ACID PRECIPITATION - ITS INFORMATION

DEPOSITION AND EFFECTS ON

LAKE WATER CHEMISTRY

A REVIEW OF THE LITERATURE

JANUARY, 1978

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ACID PRECIPITATION - ITS FORMATION,DEPOSITION AND EFFECTS ON

LAKE WATER CHEMISTRY

A REVIEW OF THE LITERATURE

MINNESOTA ENVIRONMENTAL QUALITY BOARDBeth HonetschlagerJanuary, 1978

TABLE OF CONTENTS

List of Figures.

List of Tab"les

ABSTRACT . . . .

INTRODUCTION·TO THE REGIONAL COPPER-NICKEL STUDY

INTRODUCTION . . .

PRECURSORS OF ACID PRECIPITATION

SULFUR DIOXIDE AND SULFATE EMISSION SOURCES,AMBIENT LEVELS AND TRENDS .....

CURRENT ACIDITY OF PRECIPITATION

REMOVAL MECHANISMS

ACID BUFFERING ...

EFFECTS OF ACrD PRECIPITATION ON LAKESFluctuations in Lake pHAdd i t ionalEf fee t son Wa t er Chemi st r'y

CONCLUSION

REFERENCES CITED

PAGE

ii

iv

v

1

3

6

18

22

24

. 263337

39

40

NUMBER

1

2

3

4

5

6

7

8

9

LIST OF FIGURES

Sulfate concentration in precipitation

Sulfur dioxide concentration in air

Sulfate concentration in air

Three-year running averages for S02 and S04at Minneapolis (1963-1972)

Selected precipitation pH values

Windrose diagram for Sudbury (1955~1966)

Sketch map of Sudbury area showing acontour for lakes with pH = 5.5

Lake pH

Sulfate loading from bulk precipitation

ii

PAGE

7

11

13

16

19

28

29

31

34

Nur~BER

1

2

3

4

5

LIST OF TABLES

Sulfate concentration in precipitation

Precipitcrtion pH

Rate of lake pH change due to acidprecipi t-ion

Lake pH

Sulfate loading from bulk precipitation

iii

PAGE

PAGE

8

20

30

32

35

ABSTRf-1,CT~----- ..

Current literature on acid precipitation was reviewed to determine sources,deposit-ion meehan-isms and effects on lak(~ \vater chernistl~y. Values ofprecipitation and la pH S04 content of precipitation, ambient 502 and504, and 504 loading were obtained in order to compare northeasternMinnesota with other areas of the world.

Precipitation has become increasingly acidic in regions of North Americaand Europe during the last two decades. The most highly impacted areasinclude Norv]cJY, the northeastern U.S., and the vicinity of Sudbury, Ontario,where precipitation with pH of four is not unusual. Remote areas of theworld have Seen found to have precipitation pH values near 5.7, the pH ofwater in equilibrium with carbon dioxide in the atmosphere. NortheasternMinnesota precipitation has an average pH of near five.

Decreasing precipitation pH has occurred simultaneously with increases insulfur and nitrogen oxide emissions from anthropogenic sources. Sulfuroxides are considered to be the major precursors of acid precipitation.Long distance transport of these pollutants from industrial areas causesprecipitation to be acidic in areas with no local polluters.

Lake water pH has been reduced because of acid precipitation.' Especiallyvulnerable to acidification are lakes which are poorly buffered due totheir geologic environmen North~astern Minnesota lakes have an averagepH of seven, while many lakes downwind of industrial pollution sourceshave pH values of five or less, and have experienced loss of aquatic plantand animal populations. Increased solubility of metals, which occurs at10\\1 pH'levels s causes additional stress to aquatic biota.

iv

INTRODUCTION 'ro TIlE STUDY

The Reg' , 1 Copper--Nickel Environmental Impact Study is a comprehensiveexamination of the potential cumulative environmental, social, and economicimpacts of copper-nickel mineral development in northeastern }linnesota.rTIlts study is being conducted for the Hinnesota Legislature and stateExecutive Branch a , under the direction of the Minnesota Environ-mental Quality Board (HEQB) and '\',Ti th the funding, revie'l>l, and concurrenceof the Legislative CommisSion on Ninnesota Resources.

A region along the surface contact of the Duluth Complex in St~ Louis andLake counties in northeastern Minnesota contains a major domestic resourceof copper-nickel sulfide mineralization. This region has been e).rplored byseveral mineral resource development companies for more than twenty years,and recently two firms, i~U~ and International Nickel Company, haveconsidered commercial opera tlan.s These explora tion and mine planningactivi ties indica te the poten tial establishmen t of a nev] mining and pro-­cessing industry in Minnesota. In addition, these activities indicate theneed for a comprehensive environmental social, and economic analysis bythe state in order to consider the cWTIulative regional implications of thisne~'l industry and to provide adequate infonnation for future state policyrevie\\7 and development. In January, 1976 ~ the HEQB organized and initiatedthe Regional Copper-Nickel Study. .

