced by  obvious natural  sources (i.e., fog,
precipitation and blowing dust)  (Figure 5-3); and (3) current
assessments  of natural  sulphur sources  and regional fine particles
levels (Ferman et at. 1981; Galloway and Whelpdale 1980; Pierson
et al. 1980;  Stevens et  al.  1980), anthropogenic particulate
pollution would  appear  to dominate  eastern regional haze.  Relying on
the analysis of  Ferman  et al.  (1981), it has  been estimated that in
the absence  of anthropogenic sources summertime  visibility in the
Shenandoah Valley would range  between 60 and  80  km (36-50 miles)
(USEPA 1981).  The  median daytime visual range actually observed
during the 1-month  study  at this site was  four to five times lower (9
miles).

Visible plumes of smoke,  dust, or  coloured gas obscure the sky or
horizon relatively  near their  source of emission (USEPA 1979).
Black, gray, or  bluish  plumes  are  caused by particles.  Brownish
plumes may be caused by N02 or particles.   Perception of plumes
(and regional haze) is  strongly  influenced by factors such as viewing
angle, sun angle, and background objects (USEPA  1981).  Because
visible particle plumes often  are  subject  to  opacity regulations and
because they are usually  quite localized in character, the focus here
will be on urban and larger scale regional haze.

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  15
    25
Figure 5-4.
                                                                 10"
Median 1974-76 visibilities (miles) and visibility
isopleths for suburban/nonurban airports: (a) yearly,
and (b) summertime (Trijonis and Shapland 1979).  Data
are subject to uncertainties associated with suburban
airport observations, but show general regional
patterns.  The clear differences between east and west
are parallelled by regional humidity and nonurban fine
particle levels.  Summertime fine mass averaged from 22
to 25 yg/m3 at 12 eastern nonurban  sites (Watson
et al. 1981) and about 4 pg/m3 for  40 Rocky Mountain
and southwest background sites (Snelling 1981).
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5.2.2   Evaluation of Visibility

Visibility impairment may adversely affect  public welfare  in
essentially two areas:  (1) the subjective  enjoyment  of  the
environment (aesthetics, personal  comfort and well-being), and
(2) transportation operations.  The aesthetic aspects  of visibility
values can be categorized according to:  (1) social/political
criteria, community opinions and attitudes  held  in  common  about
visibility; (2) economic criteria, the  dollar cost/benefit associated
with visibility; and (3) psychological  criteria,  the  individual  needs
and benefits resulting from visibility.  These categories  are not
exclusive, but relate to different approaches for measuring somewhat
intangible values.  Evidence on visibility  effects  is  drawn from
studies of social perception and awareness  of air pollution,  economic
studies, and visibility/air transportation  requirements.   These
studies are summarized in Table 5-3 and  evaluated briefly  below.
5.2.2.1   Aesthetic Effects

Assessment of the social, economic  and  psychological  value  of  various
levels of visibility is difficult.  The criteria  document,  an  EPA
report to Congress (USEPA 1979), Rowe and  Chestnut  (1981),  and Fox
et al. (1979), discusses and evaluates  several  approaches  that have
been used or proposed towards  this  end.  In  particular,  preliminary
studies of social awareness/perception  and the  economic  value  of
visibility in urban and nonurban areas  support  the  notion  that
visibility is an important value in both settings.

Early social awareness studies  (DHEW  1969; Schusky  1966; Wall  1973)
conducted in polluted urban areas have  generally  shown  that at higher
pollution levels an increasing  portion  of  the population is aware of
air pollution and considers it  a nuisance.   In  St.  Louis,  a linear
relationship was observed between annual particle levels (50-200
yg/m  TSP) and public awareness and concern.  At 80 ug/m  annual
geometric mean TSP, about 10%  of those  surveyed reported air
pollution as a nuisance (Schusky 1966).  Although it  is  reasonable to
attribute more of these and other perception results  to  particulate
matter than to gaseous pollutants (Barker  1976; Wall  1973),  the
relative importance of visibility degradation by plumes  and haze  as
compared to dustfall was not clearly  addressed  in these  studies.   A
more recent study of perception of  air  pollution  in Los  Angeles
(Flachsbart and Phillips 1980)  represents  the most  comprehensive
evaluation of major pollutant  indicators and perception  to  date.
Five gaseous pollutants (0^, CO, N02, NO,  S02), four  particle
related indices (TSP, dustfall, CoH, visibility) and  six averaging
times were compared with perceived  air  quality  as reported  by  475
respondents living in 22 residential areas in Los Angeles  County.
Only two indices, visibility and ozone,  were consistently
significantly related ( a = 0.001)  to perceived air quality for all
averaging times.  The highest  correlation  coefficient (Kendall's  T )
occurred for yearly visibility  ( T= -0.29) and  for  number  of days

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5-24




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visibility was  less  than  3 miles  (  T = 0.32).a  Of the other
particle indices,  only monthly  average dustfall was significantly
correlated ( T  =  0.12) with  perception.  Consistent with other
studies, the survey  also  found  that air quality is valued less by
minority groups and  long-time urban residents than by whites (all
income classes) and  those with  some history of rural residence.

The two major approaches  to  economic valuation of visibility include:
(1) survey (e.g.,  iterative  bidding),  and (2) property value studies.
The major published  iterative bidding studies of visibility,
conducted in the  rural southwest  and in the Los Angeles area (South
Coast Air Basin),  are summarized  and evaluated in Table 5-4.  The
Four Corners and  Lake Powell studies deal only with single sources
and visible plumes,  while  the Farmington and Los Angeles studies
address haze.   The preliminary  nature  of these studies makes them
useful primarily  as  qualitative indicators of the economic value of
visibility.  Among the more  important  limitations of the published
results are the following:

1.   None of these studies has  measured existence values (benefit of
     just knowing pristine areas  exist, regardless of intent to use
     them) or options values (wish  to  preserve the opportunity to
     view an unimpaired vista).  Rowe  and Chestnut (1981) suggest
     that existence  values of good  visibility in natural settings may
     be significantly greater than  measured activity values.

2.   The studies  may be subject in  varying degrees to methodological
     problems.  The  Farmington  study,  in particular, discovered a
     number of  biases probably  related to the credibility of the
     contingent market.  These  biases  were not always large but show
     the difficulty  of valuing  visibility through iterative bidding.

3.   Even if the  available results  could be taken at face value, so
     few studies  have been conducted that results cannot be directly
     transferred  to  other areas of  the country.  For example, it
     might be expected that  willingness to pay for improved
     visibility in Los Angeles  might be greater than that for areas
     in flat terrain without background hills or mountains.

Despite their limitations, the  iterative bidding studies suggest that
visibility is of  substantial economic  value in both urban and natural
settings.  Although  the value of  visibility in other areas may vary
significantly from that suggested by studies in the rural southwest
and Los Angeles,  no  a priori reason exists to suggest that visibility
is of little value in heavily populated eastern urban and rural
areas.  With respect to recreational settings,  of the 23 most heavily
used national parks  and monuments,  11  were in the East (NFS 1981).
In 1979 over 90 million visits  were recorded in all eastern National
Park Service managed facilities.
a Kendall's  T  is a nonparametric  statistic.   The negative
  correlation between the number of  people  perceiving poorer air
  quality and visibility and  the positive  correlation with the number
  of days visibility is less  than  3  miles  are  consistent with
  expectations.

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                                                                                             5-26

TABLE 5-4.  SUMMARY RESULTS OF  ITERATIVE  BIDDING VISIBILITY STUDIES (after Rowe and Chestnut 1982)
I

Design Elements/Study (Year)


Total Interviews Conducted
(Percents Usable)
Scenarios

Four Corners
NM (1972)b



1,099 (69?)
Emissions, strip
minings, trans-
Lake Powel I
UT/AZ (1975)c



104 (79?)
Air Qua I ity and
Power Plant
Farmington
NM (1977)d



130 (92%)
Air Qua 1 ity and
Power Plant
South Coast
Air Bas in
CA (1978)e



345 (NR)
Air Quality
and Health
-•





1

                               mission  lines,
                               single  power  plant





Payment Vehicle





Wi 1 1 ingness to Pay Bid
Comparisons
a) Yearly bids for
individual resi-
dents households
b) Dai ly bid for
individual rec-
reation ists min.
$1.00
c) Aggregate Yearly
Value




Tested for bias/found
biases


Comment on Total Values
















Capital letters refer to
for going from scenario A
b Randal 1 et al . 1974
<: Brookshire et at. 1976
d Rowe et al. 1980
e Brookshire et al. 1979

A-worst

B-midd le
C-best

User fees/
Electricity Bill






A-Ca $85
B-C $50
A-B
~


A-B $15.54 M
A-C $24.57 M




No/No



Values for total
affected four
corners region;
attributed mostly
to part iculate air
pol 1 ution reduc-
tion at single
source, but
difficult to
separate from
other visible
factors due to un-
standardized
scenarios.
Measured activity
values only.


scenarios listed above
(worst) to scenario C




A-No plant

B-Plant, no plume
C-Plant with plume

User Fees







__


A-C $2.95


A-B $.414 M
A-C $.727 M




No /No



Examined one of
fifteen potentially
affected parks;
pictoral represent-
ations not con-
sistent across A-C.
Measured activity
val ues onl y.









. Thus "A-C" in the
(best).




A-Visibi lity 120 km

B-Visibi lity 80 km
C-Visibi lity 44 km

Utility Bil I/
Payrol 1 Reduction
User Fee





A-Da $82
A-B $57
B-D $43
A-D $2 .44


A-B $1.47 M
A-C $1 .99 M
A-D $2.14 M
B-C $1.1 M


YesAes



Val ue for San Juan
County, New Mexico
and Mavajo recrea-
tion area only.
Affected area up to
10 times larger
strategic bias not
found, but other
bias problems with
contingent market
found. Measured
activity values
only.





A-Poor Visibi lity-W
2 mi les
B-Fair Visibi lity-^
12 miles "•
C-Good Visibi lity«
28 miles
Utility Bil I/ •
Monthly Payments »
to Conservation
Fund ^.
1
•
Pi

A-Ca $245 •
B-C $243 •
A-B $174
1
w

30? i mprovement •
•
$.58 - $.65 B



res/ res



About one-th ird
of benefits are
related to •
aesthetics, 1
two-thirds to •
health. Resu Its
reasonably con- _
sistent with •
companion pro- £
perty value
study. Measured
user values. •
Some question- B
naire design 9
biases related
to aesthetics. —
I
i
Four Corners case refers to the bids









1

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                                                                  5-27
A large number of property value studies  related  to  air  quality have
been conducted.  These have been reviewed  by  Freeman (1979a,b)  and
Rowe and Chestnut (1981).  Although a variety of  air quality
indicators have been used, the results  of  awareness/perception
studies strongly suggest visibility plays  an  important  role  in  air
quality related impacts on property values (Rowe  and Chestnut 1981).
This contention is best documented in the  case of the South  Coast  Air
Basin property value survey (Brookshire et al. 1979).  There, the
estimated annual benefit of a 25-30% improvement  in  air  quality based
on property values was about $500 U.S.  per household.  These results
are qualitatively similar to the companion iterative bidding study
(about $300 U.S./household).  The bidding  study suggests that 22-55%
of the bids to improve visibility were  related to aesthetic  effects.
Both the bidding results and the perception study (Flachsbart and
Phillips 1980) conducted in the same area  support the possibility  of
substantial impacts of visibility on Los  Angeles  area property
values.

None of the other published property value studies are  accompanied by
companion studies that suggest what portion willingness  to pay  for
improved air quality may be due to visibility.  Moreover,  theoretical
problems remain in relating willingness to pay functions from
property value differentials (Rowe and  Chestnut 1981).   No single
study has examined all of the variables that  might be important in
influencing property values.  Because air  pollution  tends  to be a
small influence compared to other variables,  earlier studies that
examined a limited number of variables  are particularly suspect.  In
essence, the available literature suggests that perceived  air
pollution, and hence visibility, may have  tangible effects on
property values in urban areas such as  Washington, Boston, Los
Angeles, and Denver (Rowe and Chestnut  1981);  nevertheless,
additional theoretical and empirical work  is  needed  before reliable
and transferable quantitative relationships for visibility evaluation
can be established.

5.2.2.2   Transportation Effects

Although all forms of transport may be  affected by poor visibility
(e.g., slowing of highway traffic by anthropogenically  induced  fog),
at current ambient levels, aircraft operations appear to be  most
sensitive.  When visibility drops below 3  miles,  both U.S. FAA  and
Canadian safety regulations restrict flight in controlled  air spaces
to those aircraft and pilots that are certified for  operation under
Instrument Flight Rules (IFR) (FAA 1980a). The most severe  impact in
such cases is usually on non-IFR general  aviation aircraft which are,
in effect, grounded or forced to search for alternate landing sites.
In 1979, there were about 210,000 active  general  aviation  aircraft
which accounted for about 84% of total  airport operations  in the U.S.
Over 23% of all general aviation aircraft  had no IFR capability
(Schwenk 1981).  Estimates of the percentage  of pilots  certified for
IFR in the U.S. and Canada are not available.   Commercial, military,
and other IFR aircraft operation also may  be  affected by reduced

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                                                                  5-28
I
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visibility.  Under IFR conditions, the number of arrivals and depar-
tures per hour can be significantly decreased as compared to Visual
Flight Rules (VFR) conditions.  The effect varies with airport, and           •
in some cases, the visual range cutoff for the most efficient visual          |
approaches (VAPs) may be 5 miles  (FAA 1980b).  For example, the per-
formance standard for one configuration at Boston Logan  International         «
Airport is 109 operations per hour for VAPs  (5 miles), 79 operations          •
per hour for "basic" VFR (3-5 miles), 79 operations per  hour for              ™
"controllers" visual approach IFR (2-3 miles), and 60 operations  per
hour for "category I" IFR (2 miles).  Thus,  depending on airport              I
configuration, schedules, and the extent and duration of haze induced         m
visibility reduction, delays in commercial and other aircraft opera-
tions can occur.  In large segments of the eastern U.S., midday               •
visibilities less than 3 miles with no obvious natural causes occur           •
2-12% of the days in the summer and 1-5% of  the time during other
seasons (USEPA 1981).  Visibilities less than 5 miles would, of               _
course, be more frequent.  Based  on typical  eastern summertime                H
diurnal cycles in humidity and light scattering (e.g., Ferman et  al.          ™
1981), the occurrence of morning  visibilities (6-8 a.m.) less than
3-5 miles would be somewhat greater than for midday visibility, even          A
discounting naturally occurring fog.                                          |

Compared with other modes of transport, air  travel is generally               «
considered to be safe.  It is not, however,  riskfree; based on                •
reasonable expectations and the available record, air pollution
visibility impairment would tend  to increase risks of aircraft
operation  (U.S. Senate 1963).  Failure to see and avoid  objects and           •
obstructions during flight is one of the ten most frequent cause              W
factors for general aviation accidents (FAA  1978).  Another important
cause factor is continued VFR flying into adverse weather.  Although          •
such action is normally attributed to errors in judgment (FAA  1978),          |
in some cases, pilots who by choice or necessity fly in  the mixing
layer, could fail to distinguish  storm fronts or thunderclouds from           ^
the prevailing haze until they are upon the  adverse weather.  The            •
available  data in the criteria document do not, however, permit any           ^
quantitative assessment of the risks to commercial and general
aviation aircraft operation associated with  reduced visibility.               ft

The available information of the  effects of  visibility on
transportation suggests that episodic eastern regional haze tends to          •
curtail substantial segments of general aviation aircraft and  slow            •
commercial, military, and other IFR operations on the order of 2-12%
of the time during the summer.  The extent of any delays varies with
airport.   Reduced visibility may  also tend to increase risks                  •
associated with aircraft operations in the mixing layer, but                  ™
quantitative assessments are not  available.
                                                                              I
5.2.3   Mechanisms  and  Quantitative  Relationships

The mechanisms  by which atmospheric  pollutants  degrade perceived              •
visibility  are  reasonably  well  understood  (Friedlander 1977;
                                                                               I

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                                                                  5-29
Middleton 1952).  Visibility impairment is the result of  light
scattering and absorption by the atmospheric aerosol  (particles  and
gases).  The "extinction" or attenuation coefficient  (oext)  is
a measure of aerosol optical properties and is the  sum  of blue sky of
Rayleigh scattering by air molecules  (tfRg), absorption by
pollutant gases (oag), and particle  scattering  (aSp)  and
absorption ( aap).  Visibility is inversely related to  total
extinction from these sources.  Blue  sky scattering is  relatively
constant and is significant only under relatively pristine
conditions.  Absorption by pollutant  gases, notably NC>2,  usually
contributes only a small amount to total extinction (USEPA 1981).
Even brown hazes in Denver and Los Angeles formerly attributed solely
to N02, are often dominated by particles (Groblicki et  al.  1980;
Husar and White 1976).  Thus atmospheric extinction and visibility
impairment are normally controlled by particulate matter.  Important
causes include natural sources (e.g., fog, dust, forest fires, sea
spray and biologic sources) and anthropogenic sources of  sulphur
oxide, soot and other particles, nitrogen oxides, and volatile
organics (USEPA 1979).

Reduction of visual range by particle extinction is normally  domin-
ated by fine particles.3  The only important exceptions are some
naturally occurring phenomena including precipitation,  fog, and  dust
storms, where larger particles control visibility.  Theoretical
calculations show that extinction/unit mass efficiencies  are
substantially greater for fine particles in the  0.1 to  2.0 size  range
than for larger particles (Faxvog and Roessler 1978).   For most
commonly observed size distributions  of particulate matter, the
increased extinction efficiency of fine particles results in  fine
particles accounting for most of total extinction even  though they
are only a third or so of the total mass of particles (Latimer et al.
1978).  This theoretical expectation  is borne out by  the  unique
experiment of Patterson and Wagman (1977) where  independent
measurement of light scattering and particle size distributions
verified the importance of fine articles in controlling scattering in
New York City.  In addition, a number of experiments  have found
consistently high correlation (0.8 to 0.98) between light scattering
and fine mass (USEPA 1981).

The relative importance of scattering and absorption  as well  as  the
extinction efficiency per unit equilibrated mass (y ) of  fine
particles varies with location.  On large regional  scales, about
80-95% of particle extinction is due  to light scattering  (Waggoner
et al. 1980; Wolff et al. 1980), with the remainder due to
absorption.  In urban areas absorption may account  for  up to  50% of
particle extinction (Waggoner et al.  1980; Weiss et al. 1978).   The
particle scattering efficiency/unit mass varies  from  about 3-5
at various sites, with higher values  tending to  occur in eastern
locations (USEPA 1981).
a For purposes of this document,  fine particles  include  those
  smaller than 2.5 ym AED.

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                                                                  5-30
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The variations in fine particle extinction noted above are due
largely to variations in size, chemical composition and  to some
extent, relative humidity.  Based on theoretical (Faxvog and Roessler         •
1978) and empirical (e.g., Groblicki et al. 1980;  Stevens et al.              |
1980;  Trijonis et al. 1978 a,b) results, two components, hygroscopic
sulphates and elemental carbon, generally tend  to  be most                     _
significant.  Sulphate, with associated ammonium,  and hydrogen ions           •
and water, often dominates regional fine mass and  extinction,                 ™
particularly in the East, while elemental carbon accounts for most of
the particle absorption observed in urban areas.   The relative                flj
importance of sulphates to extinction depends on relative humidity,           I
both at the site in question and perhaps along  the transport path
where secondary formation occurs.  Project VISTTA  found  that                  •
sulphates formed in dry desert air were of relatively low light               •
scattering efficiency, compared to sulphates apparently  formed in
more humid conditions in southern California and transported to  the           _
desert (Macias et al. 1980).  Our understanding of the role of fine           •
organics and nitrates in light scattering is hindered by the lack of          ™
reliable data.  In the eastern regional haze these components are
likely to amount to less than half of the sulphate component, but may         ft
dominate scattering in western urban areas such as Denver and                 ||
Portland (Cooper and Watson 1979; Groblicki et  al. 1980).  The
remainder of fine mass (soil-related elements,  lead and  trace                 •
species) contributes only a minor amount to extinction in most U.S.           B
atmospheres (Stevens et al. 1978).

Humidity is important to visibility because of  the presence  of fine           •
hygroscopic aerosols (e.g., sulphates) which tend  to absorb                   ™
atmospheric water and thus increase light scattering.  Measurements
in several areas suggest that the extinction due to fine particle            •
scattering will increase by a factor of about  two  as relative                 |
humidity is increased from 70% to 90% (Covert  et al.  1980).  Based on
laboratory studies, reduction in humidity from 90% to 70% might  not           ^
produce corresponding decreases in scattering  because of hysteresis           fl
(Tang  1980).  In essence, the hysteresis effect means that  the                *
aerosol may tend to retain water absorbed at higher humidities even
at lower relative humidities.  This effect has  not yet been                  •
demonstrated to occur in the ambient air.                                     £

Through the Koschmieder equation, the extinction  coefficient,                 •
measured or estimated from fine particle levels, may be  used  to               •
estimate visual range  (USEPA  1979).  The relationship has  the  general
form:
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                                                                  5-31
                                   a ext
     Where:  V = the visual range, the distance at which a  large
                 black object is just visible against  the sky.


          0ext = total extinction, the sum  of light  scattering
                 and absorption by air molecules, fine  particles,  and
                 N02.


             K = a function of the intrinsic target  brightness  and

                 observer threshold contrast (E).  E is a function of

                 the observer and of target size.


Although a number of factors may limit the  applicability of this
relationship, for homogeneous pollution,  reliable extinction
measurements, uniform illumination, large dark targets, and moderate
visual ranges, agreement between experiment and theory  is rather
good.  The correlation between visual range and the  scattering
portion of extinction is typically on the order of 0.9  where
comparisons have been made (USEPA 1981).


This relationship depends, in part, on human perception of  contrast
as well as target size and brightness.  For a typical  observer  with a
reasonable time for observation and large black targets, a

"threshold" of 0.02 is commonly assumed with K = 3.9 (USEPA 1979,
1981).  Empirical determinations of K have  yielded somewhat lower
values, ranging from 1.7 to 3.6 for studies discussed  in the EPA
criteria document (USEPA 1981).  The most complete analysis (Ferman
et al. 1981) reported a value of 3.5 for  well mixed  periods.  The
lower values likely arise from higher threshold contrasts,  nonideal
targets, (too bright and/or too small), and the exclusion of
absorption estimates.  The available data also suggest  that reported
airport visibilities may significantly underestimate standard visual

range.  Thus lower values of K may be more  appropriate for  matching
airport data with higher values for observations in  natural setting.


The relationship between extinction due to  dry particle scattering
and fine mass is sufficiently stable over a wide range  of areas that
reasonably quantitative estimates of fine/particle visibility
relationships can be made where long-term relative humidity is  low
(<70%) and particle absorption is small or  otherwise known.  For  such
purposes,  the Koschmieder relationship can  be written  as:


                         V =        K	             (2)

                              CTag + aRg +  FMC

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                                                                  5-32
Where FMC = fine mass concentration,  and


       •Y  = (°ap +°Sp)/FMC
           a ag = absorption  by  gases  (usually small in nonurban
                 areas)
                                                                          I
                                                                               •

           o ap = particle  absorption  coefficient  (in units of
                 inverse distance;  e.g.,  km~l)                                 •

           o" s p = particle  scattering  coefficient

           ° Rg = Rayleigh  or  "blue  sky  scattering"                             |
                 (Rg~ 0.12 km"1)
                                                                          I

                                                                          I
Thus , with appropriate K and Y  derived  from available  studies ,  visual
range can be estimated from fine mass.   Although less  certain,  the
measurements of Covert et  al.  (1980)  and regression relationships             A
developed by a number of investigators  can  be  used  to  estimate  fine           •
particle/visibility  relationships  for higher humidities  and
hygroscopic aerosols.  The criteria  document indicates that to
correct for the humidity effect  (as  determined by heated                      •
nepholometers and equilibrated  filters), the amount should be                 W
increased by a factor of about  1.5 at 80% RH,  and about  2 at 90% RH.
The Koschmieder relationship  strictly applies  for short-term                  •>
observations.  In estimating  long-term  (e.g.,  annual)  average                 •
visibility from long-term  fine  mass  data,  the  temporal distribution
of fine particle concentrations  (e.g.,  lognormal) must be specified,          ^
or median values used.                                                         •

Figure 5-5 presents  fine particle/visual range relationships for
three cases selected as representative  of the  range of normal                 B
situations encountered in  the  eastern North American regional haze            •
and in western urban areas:

1.    Y= 3 m2/g; representative  of a dry aerosol, (USEPA 1981)  at             •
             .  Absorption may  be  10% of extinction where
              mass =2.7 m^/g.   This  is close  to typical
                                                                               _
    measurements in western  areas  but  below most  eastern data (USEPA          •
    1981).                                                                     •

2.    Y= 6 m^/g; representative  of the same aerosol as in 1)  at 90%           fl
    humidity,  a sp increased by  a  factor  of 2.                                 w
3.    Y=  10 m^/g; representative  of  the  similar aerosol,  but with             •
    absorption accounting for  40% of  extinction.   Such high                   •
    absorption (predominantly  associated with carbon)  is  likely only
    in urban areas.
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                                                                   5-33
    50
40
   30
z
<
DC
—
>
   20
    0
                              VISUAL RANGE=3.9/^ext
                       	 CASE 1 = AEROSOL <50%RH(3m2/g;

                       	CASE 2= AEROSOL 90%RH (6m2/g)

                       	CASE 3 = AEROSOL 90%RH(10m2/g
                                                                              30
                                                              25
                                                                              20
                                                              15  E
                                                                              10
                 25          50          75          100

                        FINE  MASS CONCENTRATION  (MQ/ m3)
                                                125
                                                                         150
   Figure 5-5.
Visual range as a function  of  fine mass concentration
(determined from equilibrated  filter) and Y , assuming
the "standard" K = 3.9.   Because  K is commonly lower in
nonideal application,  results  from this relationship
should not be compared directly to airport  visibility
data.

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                                                                  5-34
 1.  Analyses  of  the  contribution of transported air pollution to
    visibility  impairment by the modeling work groups.

 2.  Further work on  the  value of visibility in the Eastern North
    American  context.
I
I
Each case may actually be representative of a variety  of aerosols.
For example, case 2 closely approximates the aerosol observed  by
Ferman et al. (1981) during their month long study  in  the  Blue Ridge          •
Mountains, even though typical .daytime humidities were less  than  70%.         |
In this study corrected   y = 5.5 m  /g as measured by heated
nephelometer and when the measured  effect of condensed water is              •
added,  y increases.  Thus, even though 90% RH  is comparatively rare          •
during the daylight hours, case 2 is likely to  be closer to  typical
summertime eastern conditions  than  is case  1.

Figure 5-5 shows the powerful  effect of humidity and carbon                   •
absorption on visual range for a given particle level.  The  curves
also indicate that visibility  becomes more  sensitive to changes to            ]•
fine particle levels below about 100-200 yg/m. Results from  this            j|
figure should not be compared  directly with airport visibility data.
Due to non-ideal targets  and observation conditions, airport                 «
visibilities will tend to be lower  than predicted by the Koschmieder          •
relationship with K = 3.9.                                                    •

When background fine particle  concentrations are understood, the              ft
Koschmieder equation can  be used to relate  predicted sulphate  levels          |
to resulting visual range.  Available nonurban  summertime  fine
particle data are summarized in Figure 5-6.  Actual impacts  must  be           •
derived from the results  of regional modelling  runs provided by              •
Workgroup II.  If the results  of the model  are  to be "tuned" to
airport visibility data,  K in  the Koschmieder  equation should  be
2.9 -  3.5 and y for eastern conditions should  be 6-8 m /g.                   •


5.2.4   Sensitive Areas and Populations                                       •

Clean  areas such as found in western North  America, are the  most
sensitive to visibility degradation.  In the U.S.,  the Clean Air  Act           «
affords special protection to  visibility in 156 'Class I'  areas,               •
including national parks  and wilderness  areas.   Many  of these  Class  I
areas  are located near the U.S./Canada border  and one  (Roosevelt-
Campobello) in Canada.  However, any area,  urban or rural, with              •
normal viewing distances  of a  mile  or more  may  be affected by                •
episodic regional haze, carrying acid  precursor substances.


5.2.5   Data needs/Research Requirements

The following instruments are  required to  complete  work related to           •
the effects of atmospheric deposition  on visibility:                           •
I

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5-35
    CU
 UH
                 S-i
                 3

                 O
                 c
                 t)0
                 3.
                 0)

                 Q)
                 o
                •H
                 §,

                 0)
                 c
                 0>
                 e
                •H
                 3
                CO
                 bo

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                                                                 5-36
3.  Continued analysis of regional North American visibility data to
    further elucidate reliability of data and implications for
    anthropogenic contribution.
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                                                                 5-37
5.3  REFERENCES


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                                                                 5-38
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Ferman, M.A.; Wolff, G.T.; and Kelly, N.A. 1981.  The nature and                •
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Ferris, B.C. 1978.  Health effects of exposure to low levels of                 •
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                                                                                I

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Freeman, A.M., III.  1979a.  The benefits of  environmental
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                                                                  5-40
Guidotti, T.H. 1978.  The higher oxides of nitrogen .'inhalation
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Hackney, J.D.; Linn, W.S.; Mohler, J.G.; and Collier,  C.R.  1977.
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Hultberg, H. , and Wenblad, A. 1980.  Acid groundwater  in southwestern          •
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Husar, R.B., and Holloway, J.M.  1981.  Visibility Trend at  Blue Hill,          |
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Husar, R.B.; Patterson, D.E.; Holloway, J.M.; Wilson,  W.E.; and                •
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Jenson, S. , and Jernelov, A.  1972.   In Mercury contamination  in  man            _
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Latimer, D.A.; Bergstrom, R.W.;  Hayes, S.R.; Liu, M.K.;  Seinfeld,
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                                                                                I

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Lave, L.B., and Seskin, E.P.  1973.  An  analysis  of  the  association
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Leonard, E.M.; Williams, M.D.; and Mutschlecner, J.P. 1977.   The
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Lindberg, S.E. 1980.  Mercury partitioning in  a  power plant plume  and
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Marians, M., and Trijonis, J. 1979.  Empirical studies  of the
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Mayfield, 1980.  Methylation  rates in sediments.  M.Sc. Thesis,
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Menlo, O.T.  1980.  Presented at the Symposium on Plumes  and
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Meranger, J.C., and Khan, T.H.  1982.   The impact of lake acidity  on
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                                                                  5-42
     Branch, Health  and Welfare  Canada,  Ottawa,  Ont.
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National Health  and Welfare  (NHW).  1980.   Guidelines for Canadian
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National Park Service  (NFS).  1981.   National parks statistical
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National Research  Council  (NRG).  1975.   Photochemical air pollution:
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_ .   1978.  Mercury  in  the  environment .  National                  •
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Patterson, R.K., and Wagman, J. 1977.  Mass  and  composition of an
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Philips, G.R.; Lenhart, T.E.;  and  Gregory, R.W.  1980.   Relation                 mm
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Piersen, W.R.; Brachaczek, W.W.; Truex, T.J.; Butler, J.W.;  and                 ™
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Rowe, R.D.; d'Arge, R.C.; and  Brookshire, D.S. 1980.  An experiment
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Schindler, D.W.  1980.  Experimental acidification of a whole  lake.
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                                                                  5-44
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Tomlinson, G.H.; Brouzes, R.J.P.; McLean,  R.A.N.;  and Kadlecek,  J.
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Trijonis, J., and Shapland, R. 1979.   Existing visibility  levels in
     the U.S.:  isopleth maps  of visibility  in suburban/nonurban
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Trijonis, J.; Yan,  K.; and Husar, R.B.  1978a.  Visibility  in the
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     Environmental  Protection  Agency,  Research Triangle  Park, NC.              «

	.  Visibility in  the northeast:   long term  visibility
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Turk, J., and Peters,  N.E. 1978.  Presented  at Public Meeting on Acid         •
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U.S. Environmental  Protection  Agency  (USEPA). 1978.   Air quality              ~
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                                                                                I
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                                                                  5-45
	.   1982.  Review of  the  national  ambient air quality
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Waggoner, A.P.; Weiss, R.E.;  Ahlquist,  N.C.;  Covert,  D.S.;  and
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Ware, J.; Thibodeau,  L.A.; Speizer,  F.E.;  Colone, S.;  and  Ferris,
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Watson, J.; Chow, J.C.; and Shah, J.J.  1981.   Analysis of  inhalable
     and fine particulate matter measurements.EPA Contract #

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Weiss, R.E.; Waggoner, A.P.;  and Charlson,  R.J.  1978.   Studies  of the

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Wolff, G.T.; Groblicki, P.J.; Cadle, S.H.;  and Countess, R.J. 1980.
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Wren, C.; MacCrimmon, H.; Frank, R; and Suda,  P.  1980.   Total and
     methyl mercury levels in wild  mammals  from  the Precambrian
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     Contam. Toxicol. 25:100-105.


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     Physiol. 19:765-768.

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           SECTION 6

EFFECTS ON MAN MADE STRUCTURES

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                                                                  6-1
                              SECTION 6
                   EFFECTS  ON MAN-MADE STRUCTURES
6.1   INTRODUCTION

Previous  sections of  this  report  have  focused  primarily upon the
effects of pollutants on sensitive  receptors in remote wilderness
areas.  In this  section, the  receptors (i.e.,  man-made structures)
are usually co-located with the pollution  sources.   The distinction
between the effects of pollutants from near or intermediate sources
(i.e., 10's to perhaps 100 km away)  and from distant sources (i.e.,
100's to  perhaps 1000's of kilometres  away) is difficult if not
impossible to make.  This  is  particularly  the  case  when local primary
species,  S02 for example,  oxidize to secondary products (SO/p")
at a nearby site which is  also receiving SO^- from distant sources
of primary S02 which has oxidized during its atmospheric residence
time.  In most cases, the  atmospheric  load from local sources tends
to dominate the  low concentrations  arriving from remote sources
upwind.

In the context of material deterioration,  the  distinction between
local and distant sources  may be  academic  since damage in general
would be  reduced through a reduction in concentration of the major
agents, regardless of the  distance  these pollutants traveled to the
deposition site.

Consideration of damage will  be limited to exterior surfaces, not
only because the wet deposition of  pollutants  and surface wetting is
primarily limited to exterior surfaces, but also because the
concentrations of corrosive species  are usually much higher outside
than inside buildings.  Textiles  and fabrics are usually associated
with confined environments and are  beyond  the  scope of this section.

Although  the economic consequences  of  material deterioration due to
air pollution are discussed elsewhere  in this  report (see Section
8.5), this section contains a brief  description of  some of the
attempts which have been made to  quantify  damage in economic terms
and the inadequacies of these assessments.  For sulphur dioxide,
perhaps the most important corrosive agent, direct  costs of
duplication, replacement or protection of  certain materials can be
approximated.  Before the  economic  implications can be adequately
addressed, a better understanding is needed of the  dose-response
relationships of materials to different pollutants, of the
distribution of materials, and of the  replacement and maintenance
factors.

In this section, there is  discussion of the effects of four types of
pollutants; S02, N0£ and 03,  NH3,  and  particulates  on four classes of
materials; metals and alloys, coatings, masonry, and elastomers.