The maj or ob:] ec ti '\les of the Regional Copper--Nickel Study are: 1) tocharacterize the region in its pre-capper-nickel development state; 2) toidentify and describe the probable technologies which may be used to exploitthe m~.neral resource and to c.onvert it into salable commodities; 3) toidentify and assess the impacts of primary copper-nickel development andsecondary regional growth; 4) to conceptualize alternative degrees ofregional copper-nickel development; and 5) to assess the cumulativeenvironmental, social, and economic impacts of such hypothetical develop­ments. The Regional Study is a scientific information gathering andanalysis effort and will not present subjective social judgements onwhe ther ~ \\1here, wben, or how copper-nickel developrnen t should or shouldnot proceed. In addition, the Study will not make or propose state. policypertaining to copper-nickel development.

lne Minnesota Environmental Quality Board is a state agency responsible forthe implementation of the Hinne-sota Environmental Policy Act and promotescooperation betVleen state agencies on environmental matters. The RegionalCopper-Nickel Study is an ad hoc effort of the HEQB and future regulatoryand site specific environmental impact studies will most likely be theresponsibility of the ltinnesota Department of Natural Resources and theMinnesota Pollution Control Agency.

v

INTRODUCTION

Rain or snow with a pH of less than 5.6 is considered acidic (Likens 1976),

since water in equilibrium with carbon dioxide in the atmosphere produces a

precipitation pH of about 5.7 (Heuss 1975, Kramer 1976a). Precipitation pH

values of close to 5.7 have been recorded in remote areas of the world, long

distances from sources of atmospheric pollution (Kramer 1976a)(see Figure 2).

Many other regions receive acid precipitation, sometimes with pH levels of

three or lower (Likens and Bormann 1974, Likens and Bormann 1975, Cogbill

1975, Likens et ale 1975, Hutchinson and Whitby 1974). Zones of highly

acidic precipitation are expanding (Hysing-Dahl et al. 1976, Likens 1976)

and precipitation pH is decreasing in many areas (Likens 1976).

Acid precipitation is of concern because of its effects on aquatic and

terrestrial ecosystems. Acidification of lakes and streams due to acid

precipitation has eliminated or severely reduced populations of aquatic,

plants and animals (Leivestad et al. 1976, Beamish and Harvey 1972,

Schofield 1976, Hendrey et al. 1976, Bolin 1971). Acid ra-in causes changes

in the rate of leaching of elements from soils s which may affect vegetation

growth (Abrahamsen et al. 1976, Malmer 1976, Likens and Bormann 1974) and

change the composition of runoff that reaches water bodies. Vegetation may

a"lso be injured by direct contact with acid precipitation (Abrahamsen et al.

1976). Other potential problems due to acid precipitation include effects

on predator-prey relationships, effects on the metabolism of organisms,

deterioration of buildings, and effects on human health (Likens and Bormann

1974, Oden 1975, Bolin 1971).

Page 2

The inc reased ac i di ty 0 f preci p'j tat ion cI uI' 'j ng the pas t 20 yea Y'S -j n nor the rn

Europe and the northeastern United States correlates with increased anthro­

pogenic emissions of sulfur dioxide and nitrogen oxides (Likens 1976).

These two pollutants are the major precursors of acid precipitation

(Likens 1976, Dovland et ale 1976, Gallov/ay et ale 1976a, SUlllmers and

Whelpdale 1975). A high correlation has been found between acid precipi­

tation episodes and storm tracks that have passed over areas of high density

anthropogenic emissions (Junge 1963, Cogbill and Likens 1974, Dovland et ale

1976, Bolin 1971). Concentrations of other pollutan ,such as heavy metals

and pesticides, have also increased in the eastern U.S., Ontario, and

Scandinavia and show the same distribution as acid precipitation (Lodge et ale

1968, Hagen and Langeland 1973, Almer et ale 1974 Conroy et ale 1975). In

recent years taller stacks have been constructed in an effort to reduce

local pollution, and the areal distribution of acid precipitation has been

observed to increase concomitantly. Thus, human activities are believed to

be the cause of increasing acidic precipitation.

This report is a review of the current literature concerning acid precipi­

tation, its formation, and its effects on lake water quality. Of particular

interest was literature dealing with acid precipitation in areas of the world

which have geologic and climatic characteristics similar to those of north­

eastern Minnesota. Copper-nickel deposits have been discovered in northeastern

r~innesota. Smelting of similar ores in Sudbury, Ontario has resulted in

acidification of precipitation due to 502 emissions, followed by acidification

of lakes, elimination of aquatic species, and damage to terrestrial

vegetation (Conroy et ala 1975, Gorham and Gordon 1960).

Page 3

The presence of acids in the atmosphere can cause precipitation to be acidic.

Strong acids have been found to be the most important contributors to acid

precip-jtation (Likens 1976~ Dov-Iand et a"l. 1976, Galloway et alb 1976a,

~ummers and Whelpdale 1975, Gorham 1975, Krupa et al. 1975), although weak

acids rnay also contribute (Galloway et ale 1975). The precursors of acid

precipitation are chloride, which forms hydrochloric acid; sulfur dioxide,

which is converted to sulfate and then to sulfuric acid; and nitrogen oxides,

which form nitric acid (Likens 1976, Dovland et ale 1976, Galloway et alb

1976a). These compounds are released to the atmosphere by var-ious natural

and hwnan activities.