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                                                                  6-2
There are several quantitative examples  of  calculated  erosion and
corrosion of materials over  time.
6.2   OVERVIEW
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All building materials degrade  to  some  extent  with time,  even in the          |
absence of air pollution.  Hence,  it  is important  to  differentiate
between expected weathering, and accelerated deterioration                    •
attributable to air pollutants.  There  are  reviews available of the           •
weather factors affecting  the corrosion of  metals  (Ashton and Sereda
1981; Sereda 1974) and the durability of stone (Julien 1884),
concrete (Maslow 1974), and polymers  (Eurin 1981).  In northern               •
climates, deterioration effects due  to  atmospheric pollution may be           •
masked in winter by the impact  of  road  deicing salts  (CaCl2 and/or
NaCl), which damage porous masonry and  are  particularly corrosive to          •
metals.  As noted above, the assessment of  deterioration, due to              f
pollutants transported over long distances,  is confounded by the
impact of pollution produced locally.                                          _

The apparent chemical/physical  degradation  processes  resulting from           *
interactions of materials  with  pollutants and  naturally occurring
atmospheric constituents have been reviewed in the literature                 B
(Benarie 1980; USEPA  1978, 1981a,b;  Yocom et al.  1982).  A number of          V
field studies estimate the relationship between deterioration and
atmospheric deposition without  full  environmental  characterization of         •
the test sites, including  measurement of meteorological and air               •
quality variables.  Laboratory  tests  have also been used to quantify
materials damage from pollutants.  However,  quantitative
relationships derived from chamber tests cannot be used directly to           •
predict damage to exposed  materials.                                           ™

At the outset it must be acknowledged that  the objective assessment           •
of the response of materials to corrosive agents  cannot provide               |
adequate estimates of "loss" resulting  from deterioration of
historic materials.  Monuments must  be  distinguished  from other               •
structures because here the net loss  by deterioration embraces                I
aesthetic and historical contributions  where monetary scales may not
apply.  Trade-offs made in mitigating the impact  of air pollutants
should address the preservation of the  qualities  that constitute the          •
significance of the monument.                                                  ™

The architectural and sculptural expressions of our two heritages are         •
a precious nonrenewable resource.  Historic structures and monumental         J[
statuary represent the most visible  aspects of historical and
cultural evolution.   In the United States,  legislative recognition of         •
the value of this cultural heritage,  giving a  mandate for its                 •
preservation, began in 1906, with  the passage  of  the  Antiquities Act,
and continues to this day, with the  passage of the Historic
Preservation Act Amendments of  1980.  The 1916 Organic legislation of         •
the National Park Service  gives a  mandate for  the  conservation of             •
"...'historic objects' .. .to provide  for the enjoyment of the same in
                                                                                I

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                                                                  6-3
such a manner  and by  such  means  as  will leave them unimpaired for the
enjoyment  of  future generations."

In Canada, there is similar  legislation.   For example,  the
Archeological  Sites Protection Act  was enacted in 1953, the same year
the Historic  Sites and  Monuments Act  was  adopted.

Studies of the economics of  damage  due to air pollution are contained
in papers  by Haynie (1980a),  Yocom  and Upham (1977),  Spence and
Haynie (1972),  Waddell  (1974), Liu  and Yu (1976), Yocom et al.
(1981), and Yocom et  al. (1982)  among others.  In these instances,
dose-response  relationships  were obtained by relating the
concentrations  present  in  the atmosphere  to the degree  of damage
observed or measured.   As  an example, a report released by the
Organization  for Economic  Cooperation and Development (OECD 1981),
indicates  that  for the  eleven European countries studied, based on an
expected production of  24.4  million metric tons of SC>2  in 1985, the
resulting  benefit of  a  50% reduction  in 862 emissions would be of
the order  of  $1.16 billion per year in terms of reduced damage.  In
this case, the  benefit  is  based  on  corrosion of a limited number of
metals and excludes masonry  and  coatings  since no exact dose-response
relationships  are available  between deposition of sulphur compounds
on these materials and  deterioration  rates.  The loss due to the
impoverishment  of cultural heritage is not assessed.   As noted
earlier, the more difficult  task of relating this damage to human
response (i.e., replacement,  substitution or protection) has not yet
been completed  and will be more  fully discussed in subsection 6.8.
6.3   MECHANISMS AND  ASSESSMENT  OF  EFFECTS

The quantitative expression  of a relationship  between exposure to a
particular pollutant,  and  the  type  and  extent  of the associated
damage to a specific material  is known  as  a  dose-response relation-
ship or a damage function  (Hershaft 1976).  The damage function
should express a quantitative  cause-to-effect  link (Benarie 1980).
A significant mathematical correlation  between a measured damage and
an ambient pollutant  concentration  is not  sufficient proof of a
causal relationship.   Because  a  particular kind of damage may also
occur in the absence  of  the  pollutant(s),  the  damage function should
explicitly describe the  incremental effect attributable to the
pollutant(s).  Moreover, in  some cases  for metals, a certain minimum
dose or threshold value  is required before an  effect is observable
and at high doses a saturation level may also  be observed.

6.3.1   Factors Influencing  Deposition

The relation between  concentration  of pollutants in ambient air and
in precipitation and  the amount  of  pollutant delivered to a
material surface is known as the deposition  velocity.   Deposition is
a two-step phenomenon  beginning  with delivery  of the pollutant to the

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                                                                  6-4
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surface controlled by aerodynamics and followed  by  pollutant  -
material interaction.  Gaseous deposition velocities  can  be  as  rapid
as 0.021 - 0.6 m/min (Judeikis 1979).  However,  large  variations  are         •
found in measured deposition velocities  (McMahon and  Denison  1979).           |
This scatter is in part due to intrinsic properties of materials  and
in part due to extrinsic  factors  (e.g.,  surface  moisture,  wind  speed         •
and temperature).                                                             •

Acidic deposition can occur on materials under both wet  and  dry
conditions.  Under wet conditions, the aqueous form of the pollutant,        I
(e.g., sulphuric acid) reacts with the material  in  question  to  form          •
reaction products.  These products may be either more or  less soluble
than the original material.  The  detailed kinetics  of these  reactions        •
are not well known and variations in  reactions may  occur  due  to the          •
surface conditions of the material and the  presence of additional
chemical species.                                                             _

Deposition may also occur under dry  conditions.   In theory,  a gaseous        •
pollutant such as S02 or  NOx can  react directly with  metals  and
masonry without going through an  aqueous phase (Torraca 1981a;  Van           •
Houte et al. 1981).  As a practical  matter, the reactions in the             |
environment always involve the presence  of  humidity.   Consequently,
reaction rates have not been studied under  completely dry conditions         •
(Haynie and Upham  1974; Judeikis  and Stewart 1976;  Spedding  1969).           •
It is assumed  that dry deposition reactions do in fact involve an
intermediate stage where  the gaseous  pollutants  are oxidized in the
presence of available surface moisture and  proceed  to attack the             •
materials in aqueous form. The major distinction between this kind          •
of deposition  and what is termed  wet deposition is  that in the latter
the moisture involved comes only  from precipitation.   Dry deposition          •
involves all sources of moisture  other  than precipitation.                    f

These other sources of moisture include  surface condensation, which           _
occurs under certain conditions  of  relative humidity, dew point, and          •
surface temperature.  There may also be  internal condensation arising         •
when warm, humidified indoor air  attains the dew point within a
cooler masonry wall (ICOMOS  1967;  Torraca  1981a; Winkler  1975).               •
Groundwater wicked up through masonry walls by capillary action is            |
another source for moisture  in masonry walls  (Melville and Gordon
1973).  Porous materials  (e.g.,  stone,  brick and concrete) may retain         •
significant amounts of moisture  in the  pores even during prolonged            •
spells  of  dry  weather.

Surface moisture  has a  strong  influence  on deposition velocities.             •
It has  also been  suggested that  the  rate-limiting step for deposition         ™
of pollutants  may  be the  atmospheric transport processes  that
controls the delivery of  gases  through  the  quasi-laminar boundary at          •
the  surface  (Hicks  1981).  These  transport  processes  would increase           |
with increased local wind speed  (Lawrence  1962).
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                                                                  6-5
Particulate matter  on  the  surface  can also affect the deposition
velocity.  Hygroscopic particulates like marine salt tend to
increase the time the  surface  is wet (Fassina 1978).  Elements
commonly found  in particulates (e.g., iron,  manganese, and copper)
have been identified as serving as catalysts in the oxidation of
S02 to S042~ (Hegg  and Hobbs 1978).

The condition of the surface itself will also influence the
deposition velocity.   A material  that has been exposed for a
significant amount  of  time may show a deposition velocity different
from the initial one (Judeikis 1979).  In the case of most metals,
iron being the  notable exception,  a tight layer of reaction products
(e.g., oxides,  carbonates  and  chlorides) will form on the surface
giving some degree  of  protection.   In stone, however, the coating of
reaction products remains  porous  and the rate of attack does not
decrease (Van Houte et al. 1981).   In fact,  it may increase as the
effective surface increases (Judeikis and Stewart 1976) or as the
greater roughness increases the atmospheric  transport processes
(Hicks 1981).

Exposure specifications such as the siting of a structure or a
material's position in a structure must also be considered.  The most
important condition is the exposure of the material to rain.  In
addition to providing  an aqueous medium for  acidic attack, the runoff
of rain water serves as a major agent in the dissolution and removal
of weathering products.  For example, it has been observed on the
Acropolis in Athens and at the Field Museum in Chicago that the
marble has reacted  with S(>2 to form an even  layer of calcium
sulphate.  This layer  several  centimetres thick remains intact on
some surfaces that  are not washed  by rain while on other parts of the
structure washed by rain,  the  layer does not exist (Gauri 1979;
Skoulikidis et  al.  1976).

The rate of deposition will increase with increased wind speed.
Although primarily  determined  by  the prevailing climate at the
location, the wind  speed at a  given point on a surface can be
influenced by the orientation  of  the structure, architectural
details, and by other  buildings in the vicinity (BRS 1970; Kotake and
Sano 1981; Lacy 1971).  For example, wind speeds around a building
will vary with height  and  increase at corners and over cornices (Lacy
1971).  The corrosion  rates for galvanized wire and fencing are
almost double that  of  galvanized  sheet, indicating the influence of
the geometry of a material on  wind speed (Haynie 1980b).  Erosion of
materials by wind-borne abrasive  particulates may also be significant
at some locations.  Finally, wind  will cause rain to fall on a slant
rather than perpendicularly to the ground.  Thus it will drive
rainfall onto vertical surfaces that otherwise would remain dry
(Marsh 1977).

Finally, the conditions of thermal exposure  will vary around a
structure.  This occurs depending  on compass orientation, angle from
vertical, and shading.   Each part  of the structure will receive

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                                                                  6-6
6.3.2   Effect of Sulphur Dioxide Pollutant/Material Interactions
                H2S04  +   Zn  5=^  ZnS04   +  H£(gas)
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differing amounts of solar radiation,  thus will  show  differing
ranges in diurnal temperature cycles.  Temperature  cycles  are  also a
function of each material's thermal  response  characteristics.                   •
Man-made sources of heat, either within  a building  or from nearby              "
sources will also modify the local thermal environment.  Ranges  in
thermal conditions influence the atmospheric  transport processes, as
well as moisture content of material surfaces and  thus,  deposition
velocities.
I

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There is general agreement  in  the  literature  that  S0£  is  the                   B
primary species causing damage  to  materials exposed to the                     •
atmosphere (Boyd and Fink 1974; Barker  et  al.  1980;  Kucera 1976;
Mansfeld 1980; Mikhailovskii and Sanko  1979;  OECD  1981; Yocom and              •
Upham 1977).                                                                    |

6.3.2.1  Zinc

The specific S0£ reactions  that cause metal corrosion  are not                  •
fully understood.  Some of  the  possible mechanisms involved have  been
discussed (Benarie 1980; USEPA  1981a).   For the  relatively simple              •
case of zinc, the overall reaction is                                           B

                    S02 + Q£ +  Zn   ^  ZnS04                                    «

Since ZnSC>4 is soluble and  readily lost from  surfaces  exposed to
rain, a protective surface  film is not  formed.   In cases  where the
S02 is converted to acidic  sulphate prior  to  reaction  with the                 •
zinc, the expected reaction would  also  result in the same soluble              B
zinc species
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Since the corrosion  rate  for  zinc  is   high for solutions having a pH
less than about 5  (Pourbaix 1966),  many acidic species are expected             B
to cause the corrosion of  zinc.  For  the case  of precipitation, it              ™
should be noted that  the  annual  average pH for most of eastern North
America is below 5 (see Figure 2-4).                                             B

In a recent publication (Haynie  1980b), data from six different
studies for the atmospheric corrosion of zinc  were reevaluated with             •
respect to the following  relationship:                                           B

                      Cz   =   ATW  +  BTWS02              (1)                    _

          where  Cz  = zinc corrosion  in micrometres                             ™
                 TW  = time of wetness in years
                S02  = average concentration of SC>2 in I'g/m-^                     B
            A  and  B  = regression coefficients.
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                                                                  6-7
The results of the coefficients evaluation  (Haynie  1980b) are  shown
in Table 6-1.


As is typical for many atmospheric  corrosion  tests,  intercomparisons
between studies are subject to many problems  due  to  differences  in
test objectives, techniques, and available  environmental monitoring.
In the studies examined by Haynie (1980b),  the  time  of  wetness was
calculated in one of three ways: (1) by  using the average  relative
humidity employing a previously evaluated empirical  equation
(Cavender et al. 1971; Haynie et al. 1976); (2) by  using the total
time the relative humidity exceeded 85%  (Haynie et  al.  1976) or  90%
(Mansfeld 1980); and (3) by using a "dew-detector"  (Guttman 1968;
Guttman and Sereda 1968).  The average concentration of S02 was
determined by using continuous instruments  (Haynie  et al.  1976;
Haynie and Upham 1970; Mansfeld 1980) using lead  peroxide  techniques
(Cavender et al. 1971; Guttman and  Sereda 1968) or  both (Guttman
1968).  In spite of the experimental differences,  it is apparent that
S02 is an important cause of degradation of zinc.   The  B
coefficient is lower for the chamber study  than for  the field-
determined values (Haynie et al. 1976).  While  this  difference was
attributed (Haynie 1980b) to a lower gas velocity in the chamber
compared to the field studies, it has been  suggested (Yocom et al.
1982) that the higher values reported for the field  studies may  be
the result of the combined effect of S02 and  particulate matter
containing sulphates, chlorides, nitrates and other  anions.  The low
B coefficient determined in the St. Louis study (Mansfeld  1980)  may
also indicate that lower particulate levels result  in lower S(>2
corrosion rates.  The tacit assumption being  made here  is  that during
the test period the particulate levels in St.  Louis  were low.


Haynie (1980b,c) has demonstrated that the  average wind speed  has an
important influence on the S02 deposition velocity  and, hence, the
corresponding corrosion rates for zinc.  Also,  the  deposition
velocity has also been shown to be  dependent  on geometry.   For
example, the corrosion rate for galvanized  wire and  fencing has  been
shown (Haynie 1980b) to be approximately twice  that  of  galvanized
sheet exposed to the same environment.   Since the lead  peroxide
method was used to determine total  sulphur  (as  SC>2)  in  two  of  the
studies (i.e., Cavender et al. 1971 and  Guttman and Sereda  1968  as
shown in Table 6-1), those values would  be  expected  to  be
wind-velocity dependent (Lynch et al. 1978).   In  contrast,  the SC>2
values measured by continuous instruments should  be  independent  of
wind velocity.  The possibility that this wind-dependence  affected
the SC>2 coefficients should be considered before  such data  are used
for any damage function calculations.


6.3.2.2  Steels


A number of atmospheric exposure studies have been  conducted for
steels (see reviews cited at beginning of Section 6.2). Only a  few

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                                                                  6-8
Table 6-1.  EXPERIMENTAL REGRESSION COEFFICIENTS WITH  ESTIMATED
            STANDARD DEVIATIONS FOR SMALL  ZINC  AND  GALVANIZED STEEL
            SPECIMENS OBTAINED FROM SIX EXPOSURE STUDIES
   Haynie and Upham (1970)    1.15+0.60    0.081+0.005      37


   Mansfeld (1980)            2.36 +  0.13    0.022  + 0.004     156
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                              A             B          Number  of
       Reference           ym/year    ym/(g/m3)year    Data  Sets           •



Cavender et al. (1971)    1.05 + 0.96   0.073 +  0.007     173              •

Guttman (1968)              1.79            0.024        large

Guttman and Sereda (1968) 2.47 _+ 0.86   0.027 _+  0.008     136              I

Haynie et al. (1976)      1.53 + 0.39   0.018 +_  0.002      96

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                                                                  6-9
studies have  been  conducted where simultaneous air quality and
deposition measurements  have been made.   In general the corrosion
rate for uncoated  low-carbon steels has  been found to depend on
S02 concentration  and exposure  time .   For example , in one study
(Haynie and Upham  1971)  the following relationship was developed


          Cs  =  9.013  [eO.00161  S02] [ (4. 768t)0-7512 - 0.00582 OX] (2)


          where Cs = corrosion  in micrometres

                t  = exposure in years

                S02 = average concentration of S02 in y g/m^

                OX = total  oxidants in yg/m^ (see discussion of

                     ozone  below) .


In this study,  similar expressions  were  developed for a weathering
steel.  Although humidity effects  were not determined,  the humidity
was approximately  the same  at all the sites used.  In another study,
Haynie and Upham (1974)  reported a similar functional dependence
          Cs = 325 tl/2 exp[0. 00275  S02  -    >]                (3)


where RH is the  relative  humidity.   In this case, oxidants were not
measured.  Equations 2 and 3 both  indicate that the corrosion rate
increases with S02 concentration but  decreases  with exposure time.
Equation 3 predicts very  low corrosion rates for low humidity,
regardless of the S(>2 level.   However, at high  humidity the steel
would corrode even in the absence  of  S02-  Although equations 2 and
3 may give a correct description of  the  interaction of S02 with low
carbon steels, they have  little  relevance, since virtually no steels
of this type are unprotected in  the  environment.   However, studies of
this material have proven useful in  estimating  the relative
corrosivities of various exposure  sites.   Even  in the case where a
painted steel begins to rust,  equations 2 and 3 probably do not
accurately describe the corrosion  occurring.


For a weathering steel, a material normally left uncoated, Haynie and
Upham (1974) reported a relationship  of  the form shown in equation 2,
with a lower S02 coefficient and a slightly different time
dependence.  On  the other hand,  studies  by Copson (1945), Cramer
et al. (1980), and Suzuki et al. (1980),  found  that sulphur
incorporated into the film improved  the  corrosion resistance for a
weathering steel , and that this  sulphur  could be related to the
average S02 level in the local environment.  The amount of copper
and tin in the steel has  been  shown  to influence its corrosion
resistance in sulphur containing atmospheres (Cramer et al . 1980).


6.3.2.3  Copper and Copper Alloys


Copper and its alloys are among  the  most  durable materials for
exterior exposure because they form  protective  patinas.  The pH

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                                                                  6-10
6.3.2.4  Aluminum
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value of precipitation is probably  a  significant  factor  determining
the development of basic carbonates and/or  oxide  protective  patina
(Guttman and Sereda  1968; Mattsson  and  Holm 1968).   Below pH of about         I
4, the protective coating may be  rapidly  dissolved  exposing  the bare          "
metal (Allaino-Rossetti and Marabelli 1976;  Gettens 1964;  Pourbaix
1966).  It is noteworthy that the mean  annual  pH  of precipitation is          •
near 4 in portions of northeastern  United States,  southern Ontario            |
and Quebec (Figure 2-4).  The presence  of S02  in  the atmosphere
appears to accelerate the formation of  the  green  patina  (Mattsson and         _
Holm 1968), normally desired on architectural  copper surfaces.                 •
Analysis of the patina of the Statue  of Liberty,  for example,                  ™
indicates that it is predominately  copper sulphate, with less  than 1%
of copper carbonate  and copper chloride (Osborn 1963).   Exposure              I
tests indicate that  the most uniform  patina forms  on unalloyed                 •
copper.  The presence of alloying elements,  primarily tin and  zinc
for bronze and brass, respectively, interferes with patina formation          •
and thus lowers corrosion resistance  of the alloy (Scholes and  Jacob          •
1970; Walker 1980).
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There are no quantified damage  functions  reported for aluminum,
although some evidence exists for  both  S02~induced damage                      •
(Benarie 1980) and  for particulate-assisted S02  pitting damage                 |
(USEPA 1981a).  Sulphur dioxide may  also  play a  role in
stress-assisted corrosion  problems for  aluminum  (Gerhard and Haynie            •
1974; Haynie et al.  1976).                                                      •

Several relatively  new aluminum and  aluminum-zinc coated steels  have
become available  commercially in  the past few years.  While no                 •
damage functions  have been reported, these coatings have been shown            •
to offer superior performance to  galvanized steels, with improvement
in service  life by  a factor of  from  two to four  times in marine,               •
rural and industrial environments  (Zoccola et al. 1978).  These                 |
coatings will have  a great influence on future materials selection
and on estimates  of  future damage  cost  related to coated steels.               _

6.3.2.5  Paints                                                                 •

A few investigations, which have  been reviewed in several recently             I
published documents, have  studied  the effects of gaseous pollutants            m
on the performance  of exterior  coatings (USEPA 1981a; Yocom et al.
1982).  Several of  these  studies  have shown that S02 can penetrate             •
into the paint film (Svoboda et al.  1973; Walsh  et al. 1977).                  •
Holbrow (1962) found sulphites  and sulphates to  be present after the
absorption  of S02 by the  paint  film.  In more recent studies, the
high erosion rate observed for  oil base house paints was associated            •
with the loss of  calcium  carbonate,  an extender  pigment of the paint.          •
These controlled  studies  involved  the exposure of several types  of
paints to atmospheric pollutants  under a prescribed dew-light cycle
(Campbell et al.  1974; Spence et  al. 1975).
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                                                                  6-11
A clear mechanism for the deterioration  of  coatings  by wet or dry
pollutant deposition cannot  be  derived from these investigations.
However, it is apparent  that moisture on the painted surfaces plays
an important role by collecting pollutants,  especially SC>2, and
thereby forming an acidic aqueous media  that facilitates reaction
with the paint film.


The study of Spence et al.  (1975) is the only investigation for
which pollutant dose-response relationships  have  been derived.
Linear regression relationships were developed for two types of
coatings:


   Oil Base     E = 14.3 +  0.0151 S02 +  0.388 RH        (4)


   Vinyl Coil   E = 2.51 +  1.60-10~5 x RH x S02        (5)


          where E = erosion  rate in ym/yr


              SC>2 = average  concentration of SC>2  in yg/m^


               RH = relative humidity  in percent.


The oil base household paint was found to have a  higher erosion rate
which was strongly correlated with  the concentration of S02 and
relative humidity.  However, the rate  is more sensitive to changes in
the humidity than S02.   For  the vinyl  coating, the S02 effect is
statistically significant but contributes less than 5% to the film
erosion rates at ambient levels of  concentration.  These functions
were obtained under controlled  conditions of simulated sunlight and
high temperatures and  should not be  applied directly to ambient
conditions.


Table 6-2 provides examples  of  material  loss in one year due to a
range of sulphur dioxide concentrations  and specific values of the
other variables contained  in equations  1 to 5.  The table is intended
to provide an indication of  corrosion  rates for a range of conditions
which might be encountered  at sites  throughout North America.


6.3.2.6  Elastomers


A chamber study has been conducted  in  which samples of auto sidewall
tires were exposed to  two  levels (0.1  and 1.0 ppm) of 03, S02 and
NC>2.  The tires were not found  to be  affected by S02 (Haynie
et al. 1976).  Observations  of  S02  damage to elastomeric materials
have not been reported  (USEPA  1981a).


6.3.2.7  Masonry


Masonry materials are  porous inorganic substances including stone
and man-made composites  such as brick, terra cotta, concrete,

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                                                                                           6-12
TABLE 6-2.   EXAMPLES OF MATERIAL LOSS IN ONE YEAR, L  IN  Urn USING EQUATIONS 1 TO 5 AND
             TYPICAL AMBIENT VALUES.
(A)
(B)
(C)
(D)
(E)
Zinc
Steel
Steel
Paint
Paint
(Low carbon)
(Weathering)
(Oil base)
(Vinyl)
L2
Lsl
Lsw
Lpo
Lpv
= 1.79
= 9.013
= 325 +
= 14.3
= 2.51
Tw + 0.024 TwS02
EXPI 0.0016 S02)
i EXPI 0.0027 5 SO
+ 0.0151 S02 + 0.
+ 1.60 10 x RH
[4.768°-7512-0-005820X]
1.63.2 ,
2 RH
388 RH
x S02
(Eq.
(Eq.
(Eq.
(Eq.
1)
3)
4)
5)
S02 Pg/m3 a
                                 10
25
40
55

(A)b


(B)c


(C)d


(D)e


(E)f

Tw = 0.05
= 0.1
= 0.2
OX = 0.05
= 0.50
= 1.00
RH = 40
= 60
= 80
RH = 40
= 60
= 80
RH = 40
= 60
= 80
0.102
0.203
0.406
27.84
27.72
27.60
5.65
22.01
43.44
29.97
37.73
45.49
2.516
2.520
2.523
0.120
0.239
0.478
28.52
28.40
28.27
5.89
22.93
45.27
30.20
37.97
45.72
2.526
2.534
2.542
0.138
0.275
0.550
29.22
29.10
28.96
6.14
23.90
47.17
30.42
38.18
45.94
2.536
2.548
2.561
0.156
0.311
0.622
29.93
29.81
29.67
6.39
24.91
49.16
30.65
38.41
46.17
2.545
2.563
2.580
    a  S02 concentrations are highly variable within urban areas but  normal ly  He within the
       range 10 to SOyg/ntj depending on city size and  industrial activity.


    b  The coefficients  1.79 and 0.024 are used for  Illustration purposes and  lie within the
       ranges given  In Table 6-1.  Note the high degree of dependence on wetness as well as
       S02 concentration.  Wetness values are approximation  for south central  (0.05), central
       (0.1) and coastal (0.2) sites in North America.


    c  The function  depends upon S02 concentrations, as stated  In the text  above, but appears
       to be not strongly dependent on OX.  In this  example  OX  Is taken to  mean Oj wtth
       values given  being representative of concentrations In clear air (0.05), smoggy air
       (0.5) and episodes (1.00).


    d  The values cited  are for the first year of exposure.  Relative Humidity values represent
       south central, central and coastal sites.  This  damage function  is strongly dependent on
       RH.   In addition, material  loss  is well correlated with S02 concentration.  Note the
       much  lower loss of zinc (A) compared with weathering  steel (C).


    e  The erosion of oil-base paint Is strongly dependent on relative  humidity and much  less
       dependent on  S02  concentration.


    f  As noted  in the text, the deterioration of vinyl paints  is not strongly dependent on

       S02.
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                                                                  6-13
mortar, stucco, and adobe.  Degradation  of  these  materials  in the
atmosphere involves disruption  of  the  interlocked mineral components
through chemical and mechanical processes.  Mechanical  degradation
disrupts the physical  structure,  through differential  thermal
expansion, freeze/thaw,  salt  crystallization,  hydration,  and
migration, or by intrusion  of root  fibriles into  the masonry matrix
(Torraca 1981a; Winkler  1978).  Chemical processes are  those where
ions react with the material  and  alter the  mineral composition to
form weathering products.   If less  soluble  than the original
material, the weathering products  will remain  as  crusts or
discolorations on the  masonry surface.   Soluble weathering  products
will be washed away with sufficient  rain water flow, eroding the
material surface.  In  the absence  of runoff, the  soluble  salts may be
transported into the body of  the masonry, and  there trigger
mechanical weathering  effects such  as  subflorescence and  spalling.

Degradation rates depend not  only  on the chemical composition of the
mineral composite, but also on  grain size and  porosity  of the matrix
(Jakucs 1977).  These  factors vary  not only between general classes
of masonry materials,  but also  from  quarry  to  quarry,  from concrete
mix to concrete mix.   Masonry materials  of  varying composition, or
varying in grain size  and porosity,  will not exhibit similar
degradation rates.  Additionally,  homogeneity  of  mineral  composition
plays a role in the durability  of  stone  building  materials.
Inclusions and veins of  minor constituents  (e.g., as feldspars or
micas) provide zones of  preferential weathering creating  microcracks
and fissures and exposing interior  areas to degradation processes.
As such, any dose-response  functions will tend to be material
specific making generalizations difficult.

Commonly used masonry  materials are  primarily  composed  of carbonates
or silicates.  Silicates are  generally more resistant  to  dissolution
by atmospheric acids than carbonates (Loughnan 1969; Winkler 1975).
Work on the interaction  of  SOX  and masonry  material has been
directed towards describing the processes and  end products
qualitatively (see Stambolov  and van Asperen de Boer 1976 for
references) and towards  estimating deposition  velocities  (Braun and
Wilson 1970; Judeikis  1979; Spedding 1969). Difficulties arise in
determining dose/response relations  partly  because of  the length of
time required to produce measurable  effects in both field and chamber
studies (Trudgill 1977)  and partly because  of  imperfect simulations
of real-world cycles of  temperature  and  moisture  in chambers
studies.

Of the commonly found  construction materials,  carbonate minerals have
been studied more extensively than other minerals. The mechanism of
S02 attack on calcite, the  major mineral constituent of carbonate
rocks and cementing materials of some  sandstones, may  proceed through
several mechanisms according  to the  following  equations (Gauri and
Holden 1981; Torraca 1981a):

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                                                                 6-14


                                                                               I
     Dry conditions:  CaC03 + SC>2 + 1/2 02  — > CaS04 + C02

     with a possible CaS03 intermediate and                                    •

     Wet conditions:  CaC03 + H2S04  — >  CaS04 +  H20 + C02
                                                                               •

Cycles of available moisture allow  for  conversion  of  anhydrite  to
the hydrates; gypsum (CaS04 . 2 H20)  and  bassanite (CaS04  .  1/2
H20).  Associated changes in crystal  size and  pressure  are                    •
significant factors in mechanical decay processes  (Arnold  1976;               •
Stambolov 1976; Winkler 1975).  Similar pressures  are exerted by
hydration of sodium and ammonia sulphates (Torraca I981a).  The               H
presence of these soluble sulphate  salts  in  the  subsurface of the             |
masonry can cause spalling of the surface under  freeze/ thaw
conditions.                                                                    M

Calcium sulphate is more soluble than calcium  carbonate, although a
range of solubilities have been reported  for both  minerals (Hardie
1967; Jakucs 1977; Keller 1978).  In  runoff  conditions, calcium               •
sulphate will dissolve and the material surface  will  be eroded.               •
Calcium sulphate may also combine with  other deposits (e.g.,  carbon
particles and soot) forming black crusts  (Fassina  et  al. 1976;  Weaver         •
1980).                                                                         |

Debates concerning the contribution of  biological  weathering to stone         _
deterioration have gone on since the  18th century. Bacteria on the           •
surface of buildings convert sulphur  dioxide from  the atmosphere into         ™
sulphuric acid for use as a digestive fluid  (Babick and Stotsky 1978;
Winkler 1978).  The digestive fluid attacks  the  calcium carbonate in          H
the limstone, marble, or sandstone, liberates  carbon  dioxide, the             •
microbe nutrient, and produces calcium  sulphate  as a  by-product.
Other studies have claimed that all deterioration  can be attributed            •
to chemical and mechanical processes, and that biological  aggression           •
is negligible (Fassina 1978; Torraca  I981b).

Several special cases of damage to  stone  structures subjected to               •
extremely high local levels of pollution  are noted in the                       M
literature:
     moisture and  temperature  cycles.
                                                                                I
1.   The effect of air pollution exposure is illustrated by  comparing
     the condition of the Elgin Marbles  (removed from  the Acropolis
     at the start of the 19th century) to the sculptures that                   •>
     remained exposed to the atmosphere  in Athens.  The Elgin                   I
     marbles, kept indoors at the British Museum, are  in much  better
     condition (Skoulikidis et al. 1976), albeit some  of the
     weathering of the exposed sculptures must be attributed to                 •
                                                                                I

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                                                                  6-15
2.   Some of the blocks in Cologne Cathedral were  put  in  place  in the
     middle of the 19th century, at  the  same time  that sandstone from
     the same quarry was used in building  Neuschwanstein  Castle in
     Bavaria.  The Cologne blocks are  significantly  more  deteriorated
     than the Neuschwanstein, where  the  sulphate deposition  is  lower
     by a factor of roughly 20  (Luckat 1976).


3.   The Ottawa Parliament House shows considerable  deterioration
     caused by sodium sulphates trapped  in the  stone.   The source of
     the sulphates is presumably a paper mill that operated  nearby
     until 1973 (Stewart et al. 1981;  Weaver 1980).
6.3.3   Effect of Nitrogen Dioxide and Ozone Pollutant/Material
        Interactions


6.3.3.1 Metals


There is little information relating NOX concentrations  to  degrada-
tion rates of metals and masonry.  No damage function  for NC>2  on
metals is given in USEPA (1981b).  Haynie  (1980a)  assessed  corrosion
rates of steels exposed to NOX,  S02 and 03 under  varying
relative humidity, temperature and wind-speed  conditions.   While no
dose-response relation has yet been determined  for steels,  it  was
found that oxides of nitrogen  (expressed as N02)  contributed
significantly to the corrosion response of zinc/copper sensors used
in an "Atmospheric Corrosion Monitor".


A recent study by Byrne and Miller (1980)  found that NOX can
influence the corrosion rate of  aluminum more  than SC^.  However,
the author suggests that S02 may reduce nitrogen  oxides  to  nitrogen
gas in the presence of a catalytic surface (e.g.,  A1203).   Hence,
this process may reduce the potential for  damage  by NOX.


Aqueous nitric acid has a more deleterious effect  on most metals,
than H2S04 or HC1 (McLeod and Rogers  1968).  In addition, metal
nitrate salts tend to be more  soluble than the  sulphate  salts, so
that nitrate corrosion products  can be readily  washed  from  surfaces,
exposing fresh metal to attack.   Conversely, sulphate  products may
remain on the surface to inhibit further corrosion.


The reported effects of ozone  on metal corrosion  appear  to  be
contradictory.  While the previously mentioned  study by  Haynie and
Upham (1971) showed that oxidants correlated with lower  steel
corrosion rates (equation 2),  a  chamber study  with ozone showed  no
effect on steel corrosion (Haynie et al. 1976).   It has  been
suggested (Benarie 1980) that  the effect observed  in the Haynie  and
Upham (1971) study was either  caused by some oxidant other  than  ozone
or was related to another factor that was  covariant with ozone (e.g.,
temperature or humidity).