Chloride is released to the atmosphere by anthropogenic emissions, and

naturally from sea spray and volcanic eruptions. Gorham (1958) observed

substantial amounts of chloi"ide in smoke solids from coal burning. Hydro=

chloric acid also has been detected in precipitation in British urban areas

in amounts too great to be accounted for by natural sources (Gorham 1958);

coal combustion is the likely source, according to Gorham (1975). Coal­

burning Tennessee Vall(~y Authority plants have been found to emit hydr'ochloric

acid in flue gases. Hydrochloric acid is not deemed as important as sulfuric

acid and nitric acid as a component of acid precipitation; however, it has

been detected in precipitation of the northeastern U.S. (Likens 1976) as

well as the Minneapolis-St. Paul area (Krupa et al. 1975).

Weak and Bronsted acids contribute only slightly to the H+ ion concentration

in northeastern U.S. precipitation (Galloway et al. 1975). In an aqueous

solution; total acidity is made up of both free and bound protons. Free

Page 4

protons constitute the measurable pH, while bound protons have no influence

on pH and can be determined only by titrat"ion (GalloltJaY et a'i. 1976a). The

dissociation of a weak acid such as H2C03 is dependent upon pH. At pH 5 or

greater, H2C03 contributes to both free and bound acidity. At pH less than

5, however, it contributes only to bound acidity, and does not affect pH.

Bronsted acids are likewise not H+ ion sources below pH 5 (Galloway et al.

1976a). AS,Figure 2 indicates, precipitation pH values of less than 5 are

not uncommon. Gallol;,ray et a1. (1975) conclude that although acid pr'ecipi­

tation is a mixture of strong and weak acids, weak acids contribute primarily

to the total acidity and only negligibly to free acidity.

Sulfuric acid is the predominant strong acid which causes acid precipitation

(Gorham 1975). Sulfur compounds are introduced to the atmosphere by three

main processes: HZS from biological decay, 504 from sea salt, and 502 from

anthropogen'ic sources, such as sulf-ide ore smelters and industr"ies which

burn fossil fuels (Dovla.nd et a"l. 1976). E1 c generating plant emissions

account for about 60 percent of the sulfur emitted by human activities in

the U.S. (U.S.EPA 1976b). Global sulfur budgets reported in the

1i terature vary greatly, and Likens (1976) is of the opinion that there is

not enough data at present to evaluate their reliability. The literature

reviewed by Gorham (1975) indicates that sulfur mobilization from natural

sources is 133 to 152 X 106 metric tons per year compared to 50 to 55 X 106

metric tons per year from anthropogenic emissions. Although natural

emissions are estimated at over twice anthropogenic emissions, natural

emissions are not considered a major factor in producing acid rain, because

they are assumed to be in balance with natural sources of neutralizing

bases (Gorham 1975). Because 502 and 504 in the atmosphere are of great

pC! 5

concern as precursors of acid precipi tion, their emission sources,

ambient concentrations, and concentration trends will be discussed in a

later section.

Nitrogen cornpoun the precursors nitric acid enter the atmosphere as

anrnonia released by biologi decay processes, and as nitrogen oxides from

biochemical reactions in soil and combustion processes (Dovland et a1. 1976).

tirna of the q ties of nitrogen compounds released from various

sources are difficult to make; however, it has been calculated that annual

global emissions nitrogen oxi s from natural sources are 150 X 106

metric tons. This compares to 8.2, 6.6, and 0.6 X 106 tons per-year from

combustion of coal, petroleum, and ural gas, respectively (Anon. 1975).

Anthropogenic nitro ern-i 55 ions been increasing, with a corresponding

in~rease in nitrogen oxide content of precipitation. Likens (1972) blames

increased N0 0 content of precipitation since about 1945 on increased use of, .)

na tur'a 1 gas and motor fue 1s. Improved fos s 'j 1 fue 1 combus t ion techn i ques ,

which use higher flame temperatures, have also caused greater nitrogen

ox-ide em-issions and precipitat-jon content (Oov<land et al. 1976). The

increased use of nitrogen fertilizers since about 1950 may have contributed

additionally to the NOx content of precipitation (Dovland et al. 1976).

Although both sulfur dioxide and nitrogen oxide emissions increased sharply

after 1960, nitrogen oxide emissions increased at twice the rate of 502

emissions between 1960 and 1970 (Likens 1976). The concentration of

nitrogen oxides in precipitation has also increased compared to sulfur

dioxide concentration. In the Hubbard Brook Experimental Forest in

New Hampsh-jre, the contribution of S04 to the acidity of precipitation in

1964-1965 was 83 percent, while in 1973-1974 it was down to 66 percent.

The N03 contribution, on the other hand, increased from 15 to 30 percent

(Likens 1976). Annual inp of hydrogen ions "in precipitation increased

by 1.4~fold during this per-iod which corre"lates highly w-ith the annual

rate of Iritrate -input. Sul te annual input d"id not increase significant"ly

(Likens et 0.1. 1975). Thus 9 a"lthough sulfuric acid remains the largest

contributor to acid precipitation, nitric acid is apparently becoming more

important in the northeaster-n U.S. (Likens et 0.1. 1975) and in northern

Europe (Dovland et 0.1. 1976).

Excess sulfate (sulfate from all sources other than sea spray) concentration

is considered by Dovland et 0.1. (1976) to be a good measure of the acid{fying

effect of precipitation in Norway. This is because the correl~tion

coefficient between the concentration of excess sulfate and strong acid in

precipitation was 0.7 to 0.9 at most of the stations observed. Sulfate

concen~ration is important in other areas of the world, also, where it is

the cause of acid precipitation. Figure 1 and Table 1 show sulfate concen­

t rat ionsin prec i pitat -j 0 n . J un 9e and ~le f' by (1958 ) rep 0 r te d 2. 2 rng/ 1 as a

good average of excess sulfate in precipitation over land for the whole

earth. This value is exceeded by most stations listed in the table.

SULFUR DIOXIDE AND SULFATE EMISSION SOURCES, AMBIENT LEVELS AND TRENDS

Sulfur oxide emissions, mostly in the form of S02' have generally increased

in recent years due to human activities. In Europe, sulfur emissions are

reported to have continuously increased by two to five percent per year

during the last fifteen years (Oden 1975). During the 1960s sulfur oxide

emissions in the U.S. increased by 45 percent (Commission on Natural

Page 7

Figure 1. Sulfate concentration in precipitation.

15 80

70

East CentralCanada

Remote

11

7 '.

6

West Coast Canada

Wes t Cen tral CanacI3

Sudbury

Fort Simpson, Canada

Sv;reden

SVleden

60

50

40

30

mg/~ 20

Non.,ay Fares t

5_____-Dunka Road, l'fi.nnesota

Spruce Road, Kinnesotaj -._-- Hoyt Lakes, Minneso ta

4 Norway South Coast/"". S'f./leden~ ~.~ Northeas tern U. s.

l~ Fernberg Road, Minnesota

3 IIubbard BrookUltuna, Sweden

.__.---Newfoundland; World average over land 19582 • Norway 100 km from coast

Remote _Antarctica snmV' profileNinnesota

1

Remote

mg/9.. 0

East Coast CanadaRam PIa teau, Canada

_____ West Coast Canada----·-Norway Forest

Table 1. Sulfate concentration in precipitation.

Location .504 (mg/l) Comments Reference

vC.J

1Oroco

Remote backgroundRam Plateau, N.W.T., CanadaFort Simpson, N.W.T.Cape Dyer, N.W.T.Resolute~ N.H.T.Antarctica

<.50.1-80.8<51.6

bulk 'sample, 1 station 6/7S-8/75PreciDitation only

k -'

sum,T eventrain eventsnm,]

Kramer 1975and Summers 1975

Kram2r 1973aGjes and 1973

NeT,.;rf ound land 2.2 station~ 1 year precip Gorham 961

Wisconsin

Ojebyn, northern Sweden

Ultuna, central Sweden

Georgetow~, British Guiana

2.9

2.5

2.6

1.3

single station, 1 year precip.

single station, 1 year precip

single station, 1 year precip

3 year average precip

Yonkers, N.Y., 24 km north of ~XC <1-204.8 mean

precipitation events 1974 Jacobson et ale 1975

Northeastern U.S.

Hubbard Brook ExperimentalForest, N. Ramp

CanadaWest CoastHest CentralEast CentralEast CoastSudbury, Ontario

Central Alberta

4.3-5.23.19-4.96

2.9

0.1-13<0.1-11<.3-80.9-3.2<.5-9.4

2.7

bulk sample, 18 sites 1965-68precipitation, 5 sites 1972-73

bulk precipitation, weightedannual mean 1964-74

bulk precipitationbulk precipitationbulk precipitationbulk precipitationprecipitation events--variationover 11 days 1,2, & 3/76152 rain samples 1967-70, mean

Pearson and Fisher 1971Cogbill and Likens 1974

Likens et a1.1975

Whelpdale and Summers 1975

Kramer 1976b

Summers and Hitchon 1973

Table 1. Cab",,'..!.