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                                                                  6-16
6.3.3.2  Masonry
                                                                               I
                                                                               I
Deposition velocities have been measured  for  NO  and NC>2  on some               I
masonry surfaces.  The measured deposition  velocities  for  NOX on              B
cement appeared to be slightly lower  than for SC>2.   However,
differences over time of exposure  in  the  behavior of the gases makes          •
it impossible to give direct  comparison  (Judeikis and  Wren 1978).              |
Since there is no proposed mechanism  of ozone effects  on masonry
deterioration, nor published  studies  describing  such an  effect,               _
dose-response relationships are not to be expected.                           I

6.3.3.3  Paints
                                                                               I
In a chamber study conducted by Spence et  al.  (1975),  ozone  was
found to be the most likely factor  to affect  the  erosion  rates of
acrylic coil coatings.  The following dose-response  relationship was          •
derived:                                                                       I

         E  = 0.159 + 0.000714 03                       (6)                     _

         where E  = erosion rate in ym/yr                                      •

               03 = concentration of 03  in yg/nH                               _

As indicated by the relationship, the effect  of ozone  on  the erosion          ™
rate is negligible, even  though it  was found  to be  statistically
significant.                                                                   I

Vinyl and acrylic coil coatings were not significantly affected  by
NC>2 at ambient levels.                                                         m

6.3.3.4  Elastomers

The cracking of rubber products results  from  the  combined effects  of          I
ozone and stress on sensitive elastomeric  material.   Sensitive                 Bi
elastomers contain olefin structures (carbon  double  bonds) which  are
susceptible to chemical attack by ozone  (Bailey 1958). Natural                •
rubber and certain synthetic elastomers  (e.g., styrene-butadiene,              |
polybutadiene, and polyisoprene) contain these chemical structures.
The ozone-olefinic reaction can result in  chain scissioning  as well           M
as cross-linking of the elastomeric material.  In the  case  of chain           I
scissioning, the molecular weight is decreased and  a loss of tensile
strength of the elastomeric material is  observed.  When cross-
linking occurs, the elastomeric material becomes  brittle  with a  loss          •
of elasticity.  If no tensil stress is applied, these  elastomers  can          •
be exposed to high concentrations of ozone for long periods  of  time
without the formation of  cracks.  However, when stressed  as  little as          •
2 - 3% in extension and exposed to  20 yg/m-* of ozone in extension,             |
surface cracks are observed at right angles to the  direction of  the
stress (Crabtree and Malm 1956).                                                •
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                                                                  6-17
The major use of these synthetic elastomers is  in  the  production  of
tires.  Antiozonants are added to the  tire formulation and  provide a
protective film against ozone degradation (Fisher  1957; Mueller and
Stickney 1970; USEPA 1978).  These additives  are expensive  and  their
cost is passed on to the consumer.  Other synthetic  elastomers  are
commercially available which have no olefinic structures  and  are
chemically resistant to ozone (e.g., silicones, chlorosulphated
polyethylenes and polyurethanes).  Although these  elastomers  are
expensive, they have captured the special-application  market
especially for use in hazardous chemical environments.


Dose-response relationships for exposure of elastomeric materials to
ozone have been developed.  Unfortunately, most of the work has
involved high ozone levels and elastomeric materials without
antiozonants.  Hence, the results do not have an application  for
tires in a normal urban environment.   An exponential function was
obtained when two styrene-butadiene formulations with  several levels
of antiozonant were exposed to 490 y g/m^ of ozone  (Edwards  and
Storey 1959),  The function relates the dose  of ozone  needed  to
produce visible cracks at certain levels of antiozonant.
6.3.4   Effect of Ammonia Pollutant/Material  Interactions


There is little information on  the effects of  atmospheric  ammonia  on
the corrosion of materials.  However,  it has  been  suggested  that
ammonia may be a major indirect contributor to  the  early stages of
atmospheric corrosion (Ross and Callaghan 1966).


Ammonia also plays a prominent  role in  the atmospheric  chemistry of
S02 resulting in the formation  of ammonium sulphate aerosols  (Bos
1980; Georgie 1970).  While there is no information on  the effect  of
this aerosol on the corrosion of materials, the chemistry  of
metal-ammonia complexes would suggest  the possibility of such
effects.  The primary process would be  the modification of stable
corrosion films by the selective dissolution  or retention  of  specific
alloy constituents.
6.3.5   Effect of Particulate Pollutant/Material  Interactions


While particulates obviously play a major  role  in soiling  of
surfaces, there appears to be no conclusive  correlation  between
particulates and materials degradation  (Del  Monte et  al. 1981;
Fassina et al. 1976; USEPA 1981a; Vittori  and Fuzzi  1975).  In  some
cases the particulates serve to increase the effect  of other
pollutants by serving as catalysts (Hegg and Hobbs 1978).


However, since particulates probably deliver to surfaces of the order
of 20% of the sulphate and, under certain  conditions, up to 50% of
the nitrate (in cities) the role they play in corrosion  processes

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                                                                  6-18
6.4   IMPLICATIONS OF TRENDS AND  EPISODICITY
6.5   DISTRIBUTION  OF  MATERIALS  AT  RISK
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must not be underestimated  (see  for  example Lindberg  and Hosper
1982).  Once the dry particles are deposited,  wetting events will             •
produce the effects described above.                                           I
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Estimates are that atmospheric  emissions  of  NOX will increase in
the order of 35% over  the next  20 years (Altshuller and  McBean                •
1980) while projections  show  that S02  emissions will remain the               •
same or increase only  slightly.  This  means  that nitric  acid in rain
will substantially increase resulting  in  increases  in potential               _
deterioration of materials.                                                    •

Episodicity encompasses  the variations in levels of air  pollutants
occur at a given site.   For example, in the  northeast, the yearly             I
peaks of S02 occur during the winter months.  Thus, resulting                 I
deposition rates may vary through the  year.

Episodicity also includes cycles of available  moisture,  specifically          |
cycles of condensation and precipitation.   In  the northeast, the
specific humidity and  temperature of the  atmosphere is lower in the
winter.  This condition  may effect the time  of wetness of  material            I
surfaces in the absence  of other sources  of  moisture.                         ™

The frequency and intensity of  rainfall in relation to dry periods is         •
another aspect of episodicity.  The erosion caused  by the  dissolving          |
of reaction products (e.g., calcium sulphate)  in rain runoff may be
more severe in intense rainfall (Trudgill 1976). Thus,  for two               M
locations having the same total annual rainfall, the erosion in the           I
one with heavier, but  less frequent rain  events may be greater than
the other, where rain  occurs  more frequently.

Furthermore, the situation in the episodes between  rain  events should         •
also be considered.  In  those cases where the  damage occurs primarily
by particulate induced attack (e.g., pitting of aluminum), more               fl
frequent rain events may wash off the  particulates  actually reducing          |
the overall rate of damage.   Variations in the pH of the rain can
influence the solubility of corrosion  and weathering products                 _
(further details available in Section  6.3.2).                                  •
I
Most buildings, structures,  and  statuary subjected to the deterior-
ating process associated with atmospheric transport and deposition            •
are found in urban areas.  Hence,  the  spatial  distribution will tend          |
to follow industrial  and demographic patterns,  rather than the
sensitive regions identified in  aquatic  and  terrestrial impact                _
sections (see Sections  3.5 and 4.5).  However,  this is not to imply           •
that materials at risk  are distributed as a  simple function of                ™
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                                                                  6-19
population.  Attempts  to  estimate  quantities of exposed materials as
a function of  aggregate population may lead to erroneous results
(Haynie  1980c; Koontz  et  al.  1981;  Stankunas et al. 1981).  Results
from field surveys  in  two cities  indicate that the period of urban
development and  the  local availability of materials are important
factors  determining  the distribution of material quantities for rural
areas.   Estimates of material  distribution have not yet been
attempted.

Inventories of historic structures  and monumental statuary have been
undertaken by  both the American and the Canadian governments.  The
Canadian inventories are  maintained by federal, provincial and
municipal agencies and list thousands  of structures of cultural
significance.  The National Register of Historic Places (U.S.)
includes  approximately 25,000  properties.  These inventories warrant
closer attention in  terms of  geographic distribution.

Determination  of materials at  risk  must take into consideration both
the susceptibility of  the material  as  well as the availability and
expense  of measures  to respond to  the  incremental damage caused by
air pollution.   The  principal  effect of air pollution damage is to
reduce the length of time the  material can serve its intended
purpose.  The  intended purpose of  house paint, for example, is
primarily to protect the  underlying wall material.  The paint's
expected  life  may be several  years.  The purpose of statuary marble,
however,  is to display the artistic inspiration of the sculptor and
is intended to last  for many  generations.  Therefore, even though the
paint may be more sensitive to a given level of air pollution than
the marble, the  marble statue  is more  at risk.

Considering the  expense and availability of remedial measures,
sculptured stone and bronze are perhaps the most sensitive materials
at risk.  Dimension  stone is next on the list since it is expensive
to replace once  it has been built  into a structure.  Sheet metals,
brick and block, and concrete  lie on the scale somewhere between
dimension stone  and  surface coatings.   The labour and raw materials
involved are less expensive than dimension stone, but more costly
than paints and  surface coatings.
6.6   DATA NEEDS AND RESEARCH  REQUIREMENTS

Although the examination of  the deterioration  of  materials  is  a well
established discipline, dose-response  relationships,  taking account
of atmospheric variables as  well as concentrations, are  rather poorly
documented.  Selection of materials to  be investigated should
consider gaps in existing knowledge and  significance  of  materials.

Dose-response relationships  need to be  better  delineated for the
range of pollutants and materials determined in  field studies,
controlled environments (including accelerated studies), and in

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                                                                  6-20
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laboratory models.  There needs  to be a  study  of  the  roles  and
possible damage caused by SO^",  SC>2> N03+,  N0£ ,  03 and  particulates,          •
both individually and synergistically.   Other  agents  in  material              I
deterioration need to be studied  to  determine  which constituents are
active on selected materials  (e.g.,  the  impact of ammonia on the
corrosion of carbon steels, low-alloy steels and  copper  alloys), the          I
effect of background levels of chloride  ions and  carbonyl sulphide            •
(Gradel et al. 1981) on the corrosion of materials, and  the effects
of biological activity on building materials.   Further,  the role of           •
microclimate, including rainfall, cycles and episodes of temperature          J|
and moisture, and wind regime needs  to be  evaluated.   Finally, study
should be made to assess mechanical  degradation of masonry, soil              •
sensitivity and underground corrosion, and  stress corrosion cracking          •
of Al and Cu alloys.

Many of these needs were discussed in a  report to the Electric Power          •
Research Institute (Yocom and Grappone 1976).   In addition  to these           •
areas of study there are certain data sets  which  would help develop
an impact assessment.  Pollutant  loads should  be  estimated  for                •
susceptible structures, giving relative  contributions by local                |
sources and distant sources.  Also,  there  needs to be more  study of
the dose-response relationships  for  pollutants and materials of               _
interest as well as an inventory of  the  distribution  of  the                   •
construction materials and cultural  resources  sites at risk.  Unit            ™
cost data for cleaning, maintenance  repair  and replacement  as well as
the human response functions  for maintenance and  replacement need to          I
be developed.                                                                  •
6.7  METHODOLOGIES

Testing of materials  to determine  their  resistance to atmospheric
corrosion or degradation  has  been  conducted  for many years at a               •
number of established sites around the world (Committee G-l 1968, for         B
metals).  Approximately 15 of these sites  are in the United States
located east of the  100°  meridian  with additional sites being                 •
maintained on a proprietary basis  by individual organizations.                |
Meteorological and air quality monitoring  have not generally been
performed at these sites. Instead, the  sites are typically                   M
characterized as  rural, urban, industrial, or marine, to reflect the          I
perceived quality of  the  environment at  each site.  Recently,
measurements of temperature,  rainfall, humidity, wind speed and
direction, solar  radiation, S02  and cloride  ion concentration, were           •
begun at the marine  site  at Kure Beach,  North Carolina (F.L. La Que           ™
Corrosion Laboratory) .  There has  been no  report of acidic
deposition, nitrogen  oxides,  oxidants, particulate matter and ammonia         •
being measured at any of  the  other material  test sites.                       |

Over the years, certain aspects  of materials testing in the                   u
atmosphere have been incorporated  into  standards by the American              •
Society for Testing  and Materials  (ASTM) to  estimate or minimize some
                                                                               I
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                                                                  6-21
of the more obvious uncertainties.   The  tests  for atmospheric
corrosion of metals range  from  the  preparation,  cleaning and
evaluation of specimens  to  the  way  tests are conducted and data are
recorded (ASTM  1980a).   Several methods  have been developed to
characterize pollutant levels in the atmosphere.  For example,
sulphur dioxide may be determined by using  lead  peroxide candles
(ASTM 1977) or  lead peroxide plates (APHA 1977).  A standard for
measuring time-of-wetness  for surfaces  exposed to the atmosphere has
been prepared in draft form (ASTM 1980b; Sereda  et al. 1980).  An
ASTM task group was recently established for calibrating the
corrosiveness of the  atmosphere at  test  sites  (Baker 1980; Baker and
Lee 1980).

The characterization  of  time-dependent  meteorological air quality
and acidic deposition variables at  test  sites, and the correlation of
these variables with  the response of materials to their environment,
while clearly relevant to  atmospheric corrosion  and degradation, has
long been recognized  as  a  complex and challenging task.  Such an
effort has usually been  considered  unnecessary where, as in most
cases, the primary goal  of  materials testing has been to determine
the relative performance of a series of  materials and, thereby, to
establish criteria for their selection,  improvement,  and preservation
in a particular environment.  Many  studies  of  this type have been
made on a variety of  metallic and nonmetallic  materials.

Among the earliest departures from  the  strategy  of comparative
testing were studies  led by Larrabee and Coburn  (1962), and pursued
on a broader scale by ASTM Committee G-l,  to measure the corrosive-
ness of the atmosphere at  different test sites for selected metal
alloys.  Underlying this interest was the  desire for a fundamental
understanding of the  interactions between  materials and atmospheric
constituents so that  the performance of  materials could be predicted
based on properties of the  material and  of  the atmosphere.  Such a
concept implies a dose-response function which defines the
relationship between  the rate of corrosion  or  degradation and:
(1) the concentration of reactants  in the  atmosphere and on the
material surface; (2) the  nature and disposition of reaction
products; and (3) meteorological and environmental factors which
affect the intensity  of  exposure to the  reactants and the fate of the
products.

The dose-response function  quantifies the material-environment
interaction, and provides  the fundamental  basis  for the development
of economic damage functions used for damage (benefit) prediction,
and for designing pollution control strategies (Benarie 1980;
Gillette 1975; Hershaft  1976; Liu and Yu 1976; Mansfeld 1980).

In some laboratory studies  of the mechanisms,  kinetics, and
thermodynamics of materials corrosion and  degradation processes, and
of the effect of specific  atmospheric constituents on these
processes, experimental  conditions  have  been well controlled and a
wide variety of sampling and analytical  techniques are available

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                                                                  6-22
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(Duncan and Spedding 1973a,b; Haynie et al.  1976,  1978;  Spence  and
Haynie 1974).  A typical experimental  approach  is  to  vary the dose             _
rate of one pollutant while holding other variables constant,  and              •
study the response of the material.  In the  case of metals,  studies            '
of this type are usually done for relatively short times compared to
the time required to form a steady-state corrosion film  (ASTM                  •
Standard Practice, ASTM 1980c for short-term accelerated tests                  |
methodology).  Hence, they are often limited to simple conditions
involving the initiation of corrosion  on a bare or slightly  oxidized           m
metal surface.  This approach is adequate for establishing specific            •
details of the responses of materials  to pollutant dose  rates.
However, it has not been effective for describing  the performance of
materials in atmospheric exposures, where the permutation and                 fl
interaction of environmental and meteorological variables is complex           •
and constantly shifting over time.

New building components and systems are constantly being designed              |
and manufactured.  The operating and stress  conditions to which they
will be subjected are difficult to predict.   Although many tests               •
have been developed to accelerate degradation processes  of building            I
materials, they are seldom fully adequate for reliability predicting
long-term performance.  A recommended  practice,  ASTM  (1980c) provides
a framework for the development of improved  durability tests.                  •
Probabilistic concepts have not been applied extensively to  materials          I
durability problems in the construction industry but  these concepts
offer new opportunities for obtaining  improved  quantitative                     •
predictions of the service life of building  materials in polluted              •
environments.

By far the greatest amount of work on  atmospheric  corrosion  and the            •
degradation of materials has involved  field  exposures at regional              *
test sites.  Here the effects of exposure are clearly defined by
changes in the character and properties of the  material  (Haynie and            I
Upham 1970, 1971; Kucera 1976; Mansfeld 1980; Spence  and Haynie 1972;          Q
Upham and Salvin 1975).  Short- and long-term effects can be
observed; effects in different environments  are readily  obtained for           •
analysis and interpretation.  On the other hand, the  local                     •
environmental conditions are obviously variable and  it is difficult
to determine cause-and-effeet relationships  from regional                      ^
meteorological/environmental data (Ashton and Sereda  1981; Haynie              •
1980a).                                                                         •

Moreover, the evidence from studies in Europe and  North  America is             •
that the meteorological and materials  data obtained  at specific sites          |
is not generally transferable and applicable to sites at other
locations.  Among other reasons, this  is because of  differences not            M
only in the composition of pollutants  but, perhaps more  importantly,           •
a consequence of differences in the properties  of  the "same
materials".  For example, bricks may be made from  clay with widely
different chemical composition, may be fired at different tempera-             •
tures and for different lengths of  time, or  may be treated with                •
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                                                                  6-23
different glazes.  Finally, when making comparisons between  exposures
at different sites, it is important to consider,  for  example,  the
orientation and pitch of the samples and  their  elevation  above ground
(ASTM 1980a).   All these variations have an  influence  on the
ultimate impact of atmospheric components.

Although it is rarely done, it is highly  desirable  to collect  and
analyze the runoff from material exposure samples whenever possible.
These samples provide a direct measure of the amount  of material
actually eroded and serve as a check against  other  techniques  such as
measuring the weight loss of the exposure sample.   In some cases, the
runoff sample can provide a reliable measurement  of material loss
over a much shorter exposure time than possible with  other
techniques.

The analysis of field test data to determine  the  sensitivity of
materials to environmental factors is largely empirical;  the funda-
mental reactions and interactions have so far proved  to be too
complex to be treated otherwise.  Three basic approaches  have  been
taken for corrosion data.  Haynie and others  (Haynie  et al.  1978;
Haynie and Upham 1971; LeGault and Pearson 1978;  Mansfeld 1980; Yocom
and Grappone 1976), utilize a power function, which describes  how the
corrosion rate varies over time as the corrosion  film ages.  The rate
constant is modified by exponential factors,  which  define the  effect
of specific atmospheric constituents.  Cramer et  al.  (1980)  employ a
similar approach but use an algebraic factor  related  to the
composition of the corrosion film to modify the rate  constant.  In
the second approach, Guttman and Sereda  (1968)  and  others have
expanded the material response function as a  Taylor series for a
specific exposure time and determined the coefficients  for the
lower-order terms by a least-squares fit  of the data.  The data do
not generally warrant more than a few linear  and  interaction terms.
In a third approach, Knotkova-Cermakova et al.  (1978) apply  feedback
principles to the mathematical analysis whereby the corrosion  rate
for the present and all previous times is thought to  influence the
corrosion rate in the future by its effect on the growth  and aging of
the corrosion film.

Of these approaches, the third appears the most satisfying from a
mechanistic viewpoint.  Applications of the first have  been  quite
useful for extrapolating experimental results.  For a given  exposure
time, the second approach more readily identifies the important
variables and interactions at a specific  site.  However,  the response
function is nonlinear.  Therefore, the results  obtained by the second
approach for different test sites are not generally comparable and
should not be used for interpolating to other conditions.

An essential difficulty particularly for  heavily  used test sites
(e.g., Kearny, NJ.; State College, PA.; and Kure  Beach, NC.),  has
been the absence of meteorological, air quality and acidic deposition
data which could be correlated with atmospheric corrosion and

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                                                                  6-24
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degradation data.  Most often, such data have been  obtained  from a
nearby monitoring or weather  station where  conditions  may  not  always            •
correspond to those at the test site (Haynie  1980a;  Haynie and Upham            •
1970, 1971; Mansfeld 1980).                                                     m

It is now generally recognized that meteorological,  acidic deposition          I
and air quality instrumentation should  be incorporated into  field              •
materials experiments.  In this way, the key  atmospheric and
meteorological effects on materials can be  determined  to provide an            •
accurate assessment of the impact of acidic deposition on  materials            •
corrosion and degradation.

In a study in St. Louis, Missouri, concurrent environmental  and                •
meteorological measurements were made  (Mansfeld  1980). Materials              ™
exposure sites were located at nine stations  where  air quality,
including total suspended particulates  (i.e., sulphate and nitrate),            I
and meteorological data were  recorded.  Precipitation  chemistry was            •
not obtained.  These measurements will  allow  the  correlation of
material damage as a function of the recorded environmental                     •
parameters.                                                                     I

In a second study begun in 1980, a temporary  monitoring station was
established at the Bowling Green U.S.  Customs House  in New York City.          •
This was a joint NPS-EPA contribution  to the  NATO-Committee  on                 •
Challenges to a Modern Society monitoring project (Livingston 1981).
The objectives of this study  were to intercompare site specific                •
measurements with the permanent Manhattan monitoring station                   |
measurements, correlate these measurements  with  material
deterioration, and investigate a variety of methods  to measure stone            «
damage.                                                                         I

A study for investigating material degradation rates over  long
exposure periods is being supported by  the  U.S.  Environmental                  •
Protection Agency.  The approach is to  measure the  erosion of marble            9
gravestones in national cemetaries across the United States  (Baer and
Herman 1980).  These standard stones,  provided by the  Veterans                 •
Administration, are obtained  from only  three  marble  quarries,                   |
providing three sets of chemically uniform  indicators. The  national
cemetary system provides over 100 exposure  sites  throughout  the                ^
country.  Since 1873, the stones have  recorded the  cumulative                  •
environmental effects at each site.
                                                                                I
6.8   ASSESSMENT OF ECONOMIC DAMAGE

Estimates of the financial losses attributable  to  air  pollution,  if            •
accompanied by appropriate statements  of  uncertainty and  of  assump-            I
tions, are useful even if the range  of error  is  fairly large.   This
is especially true now in view of increased interest in balancing              _
costs of regulation against benefits.  Damage cost is  a measure of             •
material, energy and labour consumption.   Premature consumption of             *
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                                                                  6-25
products wastes limited  natural  resources  and consumes labour in
nonproductive  tasks.   While  this may create jobs, it does not contri-
bute to an improved standard of  living.   Instead, it contributes to
inflation, and hastens the  time  when certain resources become
scarce.

The task of estimating the  damage costs  for the effects of long-
range transported air  pollution  involves  many variables.  Some of
these variables are difficult or expensive to quantify and some
relate indirectly to damage  costs.   The  values of many of these
variables can  only be  estimated, because no hard data are available.
In cases where a material is part of a work of art,  or has other
cultural value, difficulties arise  because of the lack of methodology
for the assignment of  an economic value.   Some attempts have been
made to estimate damage  costs, using conservation and restoration
costs as a surrogate for cultural value.   Although this approach
neglects the loss of unquantifiable artistic value originally present
in the structure or object,  at least it  allows the costs of restor-
ation to be compared with other  control  measures.

The literature on effects of pollutants  on materials describes
various approaches to  determining unit costs of extra maintenance,
such as more frequent  painting,  and earlier replacement resulting
from air pollutants and  acidic deposition (Haynie 1980c; Liu and Yu
1976; Yocom and Grappone 1976; Yocom and Upham 1977).  These studies
typically involve broad  assumptions about  the kinds  of materials
which are exposed in a given area and are  generally  based on a
limited variety of materials. No study  has produced completely
satisfactory results,  and estimates of costs vary widely.

The assessment of economic  damage attributable to air pollution
depends on many factors.  The rates of deterioration (physical
damage) which  can be expected for a material when it is exposed to an
environment which contains known levels  of air pollutants and
particulates must be known.   The deterioration rate  in the absence of
the pollutants must also be  known so that  the incremental effects of
air pollution  (Yocom and Grappone 1976)  and the dose-response
relationship can be determined.   The distribution of the material in
the environment needs  to be  catalogued including how the material is
used and whether or not  it is protected  or exposed.   There needs to
be accurate data on pollutant loadings coincident with the material
distribution.  Finally,  human response to  materials  damage must be
predicted.  In the latter component, there is variability on how and
when to clean, paint,  or replace as well  as on the selection of
substitute materials which may offer improved performance.  There is
also variability as to the extent structures are replaced prior to
the time significant damage  would have occurred due  to pollutants.
The accuracy of economic estimates  is compromised by uncertainties in
all of the above factors.

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The economic assessments available  today  are  crude.   In the  future
the damage functions  for new  and  old  construction materials  will be            m
determined, and methodologies for determining materials distribution           I
will be refined.  Then the  range  of uncertainty  in the aggregate cost
of pollution-induced  materials damage  undoubtedly will be  narrowed.
These damage functions and  distribution inventories  are urgently               I
needed.                                                                         •
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                                                                  6-27
6.9   REFERENCES

Allaino-Rossetti, V., and Marabelli, M.   1976.  Analyses  of  the
    patinas of a gilded horse of St. Mark's Basilica in Venice:
    corrosion mechanisms and conservation problems.  Studies  in
    Conservation 21:161-170.

Altshuller, A.P., and McBean, G.A.   1980.  The second report  of  the
    United States-Canada Research Consultation Group on the
    Long-Range Transport of Air Pollutants.  Environment  Canada,
    Ottawa, Ont.

American Public Health Association  (APHA).  1977.  Tentative  method
    of analysis of the sulfation rate of  the atmosphere (lead dioxide
    plate method - turbidimetric analysis).  In Methods of air
    sampling and analysis, 2nd edition.   American Public  Health
    Association, Intersociety Committee,  Washington, DC.  691  pp.

American Society for Testing and Materials (ASTM).  1977.  Annual
    book of standards.  Part 26, ASTM D2010-65:  536-539.

             1980a.  Annual book of  standards.  Part 10,  ANSI/ASTM
    Gl-72:  781-786; ASTM G33-72:  888-890; ANSI/ASTM 750-76:
    985-992.

   	.  1980b.  Standard recommended practice for the
    measurement of time-of-wetness on surfaces exposed to wetting
    conditions as in atmospheric corrosion testing.  G01.04.01.
    (draft)

          .  1980c.  Annual book of standards.  ANSI/ASTM E632-78.
Arnold, A.  1976.  Behavior of stone soluble salts in stone
    deterioration.  In Proc. Second Int. Symp. on the Deterioration
    of Building Stones, ed. N. Beloyannis, pp. 27-36.  Ministry of
    Culture and Science, Athens, Greece.

Ashton, H.E., and Sereda, P.J.  1981.  Environment, microenvironment
    and the durability of building materials.  J. Durability of
    Building Materials 1:49-66.

Babick, H., and Stotsky, E.  1978.  Atmospheric  sulfur compounds  and
    microbes.  Environ. Res. 15:526-531.

Baer, N.S., and Berman, S.M.  1980.  Acid rain and material damage in
    stone, final report.  Submitted to National  Atmospheric
    Deposition Program, North Carolina Agriculture Research Service,
    North Carolina State University, Raleigh, NC.

Bailey, P.S.  1958.  The reactions of ozone with organic compounds.
    Chem. Rev. 58:925-1010.

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                                                                  6-28
    corrosion test sites.  Presented at Symp. on Atmospheric
    Corrosion.  ASTM, Denver CO., 1980.  (to be published  by ASTM)
    air pollution.  Report No. EUR 6643 EN, Commission  of  the
    European Community, Environment and Consumer  Protection  Service,
    Paris, France.  65 pp.
     and  A.  Klemin,  pp.  140-170.New York:Relnhold Publishing
     Corp.
                                                                              I
                                                                              1
Baker, E.A.  1980.  ASTM Committee G 01-04, Task Group on Calibration
    of Atmospheric Test Sites, Minutes of Meeting, May 20,  1980,
    Denver, CO.                                                                •

Baker, E.A., and Lee, T.S.  1980.  Calibration of atmospheric
                                                                               I
Benarie, M.  1980.  Environment and quality of life - critical review
    of the available physico-chemical material damage functions of             •
    air pollution.  Reoort No. EUR 6643 EN. Commission of the                  ™
                                                                              I
Bos, R.  1980.  Automatic measurement  of  atmospheric  ammonia.
    J. Air Pollut. Control Assoc.  30:1222-1224.                                _

Boyd, W.K., and Fink, F.W.   1974.   Corrosion of metals  in  the                  *
    atmosphere.  Report MCIC-74-23, Metals  and Ceramics Information
    Center, Battelle Columbus Laboratories, Columbus, OH.                      •

Braun, R.C., and Wilson, M.J.G.   1970.  The removal of  atmospheric
    sulfur by building stones.   Environment 4:371-378.                         m

Building Research  Station (BRS).   1970.   The assessment of wind
    loads.  BRE Digest 119,  Department of the Environment, U.K.               _

Byrne, S.C., and Miller, A.C.   1980.   The effect  of atmospheric               •
    pollutant gasses on  the  formation  of  corrosive condensate  on
    aluminum.  Presented at  Symp.  on Atmospheric  Corrosion. ASTM,
    Denver, CO., 1980.   (to  be  published  by ASTM)

Campbell,  G.G.; Shurr, G.G.;  Slawikowski, D.E.; and Spence, J.W.              _
    1974.  Assessing air pollution damage to  coatings.   J. Paint              •
    Technol. 46:59-71.                                                         *

Cavender,  J.H.; Cox, W.M.;  Georgevich, M.;  Huey,  N.A.;  Jutze,  G.A.;           M
    and  Zimmer, C.   1971.   Interstate  surveillance;   measurements of          P
    air  pollution  using  static  monitor.  Report No. APTD 777,  U.S.
    Environmental  Protection Agency, Research Triangle  Park, NC.              fi

Copson,  H.R.   1945.  A theory of the mechanism  of rusting of low
    alloy  steels in  the  atmosphere. Proc.  Am.  Soc. Test.  Mater.              _
    45:554-580.                                                                •

Crabtree,  J. ,  and  Malm,  F.S.   1956. Deterioration of rubber from use
    and  with age.   In Engineering uses of rubber, eds.  A.T. McPherson         •
                                                                              1
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                                                                  6-29
Cramer, S.D.; Carter, J.P.; and Covino, Jr., B.S.   1980.  Atmospheric
    corrosion resistance of steels prepared from the magnetic
    fraction of urban refuse.  Report of Investigations No.  8447,
    U.S. Department of the Interior, Bureau of Mines,  Washington,  DC.
    32 pp.


Del Monte, M.; Sabbioni, C.; and Vittori, 0.   1981.  Airborne  carbon
    particles and marble deterioration.  Atmos. Environ.  15:645-652.


Duncan, J.R., and Spedding, D.J.   1973a.  Initial  reactions  of sulfur
    dioxide after adsorption onto  metals.   Corros.  Sci.  13:881-889.


	.  1973b.  Effect of relative humidity on adsorption of
    sulfur dioxide onto metal  surfaces.   Corros.  Sci.  13:993-1001.


Edwards, D.C.,  and Storey,  E.B.   1959.   A quantitative ozone test for
    small specimens.   Chem.  Can.  11:34-38.


Eurin, P.  1981.  Degradation  processes  of  building  materials and
    components:  a short  review  of  some  proposals for  research.   In
    Proc. Second Int.  Conf.  on the  Durability of  Building Materials
    and Components, pp. 354-366.  National  Bureau of Standards,
    Gaithersburg, MD.


Fassina, V.   1978.  A  survey on  air pollution and deterioration of
    stonework in Venice.  Atmos.  Environ. 12:2205-2211.


Fassina, V.;  Lazzarini, L.;  and  Biscontin,  G.  1976.  Effects of
    atmospheric pollutants  on  the composition of  black crusts
    deposited on Venetian marbles and stones.  In Proc.  Second Int.
    Symp. on  the Deterioration of Building Stones,  ed. N. Beloyannis,
    pp. 201-211.  Ministry  of  Culture and Science,  Athens, Greece.


Fisher, F.L.   1957.  Antioxidation  and antiozonation.   In Chemistry
    of natural  and synthetic rubbers, ed. F.L. Fisher, pp. 49-55.
    New York:   Reinhold Publishing  Corp.


Gauri, K.L.   1979.  Effect  of  acid  rain on structures.  Presented at
    the Symp. on Acid  Rain,  Preprint #3598, pp. 55-77.  American
    Society of  Civil Engineers,  Boston,  MA.


Gauri, K.L.,  and Holden,  1981.  Environ. Sci. Technol. 15(4):386-390.


Georgie, H.W.   1970.   Contribution  to the atmospheric sulfur budget.
    J. Geophys. Res.  75:2365-2371.


Gerhard, J.,  and Haynie,  F.H.   1974.  Air pollution effects on
    catastrophic failure  of metals.  EPA-650/3-74-009, U.S.
    Environmental  Protection Agency, Research Triangle Park, NC.

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                                                                 6-30
Guttman, H., and Sereda, P.J.  1968.  Measurement of atmospheric
    factors affecting the corrosion of met
    the atmosphere.  ASTM STP-435:326-359.
Hardie, L.A.  1967.  The gypsum-anhydrite equilibrium at one
    atmosphere pressure.  American Minerologist 52:171-200.

Harker, A.B.; Mansfeld, F.B.; Strauss, D.R.; and Landis, D.D.   1980.
    Mechanism of S02 and H2S04 aerosol zinc corrosion.
Haynie, F.H.   1980a.  Evaluation of  the  effects  of  microclimate
    differences on  corrosion.   Presented at  Symp. on Atmospheric
    Corrosion.  ASTM, Denver,  CO.,  1980.   (to  be published  by
    ASTM)

	.   1980b.  Theoretical air pollution and  climate  effects on
              1980c.   Economic  assessment  of  pollution related
     Performance  10(12):18-21.
                                                                              I
                                                                              I
Gettens, R.J. 1964.  Corrosion products of metal antiquities.  A
    volume from Smithsonian Institute Annual Report -  1963,  pp.
    547-568.  Washington, DC.                                                 •

Gillette, D.G.  1975.  Sulfur dioxide and material damage.   J. Air
    Pollut. Control Assoc. 25:1238-1243.                                      _

Gradel, I.E.; Kammlott, G.W.; and Franey, J.B.  1981.  Carbonyl               ™
    sulfide:  potential agent of atmospheric sulfur corrosion.
    Science 212:663-665.                                                      •

Guttman, H.   1968.  Effects of atmospheric factors on  the  corrosion
    of rolled zinc.  In Metal corrosion in the atmosphere.   ASTM              •
    STP-435:223-239.
    factors affecting the corrosion  of metals.  Metal  corrosion  in             •
                                                                               I
    EPA-600/ 3-80-018, U.S. Environmental  Protection Agency,  Research
    Triangle Park, NC.
                                                                              I
    materials confirmed by  zinc  corrosion  data.   In Durability of             •
    building materials and  components.   ASTM STP-691:157-175.                  *
                                                                              1
     corrosion  damage.   Presented  at the  Int.  Symp.  on Atmospheric
     Corrosion, Abstract 163.   The Electrochemical Society,  Hollywood,
     FL.,  1980.                                                                 ft

Haynie, F.H.,  and  Upham,  J.B.   1970.   Effects of  sulfur dioxide on
     the corrosion  of  zinc.  Materials Protection  and Performance              _
     9(8):35-40.                                                                •

              1971.   Effects of atmospheric pollutants on the
     corrosion  behavior  of  steels.   Materials Protection and                   •
                                                                               I

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             1974.  Correlation between corrosion  behavior  of  steel
    and atmospheric  pollution  data.   In  Corrosion in natural
    environments.  ASTM  STP-558:33-51.