LocationNon,ray

17 stationsSouth Coast100 k~ from coast'VJesternBirkenes watershed

:Forest

Sweden

SO~(!i1g/l).1-12.8-3L~

21-23.24

.05-56

7-7.33.3-6.51.5-2.7

Corm:Ilentsprecipitation eventsprecipitation 1974-75mean in precipitation 1972-73mean in precipitation 1972-73mean in precipitation 1972-73mean of 20 precipitation events,197precipitation

bulk precipitationbulk precipitation

Referenc.eScholdager 1973Summers and Hitchon 1973Dovland et al 1976

Semb 1975

or et al. 1974

Hornstrom et ale 1973&idersson 1972MaImer 197~l

CJ

r~

Northeastern KtnnesotaFernberg RoadSpruce RoadDunka RoadHoyt Lakes

Land areas, whole earth

1.43.055.14.8

2.2

single station, year precipe Gorham 1961mean, 2 bulk precip samples 3&5/77 HEQB 1977mean, 3 bulk precip samples 3,4&5/77mean, 2 bulk precip samples 4&5/77mean, 2 bulk samples 4&5/77

average based on precipe 804 Junge and Werby 1958concentrations in the literature

Page 10

Resources 1975)· however, from 1972 through 1 emiss'ions appear to have

decreased slightly (U.S.EPA 1976a). Certainly in the early 1970s, and

possibly during the 1960s, emissions in urban areas decreased as sources

began to comply with air pollution control regulations (CNR 1975~ U.S.EPA

1976b).

Large point sources located outside of cities were responsible for most of

the increased 502 emissions in the 19605, and electric power plants contri­

buted about 88 percent of the total from these sources (CNR 1975). Power

plant sulfur oxide emissions continued to increase in the early 1970s,

when the overall trend was a slight decrease (U.S.EPA 1976b). At present,

large point sources are the emitters most 1i ke"y to violate 'federal air

quality standards (U.S.EPA 1975).

Sulfur oxide emissions are expected to continue to increase if no further

abate,nent pro9rarns are implemented (CNR 1975). The National Academy of­

Engineering has predicted a 66 percent increase in emissions in

the U.S. from 1970 to 1990. Emissions from power plants are expected to

double from 1970 to 1980 and triple from 1970 to 1990 (CNR 1975).

About 80 percent of the total electric generating capacity derived from

fossil fuels in the U.S. is located in the eastern half of the country;

about 50 percent of the total is located in the northeastern states

(Shriner et ale 1977). The northeast also contributes about half the

total sulfur oxide emissions (CNR 1975), and has the highest ambient S02

and 504 levels.

Concentrations of sulfur dioxide in the air are shown in Figure 2. The

effect of different quantities of sulfur oxide emissions can be seen:

.Figure 2. Sulfur dioxide concentration in air.

S02range and mean

-:::;....:.;tom

lo--'lo--'

DATE

Eo'!'I,measure­ments

SITE

Backli\round

World;many Europeansites

Industrial Britain

ND 1Jg/m3 10

I----'l

20 30 40 50 60 70 80 REFERENCE

r~orgii 1970; Cadleet al. 1968; Lodge0. Pate 1968

Junge 1963

Meetham 1950

1964-68 Urban NASN sites

EArly 70s Urban NASN gites

448'" ~e

---~.~ .._._ ..~- ~----~ ....

U.S. Dept. or R~;

1966; U.S.EPA 1971.1972a

U.S.EPA 19720.

1964-68

1964-68

1968

Eastern urban NASNsites

Western urban NASNsites

NOrlm:ban 5:1. tes;4 eastern; 1 western

f c --e

U.S. Dept. of HE~

1966, 1968; U.S.EPA1971, 1971a

1973-76 4 Minneapolis sites

1973-76. 1 Rochester: site

1974-76 2 sites dovn~ind ofpetroleum refineries

f e

~l

Ritchie 1977

Ritchie 1971

Ritchie 1977

1977 2 northeastern Minnesota~ ~

sites; Hoyt LakesEQ13 1977

e 12

background sites have 1 s 0 f 4 p ~J / In3

0 r 1ess (Geo r 9i i 1970, Cad1e' eta1.

1968, Lodge and Pa 1966), whereas industrial and urban areas have much

higher levels. Data from the Na anal A-ir Surveillance Network (NASN) reveal

that the average 502 concentration at eastern U.S. urban sites was three

times the average concentration at western urban sites in 1964 through 1968

(Altshuller 1973). NASN data from 1963 through 1972 showed western sites

and midwestern sites west of the Mississippi to have only 10 to 20 percent

of the east coast levels (Altshuller 1976). Highest 502 levels were found

in the Northeast (Middleton 1970).

Five Minnesota sites had 502 concentrations within the early 1970 NASN

reported values, but above the NASN mean (Ritchie 1977). The two sites

downwind of petroleum refineries had much higher values. On19 two sites in

northeastern nnesota, which are probably influenced by power plant

em-Iss'ions, had enough 502 data above the detection limit to justify inclus'ion

in Fig'ur'e 2. On one par'ticu'lar date, the 502 concentration reached 28.8

3~g/m at one of the sites (MEQB 1977).

Figure 3 shows ambient sulfate concentrations. As with S02 concentrations,

eastern and urban values are higher than western and nonurban values.

Background areas throughout the world have reported S04 levels of 1 to 4

~g/m3 (Georgii 1970, Junge et al. 1969, Junge 1963), while U.S. urban NASN

3sites r'eported levels approaching 50 llg/m from 1964 through 1968 (Altshuller

1973). Western urban values are generally one- half eastern urban values

(CNR 1975), while western mountain states were found to have only 15 to 25

percent of the 504 concentration at eastern sites (Altshuller 1973).

Figure 3. Sulfate concentration in air.

504 range and mean

C'.)