Haynie, F.H.; Spence, J.W.;  and Upham, J.B.   1976.   Effects of
    gaseous  pollutants on materials  - a  chamber  study.
    EPA-600/3-76-015, U.S.  Environmental Protection Agency, Research
    Triangle Park, NC.


	.  1978.   Effects  of air pollutants on weathering steel and
    galvanized steel:  a  chamber  study.   In  Atmospheric factors
    affecting the corrosion  of  engineering metals.   ASTM
    STP-646:30-47.


Hegg, D.A., and Hobbs, P.V.   1978.   Oxidation of sulfur dioxide in
    aqueous systems  with  particular  reference to the atmosphere.
    Atmos. Environ.  12:241-253.


Hershaft,  A.  1976.  Air  pollution  damage functions.  Environ. Sci.
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                   SECTION 7


THE FEASIBILITY OF ESTIMATING THE ECONOMIC BENEFITS
OF CONTROLLING THETRANSBOUNDARY MOVEMENT OF AIR
                  POLLUTANTS

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                                                                 7-1
                               SECTION 7


 THE FEASIBILITY OF ESTIMATING THE ECONOMIC BENEFITS OF CONTROLLING
            THE TRANSBOUNDARY MOVEMENT OF AIR POLLUTANTS



7.1   INTRODUCTION


7.1.1   Purpose


This section presents  a  review of  the relevant methods of estimating

the monetary value of  benefits associated with environmental
protection efforts to  deal  with the long range transport of air
pollution (LRTAP) problems.   An important part of the development of

environmental policy  strategies is an understanding of the
relationship of benefits  and  costs.   This section focuses on
techniques to estimate benefits.


The objectives of this section are threefold.   The first is to
present an overview of economic methodologies  which may be used to

estimate the monetary  benefits associated with LRTAP control.   In
undertaking this review,  the  underlying theory is presented and the
applicability and limitations of each technique to the LRTAP receptor
categories are evaluated.


The second objective  is  to  recommend the most  appropriate techniques
for deriving monetary  values  for the increased goods and services due
to reductions in LRTAP.   In so doing,  the section reviews data
requirements, practicality  of the  methods,  and the extent to which

the methods capture the  full  measure of benefits.


Finally, the third objective  is to present  this material in a brief
and readable form, which  is readily understood by colleagues in other
disciplines involved  in  the study  of LRTAP  effects,  but without a
rigorous or extensive  knowledge of economics.   It is hoped that this
review will provide an understanding of techniques of economic
analysis, and indicate the  nature  of the information and data needed
from scientific research  to apply  the economic methods leading to
strategy appraisal.


There is a relatively  large body of  literature on environmental
economics and benefit/cost  analysis.   Our purpose here is to
summarize the current  state of  the art of the  valuation of benefits
associated with LRTAP  control recognizing that there is sufficient,
if not complete, agreement  on this matter.   Another Work Group,  3B,
is summarizing state of the art technology  and costs.


This review draws upon published works in an attempt to synthesize
theory and application.   In particular,  Freeman (1979) and Crocker
et al.  (1981) have served as  important references.

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                                                                 7-2
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7.1.2   Background

Neither physical  science  studies  of  the effects of deposition alone,         •
nor engineering and  cost  studies  of  abatement and mitigation
technologies, will suggest  appropriate levels for precursor emission         _
controls  or acidic deposition.  Governments and the public are faced         •
with choosing among  varying levels  of  damages,  effects and costs of          ™
control and mitigation, rather  than "damages or no damages".

In a world of pervasive markets,  prices alone would be sufficient            |
means of  conveying information  about the most appropriate mix of
damages,  effects  and costs  of pollution control.   Prices would               ^
indicate  relative scarcities and  provide incentives for allocation of        •
resources to the  place and  time in  which they will have the most
value.  The most  valuable allocation is called, in economic parlance,
an efficient allocation.                                                      •

Since there is not a world  of pervasive markets,  economists, in
dealing with resource allocation  issues, attempt  to simulate ones            •
with benefit/cost analysis.  They attempt to assign monetary values,         ^
which the gainers and losers would  assign,  to some change in resource
allocation.  The  algebraic  sum  of these dollars is then used in              »
determining the necessary level of  intervention.   If there is a net          •
benefit from intervention,  then the  new resource  allocation is said
to be more efficient.  The  analysis  thus shows  the benefits of the
intervention to society,  and conversely, the costs if steps are not          •
taken.                                                                        m

Consequently, benefit/cost  analysis  is useful when decision makers           |B
want to duplicate the results of  a world which reflects individual           •
values and preferences.   It is  limited, however,  in that it usually
gives an  incomplete  accounting  of value, and thus it is best seen as         ^
an aid to decision making.   At  a  minimum, it constitutes a systematic        •
and practical framework for organizing data and for making evalu-            ^
ations and comparisons.

Other methods and criteria  have been suggested, for assessing the            •
environmental effects of  resource development projects, or for
evaluating environmental  protection  strategies such as arbitrary             •
weighting procedures, overlay maps,  quality and enjoyment indices.           •
These are, for the most part, descriptive,  and generally do not
provide a consistent, well-developed theory which links human                _
preferences and value systems to  physical effects being described.           •
Moreover, these noneconomic techniques do not provide a systematic           ™
and nonarbitrary  means of weighting  the various physical and
environmental consequences  and  effects.
I
In order to compare  the  various  types  of  incommensurable entities,
such as changes in crop  yield  and  fish catches,  transformations must         •
be made to cast these  different  entities,  where  possible, into               •
comparable units. In addition, the various physical effects must be
given weights, to indicate  their relative  value  to society.  Monetary
                                                                              I

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                                                                 7-3
units admirably perform this dual function of providing  comparable
weighting units.


A fundamental focus of this paper is  to  determine  the  feasibility of
applying monetary valuations to nonmarketed  goods,  services  and
attributes, such as aesthetics, human health and life,  ecological
relationships and recreational enjoyment.  The  difficulty  of
assigning monetary values  to these  environmental attributes  is
recognized, the impossibility is not.


It is important to recognize that the monetary  value of  goods  and
services affected by environmental  quality is not  simply the
willingness-to-pay on the  part of the users  of  the goods and
services.  In fact, economists have identified  several  not neces-
sarily mutually exclusive  dimensions  of  value:   (1) activity  value
which is derived from the  direct use  of  goods and  services affected
by environmental quality;  (2)  option value  which  is derived from the
possibility that people might use these  goods and  services in  the
future; and (3)  legacy or bequest  value which  is  derived  from the
desire of people to leave  to their  descendants  a given  level of
environmental quality.  An accurate measure  of  the value of  many
goods and services affected by environmental quality would reflect
all these dimensions, where appropriate. For example,  the value of
the unique trout fishery in the Adirondacks  includes activity  value
from those who now use it  or would, if,  there were not  LRTAP;  option
value from those who might use it in  the future; and  legacy  value
from those who want to ensure that  their children  could enjoy the
area in its pristine state in the future.


At this point, a brief discussion of  terminology is appropriate.  The
terms "damages", "costs" and "benefits"  are  frequently  used  inter-
changeably in reference to LRTAP effects on  the environment.  It is
the choice of a reference  point which more clearly determines  their
specific meanings.  "Benefits" are  the  gains from  preserving existing
environmental quality and  from restoring or  improving  a degraded
area.  Since our reference point is a degraded  environment,  we will
describe the reduction or  mitigation  of  LRTAP effects  as benefits.
"Damages" are the mirror image of benefits  if,  and only if,  the path
of environmental degradation is comparable to environmental
improvement.  The reference point in  this case  is  a relatively clean
environment, and thus pollution effects  constitute "damages" or
"damage costs".  Continued or increased  emissions, in  a somewhat
polluted environment, are  also likely to have effects  which  would be
considered as damages.


For the purpose of this section, we have attempted to  be consistent
in our use of the terms.   The word  "costs" is used primarily in
reference to LRTAP control or abatement  efforts.   Benefits are the
gains associated with pollution reduction or prevention, given our
reference point of an environment already affected by  pollution.
Our economic measure of benefits is,  therefore, the value  which
people place on reducing the effects  of  LRTAP,  and our  purpose is to

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                                                                7-4
In the quadrant IV, a benefits function can be drawn which relates
the dollar value of benefits to particular LRTAP emission levels by
                                                                              I
                                                                              I
indicate how monetary values might be assigned  to the physical
effects resulting from LRTAP abatement.                                       mm


7.1.3   Emission-Benefit Relationship

The relationship between residual emissions,  (e.g.,  SOX and NOX),             w
and monetary benefits is complex, and varies  among receptor
categories.  However, the general relationship  consists of three              •
primary linkages:  (1) the relationship between emission discharges           |
and ambient environmental quality; (2) the relationship between
ambient environmental quality and the direct  and indirect effects  on         ^
people (the dose-response); and  (3) the relationship between  direct           •
and indirect effects on people and the economic value of these
effects (user value).  The linkages between the various elements can
be represented in a simple quadrant diagram in  Figure 7-1.                    I

Quadrant I shows a transformation function which relates emission
levels to deposition (used here  as inverse for  environmental                  •
quality).  In the case of acidic deposition,  long range transport             •
models are being used to show the spatial and temporal relationship
between S02 emissions and sulphate and total  sulphur deposition.              _

Quadrant II shows a functional relationship between  deposition  (or           •
environmental quality) and activity levels.   This relationship
between emissions and activity levels, is very  complex and varies             •
considerably with the receptor category.                                      |

In the case of sports fishing, the relationship in the diagram  is  a           mm
gross simplification of the linkage between sulphur  deposition  and           •
days of sports fishing activity.  There is actually  a complex affect
on the aquatic ecosystem.  The amount of  change in pH (and metal
ions) varies with the buffering  capacity  (sensitivity) of the                 •
waterbody.  The  change in pH will have various  effects on the fish            •
population (i.e., rough , warm and cold species).  Finally,
recreational fishing may be affected by the changes  in species  types          •
available as well as a reduction in the number  of days fishing  is             I
permitted.  This assumes that the stock of fish is independent  of
fishing pressures.                                                             _

Where the effects are direct (e.g., human health) the function  in              ™
quadrant II illustrates the relationship  between ambient
environmental quality (e.g., sulphate concentrations) and human               •
mortality.                                                                     |

Quadrant III relates activity to dollar values. The relationship  is          mm
direct; as activity increases, total economic value  increases.   This          •
function could illustrate the relationship between activities and
both its primary and secondary economic value.

                                                                               (B
                                                                               I

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                                                                   7-5
                                  Activity
  Benefits
   Costs
     IV
Figure 7-1.
                                                                  Deposition
                   Emissions


Conceptual  relationship between emissions  and economic
effects.

                    Activity
          $$$  L.
      IV
                                                Deposition
Figure  7-2.
                         W
Variation  in effects due to different  emission-
deposition relationships.

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                                                                 7-6
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following a given level through each quadrant.  Thus, the  total
benefits are the integral under the curve.   In addition, this
quadrant can be used to show a control cost  function  (shown  in dashed         •
lines in Figure 7-1).                                                         •
                                                                              I
Actually the functions are not as  straightforward  as  shown  in this
quadrant diagram.  There are elements of uncertainty,  which may
result from inaccuracies in measurement or  from  the use  of
assumptions drawn from insufficient data.                                     •

For example, the best estimate of  the relationship between  emissions
and deposition (i.e., the transformation function) is  represented by
a range.  The upper limit is A and  the lower  limit is  B.  The                •
benefits range in quadrant IV is no longer  a  curve.   It  is  now the            •
area WXYZ (Figure 7-2) where the range of benefits at  emission level
"a" is Z to Y.  If the functions in quadrants II and  III are                 •
similarly presented as ranges, the  total benefits  area in quadrant  IV        |
becomes an even larger area.

In the case of LRTAP, this section  reviews  the economic  methodologies        I
for assigning monetary values to benefits for the  activity  categories        ™
shown in Table 7-1.

A critical link in this process  is  the relationship  between dose and          •
response (Quadrant II).  Until more consistent research  data are
forthcoming which relate damages to various levels of  LRTAP, it  will          •
be difficult to provide reliable estimates  of the  economic  values of          •
the benefits of LRTAP reduction.
                                                                              I

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7.1.4   Efficiency and  Equity  Considerations

The physical damages  of LRTAP  result  in reduced economic benefits for
society.  Conversely,  the  reduction of  these  damages offsets these
welfare losses, which may  not  be  shared equally by all members of
society.  The  decision  by  government  to intervene or not to intervene         ^
thus has both  efficiency and equity implications.                             •

It is often possible  to reallocate resources, (e.g., spend more or
less on environmental protection) to  increase the net value of                I
production or  output  to society.   This  output encompasses goods and           V
services provided by  the environment  as well  as those produced by man
and sold in markets.   Increases  in this net value of output result in         •
an increase in economic welfare.                                               V

Changes in economic welfare associated  with environmental damages or          —
environmental  protection activities sometimes may be measured by              •
changes in the monetary values assigned by all individuals affected           ™
by an action.  Thus,  a  reallocation of  resources and efforts will
increase efficiency  if  it  results in an increase in the social value          B
of goods and services produced by the economy (or by natural                  |
environments), as  indicated by individuals' demand for them.
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                                                                 7-7
TABLE 7-1.   ACTIVITY CATEGORIES
          1.  Aquatic
          2.  Terrestrial
a. commercial
b. recreational
c. ecosystem


a. agricultural
b. forest
c. ecosystem
          3.  Man-made buildings, structures and artifacts
          4.  Water Systems
          5.  Human Health
          6.  Visibility
a. materials
b. historic


a. treatment
b. materials


a. morbidity
b. mortality


a. aesthetic

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                                                                 7-8
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The equity impact  relates  to  the  redistribution of economic welfare
amongst  individuals.   These  individuals can be further divided into
groups,  regions, countries,  or  generations.   The simplest way in             •
which  to view  this  impact  is  to examine the changes in the distri-           j|
bution of monetary  income  which result  from alternative strategies.

A wide variety  of  individuals  of  differing  nationality, income and           •
social class, and  generation, are potentially affected by LRTAP              *
effects  and LRTAP  abatement  alternatives.   Some individuals may be
more significantly  affected  than  others by  social choices to abate or        •
not to abate LRTAP.  They  may  be  located in source or sensitive              •
receptor regions or they may have a  preference for goods and services
related  to air  quality in  these regions.  A decision to maintain            A
existing air quality management practices produces gains to                 Jj
individuals who use the environment  for production (e.g., an employee
or shareholder  of  firms in source regions)  and consumption (e.g.,  use        _
of automobiles  in  source regions) purposes  or consume the products          8
and services of LRTAP-source  firms.   Damages are imposed on those
individuals who use the environment  for production (e.g.,
agriculture), consumption  activities (e.g.,  water-based recreation in       •
acid-sensitive  lakes)  or consume  the products and services of LRTAP-        •
affected firms.  The roles of gainers and losers are reversed if
LRTAP abatement is  contemplated.                                             •

The adverse effects of  pollutants result in the involuntary surrender
of rights to both  common pool resources (e.g.,  airsheds) and                _
individual property, or the  usurpation  of these rights.  For example,       •
residents in both  Canada and  the  United States involuntarily give  up        ™
some of  their rights to clean air and lakes with fish populations  to
the coal-burning utilities and  the nonferrous smelting industry.            H
A political jurisdiction may  surrender  these rights from one area  to        V
another  if it is determined  (by concensus or voting) that the
collective good of  the nation or  region is  enhanced.  However,              A
regions  or nations  may not share  in  the collective good that may            •
result from the transfer.  There  is  no  forum for arriving at a
concensus between  two  nations other  than negotiation and bargaining.

Thus, redistribution effects and  property rights among groups,              ™
regions, or generations may have  significance for social welfare,
depending upon  the  relative  weights  attached to individuals,                •
countries, or generations, and  whether  or not compensation is               |
actually paid to those affected by the  changes.

The compensation principle adds further complications to the property       •
rights issue, because  it is  unlikely that compensation will be paid
between  losers and  gainers.  A  benefit/cost analysis shows a
particular course  of action worthwhile  if the gains would be                I
sufficient to compensate the losers.  If compensation does not take         •
place and the distributional weights are important, efficiency
conditions may not  be  satisfied.   Thus,  the lack of mechanisms or            •
incentives to preserve or  compensate the rights of others may result        •
in an economically  inefficient  allocation of resources.
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                                                                 7-9
The assignment  of  implicit  or  explicit welfare weights has been
subject  to  significant  criticism.   It has been noted that data and
analytical  problems  severely limit the ability to trace the eventual
distribution of  economic effects to individuals,  as tax payers,
resource suppliers,  and consumers. The development of implicit
welfare  weights  from past governmental decisions  also requires the
assumption  that  elected officials  had full knowledge of the magnitude
and composition of the  economic effects,  when decisions were made
(Freeman 1969).  The ability of elected government officials to
generate an optimal  set of  equity  weights which would be stable over
time has also been questioned  (Steiner 1977).

There  is disagreement among applied welfare theorists,  as to the
treatment of  distributional effects.   A display of the distributional
consequences  of  social  choices is  recommended  as  a supplement to the
statement of  economic efficiency impacts  (Haveman and Weisbrod 1975;
McKean 1958;  Mishan  1971).   Some analysts have also recommended that
the display process  be  taken a step further.   A series of welfare-
weighted calculations could be used as an alternative to the
weighting functions  (Eckstein  1961).   The distributive consequences
of alternative weights  can  then be easily identified.   Freeman (1969)
outlines a  more  formal  process whereby each government agency spells
out program objectives  and  recommends weighting functions.   These
weighting functions  are then reviewed and approved by the central
budget agency (e.g., Office of Management and  Budget,  or Treasury
Board) to ensure weighting  consistency among  programs relative to
overall  governmental priorities.   Present federal project evaluation
procedures  of the  Canadian  Treasury Board (1976)  and U.S. Water
Resources Council  guidelines (1980) basically  conform to the display
format for  distributional consequences recommended in the literature.
Therefore,  the redistributive  effects are associated with most of the
benefits of LRTAP  control and  these should also be taken into
consideration.
7.2   BENEFITS: CONCEPTUAL APPROACHES

This chapter distinguishes between  primary  and  secondary  monetary
benefits associated with  changes  in activities.   Primary  benefit is
the willingness of society to  pay for  goods and  services  resulting
from changes in environmental  quality,  or the compensation required
to restore welfare to original levels.  The willingness to pay  on the
part of consumers is described graphically  as the area under  a  demand
curve.  Consumer surplus  is the difference  between willingness  to pay
and actual expenditures.  It is the change  in consumer surplus
resulting from changes in LRTAP which  provides a  useful measure  of
benefits to consumers.  The willingness to  supply on  the  part of
producers is described graphically  as  the area under  a supply curve.
Producer's surplus is the difference between the  price line and  the
supply curve and it is the change in producer surplus due to  LRTAP
which provides a useful measure of  benefits to producers.   (For  those
unfamiliar with economics, see the  Appendix which gives a few key

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                                                                 7-10
7.2.1.1 Market Approach
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concepts of economic theory).  Most of this  section will  describe  the
three basic approaches (i.e., market, imputed market  and  nonmarket)
for estimating willingness to pay on the part of  consumers  and                •
producers.  Secondary monetary benefits are  changes in  the  levels  of          "i
economic activity among regions.  Some will  gain  while  others lose.
These are not usually contributions to national economic  efficiency,          •
but are transfers from one region to another.  Nonetheless,  they are          j|
important at the regional level.


7.2.1   Primary Benefits                                                      ™
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In many cases, the value of  a  change  induced  by an improvement  of
environmental quality  can be ascertained  by direct observation  of a          •
change in the market.  For example, a reduction in LRTAP which                •
results in an improvement in environmental quality may produce
increases in crop yields and commercial fish  catches.   The  benefits          —
of a change in environmental quality  include  the total value of price        •
changes to consumers and net income to producers.   In  the following          •
paragraphs, we will present  a  few techniques  for estimating these
changes.                                                                      •

The Net Factor Income  approach provides a measure of the change in
producer's income resulting  from change in output due  to improved            _
environmental quality.  One  way to measure changes in  producer's             •
income is to specify the dose-response relationship so that the
change in output  (as measured  by yield, catch,  etc.) can be
determined.  Assuming  that the increase in output does not  affect            •
price, the change in income  is calculated by  multiplying output              •
change by the relevant market  price.   If  the  output change is
sufficiently  significant that  price  falls, the  new price should be           •
used.                                                                         |

An innovative application of the Net  Factor  Income approach is  to            _
determine the change in input  costs rather than output. Changes in           •
producer's income are  measured by the difference in the cost of              ™
production to sustain  the same yield  at different levels of LRTAP
deposition.   The  advantage of  this approach  is  that estimates can be         B
made in the absence of specific dose-response data.                          0

Partial Budgeting,  a technique similar to net factor income,                 im
estimates the extent of benefits from environmental improvement by           •
calculating the  effects  on key portions  of  a budget of a represen-
tative  (e.g., farm) enterprise.  Expansion  factors can then be  used
to extrapolate from the  effect on the enterprise to the effect  on the        •
industry, or  on  a specific crop or kind  of  livestock.   Examples of           •
this technique are  in  use  in Economics and  Statistics Services, USDA.
Economic gains are  estimated from production and sales of a certain          •
crop because  of  reduced  insect damage, or agricultural losses  to             •
farms and ranches from strip mining of coal.
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                                                                 7-11
Perfect Substitutes is another technique  to  be used where  a  change  in
environmental quality requires less of  other productive  inputs.   This
situation is best illustrated where decreases in  LRTAP deposition
result in reduced use of lime to  treat  drinking water  or maintain
lake water pH.  The value of benefits is  measured by the cost  savings
for lime.


There are some important qualifications,  which affect  the  extent to
which these market methods incorrectly  estimate the value  of
benefits.  The first of  these problems  concerns the use  of "partial
equilibrium" analysis in making estimates  of price and quantity
changes.  All other variables relevant  to  demand  and supply  of goods
and services are assumed not to change.   However, the  availability  of
substitutes is an important determinant of demand, which may well be
altered by the effects of acidic  deposition.  The a priori
implications of change in these aspects can  be noted,  but  the
empirical verification of these hypotheses in some cases is
difficult.  The market price may  generally be used as  the  relevant
measure of unit value.  However,  where  government support  or other
policies which raise prices is in effect,  use of  this  (supported or
other) price may overstate the value  of benefits.


7.2.1.2  Imputed Market Approach


Where there are no organized markets  for  the goods or  services of the
environment (e.g., visibility) or for goods  affected by  quality
(e.g., recreation), a number of imputed market approaches  are
available for deriving or inferring their monetary value.


The Property Value Method is an imputed market approach  which  has
been used to value environmental  benefits.  Economists have  long been
interested in the relationship between  property values and levels of
environmental quality.   It is suggested that variations  in the level
of environmental quality will affect  the  value of otherwise  similar
properties (Ridker 1967; Ridker and Henning  1967). The  value
obtained should reflect  tangible  and  intangible values of
environmental quality, insofar as these are  perceived  by individuals
in the property market.  This facet may pose problems  in the case of
LRTAP.  Since these effects are not well  understood,  the property
market may not accurately reflect the adjustment. Therefore,  the
property value method is not considered an appropriate method  to
measure the benefits of  LRTAP reduction.


Hedonic Price or Demand  Analysis  is a more general application of
this specific property value technique.   A demand function for a
public good is estimated through  a two  step  procedure.  First, the
implicit price of environmental quality is estimated based on
property value (in the case of visibility) or travel  cost  (in  the
case of recreation).  Then the implicit prices are compared  with
variations in environmental quality to  determine  a demand  function.
However, only under a rather broad set  of circumstances  is the demand

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                                                                 7-12
The  major  issues  involved in these techniques relate to three
categories of  bias:   hypothetical, strategic, and information.  They
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function derived as an accurate measure of willingness  to pay  for
environmental quality.

Complementary Expenditure is yet a third imputed market technique.             •
Variation in travel cost is the most frequently used  expenditure and
is the basis for imputing the value an individual  places on  a                  •
recreation experience.  The maximum expenditure of an individual is            |
the basis for deriving a demand curve.  Other expenditures (e.g.,
expenses for fishing equipment) may be used to impute values.                  _

Risk Premium is the imputed market technique most  frequently used  in
valuing mortality.  These risk premiums may include wage
differentials among occupations and insurance premiums.  The                  •
technique could possibly be used to value changes  in  morbidity as              •
well, but foregone wages and medical costs are the more common
valuation approach.                                                            •

7.2.1.3  Nonmarket Approach

A third major approach to valuation is a direct enquiry to                     •
individuals about their willingness to pay for changes  in                      ™
environmental quality.  Information is obtained through an interview
method, whereby respondents are asked to reveal their preferences  for         •
environmental services.  In some cases (e.g., visibility changes),             ^
this approach is an alternative to another major approach  (e.g.,
imputed market).  In cases where no markets exist  for estimating               «
option value, it is the only approach for valuation.                           •

The Bidding Game is a nonmarket approach to preference  revelation.
The technique consists of constructing an artificial  (i.e.,                    •
contingent) market and simulating market transactions.   The                    m
interviewer/auctioneer presents the respondents with  a  set of
possible states or contingencies for the relevant  environmental               K
service.  The respondent is asked to assign a price or  is  asked               •
whether he or she concurs with a price for each possibility.  The
auctioneer enters into a bidding process to determine if the                  _
respondent would pay  (receive) a higher  (lower) price than that               •
stated initially.  The process continues until  the auctioneer  has              ™
determined the highest (lowest) bid.

Rank Ordering is a second nonmarket technique requiring similar               |
information about hypothetical environmental situations to the
bidding game.  Also some measure of the  costs or  price  of  a  visit  was         M
required.  Individuals are asked to rank the hypothetical  situations          •
from the least  to the most desirable.  These  rankings reveal
tradeoffs among the environmental services, other  attributes of an
area and price  of admission.   These tradeoffs form the  basis for              •
estimating the  value  of various levels of environmental quality.               V
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                                                                 7-13
are  summarized  in Rowe and Chestnut (1981), but are briefly discussed
here.

Hypothetical  bias refers to the fact that the hypothetical nature of
the  question  may  not  ellicit accurate bidst  In order to minimize the
hypothetical  bias,  it is essential that the scenario which is defined
for  the  respondent  be as real and credible as is possible.
Otherwise,  the  respondents may feel that the game, being totally
hypothetical, is  not  really relevant.  In this case, they may not
treat  the  interview seriously and hence fail to reveal true bids.

Strategic  bias  is introduced if the respondents have an incentive to
conceal  their true  preferences in order either to avoid payment (be a
free rider) or  to influence the outcome.  Strategic behaviour occurs
when respondents  attempt to impose their preferences on others by
bidding  in  such a way as to influence the mean bid and hence the
outcome  (Brookshire et al.  1976).  The survey must be designed so as
to minimize the influence of these biases.

Information or  starting point bias refers to the extent to which the
information provided  to respondents may influence their bids.
7.2.2   Secondary  Benefits

The approaches  described  above  are techniques for the valuation of
the primary  (efficiency)  benefits  associated with a particular
commodity or service.   However,  the benefits of environmental
improvement  are not  limited  to  a particular good.  Changes in income
to producers in terms  of  crop  or forest products could have important
impacts on jobs and  income in  regions  where these activities are a
part of the  economic base.   Similarly,  changes in sports fishing
activity will affect the  overall sector.   These effects will be more
significant  in  areas where these activities form a greater proportion
of the economic base.   Since these secondary benefits will accrue to
different economic sectors and  to  various geographic regions,
analysis on  a sectoral/regional  scale  provides an additional measure
of welfare change.

Various regional economic analysis techniques are available to
account for  secondary  benefits.  They  measure the effects on spending
and respending patterns (multipliers)  and the direct, indirect, and
induced effects on other  economic  sectors (linkages) and on the
overall level of economic activity in  the region (Bender 1975;
Conoposk 1978).

Although the change  in the overall level  of economic activity due to
LRTAP may be a transfer from one region or country,  the effect of the
transfer is  important  to  that  region or country.   Thus, an analysis
of these secondary effects is an important part of the total estimate
of benefits.

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                                                                 7-14
7.3   BENEFIT ESTIMATION TECHNIQUES
7.3.1   Aquatic

7.3.1.1 Recreational Fishery
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The literature on benefit estimation techniques offers several                 •
approaches for transforming effects of LRTAP on various  receptors              •
into dollar values.  These have been broadly categorized  into three
groups by their reliance on market, imputed market  and nonmarket               M
mechanisms for the generation of value information.  This  section              •
examines the appropriateness of each technique for  the various LRTAP
receptor categories and the methodology employed.   It comments on  the
technique's specific application to the valuation of benefits                  •
associated with LRTAP abatement for each of the identified receptor            •
categories.

In considering which techniques are most appropriate to  LRTAP,                 jf
several factors are relevant.  The benefit estimation techniques
should have a solid theoretical basis (i.e., consistent  with economic          •
theory).  Although the techniques have theoretical  consistency, it is          •
important that the empirical implementation be practical  in terms  of
data and computational requirements.

The techniques selected should minimize the degree  of uncertainty  and          m
contentiousness associated with the results.  Application of the most
appropriate technique to a receptor category and a  clear statement of
assumptions and conditions are essential for credible results.
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The results must be obtained at a reasonable cost.   For  example,               _
survey design must balance practicality and cost with  reliability  of           •
results.  It is not feasible to interview  every member of  society.             ™
Instead, it is necessary to interview representative sample  groups
drawn from the population.                                                     •

These criteria are not independent  of each other.   An  analyst  is
forced to make tradeoffs or concessions.   Ultimately,  it is  desirable          »
to obtain the most useful results at reasonable cost for the purpose           •
at hand.                                                                       *
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The conceptually  correct  procedure  for  estimating  the  value  to users
of changes in recreational  fishing  is to  estimate  the  willingness-            «
to-pay for each site.  Willingness-to-pay is  a  function  of                     I
socioeconomic characteristics,  the  quality of the  recreational                ™
experience at the site and  at substitute  sites,  and  the  (travel and
other expenditure) cost  to  get  to the site and  substitute sites               •
(Freeman  1979).                                                                V

A demand  curve which graphically summarizes willingness-to-pay for an         •
individual site would relate  the number of fishing days  to  the prices         •
of this experience assuming no  changes  in income and tastes.  The
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                                                                 7-15
demand  curve  for  a  given lake is given in Figure 7-3.  If the price
of  admission  to  the lake is OA per day, the quantity consumed will be
OX^.  The  value  of  the recreation site given the initial level of
water quality is  the consumer surplus as measured by the area ABC.
If  no admission  is  charged (i.e., price is zero), then consumer
surplus is the area under the demand curve, (i.e., OBCD^).

Now, if acidic deposition is reduced and water quality improves, the
demand  curve  will shift to the right (02).  The net economic
benefit is the increase in willingness-to-pay as measured by the area
between the two  demand curves,  BDEC.  The net benefit is the
increased  value  to  existing users as well as the value to the new
users.

The problem with  this theoretical approach is that most recreational
fisheries  charge  a  zero price or nominal entrance fee.  Where there
is  no fee  or  variation in market price, a market approach to
valuation  is  impossible.

One imputed market  approach is the Clawson-Knetsch travel-cost
method,  which infers behavioural responses to price changes reflected
by  differences in travel  cost.   This method is site specific and
estimates  demand  for a particular park or lake and not the fishing
activity itself.  This method is done by circumscribing a
recreational  fishing site with a series of concentric zones.  For
each zone,  travel costs and visitation rates are calculated based on
a survey of the origin of visitors.

Four limitations  of  this  technique are the assumptions that all
travel  costs  are  incurred for the purpose of visiting the specified
site, that travel time can be correctly valued,  that only present
users are  accounted  for,  and that response to a  change in quality
cannot  be  inferred  from a single site.   The second can be handled by
using a  shadow price to value time but  will result in different
values  depending  on  the assumptions  used.   The third can be handled
by surveying  non-users within the region to determine their response
to water quality  improvements at a given site.   The fourth requires
data on a  number  of  sites of varying quality. However,  this method
is more  complex if  there  are several recreation  sites which are
substitutes such  as  is likely with the  effects  of LRTAP.   In this
case, the  demand  for any  one site is a function  of prices and
distances  to  other competing sites.

A second imputed  market approach,  the property value technique,  has
seldom  been applied  to changes  in water quality  due to the
difficulties  in correctly accounting for the interaction of water
quality and distance  from water  on property values.   Also it ignores
the value  of  changes  in water quality to recreationists  who do not
own property  in the  vicinity of  the  lake or stream.   This technique
is not  recommended  for a  valuation of benefits  of environmental
improvement for a recreational  fishery  for these  reasons.   In
addition,  data for other  "imputed markets  approaches" are more

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                                                                7-16
Figure 7-3.   Change in demand due to water quality  improvement.
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                                                                 7-17
readily available and it is doubtful  that  in  the  absence  of  solid
information on dose-response  relationships the  property market would
be able to reflect adequately the  pervasive effects  of  LRTAP.


A third imputed market approach is  the  participation model.   The
technique relates participation in  specific recreation  activities by
a given population to the socioeconomic characteristics of  that
population and to the supply  of recreation opportunities  available to
develop estimates of quantity.  If  participation  equations  for
specific populations are estimated,  it  is  possible  to predict  the
increase in participation to  be expected with an  increase in fishing
opportunities or ambient water quality.  The  value  of a recreation
day of particular type must be inferred by other  methods, (e.g.,
travel cost).  Then one component  of  recreation benefits  (i.e., the
value to new users) can be estimated  by multiplying the increase in
recreation days  (quantity) by the  assumed  value per day (price)
(Figure 7-3).  This approach  is limited in that it  does not  capture
the utility associated with the current level of  use (quantity Xj),
that is the area BDFC in Figure 7-3,  and there  is considerable
uncertainty about the value assigned  to a  recreation day.


A probabilistic participation model is  perhaps  the  best technique for
accounting for a broad range  of locations, accessibilities,  and fish
types affected by changes in  reductions in acidic deposition and the
interacting adjustments made  by recreational  fishermen to the
additions of available water  bodies (Russell  1981).   This method
requires:


1.   Estimation of two types  of probability-of- participation
     equations:


     a.  The probability that a randomly chosen member of the U.S.
         or Canadian population is  an angler  at all;


     b.  The probability that a randomly chosen angler spends at
         least some time in a year  fishing for  a  particular  species.


2.   Estimation  of an equation predicting  the number of days of
     fishing per year engaged in by anglers for various fish
     species.