Junge 1963

1970; Junga at a1. 1969;Junge 1963

REFERENCE2015ND ';1g/m 3 5 10I i -------?~------! ~

I' e

II e

Remote

Typical nonurban

.illL-.!?AIL-

Global average e Robinson & Robbins 1968

Frankfurt~ Germany Junge 1963

1973 France, 1 s1 te. ~ Benarie 1975

1973 Iceland, 1 s1 te f 1£ Z Renarie 1975

1973 Switzerland, 1 site ~ Banarie 1975

1973 No!"Way~ 1 site. g It ~ Benarie 1975

77

1973

11'''f1\965-68

n B IF

II " n

II II H

II PI n

MF.,QB 1977

u.s. Dept. of RB~ 1966;U.S.EPA 1971 1972a

Benarie 1975

~

b eo C

• II I

48.7----------\l\-i

.,

~

e , Q

Eastern urban NASN sites

U=ban NASN sites

Western urban NASN sites

Finland, 1 site

Eastern nonurban NASNsites

Western nonurban NASNsites

Northeastern Minnesota,4 eites

1964-68

1964-68

SO~ levels in rural areas dir

r greatly between east and west (Al huller

1973). West of the Mis issippi 504 concentrations over')

ranged from 1.5 to 5 ~g/mJ, whereas similar si in the

t and farmland

tand ~1i e1v'est')

east of the Mississippi had values of 5 to 10 ~g/mJ. Al huller (1973)

attributes this difference a residue 504 level of at least 5 ~g/m3 in

'the East, caused by long di stance transport 5°2, and the convers i on of

S02 to 504 during transport. This is due to emission patterns; sites west

of the f'~ississippi had, at most, one S02 em'ission source v".ithin 160 km

(Altshuller 1973), while eastern sites, on the average, were within 30 to

60 km of a source (Shr'iner et ale 1977). Transport and transfonnation of

502 is responsible for over 50 percent of the 504 at eastern sites and

rn-i d~'Jes tern s i east of the Mississippi, and responsible for over 75

percent of the 504 at nonurban eastern sites (Altshuller 1976).t

Recent trends in 502 and 504 concentrations have been determined for the

U.s. ~~d Minnesota. In Minnesota, nine sit~s (seven of which are shown in

Figute 2) were monitored by the Pollution Control Agency (PCA) for 502

from 1972 through 1976 (Ritchie 1977). The period of record for most sites

was not the full five years, however. The sites represented downtown,

urban residential and urban commercial-residential areas, and two sltes

were source oriented downwind of two petroleum refineries. Trend analysis

was conducted for these sites. One of the petroleum refinery influenced

sites showed a decrease in 502 concentration, and the other an increase.

Most other sites exhibited no statistically significant changes. Increases

in 502 concentration occurred at several sites in the fall and winter of

1976. These data must be used with caution, however, because increased

heating due to the extreme cold during that time may have caused greater

Page 15

502 emissions. Insufficient data did not permit regional analysis for

502 trends ~nr Minnesota.

Other urban areas outside of Minnesota showed distinct 502 concentration

trends. The 1969 through 1971 NASN data indica a decrease of about 50

percent in the average SO~ level at urban sites (CNR 1975), and from 1971• L

through 1975 a decrease of about 30 percent (U.S. EPA 1976a). In the nation

as a whole, 502 concentrations decreased rapidly from 1970 through 1973

and then ceased to decrease after this period. During 1975 the levels

remained relatively stable and had possibly begun to increase in some plac~s,

. apparently because of fa'ilure or inability of some sources to use ean

fuels (U.S.EPA 1976a). A"tshuller (1976) 1 NASN data from 1963

through 1972 and determined that 502 levels ibited a downw~rd trend at

east coast sites and rnid,vest si east of the Mississ'ippi. A smaller

downward trend may have occurred in the Southeast and West, but resultst'

were too incomplete to be certain.

Sulfate concentrat'ion decreased in the U.S. as a \1hole 5 but not to the same

extent as sulfur dioxide concentration. Sulfur dioxide concentration

decreased 55 percent at east coast sites during 1963-1965 and 1969-1971,

vlh-ile 504 concentrat'ion decreased only 15 percent. In the Midwest, east of

the Mis~issippi, 502 decreased 39 percent during 1965-1967 and 1969-1971,

while 504 concentration first decreased, then increased to slightly above

the early 1960 levels (Altshuller 1976). Shriner' et 0.1. (1977) reported

rather stable urban 504 leve-Is from 1957 through 1970. A statistical study

of NASN data showed the same for 1964 through 1970 (Frank 1974). Figure 4

shows what may be an increasing 504 concentration trend in Minneapolis,

Figure 4. Three~'year running averages for sulfur dioxide andsulfate at Hinneapolis (1963-1977)"

30

42

"" 40

7.61 ~ 38

~ 367.2

S04 llg/m,~l 8°2 llg/m 3

6.8 34

6.4 32

1963­65

196!+- 1965- 1966-~ 1967- 1968~- 1969- 1970~

66 67 68 69 70 71 72

aMeasurements for only 2 of 3 years

Adapted from Altshuller 1976.