The equations could be estimated using data on  existing water availa-
bility.  Next, changes in the probabilities and days of participation
could be projected for a condition under which  additional bodies of
water were made available for fishing due  to  reductions in acid
deposition.  Fishing days in  this  future state, less fishing days in
the present case, would give  the projected increase in fishing by
type of  fishing.  The increase in  days for each type of fishing would
then be valued at the appropriate  figure for  consumer surplus per

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                                                                 7-18
Species
Type
Lake Type
Susceptible Very Susceptible
(little buffer) (no buffer)
Fish
Population
Surviving
I
I
day.  However, the application  of  this  technique  to  the  benefits  of
reduced LRTAP effects is complex given  its  data  requirements.                  _

The major limitation in applying this technique  is in  relating
changes in total sulphur or  sulphate deposition  to changes  in water
available by species type.   The aquatic effects  work group  would  have         I
to provide an inventory of existing water bodies, differentiated  by           m
susceptibility to acidic deposition and general  species  type  (rough,
warm water and cold water).  In addition, they would have  to  provide           •
dose-response data, such as  different deposition levels  (kg of wet             •
sulphate per ha per year) that  would permit the  survival of fish
populations by species type  for each water  regime in the following             _
format:                                                                        •
                                                                              I
rough         <15 + 5 kg/ha/yr    <10  + 4 kg/ha/yr      >90%                   I
              —   —              —   —                 —                      v

warm water    £15 + 5 kg/ha/yr    <10  + 4 kg/ha/yr      _^90%

cold water    <10 + 2 kg/ha/yr   £5+2 kg/ha/yr      >90%                   •


Without this type of information,  or  another similar approximation,           |
we cannot accurately estimate the  economic  value of a change in
recreational fishing due  to  a change  in acidic deposition.                     •

For recreational fisheries a contingent market approach using
surveys can be used.  The approach attempts to elicit values of how
respondents think they would behave if a proposed water quality               •
change were to occur in a hypothetical situation.  There is some              •
skepticism about these approaches  primarily because they assume that
individuals are capable of predicting and willing to predict                  •
accurately their response behaviour to a hypothetical situation.  In          |
addition, the accuracy of the results may be questioned due to
information, strategic or starting point biases as discussed in               _
Section 2.                                                                     •

There are two limitations to the above techniques.  They fail to
capture option and legacy values of the recreational fishery or the           •
aquatic ecosystem.  They  also place emphasis on valuation of a                •
particular activity rather than the economic sector (i.e.,  recreation
and tourism), which is based on recreational fishing (i.e., secondary
benefits).
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                                                                 7-19
7.3.1.2  Commercial Fishery


The conceptually correct approach  for valuation  in the  case  of
commercial fisheries requires estimation  of  producers'  responses  and
market effects.  In the simplest case,  assume  that only a few
commercial fishermen benefit from  a reduction  in acidic deposition.
If the fishery is being appropriately managed  to maximize net
economic yield, the benefit of reducing acidic deposition is  equal to
the market value of the increased  yield.   This is net  of any  changes
in expenditure on variable factors of production.  For  existing
fisheries, there would be little variable cost change  outside of
shifting fishing grounds or shifting from less desirable to  more
desirable species.


In a more realistic case, the value of  restoring a commercial fishery
will depend upon several variables unique to a given situation.  If
there is free access to the fishery, producer  surplus would  accrue to
the existing fishermen only in the short  run.  This surplus would
attract additional fishermen to  the fishery, which would reduce it to
zero.  If the change in the commercial  catch is  significant,  then
there would be a need to estimate  price effects  (consumer surplus) as
well.


In addition, restoration of a commercial  fishery in economically
depressed areas could conceivably  be sufficient  to strengthen a
region's economic base and hence income and  employment.  Maintaining
the regional population would prevent negative external effects upon
the rest of society.  This is because there  are  higher  levels of
congestion in urban areas due to migration from  depressed fishing
areas.  Some of the secondary benefits  can be  estimated using a
regional income and employment model.


The specificity of the dose-response relationship between reductions
in LRTAP deposition and increases  in commercial  fish populations  and
catches will determine the reliability  of any  estimates of the
benefits to this economic sector.


7.3.1.3  Aquatic Ecosystem


Any valuation of the benefits of reducing acidic deposition  should
reflect the value of all changes in the aquatic  ecosystem, rather
than just recreational and commercial fisheries.  Changes in
salamander and loon populations  could result from reduced acidic
deposition, and these changes could affect activity, option  and
existence values.  Limitations in  dose-response  functions and the
absence of economic studies in this area  will  make it  difficult to
measure these values.  Insofar as  they  are excluded, the total
benefits will be underestimated.   These changes  should  therefore  be
stated in qualitative terms.

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                                                                 7-20
7.3.2   Terrestrial

7.3.2.1 Agriculture
                                                                                I
                                                                                I
                                                                                I
The conceptually correct procedure  for  valuing  changes in the
agricultural sector  is  the  determination  of  changes in producer's and           .
consumer's surplus due  to a change  in environmental quality.   The               •
changes in the surpluses depend  upon  costs of production, demand, and           *
market structure.  Since knowledge  of these  parameters suggests that
most of the benefits of reducing LRTAP  effects  will accrue to                   I
producers, benefits may be  estimated  from observed or predicted                 •
changes in net income of certain factor inputs.   The change in net
income accrues as profit to the  farmer  increases or as surplus income
increases above the  fixed factor of production.
                                                                                I
                                                                                I
In the case of acidic deposition,  there  is  limited  information about
effects on agricultural productivity.  A satisfactory estimate of the          •
change in net factor income can  be obtained from the product of                ™
changes in crop yields multiplied  by market prices.   For this
procedure to be a reasonable estimate  of benefits,  there must not be
government intervention to support the price of  affected crops nor
changes in expenditures for other  production inputs.  In addition, it
is assumed that producers have neither undertaken mitigation                   «
measures (e.g., liming), nor changed cropping patterns in response to          •
acidic deposition.

If acidic deposition is shown  to have  a  measurable  impact on some              •
crops across a large geographic  area,  then  it is recommended that              •
consideration be given to changes  in prices as well as yield.  Given
that many agricultural crops have  inelastic demand  curves (i.e., a             •
small change in quantity demanded  results in a larger proportionate            f
change in price), accounting for price effects would considerably
improve the total estimate of  benefits and  indicate the distribution           _
of benefits between producers  and  consumers.  In the absence of dose-          I
response data, an alternative  estimate of net income changes due to            •
differences in LRTAP is nonetheless possible. This approach requires
measuring the difference in the  cost of  producing a given level of             I
agricultural output under different environmental quality                      |
conditions.

7.3.2.2  Forestry                                                               I

The conceptually correct procedure for estimating the value of
changes in the forestry sector is  similar to the agriculture sector            •
where the market approach is used. Since knowledge of production,             ™
demand, and market structure suggest that the benefits of reducing
acidic deposition will accrue  to producers, benefits may be estimated
from observed or predicted changes in  net factor income.
                                                                                 I
In  the  case  of  acidic  deposition,  a frequently satisfactory technique           _
to  estimate  the change in net factor income is to use the change in             •
timber  yield multiplied by the market value differentiated by species
                                                                                 I

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                                                                 7-21
and product.  Moreover, it presumes that the demand  for  forest
products is highly inelastic  (i.e., insensitive  to price changes).
The procedure is less complex for the forestry sector  than  in the
agriculture sector, because there is less government intervention.
Also there are fewer known uses of mitigation measures or changes in
tree planting patterns due to acidic deposition.


7.3.2.3  Ecosystem


Any valuation of the benefits of reducing acidic  deposition should
reflect the value of all  changes in the  terrestrial  ecosystem,  not
just agricultural and forestry activities.  Change in  nutrient
composition of soils is a major change which may  not be  immediately
captured by changes in yields in the agriculture  and forestry
sectors.  This change, as well as changes in terrestrial animal
populations, would have some  affect on activity,  option  and existence
values.  Although these are best measured by means of  a  survey, it is
unlikely that individuals would be able  to  assign accurate  options or
values to the terrestrial ecosystem considering  the  dearth  of
dose-response information.
7.3.3   Water Supply


The conceptually correct  procedure  for  valuing a reduction in the
direct effects of  acidic  deposition on  water supplies,  is the
reduction of treatment  cost.  These changes  in treatment  costs are a
first approximation as  long  as  they do  not  change other forms of
producers activities, cause  substitutions among factor  inputs, or
change prices of outputs.


Although the use of changes  in  treatment  costs is recommended as a
benefit measure, there  may be problems  in making an empirical
estimate.  The problem  lies  in  correctly  assigning a percentage of
liming costs to the mitigation  of acidic  deposition effects.   Even if
there were no acidic deposition,  industries  and municipalities would
probably continue  their current treatment practices of  balancing the
pH of water.  Consequently,  we  would provide at best only an upper
bound on benefits  by assigning  all  liming costs in areas  of high
atmospheric acidic deposition.
7.3.4   Effects on Buildings  and  Structures


The conceptually  correct  procedure  for  valuing the reduction in the
effects of acidic deposition  on commonly used materials,  is the
annual equivalence of the  present value difference in life cycle
costs of production  processes.  The difference is appropriate for
reductions in deposition  which extend the useful  life of  materials
(including water  supply systems), reduce maintenance or repair costs,
or eliminate the  need for  higher  initial costs for damage resistant
materials.

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                                                                 7-22
                                                                               I
                                                                               I
The recommended approach would use  the  annual  equivalence  of
difference in life cycle costs for  commonly  used  material.  Annual
equivalence would be calculated in  a  two  step  procedure (Maler and            •
Wyzga 1976).  The first step estimates  the present  value of the               •
difference in the stream of current replacement costs  before  and
after acidic deposition.  The second  step calculates  the annual
equivalent flow of the present value  of the  reduction  in damages.
                                                                               I
Benefit estimation for  commonly used materials  requires  information           »
about changes in rates  of deterioration  (dose-response)  or                    •
maintenance, and distribution  of  susceptible  materials.   Thus,
information is essential to  the determination of  the  value of
benefits.                                                                      •

While the life cycle cost approach  values  the benefits of reduced
repair and replacement  costs,  it  does  not  capture the historical              •
value of buildings and  monuments.   This  is an intangible, nonmonetary         •
value, which can best be determined by a willingness-to-pay survey of
viewers for the aesthetics of  less  damaged structures and statues.
However, this method will result  in an underestimate  of  total value           •
in that it fails to capture  option  and legacy values.  A second and           •
important limitation of the  contingent valuation  method  is due  to the
lack of a proven approach.   Although  surveys  have been tested and             •
validated in other areas (e.g., recreation and  visibility),                   f
additional research would be required  prior to  their  application to
derive historical values.                                                      •
                                                                                I
7.3.5   Human Health

7.3.5.1 Mortality

An understanding of the dose-response  relationship between air                 •
pollutants and mortality  and morbidity is  needed to value changes.              •
Animal and clinical studies provide a  basis  for  confirming a
relationship between air  pollution and health.   Some epidemiological
studies estimate a dose-response  between air pollutants  and mortality          •
and morbidity.  Epidemiological and clinical studies can therefore be          "
used to indicate the probability  or risk of  mortality or morbidity
under different environmental  conditions.   These types of data must            B
also be matched with changes in population exposed to determine                0
changes in mortality or morbidity.

The amount that an individual  must be  paid to accept additional risk           •
is conceptually the correct procedure  for  estimating the value of
human life.  When aggregated over many individuals, this willingness-
to-pay, is usually referred to as the  value  of statistical life, or            •
the value of a statistical death  avoided.   It is simply a shorthand            •
way to represent the total amount of  benefits enjoyed by all the
population which benefits from risk reduction.
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                                                                 7-23
One approach for estimating the willingness  to  pay  to  avoid  a
statistical death is to observe human  behaviour in  risky situations.
Most empirical estimates, which have been  reviewed  by  Bailey (1980),
examine wage differentials among  occupations  with varying degrees of
risk.  One empirical estimate used individual choice with respect to
seat belt use.  The values (1978  dollars)  found in  the former studies
(wage differentials) ranged from  approximately  $250,000 (Thaler and
Rosen 1976) to $5.0 million (Smith 1974).  The  value found in the
seat belt study was approximately $313,000 (Blomquist  1979).


Other approaches for estimating the value  of  human  life include total
lifetime earnings, court awards,  and surveys.  Current economic
thinking questions these approaches on theoretical  and empirical
grounds.


Neither the behavioural nor the survey approach captures the
willingness-to-pay of relatives or close friends.   One study
(Needleman 1976) indicates that including  others' willingness to pay
could increase the statistical value of  life  by 25-100%.  Although
this study measured willingness to pay,  it differed from the
behavioural approach in that it placed a value  on a known human life.
The behavioural approach assigns  a value to  an  improvement in safety
for each of a large number of individuals.


Review of the significant behavioural  studies could provide  high and
low limits for the range of values of  a  statistical death avoided.
Therefore, it is the approach recommended  for valuing  the effects
associated with LRTAP.  However,  no monetary  estimates are possible
unless there is an agreed upon dose-response  relationship.


7.3.5.2  Morbidity


The conceptually correct procedure for estimating the  value  of
reductions in morbidity is also what an individual  must be paid to
accept additional risk.  Individuals must  be  paid a certain  amount to
accept lost time at work, or restricted activity days.  A more
complete analysis would also ask  what  an individual must be  paid if
he had to accept a career change  as a  result  of an  accident.


Unfortunately, there are few behavioural studies and surveys which
provide us with estimates of willingness to  accept  risk.  In lieu of
this information, average daily earnings (not wage  differentials by
occupation) for those in the labour force  can be used  as an empirical
value with the recognition that not all  morbidity results in lost
earnings (paid sick leave and sickness on  nonworking day).  Their
earning measures do not reflect loss in productivity and the pain and
discomfort they suffer.


The value of changes in morbidity would partially follow the lower
bound estimates of Freeman (1979).  Morbidity could be measured
either by work days lost or restricted activity days.   The work days
lost measure applies only to people in the labour force.  Restricted

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                                                                 7-24
also be used.
7.3.6   Visibility
                                                                              I
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                                                                              I
activity days applies  to  all  people  of  all  ages and includes degrees
of illness and  incapacitation which  are not severe enough to result
in absence from work.  Work days  lost and restricted activity days
could respectively  be  valued  at $40-$50 per day and $10-$20 per day
to provide a range,  the latter being the (U.S.) average gross daily
earning in the private nonagriculture sector in 1980.                         •

Other measures of the  value of health effects can be obtained from
changes in medical  expenditures for  health  care.   In addition,  the
costs, (e.g., relocation)  incurred  to avoid unhealthy situations can         •
                                                                              I
The conceptually  correct procedure  for  valuing changes in visibility         _
is to estimate  the willingness-to-pay  in each region (Rowe and               •
Chestnut 1981).   The  demand  curve for an individual site would relate
the number of days of  satisfactory  visibility to the price of these
days, assuming  no changes  in such things as  income and tastes (Figure        •
7-4).  If the number  of days of  satisfactory visibility is OA, the           •
value of visibility is the entire area  under the demand curve,
because there is  no expenditure  for visibility.   This assumes the            •
initial level of  visibility  is maintained.                                    •

Using a dose-response  relationship  specified by the effects group, a         _
reduction in LRTA.P with improved visibility  increases the number of          •
days of satisfactory  visibility.  This  results in a movement along           •
the demand curve.  The net economic benefit  is the increase in
willingness-to-pay as  measured by the entire area under the demand
curve.
                                                                              I
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The problem with  this  theoretical  approach for valuing visibility, as        •
with  many environmental goods,  is  due  to  its  special status as a            •
"public good."  There  are  no  markets  for which prices and demand
curves can be directly obtained.   Thus,  imputed market and nonmarket
approaches are proposed as  valuation  techniques in this field.                •

The imputed market approach (hedonic  prices/demand analysis) uses
existing market data,  in cases  where  the selection of a market  good
may vary with visibility levels,  (e.g.,  the choice of residential
location).  This  approach  further  assumes  that the intensity of these
preferences is revealed by  individuals'  behaviour and their demand           _
for associated market  goods (e.g.,  how  much more individuals pay for         •
homes in neighbourhoods with  clean  air,  and the degree to which
vacationers change their travel plans reveal how much they value
visibility).  Technical measures  of pollution  concentrations or              •
visibility levels must be  reasonable  representations of the                  •
environmental attributes that individuals  value.   These measures must
be able to be used to  identify  that part of an individual's behaviour        •
attributable to the component of  environmental quality being                 •
studied.
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                                                                  7-25
               $
                  0
B
                                                    days  of good
                                                    visibility
Figure 7-4.  Change  in demand due to visibility  improvement.

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                                                                 7-26
7.3.7   Summary
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The nonmarket approaches  (e.g., Bidding  Game  and Rank Ordering)
attempt to elicit values  through  surveys of how respondents think            •
they would react to a proposed  visibility change.   In contrast to the        •
market approaches, nonmarket approaches  do not  attempt to infer
values of a component of  environmental quality  from observation  of
individuals' actual behaviour in  response to  a  change in                     •
environmental quality.  Instead,  individuals  are asked to predict how        •
they would respond to a change  in environmental quality.   Bias of
values determined by this method  may  be  due to  the  level of                  •
information conveyed to respondents.  This approach presupposes  that         |
a particular change in environmental  quality  can be described to the
respondents, usually with photographs and verbal descriptions, in a          _
way that corresponds to what their perceptions  of  the actual                 •
experience would be.  For example,  it is assumed that a photograph of
the Grand Canyon obscured by pollution will elicit  a response that
corresponds to what the response  to the  actual  situation would be.           •
This type of approach also assumes that  individuals are capable  and          •
willing to predict their  response behaviour to  a hypothetical
situation that they may not have  ever experienced.                            •

It is recommended that a  review of empirical  studies on the value of
visibility be undertaken  to provide a range of  values for various            _
regions, and for urban and rural  areas.                                       •
I
The following  table provides a  summary  of  methods  and their
applicability  to  the various LRTAP  affected  receptor categories.              •
The 'X' denotes that the method  can be  used,  whereas 5C denotes the           •
method which is recommended as  most appropriate.   The methods capture
only the primary  values and that  regional  econometric analysis is            _
necessary to draw out  the  secondary economic  effects (e.g., jobs  and         •
income) in a given sector  and in  a  specific area.                             •


7.4   QUALIFICATIONS,  CONCLUSIONS AND RECOMMENDATIONS                        |

This section has  provided  a review  of methods which can be employed          «
to determine the  primary economic benefits of LRTAP reduction on              •
specific receptor categories, as  well as  the  secondary economic
effects.


7.4.1   Qualifications

Although numerous limitations and qualifications  have been noted,            |
with respect to specific methods  or issues,  there  are three
significant qualifications which  are relevant to  LRTAP-related               _
environmental  effects:                                                        •
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1
1
1

1
v^v


1

1

1
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^^p
1
1

1

1
1

1
1
1
1


TABLE 7-2. SUMMARY OF METHODS
Market
Factor Substi- Travel
Income tutes Cost
A. Aquatic
1. Sports
Fishery X
2. Commercial
Fishery Xa
3. Ecosystem
B. Terrestrial
1 . Crops Xa
2. Forests Xa
3. Ecosystem
C. Buildings,
Structures
1 . Materials Xa
2. Historic
D. Water Systems Xa
E. Health
1. Morbidity
2. Mortality
F. Visibility


a X denotes the method is recommended as


7-27


Imputed Market Nonmarket
Property Observed Survey
Value Behaviour


Xa X


Xa

X
X
Xa

X
Xa


Xa
Xa
X Xa


the most appropriate.



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                                                                 7-28
7.4.1.2  Inclusion of All Values
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     1)   there is a lack of dose-response relationship information;
     2)   there is difficulty in capturing all benefit values;  and
     3)   there needs to be an evaluation of irreversibilities  and            •
          the all or nothing feature.                                         •

7.4.1.1  Dose-Response Relationship                                           •

The need for data from the Effects Groups for the various  receptor
categories has been stressed at several points.  Although  some  data          •
are available, a clear statement is needed of changes in output              •
(e.g., water availability with fish populations) as  related  to  LRTAP          ™
effects (i.e., changes in pH).  This must be further extrapolated
over geographical areas and over the short and long  term to  derive            •
estimates of total quantity changes (Table 7-3).                              •

In the absence of these data, meaningful benefit estimates are                •
impossible.  Changes in producer cost would provide  an alternative            •
estimate of benefits of LRTAP control with yield and catch held
constant.
I
A second concern is the extent  to which  the  methods  recommended will          •
fully capture the value of  the  benefits.   Some  methods  can provide            J
only a partial measure, since they  cannot  capture  option  and  legacy
values.  Although their exclusion results  in an underestimate,                 M
determination of the actual size of  this underestimate  is difficult.          •
Some economists think  the underestimates are large in situations
dealing with unique assets, or  major changes in an entire
geographical region (e.g.,  New  England).   The matter is further               •
complicated by the issue of property rights, discussed  under  equity           ™
consideration.  Thus,  one should be  cautious in assuming  that any
benefit figure is a reflection  of the full value to  society.   This            •
may be less of a concern where  measurable  values are sufficient to            |
indicate the desired choices.

7.4.1.3  Irreversibilities  and  the  All or  Nothing  Feature                     •

There are additional limitations to  conventional economic analysis.
The physical dose-response  relationships with respect to  LRTAP                I
deposition may be irreversible  and  the rate  of  damage may not be              •
monotonically related  to deposition.  This is called the  all  or
nothing feature or nonconvexities.                                             •

First, once a certain  level of  damage has  occurred,  reduction in
LRTAP may not result in an  improvement in  environmental quality.
Hence, the effects of  LRTAP may be  irreversible (i.e.,  certain                •
species may never be restored).  If  so,  current market  or inferred            •
prices will substantially understate the value  of  these resources to
society.  From the perspective  of benefit  valuation, it is imperative         •
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TABLE 7-3.   SUMMARY  OF  PHYSICAL  SCIENCE  DATA NEEDED  FOR BENEFIT
             EVALUATION
                               Inventory
                                  Dose-Response
A.  Aquatic

    1. Sports
       Fishery
water availability by
susceptibility, geographical
area and species type
    2. Commercial    water availability  by
       Fishery       susceptibility,  geographical
                     area and  species  type
    3. Ecosystem
B.  Terrestrial
species diversity, numbers
    1. Agricultural  crop  pattern  by  geographical
       Crops         area
    2. Forests
    3. Ecosystem
C.  Buildings,
    Structures

    1. Material
    2. Historic



D.  Water Systems



E.  Health

    1. Morbidity


    2. Mortality


F.  Visibility
cover type, age, stocking
and size by geographical
area

species diversity, numbers
geographical distribution
by type of material and by
use

geographical distribution
by type of material
geographical distribution
of systems on susceptible
water bodies
population
population
population
change in fish
population with
varying deposition
levels

change in fish
population with
varying deposition
levels

changes in species
diversity and numbers
change in marketable
yield with varying
deposition levels

change in marketable
yield with varying
deposition levels

changes in species
diversity and numbers
deterioration rate
as a function of
total sulphur

deterioration rate
as a function of
total sulphur

change in lake/stream
intake pH
sickness per
deaths per yg/m3
change in km of
visibility per
    3 S042~

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                                                                 7-30
that option, existence, and legacy values be included  in  the
estimates.
      property rights.
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Second, after a certain level of pollution, the  rate  of  damages
declines (Crocker and Forster 1981).  Such would be the  case  where
most of the fish are gone and further pollution  has little  or no              •
impact.  This feature of nonconvexity would suggest that benefits  of          |
LRTAP control are much higher, increasing at a faster rate  in a
relatively unpolluted environment.  Once the rate of  damages  starts            •
to decline, the benefits of abatement would be commensurately lower.          •
The limitation of this suggestion is that it is  based on the  adverse
effect on a few species.  If acidic deposition affects numerous
species, any mitigation effort even at high levels of pollution  could         •
show significant benefits.                                                     •
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7.4.2   Conclusions and Recommendations

This paper has attempted to provide an overview  of  techniques  of              .
deriving the economic value of benefits  associated  with LRTAP                  •
abatement.  There is a large body of economic  literature which deals          ™
more thoroughly with the intricacies of  the  theory  and  is replete
with numerous empirical studies.  However, many  of  the  latter  have            H
not dealt specifically with the  effects  of LRTAP.                              |

Four conclusions arise from the  material presented  here.                      •

1.   There are several techniques which  can  be applied  to determine
     the primary economic  benefits  associated  with  a particular
     activity category.  The values are  underestimated  since they             •
     fail to include option and  legacy values  for  some  effects.               B
     However, the lack of  data on dose-response  relationships  limits
     the application of these techniques at  this time.                         •

2.   Even in the absence of dose-response data,  a variation in the
     factor income  approach is available to  estimate the benefits of          _
     changes due to reduced LRTAP deposition.   This approach provides         I
     benefit estimates on  the basis of the differences  due to  various         ™
     levels of LRTAP in production  costs for a given level of  output
     and could be applied  to commercial  fisheries,  agriculture,               H
     forestry, and  buildings and structures.                                  •

3.   The value of the benefits can  be  further  estimated for specific          •
     economic sectors, and hence regions, to derive an estimate of            •
     the impacts in various geographical areas.

4.   It is evident  that more economic  research is required.  Economic         •
     techniques have yet to be rigorously tested in some sectors,             ^
     (e.g., historical value) and  are  limited  in their treatment of
     option and legacy values and  in  dealing with the issue of                •
                                                                                I

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                                                                 7-31
The following recommendations can be made:


1.   Dose-response data are available  for  the  aquatic  receptor and
     the geographically - specific  studies  now being undertaken tend
     to ignore substitution among fishing  sites.   Therefore,  the
     participation model should  be  applied  on  a U.S./Canada basis to
     sports fishing to determine the value  of  primary  benefits due to
     LRTAP reduction.


2.   A regional economic analysis should be undertaken to derive the
     secondary value of the recreation and  tourism sector in areas of
     the U.S. and Canada affected by LRTAP (e.g.,  Adirondacks and
     Muskoka-Haliburton).


3.   To develop benefit estimates for  LRTAP reduction  for commercial
     fisheries, agriculture,  forestry, and  buildings and structures,
     a variation on the standard factor income approach should be
     used.  Here the differential in the cost  of producing a given
     level of output is determined.


4.   Further research  should  be  undertaken to  determine the most
     appropriate value for  changes  in  morbidity.


5.   Further research  needs to be initiated to apply the survey
     (contingent market) methodologies to  the  derivation of primary
     benefit values of visibility in the eastern U.S.  and Canada and
     to historical sites, because of the lack  of information about
     these values.


6.   Further work needs to  be undertaken with  respect  to the issues
     relating to property rights.   These are an important part of the
     distributional aspect  of the long range transport of
     pollutants.


7.   The relationship  between activity and other (option and legacy)
     values for the various receptor categories should be further
     investigated in order  to derive a sense of the underestimate of
     the total benefits due to the  omission of the latter values.

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                                                                7-32
7.5    REFERENCES
        Baltimore, MD.:   Johns  Hopkins  University Press  for Resources
        for  the  Future.
I
I
Bailey, M. J. 1980.  Reducing risks to^ life.  American Enterprise              I
       Institute, Washington, DC.                                              •

Bender, L.D. 1975.  Predicting employment in four regions of the               •
       western United States.  Technical Bulletin No. 1529, Economic           |
       Research Service, U.S. Department of Agriculture, in
       cooperation with Montana State University Agricultural                  _
       Experiment Station.                                                     I

Blomquist, G. 1979.  Value of life saving:  implications of
       consumption activity.  Journal of Political Economy (87).               I

Brookshire, D.B.; Ives, B.; and Schulze, W.D. 1976.  The valuation of
       aesthetic preferences.  JEEM 325-46.                                    •

Canadian Treasury Board.  1976.  Benefit-cost analysis guide.
       Canadian Treasury Board Planning Branch, Information Canada,            _
       Ottawa, Ont.                                                            •

Conoposk, J.V. 1978.  A data-pooling approach to estimate employment
       multipliers for small regional economies.  Technical Bulletin           •
       No. 1583, Economics, Statistics, and Cooperatives Service,              |j
       U.S. Department of Agriculture, in cooperation with the U.S.
       Environmental Protection Agency.                                        •

Crocker, T.D., and Forster, B.A.  1981.  Decision problems in the               *
       control of acid precipitation:  nonconvexities and
       irreversibilities.  J. Air Pollut. Control Assoc. 31(1):                B
       31-37.                                                                  1

Crocker, T.D.; Tschirhart, J.T.;  Adams, R.N.; and Forster, B.   1981.           •
       Methods development for assessing acid precipitation control            B
       benefits.  U.S. Environmental Protection Agency, draft
       report.                                                                 _

Eckstein, 0. 1961.  A survey of  public expenditure criteria.   In               ™
       Public finance:  needs, sources, and utilization.
       Universities-National Bureau Committee on Economic Research,            B
       Princeton, NJ.:  Princeton University Press.                            B

Freeman, A.M. III.  1969.  Project design and evaluation with multiple          mm
       objectives.  In The analysis and evaluation of public                   I
       expenditures:  the PPB system,  subcommittee on Economy  in
       Government,  U.S. Congress  Joint Economic Committee,
       Washington,  DC.                                                         I

              1979.  The  benefits of environmental improvement.
 I

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                                                                 7-33
Haveman, R.H., and Weisbrod, B.A.  1975.  The concept  of benefits  in
       cost-benefit analysis:  with emphasis on water pollution
       control activities.   In Cost-benefit analysis  and water
       pollution policy, eds. H.M. Peskin and E.P.  Seskin.   Urban
       Institute, Washington, DC.


Maler, K.G., and Wyzgon, R.E. 1976.  Economic measurement of
       environmental damage:  a technical handbook.   Paris:   OECD.


McKean, R.N. 1958.  Efficiency in government through  systems
       analysis.  New York:  John Wiley and Sons.


Mishan, E.J. 1971.  Cost-benefit analysis.  New York:  Praeger.


Needleman L. 1976.  Valuing  other people's lives.   Manchester School
       of Economic and Social Studies  44: 309-342.


Ridker, R.  1967.  Economic costs of air pollution.  New York:
       Praeger.


Ridker, R. , and Henning, J.  1967.  The determinants of residential
       property values with  special reference to air  pollution.
       Review of Economics and Statistics 49: 246-257.


Rowe, R.D., and Chestnut, L.G. 1981.  Visibility benefits assessment
       guidebook.  Interim Report to U.S. Environmental Protection
       Agency, Contract Number 68-02-3528.


Russell, C.S. 1981.  Measuring the damages of acid  precipitation
       deposition;  recreational fishing.  Memo to  USEPA.


Steiner, P.O. 1977.  The public sector and the public  interest.   In
       Public expenditure and policy analysis, 2nd  edition,  eds.  R.H.
       Haveman and J. Margolis.  Chicago:  Rand-McNally.


Thaler, R., and Rosen, S. 1976.  The value of saving  a life.  In
       Household production  and consumption, ed. N.E.  Terleckyj.
       National Bureau of Economic Research, New York, NY.


U.S. Water Resources Council. 1980.  Proposed rules;  principles,
       standards and procedures for planning water  and related land
       resources.  Federal Register Vol. 45 April 14.

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                                                                 7-34
APPENDIX - REVIEW OF  RELEVANT  ECONOMIC CONCEPTS
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Two basic economic concepts which  provide  a  measure  of changes in              •
social welfare (satisfaction)  are  consumer's surplus and producer's            ™
surplus.  Changes in these measures  are  regarded  as  being the most
theoretically relevant  indicators  of social  welfare  loss or gain,              •
resulting from specific activities or events.                                   |


A. 1   Consumer's Surplus                                                        I

Traditional economic theory presumes that  the  individual consumer is
the best judge of his own personal well-being  or  utility given                 I
currently available information.   If an  individual is made better              •
off, other things being equal,  then  his  social well-being or welfare
is increased.                                                                   •

The individual consumer allocates  his money  income across the various
commodities in such a fashion  that he maximizes his  welfare or                 •
utility.  In general, his desired  purchase of  a commodity will depend          I
upon his tastes, the prices of  all goods,  and  his income.

The demand curve graphically  represents  the  relationship between the           •
desired purchase of a commodity and  its  price  (or the willingness-             •
to-pay).  For each additional  unit,  the  consumer  is  willing to pay
less than for the previous unit.   Hence, the curve slopes down to the
right.  This is called  the ordinary  demand curve  or  the Marshallian
demand curve.  If we assume that more of the good will be purchased
at lower prices if prices fall  (a  "normal" good), then a consumer's            _
ordinary demand curve is represented in  Figure 7-5.                             •

A point on the demand curve is  the maximum price  that the individual
would be willing to pay for a  specified  amount of good, and is noted           I
by an ordered pair (x,  p).  Alternatively, for a  given price p, x              •
represents the most the consumer would willingly  purchase.  A maximum
price exists for every  potential consumption level for the good, and
is given as the relevant p-point on  the  demand curve.
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Suppose that the commodity  sells  in the  market  for PI and the con-             _
sumer purchases Xj.  The  consumer's expenditure on x is Pj X^                  B
(price times quantity).   The  triangular  area denoted PjAB, which               •
lies above the expenditure  rectangle OPjBXj  is  what economists
call the Consumer's  Surplus.   It  is a surplus,  since it represents a           I
saving to the individual  in terms of what  he would have been prepared          |
to pay for levels of consumption  smaller than X,  as shown by the
associated prices on the  demand curve.   Instead of paying the maximum          M
price for each level of commodity x, the consumer pays Pj for all              B
units.  If all of the  savings  are added  up,  then  we obtain the area
P^AB.  Since the price is given in money units, consumer surplus is
a monetary measure.  The  area OP^BX^, plus the  area PjAB                       B
(consumer expenditure  plus  consumer surplus), is  a measure of the              B
gross benefits to the  individual  of consuming Xj  units.  Consumer's
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^V
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X1

Figure 7-5. Measure of consumer surplus.
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P1
P2
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V

\ox
x1 x2

Figure 7-6. Change in consumer surplus.
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7-35

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                                                                 7-36
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surplus is the net benefit to the individual consuming x° units,
that is, total willingness-to-pay minus expenditure.

Changes in the value of consumer's surplus are a measure of the                 •
welfare associated with the activity which caused the change.
Consider the case in which the price of the commodity falls from  P^             H
to ?2 due to an environmental improvement as illustrated in Figure              |
7-6.  At price ?2, the consumer can both purchase more of the
commodity, and pay less per unit.  In addition, his consumer's                  _
surplus is increased by the trapezoidal area P2PiEB.  This                      I
geometric area represents a monetary measure of the welfare effect              ™
associated with the price change.

Consumer's surplus can be estimated for an individual, using observed           •
price and quantity data.  However, instead of estimating individual
demand curves, economists use aggregated data and estimate market               •
demand curves.  Market demand curves are obtained by aggregating                •
individual demand curves, that is, adding up horizontally (along  the
quantity axis).  This implies that tastes and preferences can be                _
aggregated across individuals.  If, however, individuals have                   •
different incomes, or if the distribution of income is altered                  ™
significantly, then aggregations can lead to biases in estimates.
Simple linear summation of these demand curves is inadequate.  Then,            H
one must resort to Engel curves.                                                I

There are two alternative monetary measures of the effects of a price           •
change, known as equivalent and compensating variation (denoted as EV           •
and CV respectively), which can be translated into a change in
income.  Under the circumstances where a decrease in LRTAP effects
results in a price decrease, EV and CV can be defined as follows:               I

Compensating Variation is the change in income which, given the price
decrease, maintains the consumer's original utility.  CV is equal to
the income which would be withdrawn to offset the price decrease.
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Equivalent Variation is the change  in  income which, given  the                   _
original price, would leave the consumer's  satisfaction  or utility             I
unchanged if price decreases.  An increase  in  income equal to  EV
would be given to the consumer to maintain  welfare.

While EV and CV are technically the more  correct measures  of welfare            |
change, they are difficult to estimate.   The value of  consumer
surplus, which is closely related to CV and EV,  is easier  to measure            •
and is therefore recommended for this  analysis.                                 I

Public Goods                                                                    —

In the above discussion, we assumed that  commodity x was traded  in an          •
organized market at a nonzero price.   The impact of LRTAP  on the
price of a particular commodity was subsequently considered.   This             •
scenario is, of course, an over simplification.  Now let us consider            |
a certain commodity which is a "public good" such as an  environmental
                                                                                I

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                                                                 7-37
commodity (e.g., clean air).  This type of commodity is not  traded  in
an organized market but it does have a value to  society.   The  levels
of this environmental commodity are assumed to be  outside  the  control
of the individual.  Hence, the overall level of  consumer welfare
depends not only upon prices of market commodities and money income,
but also upon the level of environmental commodities he consumes.


Where there are no markets and hence no prices,  it is difficult to
derive a demand curve.  Demand is derived through  other means  as
discussed in Sections 2 and 3.  Again, the measure of consumer's
surplus is the area under the demand curve.  In  this case, consumer's
surplus is the total area since the price is zero. The change in
consumer surplus would be measured by the change in quantity if, for
example, visibility increases due to reduced LRTAP (Figure 7-7).


While willingness-to-pay is used to determine demand curves, this is
not the real test of the value of visibility.  However, it is  an
easier measure.  The change in quantity has affected consumer
utility, and the consumer effectively enjoys an  increase in  income.


We can therefore obtain a monetary measure of the  welfare  change, by
considering the change in income which will have the same  impact as
the change in environmental quality.  Here there are two measures —
compensating and equivalent surplus (denoted as  CS and ES),  depending
upon which welfare position is used for the initial starting point
for comparison.


Compensating surplus is the change in income which results in  the
same level of utility, given the change in quantity (Figure  7-8).
Equivalent surplus is a change in income which produces a  change in
utility equal to the change in quantity, at the  original quantity
level.
A.2   Producer's Surplus


The discussion thus far has been concerned with consumer's  surplus
as one measure of economic welfare.   It is possible to define an
analogous concept for producers in the economy.  This is  called
producer's surplus.  The concept of consumer's surplus is defined
with respect to the consumer's demand curve.  Producer's  surplus is
defined with respect to the producer's supply curve of the  relevant
commodity.  Figure 7-9 presents a supply curve, which presumes that
more of the output will be produced as price rises.  Higher prices
are required to cover increased production costs at higher  output
levels.


In Figure 7-9 a point (Xj, Pj) on the supply curve can be given
two interpretations.  For a given price P^, the output Xj is the
largest that the firm is prepared to supply at that price.  For a
given output Xj, the price PI is the minimum price that the firm
will accept for supplying X^.  In the market all units sell for the

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                                                                 7-38
                $
0
                                        A   B       days of good
                                                    visibility
Figure 7-7.   Change in demand due  to visibility improvement,
          Income
                 M
Figure  7-8.    Compensating  and  equivalent surplus.
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              Figure 7-9.   Producer's surplus.
                               A


                               E
                                0
              Figure  7-10.    Change in producer's surplus due to change in supply.

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                                                                 7-40
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same price and the producer gains on all unit levels which are  lower
than the total sale.  This is because the market  price  exceeds  the
minimum the producer needs.  This gain is called  producer's  surplus,           •
and is represented by the area AP^B, the area above the supply                  |
curve bounded by the market price (Figure 7-9).

Changes in the value of this producer's surplus are interpreted as  a           •
measure of welfare change.  This change causes a  supply shift from  S
to Sj, due, for example, to an increase in crop yields  from  reduced
LRTAP (Figure 7-10).                                                            •

The area ABCE represents the welfare gain to the  producer caused by a
shift in the supply curve from S to S^.  The minimum price required            •
to supply each level of output is now lower, and  is everywhere                  £
further from the market price received by the producer.

Changes in net social welfare caused by LRTAP effects on marketable            I
commodities can be determined by examining the net change in
consumer's and producer's surpluses.  Suppose, for example,  that the
reduction of LRTAP deposition results in an increased supply of some           I
product.  The supply curve has then shifted to the right from S to              m
Sj_, while the demand curve for the product remains stationary at D,
(Figure 7-11).                                                                  •

The area EP2C is the new producer's surplus, caused by  the price
fall due to the supply increase, compared to AP^B at the original              _
supply and price levels.  Producer's surplus changes for two reasons.          •
The producer's surplus is increased by EAFC as a  result of increased           ™
production at lower cost, with a given market price.  Producer's
surplus decreases by P2P^BF a result of market pressures                       •
decreasing output prices and stimulating production.  The net change           |
in surplus is therefore ABCE.
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             Pl

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Figure 7-11.   Hypothetical change in producer's  surplus due  to
               reduction in LRTAP deposition.

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               SECTION 8

NATURAL AND MATERIAL RESOURCES INVENTORY

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                                                                  8-1
                               SECTION 8
              NATURAL AND MATERIAL  RESOURCES  INVENTORY
8.1   INTRODUCTION

The objective of an  economic  evaluation  of  acidic deposition is to
estimate the value of reduced  adverse  effects  achieved by a given
reduction in emissions.   This  objective  is  pursued in six steps:

1.  Inventory:  Identify  the  totality  of  the resource of interest.
2.  Sensitivity:  Divide  the  resource  inventory into sensitivity
    classes.
3.  Exposure:  Subdivide  each  sensitivity class by the severity of
    some indicator of deposition.
4.  Response:  Measure  the  adverse  response expected absent of
    mitigative measures,  for  each sensitivity-exposure subdivision.
5.  Mitigation:  Determine  reduction in  deposition resulting from
    mitigation measures and calculate  the fraction of the adverse
    effects estimated in  (4)  that would  be  reduced.
6.  Valuation:  Estimate  the value  of  the adverse effects reduced.

The long-range transport  of air  pollutants  (LRTAP) inventory of
resources potentially at  risk  includes aquatic,  terrestrial, and
man-made resources.  In all cases,  the inventories now available are
incomplete and generally  lacking in the  detail needed for a
benefit/cost evaluation.  The  aquatic  inventory is limited to large
streams and lakes, and does not  include  potentially  affected fish
populations or the many plants,  insects  and animals  living in or
adjacent to water bodies.  The terrestrial  ecosystem consists of two
major components, agriculture  and forestry.  The inventory of each
will be conducted separately.  Only major crop values and production
are surveyed for the agricultural inventory.   The forest inventory
differentiates only  between major forest  types and does  not include
any information on shrubs and  grasses.   The materials inventory is
far. from complete in that it does not  include  common construction
materials, such as galvanized  steel and  chain  link fence.  It lacks
detail in describing historic  places,  landmarks  and  parks, and is the
least comprehensive  of  the  three categories.

This LRTAP inventory of resources potentially  at risk does not
include all natural  and man-made resources  in  eastern North America.
Wherever data are available,  the inventory  is  geographically
selective by two important criteria: (1)  sensitivity, and (2)
deposition regime.

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                                                                  8-2
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The first criterion is the sensitivity  of  the  various  natural  and
man-made systems to acidic deposition.   (The concept  of  sensitivity
is explained in more detail in  sections 3.5 and  4.5 of this  report).           •
The sensitivity of aquatic ecosystems is a function of soil                    |
characteristics, bedrock geology,  topography,  and  alkalinity of  the
receiving waters.  The sensitivity of terrestrial  ecosystems is  a             M
function of soil characteristics and management  practices  and  bedrock         B
geology.  It should be noted  that  even  if  a forest ecosystem is  not
in a sensitive area, its foliar system  may still be affected by
acidic deposition.  The sensitivity of  man-made  structures is  a                B
function of the specific material  and the  mitigation  measures                  B
undertaken by man.  For example, the sensitivity of metals is  a
function of their composition and  of the surface platings  or coatings         •
of corrosion resistant materials.   Calcareous  stone and  masonry  are           |
sensitive materials unless protected.

The second criterion is the intensity of acidic  deposition.   Wet              B
sulphate deposition is used herein as an indicator because data  are
available and because wet  sulphate deposition  is clearly an important
contribution to overall acidification.   Other  factors, (e.g.,  dry             B
deposition, nitrates, and  seasonability of deposition),  are known to          |
affect the acidification potential of deposition,  but an indicator
which combines all of those factors is  not yet available.   It is              m
known that ambient sulphur dioxide concentration is a more                    B
appropriate indicator of the  potential  damage  to materials than wet
sulphate, so SC>2 is used in place  of  sulphate  when considering                —
materials.  Wet sulphate deposition is  divided into three  ranges as           I
shown in Figures 8-la and  8-lb: low  (10-20 kg/ha.yr), moderate               B
(20-40 kg/ha.yr), and high (greater than 40 kg/ha.yr).


deposition intensity to define  resources potentially  at risk is  best
explained by a simple graphic (Figure 8-2).   Each  data category               ^
(e.g., resource distribution, sensitivity  and  deposition)  constitutes         B
one set.  Any overlap of the  three sets defines  the resource                  *
potentially at risk.  Thus, the inventories provide information on
the quantity and nature of resources within  each of the three                 I
deposition zones.  In the  case  of  aquatic  resources,  this  is                  |
supplemented by estimates  of  the potential of  the  soils and bedrock
to reduce (or buffer) acidity.                                                 •

The estimates of resources at risk presented  in the following
sections are based on steps  1 to  3, (i.e., inventory, sensitivity,            —
and exposure; page 8-1) and  are illustrated  in Figure 8-2.  Steps 4           I
to 6  (i.e., response, mitigation,  valuation),  as well as better data          ™
for steps 1 to 3, will  further reduce  the  amount of the resource of
interest in evaluating  an  emission reduction  measure.  It should be           •
clear from the other  sections in  this  report  that  our ability to              B
perform  steps 4 to  6  is  limited at present.   Therefore, the estimates
below should not be  interpreted as representing the value attri-
butable  to a deposition  control measure, but  rather as categories  of
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8-3
                                                                            0-10  KG/HR


                                                                            10-20 KG/HR


                                                                            20-40 KG/HR


                                                                            >MO  KG/HR
             Figure 8-la.    Annual sulphate deposition regime for eastern United
                            States, based on NADP data covering April 1979 to
                            March 1980.

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8-4
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                                                            8-5
                                  SPECIFIC RESOURCE

                                     SENSITIVITY
 RESOURCE INVENTORY
                             DEPOSITION PATTERN
Figure 8-2.   Conceptual scheme  for identifying resources
             potentially at risk.

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                                                                  8-6
                                                                                I
                                                                                I
resources potentially  at  risk  from which actual damages remain to be
derived.

The resource inventory has drawn  on data from a variety of sources.             |
Although none of it was compiled  specificially for acidic deposition,
the best estimates have been made  using this  information compiled for          •
different purposes, in different  ways  and for various years.                   •
Attempts were made to  ensure that  the  U.S.  and Canadian inventories
are reasonably comparable.  Despite the minor differences it is
believed that the inventory presented  here  represents the best data             •
available.  Additional data collection will be necessary to improve             I
the inventory both in  coverage  and specificity (e.g., tree species).
                                                                                I
                                                                                I
8.2   AQUATIC ECOSYSTEM

For the purpose of defining  potential  resources  at risk, the aquatic           I
ecosystem identified here pertains  only to  lake  and stream area
measures.  A census of surface  water resources within each
combination of sensitivity/deposition  regimes  has been taken to                M
provide quantitative estimates  of  the  total area of surface waters             •
(i.e., lakes and streams) potentially  at  risk.


8.2.1   U.S. Aquatic Resources

The Work Group took as its starting point for  an inventory of surface          •
water areas the Geoecology Data Base maintained  by Oak Ridge National          ™
Laboratory (ORNL).  The  surface water  inventory in the Geoecology
Data Base includes all lakes  greater than 2 acres and permanent
streams.  The primary advantages of using the  inventory in the
Geoecology Data Base are the  completeness of the surface water
inventory and that ORNL  prepared the map  of sensitive areas for the            M
Aquatics Subgroup (Figure 3-10;  Olson  et  al. 1982).  The primary               •
disadvantages of using the Geoecology  Data  Base are the absence of             '
data on surface water chemistry (i.e.,  alkalinity) and the inability
to discriminate among various sizes of lakes and streams.  The                 B
inventory includes several large lakes and  streams which even in               •
sensitive areas would probably  not  be  adversely affected by acidic
deposition.                                                                     •

The Work Group limited its inventory effort to 38 states; those east
of the 100° meridian.  The surface  water  area  in all counties with             _
50% of the land area in  urban and  agriculture  uses was assigned to a           •
special category rather  than one of the three  sensitivity categories.          ™
Surface water in this category  were assumed to be more adversely
affected by urban and agricultural  activities  than by acidic                   •
deposition.  The remaining surface  water  area  was assigned to one of           |
four deposition categories.   The disaggregated results of the
classification are included  in  Appendix Tables 8-1 to 8-3.                     M
                                                                                 I

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                                                                  8-7
Approximately 25% of the U.S. surface water area  is  located in areas
with limited (low and moderate) potential  to  reduce  acidity and of
deposition greater  than 20 kg S042-/ha.yr  (Table  8-1).   Only
10% are located in  areas with the most  limited  (low  only)  potential
to reduce acidity and of deposition  greater than  20  kg  SC>42-/ha.yr.
The actual surface  water area would  be  more limited  if  data were
available on surface water chemistry (i.e., alkalinity).   Additional
refinements of the  inventory should  include data  on  this variable as
well as more accurate measurements of  surface water  area.

Although the aggregate 38-state data show  that  approximately 25% of
the U.S. surface water area  is potentially at risk,  data disaggre-
gated at the state  level show a much higher percentage  in  some states
(Table 8-2).  All of the New England states have  at  least  70% or more
of the surface waters potentially at risk.  Three mid-Atlantic states
(Maryland, New Jersey, and New York) and three  southern stated
(Georgia, North Carolina, and Virginia) have  at least 50%  or more of
their surface water potentially at risk.  Most  of the states in the
mid-west, west and  southwest have very  limited, if any, surface water
potentially at risk except for Michigan and Arkansas.  In  some states
with low potential  to reduce acidity and numerous lakes, such as
Wisconsin and Minnesota, the annual  sulphate  deposition loading is
less than 20 kg/ha.yr, so the surface water area  is  not considered at
risk.  In all cases, these estimates of surface water potentially at
risk will be reduced to some degree  when data on  stream chemistry are
available.
8.2.2    Canadian Aquatic  Resources

The basis for  the  inventory  was  provided by the map indicating the
potential of soils and  bedrock to  reduce the acidity of atmospheric
deposition  (Figure 3-9; Lucas  and  Cowell 1982).  This was overlaid
with the map of sulphate  deposition (Figure 8-lb).   Finally, data on
the proportion of  surface water  area for each province was combined
with the deposition/acidity  reduction capability information to
derive estimates of  the total  area  of surface waters at risk.

The data on surface  waters were  drawn from two main sources.  In
Ontario, detailed  lake  counts  and  measurements (Cox 1978) provided
data on  a watershed  basis.  For  Quebec and the Maritimes, the
Ecodistrict Data Base developed  by  Environment Canada (1981a,b) was
utilized.   The data presented  here  provide an estimated ratio of
water to land  for  each  Ecodistrict.  No data were available for
Newfoundland and Labrador. Two other serious omissions of this
inventory are  a lack of information on lake alkalinity and data on
specific aquatic biota  associated  with the various deposition regimes
on a provincial basis.

Table 8-3 provides a provincial  summary of the aquatic resources at
risk based  on  surface water  sensitivity (as estimated by the

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                                                                  8-8
TABLE 8-1.   SUMMARY OF EASTERN U.S.  SURFACE WATER AREA (km2)
             CROSS CLASSIFICATION BY  SENSITIVITY AND DEPOSITION
             (USDA 1971, 1978a)
 Sulphate    Urban and
Deposition  Agricultural
(kg/ha.yr)     Area
 AREA km2 (Percent of Total)


 Potential to Reduce Acidity
Low3
Moderate
High
Totalb
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  0-10        2,290(2)       10(<1)     1,240(1)


 10-20       17,240(12)   5,410(4)     11,470(8)


 20-40       11,120(8)   13,940(10)    19,970(14)


    40        5,070(3)      210(<1)     2,190(1)


 TOTALb      35,720(25)  19,570(15)    34,870(25)
                         3,950(3)     7,490(5)


                        15,740(10)   49,860(35)


                        27,400(19)   72,430(50)


                         7,620(5)    15,090(10)


                        54,710(35)   144,870(100)
a A low potential to reduce acidity  is  interpreted  as  a  high
  sensitivity.


k Rounded to the nearest 5%.

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                                                                  8-9
TABLE 8-2.   SURFACE WATER AREA WITH LOW AND MODERATE POTENTIAL TO
             REDUCE ACIDITY RECEIVING GREATER THAN  20 kg/ha.yr
             SULPHATE DEPOSITION (USDA 1971, 1978a)
                               km2 (percent of  State Total)
                      Low Potential  to
                       Reduce Acidity
Moderate Potential
 to Reduce Acidity
REGION I
Connecticut
Maine
Massachusetts
New Hampshire
Rhode Island
Vermont
REGION II
New Jersey
New York
REGION III
Delaware
Dist. of Columbia
Maryland
Pennsylvania
Virginia
W. Virginia
REGION IV
Alabama
Florida
Kentucky
Georgia
Mississippi
North Carolina
South Carolina
Tennessee
REGION V
Illinois
Indiana
Michigan
Minnesota
Ohio
Wisconsin
REGION VI
Arkansas
Louisiana
Oklahoma
Texas

340
6,010
970
860
340
720

150
1,930

0
0
20
40
70
120

10
0
30
250
60
310
0
90

0
10
1,690
0
0
0

130
0
0
0

( 70)
(100)
( 90)
(100)
( 75)
( 70)

( 15)
( 40)

( 0)
( 0)
( <5)
( <5)
( <5)
( 25)

( <5)
( 0)
( <5)
( 10)
( <5)
( 5)
( 0)
( <5)

( 0)
( <5)
( 40)
( 0)
( 0)
( 0)

( 5)
( 0)
( 0)
( 0)

0
0
0
0
0
0

660
1,250

0
0
1,020
550
1,660
20

1,280
410
400
1,660
810
9,010
640
110

0
40
0
0
0
0

1,350
0
1,090
10

( 0)
( 0)
( 0)
( 0)
( 0)
( 0)

(75)
(20)

( 0)
( 0)
(50)
(35)
(55)
( 5)

(35)
( 5)
(15)
(55)
(40)
(85)
(25)
(<5)

( 0)
(<5)
( 0)
( 0)
( 0)
( 0)

(35)
( 0)
(25)
(<5)

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                                                                  8-10
TABLE 8-2.   CONTINUED
                               km2 (Percent of State Total)
REGION VII
  Iowa
  Kansas
  Missouri
  Nebraska


REGION VIII
  North Dakota
  South Dakota
                      Low Potential to
                       Reduce Acidity
0  (  0)
0  (  0)
0  (  0)
0  (  0)
0  (  0)
0  (  0)
                   Moderate Potential
                    to Reduce Acidity
0  ( 0)
0  ( 0)
0  ( 0)
0  ( 0)
0
0
( 0)
( 0)
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                                                                  8-11
TABLE 8-3.   SUMMARY OF SURFACE WATER AREA  (km2)  IN EASTERN CANADA
             CROSS CLASSIFICATION BY SENSITIVITY  AND DEPOSITION

Ontario


Quebec


Maritimes


TOTAL
Sulphate
Deposition
(kg/ha. yr)
10-20
20-40
>40
10-20
20-40
>40
10-20
20-40
>40

AREA km2
Potential
Lowb
11,254(12)
8,452(9)
408(<1)
20,474(22)
10,137(11)
-
-
8,719(9)
-
59,444(63)
(Percent of
Total)3

to Reduce Acidity
Moderate
4,142(4)
1,890(2)
98(<1)
2,532(3)
730(<1)
456(<1)
-
13,447(14)
-
23,295(25)
High
1,672(2)
2,120(2)
408(<1)
2,972(3)
3,006(3)
252(<1)
-
1,482(2)
-
11,912(13)
Total
17,068(18)
12,462(13)
914(1)
25,978(27)
13,873(15)
708(<1)
-
23,648(25)
-
94,651(100)
a  Total surface water area receiving more  than  10 kg/ha.yr  sulphate
   deposition.


"  A low potential to reduce acidity is  interpreted  as  a high sensitivity,

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                                                                  8-12
8.3.1   U.S. Agricultural Resources
I
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potential of surrounding soils and  bedrock  to  reduce  acidity)  and
sulphate deposition.

Of the total estimated surface water  area of 51,605 km2  located  in            |
regions sustaining over 20 kg/ha.yr of  sulphate  deposition,
44,337 km2 (86%) are in areas with  either low  or moderate potential           M
to reduce acidity.  More than half  of this  (27,716 km2)  are  in                •
areas of low potential alone.  Within the moderate and high  deposi-
tion zones, the majority of  surface water is receiving between 20 and
40 kg/ha.yr of sulphate; only 1.9%  (962 km2) both receive more than           •
40 kg/ha.yr sulphate and have low or  moderate  potential  to reduce             •
acidity.

The provincial breakdown indicates  that 94%  (22,166 km2)  of  the                |
surface water surveyed (i.e., receiving more than 10  kg/ha.yr
sulphate) in the Maritimes both  receive at  least 20 kg/ha.yr of                •
sulphate and have a low or moderate potential  to reduce  acidity.               •
Although Quebec has the greatest total  surface water  area
(40,559 km2) only 28% (11,323 km2)  are  within  areas of low and
moderate potential to reduce acidity  receiving more than 20  kg/ha.yr          M
sulphate.  Thirty-six percent (10,848 km2)  of  surface water                    •
surveyed in Ontario are in a moderate or high  deposition zone
combined with a low or moderate  potential to reduce acidity.                  •
                                                                               1

8.3      AGRICULTURAL RESOURCES                                                —

The majority of crops listed in  the inventory  have been  selected due
to their significance in terms of value or  production.   The  six  most
important crops are corn, soybeans, wheat,  hay,  tobacco  and  potatoes.         B
This basic list has been supplemented by other crops  which                    •
individually ranked high in  the  U.S.  (cottonlint and  sorghum)  and
Canada (barley and vegetables).  Maps which provided  crop data on a           •
county or census tract basis were overlaid  with  deposition informa-           I
tion to provide the quantitative crop information.  The  inventory
presented here provides data on  crop  yields  and  values by state  or
province for each of the three deposition zones.                              •
 I
The growing of agricultural  crops  is  a major economic industry in the
United States.  Farms  in  the U.S.  in  1978 produced over $64.9                  m
billion worth of  crops  (USDA  1980).                                             I

The U.S. Department  of  Agriculture each year publishes its estimates
of the previous three  years  crop  statistics  in Agricultural                    •
Statistics (USDA  1980).   In  addition  to data on agricultural                   I
supplies, consumption,  costs,  and  returns, this reference book lists
data on acreage,  production,  yield, and value of 99 crops grown in             ft
the U.S.  Of these  crops,  about 34 have been studied for their yield           |
                                                                                I

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                                                                  8-13
response to acidic deposition.  The  inventory  in this  section was
limited to those crops of major economic  importance among the 34
crops.


The major crops were identified by ranking  all of the  crops by their

1978 estimated value of production (USDA  1980).   Table 8-4 presents
this ranking for the entire U.S.  and each crop's cumulative percent-
age of the total.  It was found that the  top eight accounted for
almost 75% of the total value  of  all U.S. crops.


Of these eight crops, there are research  studies on the effects of
acidic deposition on the yields of six.   There are no  effects data on
cottonlint and sorghum.  Consequently, yield of  only the six crops
studied is matched with sulphur deposition  patterns.


Data on yield of these six crops  in  the states east of the 100°
meridian (38 states) is displayed in Appendix  Tables 8-4 to 8-7.
The four tables describe yield for the six  crops by deposition
pattern (i.e., 10-20 kg/ha.yr, 20-40 kg/ha.yr  and greater than 40
kg/ha.yr) and total yield.  Many  states produce  some of these crops
under all three deposition patterns.


The total yield of each crop under four deposition patterns shows

considerable variation (Table  8-5).   Soybeans  and tobacco are the
only crops with any significant proportion  of  their yield in areas
with sulphur deposition greater than 40 kg/ha.yr.  For the remainder
of the crops, less than 15% of their total  yield is grown in areas of
high deposition.


Although the aggregate 38-state data show that only 20% or more of
the yield of two of the six major crops receives sulphate deposition
greater than 40 kg/ha.yr, disaggregated data show that a higher
percentage of crops in some states receive  a high rate of sulphate
deposition (Table 8-6).  More  than 50% of soybean yield in five
states and of tobacco yield in two states receive sulphate deposition
greater than 40 kg/ha.yr.  In  addition, a significant  portion of the
six crops in some states receive  a high rate of  deposition.  At least
50% of three crops in the states  of  Arkansas,  Kentucky, Michigan,
Ohio and Tennessee receives 40 kg S04^~/ha.yr.
8.3.2   Canadian Agricultural Resources


Agriculture is an important  economic  activity for all provinces in
eastern Canada with most of  the yield  and  value  centred in Ontario
and Quebec. Data have been assembled  from  Statistics  Canada and
provincial agriculture ministries  to  provide  an  overview of the
types, yields, and values of crops  at  risk within each of the three
identified deposition regimes.  The crops  of  importance are primarily
grains, but data on certain  vegetables are also  included, although
they represent only about 1% of the total  value  of production.

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TABLE 8-4.


CROP
Corn
Soybeans
Hay
Wheat
Cottonlint
Tobacco
Sorghum
Potatoes
TOTAL










8-14

RANKING OF U.S. CROPS BY 1978 VALUE OF PRODUCTION
(USDA 1980)

1978 $ Value Percent Cumulative Production
(106) of Total Percent (Metric Tons 106)
15,900 24 24 177.2
12,500 19 43 50.9
6,600 10 53 126.6
5,400 8 61 48.9
3,000 5 66 2.4
2,700 4 70 .9
1,500 2 72 19.0
1,200 2 74 16.3

48,800










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                                                                  8-15
TABLE 8-5.   1978 YIELD OF  SIX  CROPS  IN 38 STATES BY DEPOSITION
             REGIME (USDC 1979)
Metric Tons 106
(Percent of 38-State Total)*
Sulphate Deposition kg/ha. yr
CROP
Corn
Soybeans
Hay
Wheat
Tobacco
Potatoes
<10
7.2
(5)
.2
(0)
4.6
(5)
7.5
(25)
0
(0)
<.l
(0)
10-20
76.7
(45)
13.7
(30)
41.4
(45)
17.6
(60)
<.l
(0)
2.7
(50)
20-40
68.4
(40)
21.7
(45)
32.2
(35)
3.1
(10)
.7
(80)
2.3
(45)
> 40
16.7
(10)
11.3
(25)
13.8
(15)
2.2
(5)
.2
(20)
.3
(5)
Total
169.0
46.9
92.0
30.4
.9
5.3
   To the nearest 5%.

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                                                                  8-16
TABLE 8-6.   SELECT U.S. AGRICULTURAL  CROPS  BY  STATE  RECEIVING
             GREATER THAN 40 kg/ha.yr  SULPHATE  DEPOSITION
             (USDC 1979)
                                  Metric Tons 103
                              (Percent of State Total)3

REGION II
New York

REGION III
Maryland

Pennsylvania

W. Virginia

REGION IV
Kentucky

Mississippi

Tennessee

REGION V
Illinois

Indiana

Michigan

Ohio

REGION VI
Arkansas

Louisiana

Oklahoma

Texas

REGION VII
Missouri

Corn

404.7
(30)

7.9
( <5)
392.9
(15)
52.2
(35)

2,027.3
(70)
21.5
(15)
621.6
(60)

390.8
(<5)
1,107.6
(5)
2,268.1
(50)
8,565.1
(95)

26.5
(95)
3.2
(5)
.1
(<5)
312.9
(10)

430.1
(10)
Soybeans

0
(0)

0
(0)
2.7
(5)
0
(0)

839.5
(85)
805.7
(40)
1,133.1
(85)

263.4
(5)
405.9
(10)
316.6
(55)
3,276.9
(100)

2,850.2
(100)
200.3
(10)
8.0
(5)
176.2
(40)

991.8
(25)
Hay

963.6
(20)

49.4
(10)
95.5
(<5)
365.0
(55)

1,604.7
(65)
101.6
(10)
470.7
(30)

147.8
(5)
1,604.7
(10)
1,209.6
(40)
2,722.9
(90)

780.9
(65)
244.4
(40)
44.0
(<5)
1,978.2
(40)

268.2
(5)
Wheat Tobacco Potatoes

25.3
(40)

.2
(<5)
15.0
(10)
1.8
(40)

140.0
(85)
34.2
(70)
96.7
(70)

45.9
(5)
110.3
(20)
218.3
(55)
967.6
(95)

232.2
(100)
5.0
(50)
1.4
(<5)
37.4
(<5)

27.7
(5)

0
(0)

0
(0)
0
(0)
.3
(0)

142.0
(70)
0
(0)
19.3
(35)

0
(0)
1.9
(30)
0
(0)
19.3
(100)

0
(0)
0
(0)
0
(0)
0
(0)

0
(0)

110.5
(20)

0
(0)
45.5
(20)
2.0
(40)

0
(0)
0
(0)
0
(0)

0
(0)
0
(0)
57.3
(15)
0
(90)

0
(0)
0
(0)
0
(0)
0
(0)

0
(0)
a  To the nearest
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                                                                  8-17
Table 8-7 provides a ranking on the basis of production  value  of  all
crops included in the inventory.  From  this table  it  is  clear  that
grain, corn and hay are most important, accounting for just  over  50%
of total production value in eastern Canada.


A breakdown of the value and yield for  each of  these  twelve  crops by
deposition zone are provided in Tables  8-8a and  8-8b, respectively.
For many of the crops, more than  50% of their total yield  is grown in
areas of high sulphate deposition, (over 40 kg/ha.yr).   By contrast,
very small proportions (4% or less) are grown in areas experiencing
only 10 - 20 kg/ha.yr of sulphate deposition.   It  is  evident that a
very significant proportion of Canada's agricultural  crops are grown
in areas experiencing high deposition levels.


In order to obtain a better understanding of the geographical
distribution of these crops, Table 8-9  was prepared.  This provides a
breakdown of production values for each province receiving more than
40 kg/ha.yr sulphate deposition.  Appendix Tables  8-12 through 8-14
provide more detail.


Only Ontario and Quebec, which are significant  agricultural
producers of all crops, have areas exposed to sulphate deposition in
excess of 40 kg/ha.yr.  The most  important crops in these  areas
(based on value of production), are grain corn,  hay and  soybeans.  In
the case of soybeans which is a small crop by volume, 95%  of its
total volume of production is in  the high deposition  zone.  This  is
the highest proportion for any single crop, and all of  this produc-
tion takes place in southwestern  Ontario.


Overall, the most important crops in terms of value which  are  grown
in areas receiving 20 - 40 kg/ha.yr sulphate are hay, grain corn,
potatoes and tobacco.  On a provincial  basis, hay  and grain corn are
a greater proportion of total value of  production  in Ontario and
Quebec, where potatoes are an important crop in the Maritime
provinces.


It is evident even from this preliminary analysis  that  a very  large
proportion of eastern Canada's agricultural yields are  grown in areas
of high and moderate deposition.  In turn, the  geographic  distribu-
tion of crops varies so that certain crops represent  a more signifi-
cant proportion of total value of production in each province.  This
inventory has provided a preliminary overview of the  agricultural
resources at risk, particularly in the  high and medium  deposition
zones.  Better data on the responses of individual crop  species to
these deposition regimes will provide the basis for a more accurate
quantification of the extent of risk.

-------
                                                                 8-18
TABLE 8-7.   RANKING OF CROPS IN EASTERN CANADA BY 1980 VALUE OF
             PRODUCTION (1980 $ Cdn)
CROP
Grain Corn
Hay
Tobacco
Potatoes
Soybeans
Fodder Corn
Wheat
Oats
Barley
Cabbage
Lettuce
Spinach
TOTAL
1980 $ Value
(103)
794,173
658,550
333,821
279,940
228,499
253,084
128,605
100,595
88,756
15,878
9,332
1,222
2,892,495
Percent
of Total
28
24
12
10
8
6
5
4
3
<1
<1
<1
Cumulative
Percent
28
52
64
74
82
88
92
96
99
100
100
100
Production
(Metric Tons)
5,990.0
13,278.0
115.0
1,843.6
962.9
12,984.4
1,207.2
796.9
714.6
119.6
35,793.0
3,003.0
 Source:  Appendix Tables 8-12 and  8-13
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8-19
TABLE 8-8a. VALUE AND PERCENTAGE OF TOTAL 1980 YIELD OF EACH CROP
IN EASTERN CANADA BY DEPOSITION REGIME
Value 1980 $
(Percent of 1980

CROP
Grain Corn

Hay
Tobacco
Potatoes
Soybeans

Fodder Corn

Wheat

Oats

Barley

Cabbage

Lettuce

Spinach



Sulphate
Deposition
103


Yield)
kg/ ha
<10 10-20 20-40
0
(0)
0 21,
(0)
0
(0)
0 1,
(0)
0
(0)
0
(0)
0
(0)
0 3,
(0)
0 3,
(0)
0
(0)
0
(0)
0
(0)



0 226
(0)
271 354
(4)
0 159
(0)
607 217
0 10
(0)
25 104
(40
567,191
(62)
283,184
(43)
174,329
(51)
61,123
(21)
218,070
(95)
148,449
(56)
88,020
(67)
34,372
(31)
49,538
(52)
2,867
(20)
2,981
(25)
374
(34)




Total
794,173

658,550
333,821
279,940
228,499

253,084

128,605

100,595

88,756

15,878

9,332

1,222




-------


TABLE 8-8b.