Pa 17

Minnesota, as well as 502 concentra on changes, from 1963 through 1972.

NASN 502 data do not, however, correlate with PCA data (Ritchie, personal

communi cat..ion).

It may appear to be a paradox that sulfur oxide emissions in the U.S.

increased about 45 percent in the 1960s, whereas urban 502 concentrations

decreased, and urban 504 concentrations rema ned approximately the same

(CNR 1975): However, as mentioned e ier, the major increase in sulfur

oxide emissions occurred at large point sources outside of urban areas.

Rural areas have not typically been as intensely monitored as urban areas.

In 1973~ for example, of 213 502 surveillance sites operated by the EPA,

93 ~ercent were in heavily populated areas, and only 5 percent in background

areas, and 2 percent source-oriented (U.S.EPA 1974). Because nonurban

areas are not adequately reflected in 502 and 504 trend data bases, the

effects of shifting emission patterns may be difficult to ascertain.

Nonurban 502 data are too sparse to justify trend analysis (CNR 1975,

Altshuller 1976), although a slightly perceptible decrease was seen at

10 background s·ites fl'orn 1970 through 1973 (Shriner et ala 1977).

More extensive data are available for non urban 504 concentrations.

Altshuller (1976) found an increase in most regions of the u.s. between

1965 and 1972. A genera 1 increase· from 1962 through 1970 was a1so found by CNR

(1975). It appears as though man-made sulfate increased by 40 to 100

percent in non urban areas during the 1960s. This increase is in agreement

with sulfur oxide emission trends (CNR 1975). The limited data obtainable

suggest that nonurban 504 trends may reflect the influence of S02 emission

charges more closely than urban 504 trends (Shriner et ale 1977).

Pasw 1B

Non urba n rlji nnesota 502 and amb-i en t concen t;i ons and t ren ds \tlC:' re not

discussed in the literature. From information available, however, it is

c"lear that areas ~vith 10\1'1 SO'") emiss"lons (such as northeastern Minnesota,(-

the northeastern U.S., and northern Europe) may have 504 levels well above

background concentrations due to long distance transport and transformation

of 502' and ~herefore, may have acid precipitation problems (CNR 1975,

Altshuller 1976).

Increases in pt'ecipitation acidity have occurred simultaneously with 502

and NOx emission increases. Likens (1976) reports that the pH of precipi-

tation in the eastern U.s. dropped significantly between 1930 and 1950.

Free acidity (pH) was not measured prior to 1940, so exact pH values are

not known; however, methyl orange tests indicated that the pH was above 4.6

(Likens and Bormann 1974). In addition, relatively large amounts of HCO~w ~

were found in precipitation at Geneva, New York, before 1930 (Collison and

Mensching 1932). This probably indicates that pH values were 5.7 or higher

(Likens and Bormann 1974).

A marked decrease in mean precipitation pH in Norway occurred throughout

the 1955 to 1976 period (Dovland et al. 1976). The rate of pH change of

bulk precipitation (both wet and dry deposition) in Sweden and NOnJay was

-.03 to -.08 pH units per year from 1955 to 1969 (Oden 1975). Other sources

indicate a drop of .05 to .09 pH units per year in Swedish precipitation

from 1955 to 1975 (Dickson 1975, Andersson 1972).

Recent precipitation pH values in the literature ranged from 2.1 to 8.6

(see Figure ~) and Table 2). Areas defined by the literature as Ilremotell

Pa 19

Figure 5. Selected precipitation pH values.

9 ,J.

Alkaline dust 8

Alkaline dust

North Dakota

North Dal(ota

Remote 7 Fort Simpson, Canada

Remote Pilltarctica snow profileNortheas tern Hinneso ta

6Slightly irnpacted(Kentville),

Remote(Resolute)

SvJeden-~Kentville, Nova Scotia; Resolute, Canada

Plateau, Ca.nada

Remote 5 T Cape , Canadar~'-NortheasternHinnesota

/Sudbury~;:::-La Cloche Mts.; Sou th Coas t Norway; Adirondacks

jB Northeastern U.S.··rc Adirondacks; Northeas tern Minnesota; Hubbard Brook

I• Fort Simpson, Canada; Ithaca, N.Y.Sudbuly

31~~~:::d BrookLa Cloche Hountains; Sudbury

L}Serni-urban(Ithaca),Remote(Ft. Simpson)

Through smelter Plume

12 miles from smel te:rRemote(La Cloche Mts)

Remote(La Cloche)1 mile from smelter(Sudbury)

2pH

Northeastern U.S.

Table 2. Precipitation pH.