1980 YIELD
DEPOSITION



OF MAJOR CROPS
REGIME



IN EASTERN


8-20

CANADA BY


Metric Tons 103


(Percent of
1980 Yield)
Sulphate Deposition kg/ha.
CROP
Grain Corn

Hay

Tobacco
Potatoes
Soybeans

Fodder Corn

Wheat

Oats

Barley

Cabbage

Lettuce

Spinach



<10
0
(0)
0
(0)
0
(0)
0
(0)
0
(0)
0
(0)
0
(0)
0
(0)
0
(0)
0
(0)
0
(0)
0
(0)



10-20
0
(0)
419.0
(3)
0
(0)
7.6
0
(0)
1.4
<
24.9
(3)
24.6
(4)
.2
(<1)
0
(0)
0
(0)



20-40
2,274.0
(38)
7,087.0
(53)
57.0
(50)
1,452.0
(79)
43.9
(5)
5,667.0
(44)
394.0
(33)
524.0
(66)
316.0
(44)
96.0
(80)
26.7
(75)
2.0
(66)




yr
> 40 Total
3,716.0 5,990.0
(62)
5,772.0 13,278.0
(44)
58.0 115.0
(50)
384.0 1,843.6
(21)
919.0 962.9
(95)
7,316.0 12,984.4
(56)
809.0 1,207.2
(67)
248.0 796.9
(31)
374.0 714.6
(52)
23.4 119.6
(20)
9.1 35.8
(25)
1.0 3.0
(34)



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8-21









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                                                                  8-22
8.4.1   U.S. Forest Resources
                                                                                I
                                                                                I
8.4   FOREST RESOURCES

Data on forest resources are  aggregated  and  information on individual          I
tree species are not provided  in  any  terms.   For the U.S., the
forests are differentiated  into two categories  (i.e.,  hardwood and
softwood), while in Canada  there  are  three  categories  (i.e.,  hard-             •
wood, mixed and softwood).  Quantitative information of the total              •
volume of forest resources  (yield), its  growth  (or annual yield) and
value is provided in the inventory for each  state or province and              •
deposition regime.                                                              |g
                                                                                I
As of 1977, total commercial  forest  land  in the  U.S.  was 197 x 106
hectares, and the total  timber  volume  was 22.6 x 10^  m3 (USDA                  B
1978b).  The annual growth  was  350 x 10*>  m3 of  softwoods and 270               m
x ID** m3 of hardwoods.   The average  stumpage price in 1978
dollars was $27.50 per m3 for softwoods and $8.60 per m3 for                   •
hardwoods (Ulrich 1981).  Combining  the annual growth and appropriate          g
value estimates gives a  value of  $11.9 billion  to the net annual
growth.                                                                         _

The total forest land area  in those  states east  of the 100° meridian           '
was 145 x 10" hectares,  and the total  timber volume was 9.8 x 10^
m3.  The annual growth was  224  x  10^ m3 of softwood and 252 x                  B
10^ m3 of hardwoods.  Combining the  annual growth and appropriate              |
value estimates results  in  a  value of  $8.3 billion for the net annual
growth in the eastern United  States.                                           •

The total forest volume  and annual growth grouped by  the two higher
deposition categories are displayed  in the Appendix to this section.           —
Note that the data on annual  growth  are incomplete for several                 •
states.  These data are  not available  on  a county basis, so they did           •
not appear in the data summary.

The volume and growth increments  show a similar  distribution among             |
the four deposition categories  (Table  8-10). Approximately 10% of
the hardwood and softwood growth  is  found in areas of highest deposi-          «
tions and over 75% of the hardwood and softwood  growth is found in             •
areas of moderate deposition.

Although the aggregate 38 state data show that  only 15% of the forest          I
volume is exposed to sulphate deposition  greater than 40 kg/ha. yr,             •
individual state data show  a  different picture  (Table 8-11).  A
significant portion of the  forest areas in the  states of Arkansas,             •
Ohio and Texas receives  sulphate  deposition greater than 40 kg/ha. yr.          f
In nine states 30% or more  of the forest  area receives sulphate
deposition greater than  40  kg/ha. yr.                                            _
                                                                                 I

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                                                                  8-23
TABLE 8-10.
U.S. HARDWOOD AND SOFTWOOD VOLUME  AND  GROWTH
(Olson et al. 1980)

Volume
Hardwood Volume3
Softwood Volume3
Total Volume
Growth
Hardwood Growtha
Softwood Growtha
Total Growth

<10

0
(0)
40
(0)
40
(0)

(0)
(0)
(0)
(Percent
Sulphate
10-20

780
(10)
480
(15)
1,290
(10)

10
(10)
20
(15)
30
(15)
m3 106
of 38 State
Deposition
20-40

4,040
(70)
2,690
(75)
6,930 1
(70)

110
(80)
140
(75)
250
(75)
Total )b
kg/ha. yr
>40

940
(15)
480
(10)
,540
(15)

20
(10)
20
(10)
40
(10)

Total

5,750
3,690
9,800

140
190
330
a These  numbers  may  not  add to total numbers because data for some
  states do not  distinguish between hardwood and softwood.


  To  the nearest 5%.

-------
                                                                 8-24
TABLE 8-11.   U.S. FOREST VOLUME BY STATE RECEIVING GREATER THAN
              40 kg/ha.yr SULPHATE DEPOSITION (Olson et al. 1980)
Volume m
REGION II
New York
REGION III
Maryland
Pennsylvania
West Virginia
REGION IV
Kentucky
Mississippi
Tennessee
REGION V
Illinois
Indiana
Michigan
Ohio
REGION VI
Arkansas
Louisiana
Oklahoma
Texas
REGION VII
Missouri
3 . 10^ (Percent of

41,900

7,800
180,200
125,400

123,300
45,400
102,000

14,200
5,300
25,800
113,300

195,300
194,200
18,500
308,900

35,000
State Total)3

(10)

(10)
(30)
(35)

(40)
(10)
(35)

(20)
(5)
(5)
(95)

(80)
(40)
(30)
(100)

(20)
   See Appendix Table 8-11 for growth data.
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                                                                  8-25
8.4.2   Canadian Forest Resources


The wood industry is an important  component  of  the  Canadian economy.
Forest industries valued at $22 billion  Cdn.  annually constitute
Canada's largest manufacturing industry  as well as  the largest single
contributor to the positive side of  our  balance of  payments (Sidor
1981).  One in ten Canadian jobs depends  on  the forestry sector.


The importance of the forest  industry  in  the  eastern Canadian
provinces to the wood industry is  substantial.   Approximately 35% of
the country's total productive forest  land lies within the  boundaries
of eastern Canada.  Further,  the eastern  Canadian provinces accounted
for about 64% ($3.5 billion Cdn.)  of Canada's total value added in
the forest industry (Sidor 1981).  Total  value  of the annual forest
growth of 150,241,000 m3 is estimated  to  be  $3.9 billion Cdn. This
is based on an average wood value  of $26.25  Cdn. per m3 (1981).


Figure 8-3 illustrates the pattern of  acidic  deposition (kg SO^"
/ha.yr) and forest type.  In  eastern Canada  higher  levels of
8042- are most often associated with deciduous  forests and
lower 8042- levels with coniferous.


Table 8-12 lists the annual growth by  forest  type and deposition
regime.  Although only 4% (5,436 m^.lO3)  of  the annual growth
occurs in areas receiving more than  40 kg/ha.yr sulphate deposition
this does represent 10% of the hardwood  annual  yield.  Although
deposition exceeding 40 kg/ha.yr sulphate affects the smallest area
of forested land (2,048.000 ha), this  is  the  area of highest mean
annual increment (2.1 m-Vha)  affecting mixed  and hardwood forests.
The bulk of hardwood and mixed wood  growth occurs in areas  receiving
20 - 40 kg/ha.yr sulphate, representing  64%  and 70% of annual growth
by forest type, respectively.


The provincial summary (Table 8-13)  illustrates the geographic
variation in annual growth.  While only  41%  and 30% of the  annual
growth for Quebec and Ontario are  receiving  more than 20 kg/ha.yr of
sulphate, 100% of the annual  growth  in the Maritime provinces are
under the moderate deposition regime.  Sixty-seven  percent  of
Newfoundland's forest growth  occurs under similar conditions
receiving 20 - 40 kg/ha.yr of sulphate.
8.5   MAN-MADE STRUCTURES


Man-made materials can be grouped  into  three  classes  (i.e.,  metals,
masonary and organic materials).   Organic  materials  include  paints,
coatings, textiles and wood.  Materials  within  each  one of  these
classes behaves differently when exposed to air and  water
pollutants.

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8-26
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                                                                  8-27
TABLE 8-12.   HARDWOOD, SOFTWOOD AND MIXED WOOD ANNUAL GROWTH
              (m3.!03) IN EASTERN CANADA BY DEPOSITION REGIME


Annual Growth m
3.103

(Percent of Total)
Sulphate Deposition
10-20 20-40
Hardwooda
Sof twooda
Mixed Wooda
Total Annual
Growth
5,082
(26)
66,753
(71)
8,327
(23)

80,162
(53)
12,491
(64)
26,814
(28)
25,341
(70)

64,646
(43)
kg/ha. yr
>40
1,825
(10)
815
(1)
2,760
(8)

5,400
(4)
Tot alb
19,398
94,382
36,428

150,208
a Hardwood and softwood  forests  contain  70%  or  more of  the
  specified type.  Mixed wood forests  contain less  than 70% of  either
  hardwood or softwood species.


b Total annual growth does not include data  on  regions  receiving
  less than 10 kg/ha.yr  sulphate  desposition.

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                                                                  8-28
                                                                I
TABLE 8-13.
ANNUAL FOREST GROWTH (m3.103) BY PROVINCE RECEIVING
GREATER THAN 20 kg/ha.yr SULPHATE DEPOSITION
 Ontario
 Quebec
 New Brunswick
 Nova Scotia
 Prince Edward Island
 Newfoundland
                                    Annual Growth mj
                                 (Percent of Provincial Total)
                                  Sulphate Deposition kg/ha.yr
                                 20-40                 >40
                  12,544(28)
                  29,659(36)
                  11,474(100)
                   7,077(100)
                     443(100)
                   3,456(67)
  998(2)
4,438(5)
    0(0)
    0(0)
    0(0)
    0(0)
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                                                                  8-29
An inventory of man-made  structures must  distinguish between renew-
able materials and cultural materials.  Renewable  materials are those
which are easily replaceable.   They include  such items as surface
coatings (paint), chain link fence and  galvanized  roofing.   Cultural
materials are those which are difficult to replace because  of the
scarcity of material and  requirements for skilled  craftsmen to
recreate the resource.  They include such items  as sculptured stone
and metals and dimension  stone.  There  are several materials (e.g.,
adobe, plaster concrete and unit masonry) which  could fall  into
either category depending on the craftsmanship requirements.


There is no national inventory  of  renewable  materials which are
susceptible to acidic deposition.  Past efforts  to create a national
inventory for urban areas have  combined per  capita material
estimates, based on limited survey data,  and census data on
population distribution.   Although this approach to creating an
inventory of renewable resources has been used,  the resulting urban
inventories are of questionable value due to the uncertainties
associated with the per capita  material estimates  (Koontz et al.
1981; Stankunas et al. 1981).   Results  in two Standard Metropolitan
Statistical Areas (SMSA)  indicate  that  the area  of urban development
and local availability of materials are important  factors in the
distribution of material  quantities.  There  are  no estimates of
renewable materials in rural areas.  Until additional survey work is
complete, the Work Group  cannot provide an acceptable national
inventory of renewable materials or an  estimate  of materials by
sulphur deposition regimes.


Complete national inventories of cultural materials are not available
for either Canada or the  U.S.   Such national inventories would
include all significant cultural materials,  both historic and
contemporary.  The only inventory of cultural materials that can be
assembled at this time is one of major  historical  resources.  Both
the U.S. and Canada maintain lists of significant  historic  sites and
artifacts.  The limitations of  these sources are that they  are
incomplete in not listing all significant materials, such as sculpted
stone and metals in urban areas and that  the data  on those  items is
not always adequate for an analysis of  potential damage from air
pollution.
8.5.1   U.S. Historic Inventory


The Work Group compiled a general U.S.  inventory  of  historic
resources based on Federal data sources.   These sources  were the
National Register of Historic Places  (U.S.  Federal Register 1979,
1980, 1981, 1982), National Historic  Landmarks  (USDI 1976)  and
National Historic Parks (USDI 1982).  The  National Register of
Historic Places includes sites because  of  their association with an
event or person, of their architectural or  engineering qualities,  or
of their potential contribution to historic studies. It consists  of
approximately 26,000 sites and is the most  comprehensive of all three

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                                                                  8-30
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sources.  National Historic Landmarks are those historic places
designated by the Secretary of Interior to be of national  signifi-
cance.  It consists of about  1,500 sites.  National Historic  Parks  is          •
used as a generic designation of properties of national sigificance           •
owned by the Federal government.  It includes historic sites,
military battlefields and historic monuments and numbers about  150
sites.
I
The Work Group cross-classified historical  resources  by  three  ambient          •
S0£ categories at the county  level.  The  three  ambient categories              •
at the county level were chosen arbitrarily because  there  is no S02
standard designated for protecting materials  resources nor did the
Material Effects Work Group establish  damage  functions for material            •
damages (see Section 5).  The results  of  the  tabulation  are                   •
summarized by state in Table  8-14.   The sum of  all  such  sites  in the
three ambient categories is the total  for each  state.  No  attempt  was          •
made to distinguish a major and minor  site  within each category so            •
the numbers should be interpreted with great  care.

Only historic sites in seven  out  of  the 38  states under  consideration          •
experience ambient S02 concentrations  greater than 80 yg/m3.                   ™
Within those states, the majority  of historic places, landmarks and
monuments are located in counties with ambient  S02 concentrations              •
less than 60 yg/m3.  Only in  the  states of  Illinois and  New York              •
are there more than 20% of the historic sites in counties  with
ambient concentrations greater than  80 yg/m3.  in total, approxi-              •
mately 3% of the historic places,  3% of the historic landmarks and 2%          •
of the historic parks and monuments  are located in counties with
ambient concentrations greater than  80 yg/m3.


8.5.2   Canadian Historic Inventory

For the purposes of this inventory,  there are three categories (i.e.,          I
national historic sites, buildings  and museums, and monuments  and
parks).  Data for all of these categories are available  only for              _
Ontario.  For the other provinces  of eastern Canada, only national            •
historic sites are included.  These  have  been further subdivided into          *
two deposition regimes; under 40  and over 40 kg/ha.yr.   Although with
structures,  concentrations  of S02 (in yg/m3) is perhaps  more                  I
appropriate, no ambient air quality  data  are available  from which             •
areas  of uniform concentrations  can be drawn.  Generally,  higher
levels  (i.e., above 55 yg/m3  of  802) are  found in the major                   •
cities, and  even then the annual  averages are much lower.                      •

The inventory data  presented  in  Table  8-15  indicate that the majority
of national  historic  sites  in areas  of high deposition are found in           •
Ontario, with the balance  in  Quebec, in the vicinity of  Quebec City,          •
the oldest  settlement in  eastern North America.
                                                                                I

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                                                                  8-31
TABLE 8-14.
U.S. HISTORIC SITES BY AMBIENT S02 (yg/m3) (USDI
1976;  USEPA 1980)



REGION I
Connecticut
Maine
Massachusetts
New Hampshire
Rhode Island
Vermont
REGION II
New Jersey
New York
REGION III
Delaware
Dist. of Col.
Maryland
Pennsylvania 1
Virginia
W. Virginia
REGION IV
Alabama
Florida
Georgia
Kentucky
Mississippi
North Carolina
South Carolina
Tennessee
REGION V
Illinois
Indiana
Michigan
Ohio 1
Wisconsin
REGION VI
Arkansas
Louisiana
Oklahoma
Texas
Historic
Places
<60 60-80 >80

459
384 170 36
649
226 - 6
324
297

485
827 126 211

273
224
510
,201 - 163
916
255 - 2

303
363
705
543 142
426
617
460
465 1

419 - 148
326 27 9
468
,193 404 16
603

409
367
357
731
Historic
Landmarks
<60 60-80 >80

29
23 - 1
105
16 - 12
23
10

23
87 - 16

11
37
42
66
78
3 - -

14
15
25
11 3 -
15
19
59
18

18 - 12
7 - 1
7 - -
25 - 1
12

0 — —
34
13
21
Historic

<60

-
-
9
1
2
-

4
9

-
12
9
12
12
2

2
-
6
3
3
5
3
6

1
1
-
1
—

3
3
1
5
Parks
60-80

-
-
-
-
-
-

-
1

-
-
-
5
-
—

-
-
-
-
-
-
-
-

-
-
-
-
—

-
-
-


>80

-
-
-
-
-
-

-
3

-
-
-
-
-
—

-
-
-
-
-
-
-
-

-
-
-
-
—

-
-
-


-------
                                                                 8-32
TABLE 8-14.   CONTINUED



REGION VII
Iowa
Kansas
Missouri
Nebraska
REGION VIII
North Dakota
South Dakota
TOTAL


<60

497
292
550
279

106
209
18,766
Historic
Places
60-80 >80

22
-
20
- -

-
-
912 591
Historic
Landmarks
<60 60-80 >80

9
14
19 2 -
14

1 - -
10
948 5 33
Historic
Parks
<60 60-80

1
2
3
1

2
-
124 6


>80

-
-
-
-

-
-
3
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                                                                  8-33
              TABLE  8-15.    CANADIAN HISTORIC INVENTORY BY PROVINCE AND DEPOSITION
 —                          (OMCR 1978;  Parks Canada 1981)

 •                                        National        Buildings     Monuments
 ™                         Sulphate    Historic Sites	and Museums    and Parks
                           Deposition  <40        >40    <40     >40   <40    >40
 fl           Province     (kg/ha.yr)	
              Ontario                   21         23    129      72     8      3
 J           Quebec                   13          5         N/A           N/A
 _           Prince Edward
 •           Island                    4                    N/A           N/A
              Nova Scotia               13                    N/A           N/A
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New Brunswick             2                    N/A            N/A
Newfoundland              6                    N/A            N/A

TOTAL                    59         28

-------
                                                                  8-34
     Quebec Region,  Ste-Foy, P.Q.   (unpublished)
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8.6  REFERENCES

Bickerstaff, A.; Wallace, W.L.; and Evert,  F.   1981.  Growth  of                 •
     forests in Canada, Part 2.  A quantitative description of the              •
     land base and the mean annual increment.   Information Report
     Pl-X-1, Canadian Forestry Service, Environment Canada, Ottawa,
     Ont.                                                                       I

Cox, E.T.   1978.  Counts and measurements of Ontario lakes, 1978.
     Ontario Ministry of Natural Resources, Toronto, Ont.  114 pp.              •

Environment Canada.  198la.  Ecodistrict maps  and  descriptions for
     the Atlantic provinces.   Lands Directorate, Atlantic Region,               «
     Halifax, N.S. (unpublished)                                                •

	.  1981b.  Les ecodistricts du Quebec.   Lands Directorate,
I
Koontz, M.D.; McFadden, J.E.; and Haynie,  F.H.   1981.   Estimation  of
     total  surface and  spatial distribution  of  exposed  building                 •
     materials  from  commonly  available  information  for  U.S.                     |
     metropolitan areas.   In  Proc.  Second  Int.  Conf. on the
     Durability of Building Materials and  Components, 1981.                     _

Lucas, A.E., and Cowell, D.W.  1982.  A regional  assessment  of
     sensitivity to  acidic deposition for  eastern Canada.  Presented
     at Symp. Acid Precipitation.   Am.  Chem.  Soc.,  Las  Vegas, NV.,              I
     1982.                                                                      •

New Brunswick Department of Agriculture and  Rural Development.                  •
     Telephone  Inquiry, March 3,  1982.                                          I

Newfoundland Department of Agriculture  and Forestry.  Telephone                 _
     Inquiry, March  3,  1982.                                                    •

Nova Scotia Department  of  Agriculture and  Marketing.  Telephone
     Inquiry, March  3,  1982.                                                    •

Olson, R.J.; Johnson, D.W.; and Shriner, D.S.   1982.  Regional
     assessment of potential  sensitivity of  soils in the eastern               •
     United States to acid precipitation.  Oak  Ridge National                   I
     Laboratory, Oak Ridge, TN.   31 pp. (in press)

Ontario Ministry of  Agriculture and Food (OMAF).   1981.  Agricultural          •
     Statistics for  Ontario,  1980.   Publication 20, Toronto,  Ont.               ™

Ontario Ministry of  Agriculture and Food (OMAF).   1981.  Seasonal               •
     fruit  and  vegetable report,  fruit  and vegetable production  in             |
     Ontario, 1980.  Toronto, Ont.

Ontario Ministry of  Culture and Recreation (OMCR).   1978. Ontario             I
     historic sites, museums, galleries and  plaques.  Toronto,  Ont.
                                                                                I

                                                                                I

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                                                                 8-35
Parks Canada.  1981.  List of all positive recommendations of the
     historic sites and monuments board of Canada, from 1919 to
     June 1, 1981.  Ottawa, Ont. (unpublished)


Prince Edward Island, Department of Agriculture and Forestry.
     Telephone Inquiry, March 3, 1982.


Quebec Bureau de  la Statistique (QBS).  1978.  Grandes cultures,
     1977.  Superficie, production et valeur.  Quebec, P.Q.


Sidor, N.   1981.  Forest industry development policies:  industrial
     strategy or  corporate welfare?  Canadian Centre for Policy
     Alternatives, Pub. #3, Inaugural Conference Proceedings.


Stankounas, A.R.; Unites, D.F.; and McCarthy, E.F.  1981.  Air
     pollution damage to man-made materials:  physical and economic
     estimates^Final Report to EPRI #RT1004.


Statistics  Canada.  1976.  Census of agriculture.  Census of Canada,
     Volume XI, Ottawa, Ont.:
          1976a.  Quebec.  Catalogue 96-805.
          1976b.  Ontario.  Catalogue 96-806.
          1976c.  Newfoundland.  Catalogue 96-801.
          1976d.  Prince Edward Island.  Catalogue 96-802.
          1976e.  Nova Scotia.  Catalogue 96-803.
          1976f.  New Brunswick.  Catalogue 96-804.


	.  1981a.  Field crop reporting.  Catalogue 22-002, Ottawa,
     Ont.
              1981b.  Fruit and vegetable production.  Catalogue
     22-003, Ottawa, Ont.


Ulrich, A.   1981.  U.S. timber production, trade, consumption and
     price statistics,  1950-80.  USDA Forest Service, Washington,
     DC.


U.S. Department of Agriculture (USDA).   1971.  Basic statistics -
     national inventory of soil and water conservation needs, 1967.
     Statistics Bulletin No. 461, USDA,  Washington, DC.  211 pp.


             1978a.  National resource inventories.  USDA Soil
     Conservation Service, Washington, DC.


           .   1978b.  Forest  Statistics of the U.S.  USDA Forest
     Service, Washington, DC.


     	.  1979.  Volume and value of sawtimber stumpage sold from
     national forests by selected species and region,  1978.  USDA
     Forest Service, Washington, DC.  (mimeo)


     	.  1980.  Agricultural Statistics.  Washington, DC.

-------
                                                                 8-36
U.S. Federal Register.  Nation register of historic places.
           1979.  February 6, 1979.
           1980.  March  18,  1980.
           1981.  February 3, 1981.
           1982.  February 2, 1982.
I
I
U.S. Department of Commerce (USDC).  1979.  Census of agriculture,
     1978.  Preliminary file, Technical documentation, Bureau of               _
     Census, USDC, Washington, DC.                                             I
U.S. Department of Interior (USDI).  1976.  National Historic
     Landmarks, Washington, DC.                                                •
	.  1982.  List of classified structures.  National Park
     Service.  Computer Printout.                                              •
U.S. Environmental Protection Agency (USEPA).   1980.  Ambient S02
     data 1979-1980.  Office of Air Quality, Planning and Standards.
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APPENDIX TABLE 8-1.
                                                                  8-37
U.S. AQUATIC RESOURCES BY STATE AND SENSITIVITY
CATEGORY (km2) 10-20 kg/ha.yr SULPHATE
DEPOSITION (USDA 1971, 1978)

REGION III
Virginia
West Virginia
REGION IV
Florida
Georgia
REGION V
Illinois*
Michigan
Minnesota
Wisconsin
REGION VI
Oklahoma
Texas
REGION VII
Iowa a
Kansas
Missouri^
Nebraska*
REGION VIII
North Dakota
South Dakota
TOTAL
Low
Potential
to Reduce
Acidity

10
10

0
280

0
1,350
1,460
2,310

0
0

0
0
0
0

0
0
5,420
Moderate
Potential
to Reduce
Acidity

20
0

100
210

0
0
8,440
1,240

0
0

0
0
0
0

620
410
11,040
High
Potential
to Reduce
Acidity

40
0

9,560
180

0
190
890
240

1,170
1,060

0
1,000
0
0

200
1,210
15,740
Total
Surface
Water Area
in the State

2,950
480

13,130
3,000

2,110
4,180
13,810
5,420

4,440
15 -,260

990
3,140
2,770
2,330

4,540
4,240
82,790
a These states are included, even  though  they  do  not  have  surface
  water area in counties falling into  one  of the  three  sensitivity
  categories, because they have surface water  area  falling  into  the
  urban/agricultural category receiving 10-20  kg  sulphate/ha.yr.

-------
APPENDIX TABLE 8-2.
                                                                 8-38
U.S. AQUATIC RESOURCES BY STATE AND SENSITIVITY
CATEGORY (km2) 20-40 kg/ha.yr SULPHATE
DEPOSITION (USDA 1971, 1978)

REGION I
Connecticut
Maine
Massachusetts
New Hampshire
Rhode Island
Vermont
REGION II
New Jersey
New York
REGION III
Delaware
Dist. of Columbiab
Maryland
Pennsylvania
Virginia
W. Virginia
REGION IV
Alabama
Florida
Georgia
Kentucky
Mississippi
North Carolina
South Carolina
REGION V
Illinois
Indiana
Michigan
Ohio
Wisconsin^
Tennessee
REGION VI
Arkansas
Louisiana
Oklahoma
Texas
Low
Potential
to Reduce
Acidity

340
6,010
970
860
340
720

150
1,930

0
0
0
40
70
110

10
0
250
30
60
310
0

0
0
1,650
0
0
90

0
0
0
0
Moderate
Potential
to Reduce
Acidity

0
0
0
0
0
0

660
1,050

0
0
1,020
300
1,600
20

1,280
410
1,660
140
970
9,010
640

0
40
0
0
0
100

180
0
880
10
High
Potential
to Reduce
Acidity

0
0
0
0
0
0

10
520

0
0
80
400
840
120

1,590
960
560
410
620
1,110
2,100

90
150
140
20
0
1,440

500
10,050
1,330
3,040
Total
Surface
Water Area
in the State

500
6,010
1,100
860
460
1,000

920
5,260

330
0
1,900
1,620
2,950
480

3,040
13,130
3,000
2,320
2,470
10,480
2,750

2,110
930
4,180
970
5,420
3,140

3,670
11,390
4,440
15,260
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                                                                  8-39
APPENDIX TABLE 8-2.   CONTINUED




REGION VII
lowab
Kansas^
Missouri
Low
Potential
to Reduce
Acidity

0
0
0
Moderate
Potential
to Reduce
Acidity

0
0
0
High
Potential
to Reduce
Acidity

0
0
1,320
Total
Surface
Water Area
in the State

990
3,140
2,770
    TOTAL              13,940      19,970     27,400        107,890
a The states of Minnesota (13,810 km2), Nebraska  (2,330 km2),
  North Dakota (4,540 km2) and South Dakota  (4,240 km2) received
  less than 20 kg/ha.yr sulphate deposition  in  1979-80.


" These states are included, even though  they do  not  have  surface
  water area in counties falling into one of the  three sensitivity
  categories because they have surface water area falling  into  the
  urban/ agricultural category receiving  20-40  kg sulphate/ha.yr.

-------
APPENDIX TABLE 8-3.
                                                                  8-40
U.S. AQUATIC RESOURCES BY STATE AND ACID
SENSITIVITY CATEGORY (km2) FOR GREATER THAN 40
kg/ha.yr SULPHATE DEPOSITION (USDA 1971,  1978)

REGION II
New York
REGION III
Maryland
Pennsylvania
W. Virginia
REGION IV
Kentucky
Mississippi
Tennessee
REGION V
Illinois
Indiana
Michigan
Ohio
REGION VI
Arkansas
Louisiana
Oklahoma
Texas
REGION VII
Missouri
TOTAL
Low
Potential
to Reduce
Acidity

0

20
0
10

0
0
0

0
10
40
0

130
0
0
0

	 0
210
Moderate
Potential
to Reduce
Acidity

200

0
250
0

260
90
10

0
0
0
0

1,170
0
210
0

0
2,190
High
Potential
to Reduce
Acidity

0

0
220
210

480
10
640

80
0
40
360

400
1,050
0
4,050

80
7,620
Total
Surface
Water Area
in the State

5,260

1,900
1,620
480

2,320
2,470
3,140

2,110
930
4,180
970

3,670
11,390
4,440
15,260

2,770
62,910
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-------
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
APPENDIX TABLE 8-8.
                                                                  8-47
U.S. FOREST RESOURCES IN AREAS RECEIVING 20-40
kg/ha.yr SULPHATE DEPOSITION - VOLUME (m3.103)
(Olson et al. 1980)

REGION I
Connecticut
Maine
Massachusetts
New Hampshire
Rhode Island
Vermont
REGION II
New Jersey
New York
REGION III
Delaware
District of
Columbia
Maryland
Pennsylvania
Virginia
W. Virginia
REGION IV
Alabama
Florida
Georgia
Kentucky
Mississippi
North Carolina
South Carolina
Tennessee
REGION V
Illinois
Indiana
Michigan
Ohio
Wisconsin
Total
Volume

66,600
601,800
96,100
186,300
9,800
133,900

41,600
303,600

16,600
-

91,100
445,600
509,600
251,800

572,300
75,900
647,000
200,700
440,600
702,400
486,500
192,400

51,200
93,900
184,800
5,200
8,200
Softwood
Volume

10,100
418,000
35,900
88,900
2,100
48,600

7,300
84,100

5,200
-

22,000
28,500
144,000
17,300

319,500
48,100
370,300
-
239,700
294,000
252,800
44,300

100
1,700
33,400
100
500
Hardwood
Volume

56,500
183,800
60,200
97,400
7,700
85,300

34,300
219,500

11,400
-

69,000
417,200
365,600
234,500

252,800
27,800
276,700
-
201,000
408,400
233,700
148,100

51,100
92,200
151,500
5,100
7,700
Total Volume
in State3

66,600
601,800
96,100
186,300
9,800
133,900

41,600
345,400

16,600
-

98,900
625,800
548,600
382,700

572,300
367,100
714,600
324,000
486,000
702,400
486,500
294,400

66,400
99,200
425,400
118,500
315,400

-------
                                                                 8-48
APPENDIX TABLE 8-8.   CONTINUED
REGION VI
Arkansas
Louisiana
Oklahoma
Texas
REGION VII
Iowa
Kansas
Missouri
TOTAL
Total
Volume
56,700
278,600
39,900
6,900
3,500
600
127,600
6,929,500
Softwood
Volume
11,200
132,500
17,300
3,800
0
6,600
2,688,000
Hardwood
Volume
45,500
146,100
22,600
3,100
600
121,000
4,037,400
Total Volume
in State3
252,000
472,800
58,400
315,800
29,900
8,400
172,100
9,435,700
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
a  Under all deposition regimes.
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I

-------

                                                                  8-49
APPENDIX TABLE 8-9.   U.S. FOREST RESOURCES IN AREAS RECEIVING  20-40
                      kg/ha.yr SULPHATE DEPOSITION - GROWTH  (m3.103)
                      (Olson et al.  1980)
                    Total
                    Growth
Softwood
 Growth
Hardwood
 Growth
REGION I
  Connecticut         1,700
  Maine             18,000
  Massachusetts       3,100
  New Hampshire       6,700
  Rhode Island         300
  Vermont             3,000

REGION II
  New Jersey           700
  New York

REGION III
  Delaware             500
  District of
    Columbia
  Maryland
  Pennsylvania
  Virginia          21,400
  W. Virginia
     300
  14,000
   1,200
   3,600
     100
   1,300
     200
   1,300
   6,500
   1,400
   4,000
   2,000
   3,140
     200
   1,700
     500
     400
  14,900
Total Growth
  in State3
     1,700
    18,000
     3,200
     6,700
       300
     3,000
       700
       500
    23,000
REGION IV
Alabama
Florida
Georgia
Kentucky
Mississippi
North Carolina
South Carolina
Tennessee
REGION V
Illinois
Indiana
Michigan
Ohio
Wisconsin

33,600
4,400
40,800
-
26,100
31,900
27,300
9,400

1,900
-
-
-


22,300
3,400
29,400
-
15,800
15,200
17,500
2,500

0
-
-
-


11,300
1,000
11,400
-
10,300
16,700
9,800
6,900

1,900
-
-
-


33,600
21,500
44,500
-
28,700
31,900
27,300
14,400

2,400
-
-
-


-------
                                                                 8-50
APPENDIX TABLE 8-9.   CONTINUED

REGION VI
Arkansas
Louisiana
Oklahoma
Texas
REGION VII
Iowa
Kansas
Missouri
TOTAL
Total
Growth

-
14,300
2,400
300

-
-
2,700
251,500
Softwood
Growth

-
8,400
1,000
200

-
-
300
143,100
Hardwood
Growth

-
5,900
1,400
100

-
-
3,400
108,400
Total Growth
in State3

-
26,300
3,400
18,300

-
-
5,100
314,500
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
a  Under all deposition regimes.
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I

-------
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I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
                                                                  8-51
APPENDIX TABLE 8-10.
U.S. FOREST RESOURCES IN AREAS RECEIVING
GREATER THAN 40 kg/ha.yr SULPHATE DEPOSITION
VOLUME (m3.103) (Olson et al. 1980)

REGION II
New York
REGION III
Maryland
Pennsylvania
W. Virginia
REGION IV
Kentucky
Mississippi
Tennessee
REGION V
Illinois
Indiana
Michigan
Ohio
REGION VI
Arkansas
Louisiana
Oklahoma
Texas
REGION VII
Missouri
TOTAL
Total
Volume
41,900
7,800
180,200
125,400
123,300
45,400
102,000
14,200
5,300
25,800
113,300
195,300
194,200
18,500
308,900
35,000
1,536,500
Softwood
Volume
6,000
400
8,600
10,500
13,200
6,600
400
0
1,000
3,200
80,900
123,500
11,300
205,700
3,900
475,300
Hardwood
Volume
35,900
7,400
171,600
114,900
32,200
95,300
13,800
5,300
24,800
110,100
144,400
70,700
7,200
103,200
31,100
937,800
Total Volume
in State3
345,400
98,900
625,800
382,700
324,000
486,000
294,400
66,400
99,200
425,400
118,500
252,000
472,800
58,400
315,800
172,100
45,378,000
   Under all deposition regimes.

-------
                                                                 8-52
APPENDIX TABLE 8-11.
U.S. FOREST RESOURCES IN AREAS RECEIVING
GREATER THAN 40 kg/ha.yr SULPHATE DEPOSITION
GROWTH (m3.103) (Olson et al. 1980)

REGION II
New York
REGION III
Maryland
Pennsylvania
W. Virginia
REGION IV
Kentucky
Mississippi
Tennessee
REGION V
Illinois
Indiana
Michigan
Ohio
REGION VI
Arkansas
Oklahoma
Louisiana
Texas
REGION VII
Missouri
TOTAL
Total
Growth
_
-
2,600
5,100

400
-
-
—

-
900
12,000
18,000

1,100
40,100
Softwood
Growth
-
-
900
500

0
-
-
—

-
500
8,700
12,000

100
22,800
Hardwood Total Growth
Growth in State3
-
-
1,700
4,600

400
-
-
—

-
400
3,300
6,000

1,000
17,300
-
-
28,700
14,400

2,400
-
-
—

-
3,400
26,300
18,300

5,100
98,600
a  Under all deposition regimes.
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-------

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                                          SECTION 9



                                            LIMING
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                                                                  9-1
                              SECTION  9
                               LIMING
9.1  INTRODUCTION


This chapter reviews the potential  of  adding  neutralizing or
buffering materials to correct or modify  the  adverse  effects
associated with acidic deposition.   Such  activities  are commonly
called "liming" and they are  limited in practice  to  correcting to
some degree adverse effects on aquatic, terrestrial  and drinking
water systems.  It is not possible  to  use  liming  to  mitigate effects
on materials, visibility, and adverse  health  effects  resulting from
direct inhalation of airborne pollutants.   Each section of this
chapter discusses the effectiveness of liming for the particular
system and then the unit cost associated  with liming  that system.
9.2  AQUATIC


It has been shown in many  areas  of  the  world  that acid loadings due
to long range transport  are  capable  of  acidifying surface waters.   In
theory however, even the most  acidic loadings  could  periodically be
neutralized if limestone were  added  to  the  affected  systems in
amounts ranging from 50  to 100 kg/ha.yr.  In  areas with calcareous
soils, this amount  of neutralizing  capacity is available inherently
for very long periods of time  (i.e., 1  cm of  soil covering 1 ha is
about 150 metric tons, which is  capable of  neutralizing present
maximum acid loading for about 3,000 years).   In hard rock areas with
little or no calcareous  soil some present acid loadings cannot be
neutralized fast enough  resulting in acidic runoff.   In order to
reverse or prevent  the resulting effect, at least five different
jurisdictions (Sweden, Norway, New  York State,  Nova  Scotia, and
Ontario) have added neutralizing agents to  surface water systems.
The numbers of lakes and rivers  treated and the methods used in the
application of neutralizing  agents  vary greatly from area to area.
Limestone is most often  used although other chemicals have been
tried.  The term "liming"  is used to describe  artificial
neutralization regardless  of the chemical or  chemicals actually
used.
9.2.1   Liming as a Mitigative Measure


In certain cases, a species  or a  unique  race  of  organisms may be
threatened by acidification  of its  natural  habitat.   In these cases,
liming or other mitigative measures might be  undertaken on lakes,
rivers or parts of rivers  in order  to preserve a population of the
endangered organism.   Very small  populations  become  inbred and so
the preserved habitat  must be large enough  to support a reasonably

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                                                                  9-2
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large population.  The populations saved  in  this  way  might  play an
important part in the restoration of  fisheries  to waters  where  fish
have been exterminated by acidification or other  causes.                       «

The future value of any species or organism  cannot be foreseen.
Therefore, the extinction of any species  could  be a great loss  to
man.  As the extinction of a species  can  never  be remedied,  the               •
threat of extinction of any species by acid  rain  would justify  lake           •
liming or virtually any other feasible protective measure regardless
of immediate costs or benefits.                                                •

If a population of fish is considered an  especially suitable source
of stock for the rehabilitation of acidified rivers or lakes, then            ^
liming or other measures to protect its natural habitat would be              I
justified to protect it from acidification.   Liming of an acidified
habitat would also be justified if it were inhabited  by a population
which was genetically unique and consequently for which no  replace-           •
ment could be found if it were exterminated.                                  •


9.2.2   Liming Programs                                                        I

9.2.2.1 Sweden

Sweden has conducted the greatest number  of  experiments on  lake               ™
liming of any country.  A 5-year program  designed to  evaluate both
lake and stream liming was completed  in  1981 and  a final  summary              •
report was prepared (National Fisheries Board and National                     ||
Environmental Protection Board 1981). During the 5-year  period, 304
projects were started which involved  over 700 lakes and streams.              M
While there were some negative aspects to the results, the  program            •
was deemed to be a success by the National Board  of Fisheries.
Success was generally measured in terms  of a favourable response in
the sport fish, mainly salmon, trout  and  arctic char, although  some           •
lakes were treated with environmental conservation as the prime               |
objective.  Limestone has been applied at rates of 100-200  kg/ha of
lake surface which corresponds to 50-75 kg/ha of  watershed  per  year.          •
Application on land required up to  100 times this amount  to give an           •
acceptable runoff quality.  Application  directly  to water was found
to be the most economical treatment method (Bengtsson et  al. 1980).           _

Hultberg and Andersson (1982) reported detailed studies on  six  lakes          9
in two areas of Sweden.  Four lakes were  limed  and two held as
reference lakes.  Although they reported  favourable biological                 B
results, there was concern over continued biological  and  chemical             |
damage from liming, resulting from  the input of aluminum  in acidified
runoff from the watershed.  Most  of  the  lakes and streams had a               •
relatively small number of species  of fish (three or  four).  The              •
improved water quality generally  resulted in increased numbers  of
fish, and hence an improved sport fishery.   Bengtsson (pers. comm.)
                                                                                I

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                                                                  9-3
reported that, in some cases, nonsport  fish  species  responded the
most dramatically.


Bengtsson et al. (1980) summarized  some  of the  problems  with lake
neutralization as follows:


    "Obtaining yearly leaching of a certain  amount of  bicarbonate or
     an acceptable yearly pH-medium value is  not  the problem.  The
     problem is to keep an acceptable value  at  high  flow (i.e.,
     during snowmelt).  At this time the  lake waters become highly
     stratified with the cold acid  melting-water  on  top.  As a result
     it does not mix with the water below which is of  better
     quality.


     The running waters carrying  this melting-water  represent an even
     greater problem.  To neutralize the  acidified melting-water,
     either large overdosing is needed  when  applied  to water or on
     land or every year lime has  to be  applied  on the  snow pack.


     Moreover, the acidification  is not  just a  pH-problem but is also
     coupled to the anthropogenic pollution  of  metals  deposited from
     the atmosphere and the increased leaching  of metals from acidi-
     fied soils.


     The toxicity of most metals  is higher in neutral  than in acid
     water.  Thus, when liming an acid  lake  the organisms suffer a
     transition period before the metals  have precipitated.  Aluminum
     leached from the soil is highly aggressive to fish  gills in the
     pH range 4.5-6 and liming  has even killed  salmon  and trout
     when the aim was to save the fish."


The situation in North America may  be even more complicated because
generally, the lakes contain more species of  fish than many of the
Scandinavian lakes.  The potential  for  disruption of the aquatic food
chain is greater.  It could happen  that  fish populations would
survive in the treated lakes but  the normal  distribution of species
might be altered.  For example, inputs  of aluminum might disrupt the
life cycle of some species more than others,  changing  the ecological
balance among species.


9.2.2.2  Norway


The Norwegian government is conducting  a  liming project  at Lake
Hovvatn in southern Norway.  The  lake is  about  one square kilometre
and has a mean residence time of  1.1 years.   The  drainage basin is
interspersed forest and bog with  numerous granite outcroppings.  The
project was begun in May 1980 with  background sampling at two month
intervals at five lake stations and five  inlet  streams.   Analyses
include pH, alkalinity, conductivity, all major ions and metals.
Zooplankton and phytoplankton are also  being  monitored.   In March
1981, the lake was treated with 240 metric tons of agricultural
limestone spread on the ice near  the shore.   As the  ice  melted in

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                                                                  9-4
State
Kansas
Massachusetts
New Jersey
New York
West Virginia
Wisconsin
Ponded Waters
Per Average
5
2-3
2
7
1
2
Treated
Year
(10 ha)
(81 ha)
( 8 ha)
(81 ha)
(17 ha)
(12 ha)
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April the pH went from 4.5 to 6.0.  Sampling and analyses  are
expected to continue for years.  The lake was  stocked  with brown
trout in June 1981.  A smaller lake draining into  Hovvatn  was  not
limed and serves as a control.

9.2.2.3  United States

A paper by Pfeiffer (1982) reported results of a January  1981
questionnaire he circulated to Fisheries Chiefs or Directors  in the
50 United States.  Forty states responded to his acidic deposition            •
questions.  Nonrespondents included the states of  Florida, Louisiana,          •
Maryland, Michigan, Missouri, New Mexico, North Carolina,  North
Dakota, Vermont and Virginia.  Seven of 40 states  replied  that they           •
are presently engaged in a liming program for  ponded waters.   The              |
summary is as follows:
                                                                               I

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West Virginia was  the only  state  that  indicated that they were liming         •
streams.  The figures provided were  16 km,  representing approximately         ™
12 ha.  There were no questions on future  considerations for liming
programs.                                                                      •

Festa  (pers. comm.)  reported  that the  New  York Department of
Environmental Conservation  had treated 16  small ponds (0.5 to 3.0 ha)         M
which  were operated  mainly  as put-grow-and-take brook trout                   •
fisheries.  The  treated  lakes had a  simple food chain with only one
fish species stocked.  Fish growth was good and the fish were
harvested by angling in  the autumn.  There was no attempt to                  •
establish a self-sustaining population.                                       •

9.2.2.4  Ontario,  Canada                                                      •

Limestone and slaked lime were added to Middle, Hannah, Lohi and
Nelson Lakes, four acidic lakes near Sudbury,  Ontario between 1973            «
and  1976.  Contamination by metals,  especially Cu and Ni, prevented           •
reestablishment  of trout populations in the first three lakes which           •
are  situated within  13 km of  Sudbury (Yan  et al. 1979), even though
pH was increased from about 4.4 to >6.0.  Nelson Lake (3.09 km2)              •
was  acid-stressed  (pH -5.5-6.0) prior  to additions of crushed                 |
limestone (51 metric tons)  and slaked  lime (68 metric tons) in the
fall of 1975 and the spring of  1976  (Yan et al. 1977).  The decline           f
of the lake's fisheries  was indicated  by the dominance of yellow              •
perch  and the disappearance of smallmouth  bass.  Lake trout
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                                                                  9-5
populations were low but by  the winter  of  1979-1980 winter  fishing
for lake trout was very successful  (summarized  in Yan and Dillon
1982).
9.2.3   Economic Aspects of Lake Liming

Estimating the total cost of liming  aquatic  systems  is  very difficult
but some unit cost figures are available  for Sweden,  New York State,
Norway and Nova Scotia.  Generally  there  are three categories of cost
associated with liming programs:  supply  of  chemicals,  distribution
of chemicals, and monitoring of the  systems  before and  after the
applications.

9.2.3.1 Costs in Sweden

Although the costs in Sweden cannot  be expected  to apply directly in
North America, they serve as a guide  in estimating North American
costs.  Results from their 5-year experimental program  which dealt
with over 700 lakes (Bengtsson et al.  1980)  have given  good cost
estimates.  The cost of limestone application, including materials
and distribution ranged from 500 to  1100  Skr ($115-253  Cdn.) per
metric ton using eight different spreading methods.   The average cost
for the whole program was about $140  Cdn. per metric ton.  Manual
applications had the lowest cost of  about $115 Cdn.  per metric ton
while aerial applications were the  most expensive at about $250
Canadian per metric ton (National Fisheries  Board and National
Environmental Protection Board 1981).  The cost  of scientific surveys
to document effects can range from  a  very small  amount  for some pH
and alkalinity measurements to several thousand  dollars.  In Sweden,
the average cost of research has been about  $16,000  for each project.
However, each project may have more  than  one lake or river involved.

9.2.3.2 Costs in Norway

Limited cost information is available but a  total experimental cost
of $80,000 for each of the five study lakes  has  been projected.  In
addition there is support from universities  with separate funding and
support from local residents.

9.2.3.3 Costs in New York State

New York State Department of Environmental Conservation has been
adding limestone to 16 small lakes  (0.5 to 3 ha) and started a 40 ha
lake in 1979.  They found the costs  of limestone application to range
from $60 U.S. to $225 U.S. per hectare for a 3-year  treatment ($20 to
$75 U.S./ha.yr).  They conducted a  very limited  technical evaluation
of the lakes.  The lakes were essentially devoid of  fish to start
with and the objectives were to establish put-and-take  brook trout
fisheries.

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                                                                  9-6
9.2.3.4  Costs in Canada
9.2.4   Technical Evaluations Necessary in Liming Programs
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Watt (pers. comm.) has  recorded  actual  cost  figures  for purchase,               •
delivery and distribution of  crushed  bagged  limestone to Sandy Lake            |
in Nova Scotia.  The loading  rate  was about  one  metric ton/ha.  The
experiment was designed to protect salmon populations in downstream            •
rivers.  The lake was easily  accessible,  and crushed limestone was             I
readily available.  The total  cost for  liming the 70 ha lake was in
excess of $11,000, or about $160 Cdn. per hectare.

Although costs per lake will vary  according  to dose  required,                  •
generally application rates for  lakes appear to  vary from about 380
(Yan and Dillon  1982) to 1000  kg/ha which Watt has  used in Nova                •
Scotia.  The Ontario example given by Yan and Dillon (1982) has                |
maintained the lake pH  for at  least five  years.   Generally, average
application rates of about 500 kg/ha  are  necessary  to give multi-year          .
pH stability.                                                                   •
I
The calculation of  costs  associated  with neutralization programs must
be accompanied by the necessary  technical evaluations.   Any system,            •
considered for liming must  be  studied  in a variety of ways (e.g.,              •
depth, flushing time, water chemistry,  and biota).  Swedish treatment
and research  costs  of about $16,000  Cdn. per project are based on 304
projects which cover at least  700  individual lakes (Bengtsson et al.           •
1980).  Therefore,  average  monitoring  costs appear to be about $8,000          •
per lake.  A minimum sample program  of  only twice per year would
still cost at least $1,000  per lake  including labour, analyses and             •
data reporting.  Meaningful evaluation  of chemical and  biological              |
conditions would cost in  the order of  $10,000 per lake  per year.

Control and management of the  fisheries in treated systems would also          •
add substantially to overall costs.

It is worth noting  that the situation  concerning fishing rights in             I
Scandinavia and North America  is quite  different.  In Sweden the               •
rights to fish are  privately owned,  with the owners on  some rivers
issuing fishing licenses  and to  some extent controlling fish harvest.          •
This element  of "self interest"  allows  for easier control of fishing           •
activities which can affect the  success of fish survival and repro-
duction.                                                                        .


9.3  TERRESTRIAL LIMING

The addition  of alkaline  materials has  been proposed as a means for            •
ameliorating  the effects  of acidic deposition on terrestrial
ecosystems.  While  lime applications have an important  place in the            •
efficient management of agricultural soils and much research has been          •
conducted to  determine optimum dosages  for different crops and soils,
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                                                                  9-7
the scope for lime  in  temperate  and  boreal forestry is much more
limited.  Moreover,  few  field  trials have been concerned with entire
forested catchments.   In this  sub-section positive and negative
aspects of the liming  technique  will be  discussed.

Numerous calcium-based alkaline  materials are available for the
neutralization of acidified  soil.  However,  for most situations,
crushed limestone (CaC03),  flaked  or hydrated lime (Ca(OH)2>, and
unslaked lime or quicklime  (CaO) are the most readily available and
effective materials.  A  variety  of substances have been proposed for
use as neutralization  agents (Grahn  and  Hultberg 1975).

The data available  up  to now do  not  indicate obvious effects on
forest ecosystems caused by  acid deposition.  However, the potential
of the available techniques  for  remedial action warrant examination
in the event that subsequent data  indicate forest degradation.


9.3.1   The Application  of Lime  to Agricultural Soils

Microorganisms and  higher plants respond to  their chemical environ-
ment, and soil kinetics  are  a  key  factor in  determining agricultural
soil productivity.   There are  two  major  groups of factors which bring
about large changes  in soil  pH:  (1) those which result in increased
adsorbed hydrogen and  in turn  release aluminum, and (2) those which
increase the content of  adsorbed bases.   Both organic and inorganic
acids are formed when  organic  matter is  decomposed.  The simplest and
perhaps the most widely  found  is carbonic acid (H2C03) which
results from the reaction of C02 and water.   The solvent action of
H2C03 on the mineral constituents  of the soil is exemplified by
its dissolution of  limestone or  calcium  carbonate.  Because carbonic
acid is relatively  weak,  it  cannot account for the low pH values
found in many soils.   Inorganic  acids such as H2S04 and HN03
are suppliers of hydrogen ions in  the soil.   These acids, along with
the organic acids,  contribute  to the development of acid conditions.
Sulphuric and nitric acids  are formed, not only by the organic decay
processes, but also  from the microbial action on certain fertilizer
materials such as sulphur and  ammonium sulphate.  In the latter case
both nitric and sulphuric acids  are  formed.

Podzolization is an example  of a process by  which strong organic
acids are formed.   The organic debris is attacked largely by fungi
which have among their important metabolic end products relatively
complex but strong  organic  acids.  As these  are leached into the
mineral portion of  the soil, they  not only supply hydrogen for
adsorption, but they also replace  bases  and  encourage their solution
from the soil minerals.   Leaching  also encourages acidity.
Therefore, bases which have  been replaced from the colloidal complex
or which have been  dissolved by  percolating  acids are removed in the
drainage waters.  This process encourages the development of acidity
in an indirect way  by  removing those metallic cations which might
compete with hydrogen and aluminum on the exchange complex.

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                                                                  9-8
When lime is added to  the soil,  two  changes  occur:
                                                                               I
                                                                               I
     1)  the calcium and magnesium  compounds  applied  undergo  solution         •
         under the influence of  a variable  partial  pressure of carbon         •
         dioxide; and

     2)  an acid colloidal  complex  will  adsorb considerable amounts           |
         of calcium and magnesium ions.

When lime, whether the oxide, hydroxide,  or the carbonate,  is applied         I
to an acid soil, the movement, as solution  occurs,  is toward  the              ™
bicarbonate form.  This is  because  the partial pressure of  carbon
dioxide, usually several hundred times greater than that of                   •
atmospheric air, generally  is intense enough to prevent the existence         I
of the hydroxide or even the carbonate.   The reactions, written only
for the purely calcium limes, are as  follows:                                 m

     CaO + H20 ^a* Ca(OH)2

     Ca(OH)2 + 2H2C03 ^=* Ca(HC03>2 + 2H20                                     I

             H2C03 ^» Ca(HC03)2
The above equations represent only the  solution  of  the  lime  in                •
carbonated water.  However, the soil  situation is not as  simple as
these reactions might lead one to assume.   This  is  because the soil           «
colloidal matter upsets the equilibrium tendencies  by adsorbing the           •
ions of calcium and magnesium.  These ions  may be taken from the soil
solution proper or directly from  the  solid  phase if the contact is
sufficiently close (Buckman and Brady 1969).                                   •

The changes of lime in  the soil are many and  complicated.  If a soil
of pH 5.0 is limed to a more suitable pH value  (e.g., pH 6.5) then  a          m
number of significant chemical changes  occur.  For  example:  (1) the           •
concentration of H+ ions will decrease;  (2) the  concentration of
OH~ ions will increase; (3) the solubility  of  iron, aluminum and              _
manganese will decline; (4) the availability  of  phosphates and                •
molybdates will be augmented; (5) the exchangeable  calcium and                ™
magnesium will increase; (6) the  percentage base saturation  will
increase; and (7) the availability of potassium  may be  increased or
decreased, depending on soil conditions.

Overliming is an important phenomemon which must be considered.  A             ^
potential problem is the addition of  lime until  the pH  of the soil  is          •
above that required for optimum plant growth.   Under such conditions,          *
many crops that ordinarily respond to lime  are detrimentally
affected, especially during the first season  following  the lime                I
application.  With heavy soils, and when farmers can afford  to apply           •
only moderate amounts of lime,  the danger is  negligible.  But on
sandy soils (low in organic matter and  therefore lightly buffered)  it
is easy to injure certain  crops,  even with  a  relatively moderate
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                                                                  9-9
application of lime (Buckman and Brady  1969).   Some of  the
detrimental influences of excess lime are:


1.   Deficiencies of available iron, manganese, copper,  or  zinc may
     be induced.


2.   Phosphate availability may decrease due  to the formation  of
     complex and insoluble calcium phosphates.


3.   The absorption of phosphorus by plants and especially  its
     metabolic use may be interfered with.


4.   The uptake and utilization of boron may  be hindered.


5.   The drastic change in pH may, in itself,  be  detrimental.



9.3.2   Economics of Agricultural Liming


On judging the amounts of lime to apply, a number of  factors should
be considered:  (1) cost of liming material;  (2)  the  soil surface  pH,
texture and structure, and the amount of organic  matter;  (3) the
subsoil pH, texture and structure; (4)  the crops  to be  grown;  (5)  the
length of the rotation; (6) the kind of lime  used and its chemical
composition; (7) the fineness of the limestone; and (8)  operational
experience.
9.3.3   Forest Liming


While much is known about agricultural  liming  practices  (materials,
techniques, beneficial effects, and potential  problems),  much less  is
known about liming forested ecosystems.  For the  boreal,  north
temperate and temperate forests, such as are present  in northeastern
North America, Scandinavia and northwestern Europe, liming  has
considerable tradition for many centuries  (Evelyn 1776).


Where forest liming is viewed more as a fertilizer or nutritional
measure, rather than as an aid to soil  restoration, its promise  is
far less re-assuring.  This is because  calcium deficiencies have
seldom been demonstrated and fertilizer trials embodying  a  calcium
treatment have rarely shown a positive  response by tree growth.
Thus major reviews of fertilizer research  for  Canada  (Rennie 1972),
the United States (Bengtsson 1977; Mustanoja and  Leaf 1965), Sweden
(Holmen 1976), Great Britain (Everard 1974) and Germany  (Baule and
Fricker 1970), show calcium trials to be extremely few compared  with
those for nitrogen, potassium and phosphorus,  with very few
indications of positive growth responses.


Forest liming has not been widely implemented  because it  has not yet
been shown statistically that acidic deposition has caused  adverse

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                                                                  9-10
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effects in forest growth.  Forest liming  is  further  complicated
because the inaccessibility of forests makes  application difficult
(Bache 1980).                                                                   •

Sweden is one of the few  countries where  forest  liming is practised.
The first attempts to lime forest lands in  Sweden  were made 67 years            •
ago.  The most recent lime applications were  made  at a rate of 5 -  10          I
metric tons/ha on 0.2 hectare plots  in 12 areas.   Various
combinations of fertilizer were also applied.   It  was pointed out
(Fraser et al. 1982) that after 25 years  50%  of  the  lime was not               I
leached from the soil.  Research from 1971  to 1978 at Lisselbo                 •
(Fraser et al. 1982) where sulphuric acid and lime were applied  to
plots, was described.  Annual precipitation of 700 mm leaches between          •
2.0% and 11.6% of the lime since application.   Two preliminary                 |
conclusions from these studies are important:   (1) liming has little
effect on the growth of forest trees and  (2)  lime  persists in                  _
undisturbed forest soils, despite 700 mm  of annual precipitation.              •

Tveite and Abrahamsen (1980) report  the results  of field experiments
located in two different  areas of southern  Norway.  The authors                 B
present results from the  Norwegian field  experiments with artificial            |
acidic deposition and liming added to pine  and spruce forests.  All
experiments included treatment with  25 or 50 mm/month of artificial            mm
acidic deposition with different pH, applied during  the frost-free              •
time of the year.  After  five years  of treatment no  negative growth
effects of the acid applications are apparent and  there were no                 _
effects of liming found.                                                        •

No useful purpose would be served by documenting here a comprehensive
list of such trials, but  a few typical published results exemplify              •
the unattractiveness of the approach. For  45-year old jack pine               |
(Pinus banksiana Lamb.) in the Boreal Forest  of Ontario, calcium at
448 kg/ha gave no response except where nitrogen,  phosphorus and               •
potassium had also been applied  (Morrison et al. 1977b).  A further            •
trial with 55-year old but poorer quality jack pine, also north of
Lake Superior, again only snowed a growth response to lime where
nitrogen, phosphorus and  potassium has also been applied.  Indeed,              •
the suggestion was the lime by itself exercised a  depressive effect            •
upon growth by adversely  affecting soil microbiological processes
(Morrison et al. 1977a).  The complexity  of lime effects is apparent           •
from the work of Adams and his colleagues (1978) on  the acid peaty             £
gleys of Northern Ireland.  There, lime did not increase the growth
of Sitka spruce (Picea sitchensis Carr.), but it did affect the soil           _
microbiology and the viability of the mycorrhizal  root association.            I
As might be expected, the pH of  the  litter  was raised from 4.0 to 6.0          •
- 6.5, a result that has  been of serious  concern to  those aware  of
the optimum soil conditions for  the  spread  of rot  fungi such as                 B
Formes annosus (de Azevedo and Moniz 1974).                                    |

The possible effects associated  with liming forested ecosystems are            •
still unknown but experiments of watershed  liming  may provide some             •
insight.  Bengtsson et al.  (1980) report  on experiments of watershed
                                                                                 I

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                                                                  9-11
liming conducted in Sweden.  Agricultural  lime (i.e.,  powdered

CaC03) is generally transported  to  the watershed in large trucks
and applied as a slurry  with a sprayer truck.   The CaCo3 dose
required to achieve adequate neutralization of watershed systems is
generally two orders of  magnitude greater  than that of direct water
addition which is due  to the many base consuming processes that occur
within the forest soil systems (Bengtsson  et al. 1980).  There have
been application rates reported  in  the range of 5,000-7,000 kg

CaC03/ha.yr.  Hultberg and Andersson (1982) reported that some
damage to the terrestrial environment  may  be associated with liming.
Sphagnum moss was severely damaged  with CaC03  addition.  Damage to
lichens, mosses and spruce needles  was also observed.


Smelters at Sudbury, Ontario,  represent the greatest single source of
sulphur dioxide emission in the  world.  Over the past  several years,
a terrestrial liming/reclamation program has been operated (Fraser
et al. 1982).  The affected lands have a pH of approximately 4.0 and
concentrations of copper and nickel were measured up to 10 ppm.  To
reclaim this land, crushed agricultural limestone is applied at a
rate of 12.4 short tons/ha, then fertilized with a nitrogen-
phosphorus-potash mixture (6-24-24,  respectively),  and seeded with a
variety of blended grasses.  The limestone application is labor
intensive with 400 students adding  the limestone by hand.  Over 1000
hectares have been reclaimed to  date.   According to the authors, this
terrestrial liming project has been extremely  successful in raising
the pH of the soil and complexing the  heavy metals (although there is
still some minor nickel  toxicity).   The authors report that grass is
now able to grow on barren areas and the resultant shading and
lowering of ground temperature has  enabled some natural vegetation
(e.g., quaking aspen seedlings)  to  become  reestablished.  The newly
established vegetation is monitored and analyzed, as is the recovery
of populations of insects, birds, and  small mammals.


Limited information is available on the changes to terrestrial flora
and fauna after the addition of  lime to forested soils.  Tamm (1976)
stated that when lime  was added  to  forest  soils in small-scale
experiments, tree growth rates typically was not enhanced, because of
the tendency of lime to  immobilize  the nitrogen in organic matter and
thereby reduce its availability  to  trees.   Fraser et al. (1982)
report that lime had little effect  on  the  growth of forest trees,
based on preliminary conclusions from  forest liming studies conducted
in Sweden from 1971 to 1978.   Abrahamsen et al. (1980) reported that
soil animal populations  nearly always  fail to  increase when soil
acidity was reduced by liming.   Hultberg and Andersson (1982) report
that the liming of watersheds  in addition  to lakes and streams would
release additional phosphorous to the  waterbodies and  enable these
aquatic systems to increase their primary  productivity.

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                                                                  9-12
9.3.4   Terrestrial Liming Summary
9.4   DRINKING WATER SUPPLY
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In conclusion, although in principle the  liming  of  land might                  I
neutralize an acidifying pollutant  (Ulrich  1972)  it has the  following         I
serious limitations.  First, it would not prevent direct  injury  to
plant tissues, even where in agricultural situations it is already            •
being used as a soil amendment.  Secondly,  in  the typical forest              •
situation it would be very difficult to apply.   Thirdly,  the effects
of lime in the boreal and north temperature forest  are complex and
often far from beneficial.                                                     •
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Low pH conditions  in  municipal  water supplies  can cause corrosion of
the plumbing materials.   The  estimated  costs for controlling                   «
corrosion were based  on  adding  lime  to  water to stabilize it.   This            •
should control corrosion of  lead  pipes  as  well as corrosion of cast
iron water mains,  and is the  corrosion  control technique most  likely
to be used by water utilities.                                                  I


9.5   COSTS OF CORROSION CONTROL                                                M

Costs for corrosion control  by  lime  stabilization were estimated by
Hudson and Gilcreas (1976) to total  $0.30  U.S. per capita for
operation and amortization costs  in  1976.   Average per capita  costs            •
for lime stabilization were  estimated by Davis et al. (1979) to                *
range from $0.18  to $0.57 U.S., depending  on the extent of chemical
treatment provided to stabilize the  water.
 I
Corrosion  control  by calcium carbonate stabilization and deposition
of  a  protective  calcium carbonate film has been suggested by EPA as            •
an  effective  approach to nonselectively provide protection to a                •
number  of  materials, including asbestos cement, lead, iron,
galvanized steel,  copper,  and alloys that may be used in water
distribution  systems or plumbing.  Annual per capita costs for                 •
corrosion  control  by addition of lime were estimated by USEPA (1979).          •
Costs are  a function of plant size, as shown in Table 9-1.

The methods used to  calculate corrosion costs in the USEPA Statement           J|
of  Basis  and  Purpose were developed by Gumerman et al. (1979).  An
example of calculation of cost for corrosion control by addition of            _
lime  at 30 mg/L  for  pH control in a 5 million gallons per day (MGD)            •
plant is  given in Table 9-2.  The costs are shown for operation at             •
70% of  capacity  (3.5 MGD).  The principle items of expense are
capital amortization, labor, and chemical used.  Chemical consumption          I
is  the  cost category most sensitive to water quality changes.                  |
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                                                                  9-13
TABLE 9-1.   COST OF CORROSION CONTROL BY LIME  ADDITION  AS A FUNCTION
             OF PLANT SIZE
Plant Size
Gallons Per Day
2,500
50,000
5,000,000
100,000,000
(t/ 1,000 Gallons
Treated - 70% Capacity
56.9
16.4
2.7
1.1
Annual Per Capita
Costa - $
20.50
6.00
1.00
0.40
  Cost stated in $ U.S. 1981, December.

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                                                                  9-14
TABLE 9-2.   EXAMPLE OF COST CALCULATION FOR FEEDING  LIME  AT A
             5 MILLION GALLONS PER DAY PLANT
                                                          $/Yeara
a  Cost per 1,000 gallons  treated =  2.68
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                                                                 9-15
9.6  REFERENCES
Abrahamsen, G.; Hovland, J.; and Hagvar, S.   1980.  Effects of
     artificial rain and liming on soil organisms and the
     decomposition of organic matter.  In Effects of acid
     precipitation on terrestrial ecosystems, eds. T.C. Hutchinson
     and M. Havas, pp. 341-362.  New York:  Plenum Press.


Adams, S.N.; Cooper, J.E.; Dickson, E.L.; and Seaby, D.A.   1978.
     Some effects of lime and fertilizer on a Sitka spruce
     plantation.  Forestry 51(1):57-65.


Bache, B.W.  1980.  The acidification of soils.  In Effects of acid
     precipitation on terrestrial ecosystems, eds. T.C. Hutchinson
     and M. Havas, pp. 183-202.  New York:  Plenum Press.


Baule, H., and Fricker, C.  1970.  The fertilizer treatment of forest
     trees.  Munich:  BLV-Verlag.


Bengtsson, B.  Personal communication.  Swedish Water and Air
     Pollution Research Institute (IVL), Goteborg, Sweden.


Bengtsson B.; Dickson, W.; and Nyberg, P.  1980.  Liming acid lakes

     in Sweden.  Ambio 9(l):34-36.


Bengtsson, G.W.  1977.  Fertilizers in use and under evaluation in

     silviculture;  a status report.  International Union of Forestry
     Research Organizations, XVI World Congress, Oslo.  32  pp.


Buckman, H.D., and Brady, N.C.   1969.  Nature and properties of
     soils.  New York:  McMillan Co.


Davis, M.J., et al.  1979.  Occurrence, economic implication and
     health effects associated with agressive waters in public water
     systems.Final Report, MRI Project No.  4552-L, Prepared for A/C
     Type Producers Association.


de Azevedo, N.F., and Moniz, M.  1974.  Influence of temperature, pH
     and nutrients on the growth of Fomes annosus isolates.  In
     Fourth Int. Conf. on Fomes Annosus, pp.  163-168.  IUFRO, Section
     24, Athens, Georgia, USDA Forest Service, Washington,  DC.


Evelyn, J.  1776.  Silya, a discourse of forest trees, new  edition,
     with Notes by 7^. Hunter.  York.


Everard, J.E.  1974.  Fertilizers in the establishment of conifers in
     Wales and southern England.Forestry Commission Booklet,

     No. 41, HMSO, London.  49 pp.


Festa, P.J.  Personal communication.  Department of Environmental
     Conservation, Albany, NY.

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                                                                 9-16
Fraser, J.; Hinckley, D.; Burt, R.; Severn, R.R.; and Wisniewski, J.
     1982.  A feasibility study to utilize liming as a technique to
     mitigate surface water acidification.  EA-2362 Final Report,
     Electric Power Research Institute, Palo Alto, CA.
Hudson, H.E., Jr., and Gilcreas, F.W.  1976.  Health and economic
     aspects of water hard
     Assoc. 68(4):201-204.
     1981.   (in press)
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Grahn, 0., and Hultberg, H.  1975.  The neutralizing capacity of  12             «
     different lime products used for pH-adjustment of acid water.              •
     Vatten 2:120-21.                                                           *

Gumerman, R.C.; Gulp, R.L.; and Hansen, S.P.  1979.  Estimating water           •
     treatment costs.  Volume 2.  Cost curves applicable to 1 to  200            •
     mgd treatment plants.  Final Report EPA-600/2-79-162B, U.S.
     Environmental Protection Agency, Santa Ana, CA.                            •

Holmen, H.  1976.  Forest fertilization in Sweden  1975.  Kungl.
     Skogs-och Lantbruksakadamiens Tidskrift 1976(3) Medd. No. 7.               _
     9 PP.
aspects of water hardness and corrosiveness.  J. Am. Water Works^           •
Hultberg, H., and Andersson, I.E.  1982.  Liming of acidified  lakes:            •
     induced long-term changes.  Water, Air, Soil Pollut.  17.  (in               •
     press)

Morrison, I.K.; Swan, H.S.D.; Foster, N.W.; and Winston, D.A.   1977a.           I
     Ten-year growth in two fertilization experiments in a  semi-
     mature jack pine stand in northwestern Ontario.  For.  Chron.
     53:142-146.                                                                •

Morrison, I.K.; Winston, D.A.; and Foster, N.W.  1977b.  Effect of
     calcium and magnesium, with and without NPK on growth  of  semi-             •
     mature jack pine forest, Chapleau, Ontario:  fifth-year results.           •
     Can. For. Serv. Report O-X-259, Sault Ste Marie, Ont.   11  pp.

Mustanoja, K.J., and Leaf, A.L.  1965.  Forest fertilization                    •
     research, 1957-1964.  Bot. Rev. 31(2):151-246.                             •

National Fisheries Board and National Environmental Protection Board.
     1981.  Liming of lakes and rivers, 1977-1981, in Sweden,  eds.
     B. Bengtsson, and L. Henriksson, Goteborg, Sweden.

Pfeiffer, M.H.  1982.  Recent impacts of acidification on  fisheries             •
     resources in the U.S.  In Proc. Int. Symp. Acidic
     Precipitation and Fishery Impacts in Northeastern North America.
     American Fisheries Society, Cornell University, Ithaca, NY.,               •
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