Location

Remote backgroundRam Plateau, N.W.T, CanadaFort SLupson, N.W.T.Cape Dyer, N.W.T.Resolute, N.W.T.fuitarctica

North Dakota

Northeastern MinnesotaEly

Kawishiwi Lab

Burntside LakeAverage 3 stations

pH

5.553.8-7.05.05.76.32

7.9,8.1

!+.O,L~.5,4.8,4.8,

5.0,5.24,3.4.7,4.7,4.8,6.25.74.9

COIIlTD.ents

bul.Iz sctmpl-:3prec tationsno,;,r e'ven t

rain eventsnow profile

snow--dustfall from aridlands raises

rain events, 1977

rain events, 1977

ra~n e-\,Tent, 197712 rain events, 1977

Reference

K.ramer 1975... ,r'l ~ n- r-ana ,::,urmners 1 ~·I :J

Kramer 1973aGjes and Gjessing 1973

Adomaitis et al.

HEQB 1977

vOJ

N12;

Northeastern U.S. 2.1-3.04.0-~l.2

individual storm minimumsannual average,

Likens and BormannBorman 1975,

1974, Likens and10"'­l../!:J

Hubbard Brook ExperimentalForest, N. Hamp. (nonearby industrial orpop~lation centers)

Ithaca, N.Y.

4.03-4.21

3.0

3.82-4.18

average annual Likens et al. 1975pH 1964-74event minimum

rain and, snow, Feb-June 1975 Galloway et ala 1975

Adirondacks

Sudbury, Ontario

4.05-4.31

<4

2.85

4.34

rain and snoT,rJ"

rain and snow average,within 10 miles of Sudburyrainfall, dust fall average1 mile south of ConistonSmelterrainfall, dustfall average12 miles east of CouistonSmelter

Schofield 1975

Hutchinson and ~~itby 1974

Table 2. (cop' ',)

Location

Sudbury contd.

LaCloche Mountains, Ontario(remote area southwest ofSudbury)

Kentville, Nova Scotia(agricultural area, littleindustrial pollution)

Norway

S'Yv·eden

pH

3.6

3.8-5.2

4.3

3.6-5.52.9

5.7

4.3

3.5

3.7-4.93.35-5.8

4.3-4.43.9-5.9

Comments

rain event falling throughplumeprecipitation events,variation over 11 days

average of ,18 tationev,ents 1972-735 rainfall events, 1969-71

tioneventminimum

23 rain and snow samples1952-54

annual mean--south coast,area of most acidic precip

mln1.mumseveral stations

eve.ntsforest) precipitation

bulk sample

Reference

l'Tiebe and ~~111elpdale 1975

Kramer 1976b

Beamish and Van Loon 19,

Beamish and HarJey 1972

Herman and Gorham 1957

Dovland et ale 1976

Scholdager 1973Bjor et al. 1974

Hornstrom et al. 1973Andersson 1972

1".:'1-'

Page 22

generally have pH values a 5, whereas values near 4 re not unusual in

highly impacted areas. In much of nort stern U.S. precipitation has

an average pH of between 4.0 and 4.2 (Li 1976). The average precip"i=

tation pH in the Sudbul"y area "is repor-ted to be about 4.5 (Kr'amer 1976a).

Most precipitation pH values in Figure 2 are below 5.7, indicating acidic

precipitation.

REMOVAL MECHANISMS-~-_._~--

Po 11 utants are removed from the atmosphe-r'e by severa1 d-j fferent rnechani sms.

Wet deposition, in the of rain and snow; and dry deposition, composed

of dry fallout, impacted S, and adsorbed gases; contribute to the

total amount of pollutant which rea 1a d and r su ces (Galloway

and Likens 1977). Bulk p h and dry deposition.

Types of precip'j tion co"llector's are discussed generally in Gal"loway and

Liken~ (1977), and in more detail in Galloway and Likens (1975).

Rain is a more efficient scavenger of pollutants from the air than snow

(Summers and Hitchon 1973 Hennan and Gorham 1957). Nova Scotian rain and

snow samples collected for 16 months from J.95;2 through 1954 revealed 40

percent as much sulfur~ 33 percent as much almlonia, and 50 percent as much

nitrate in snow as in rain (Summers and Hitchon 1973). Average S04

concentrations in precipitation in Alberta were 2.0 to 3.0 mg/l in summer

and less than 0.5 mg/l in winter (Summers and Hitchon 1973). Kramer (1975)

found maximum S04 loadings in summer and Likens (1972) found summer rains

to be generally more acidic than winter precipitation. In the northeastern

u.s. higher hydrogen ion concentrations occur in summer precipitation than

in winter precipitation (Hornbeck et a"l. 1975). Sulfate deposition exhibited

a nearly identical seasonal pattern as hydt~ogen ion deposition.

Page 23

Several hypotheses have been advanced to explain the different concentrations

of pollutants in rain and snow. Herman and Gorham (1957) suggest that either

snovJfl a have a 10\'Jer ciency of remov'ing material from the atmosphere

than raindrops, or that air masses from which snow falls have lower concen-

trations als than air masses from which rain falls. Summer convective

storms are ve ci in removing S02 from the atmosphere, whereas stable

air masses from v'Jhich snow occur's have very little vertica-' transport of

air, causing 502 emissions to be trapped in the lowest few thousand feet of

the atmosphere and not enter the precipitation mechanism (Summers and Hitchon

1973). Honibeck et al. (1975) su9gest that summer electric power gener-at-ion

produces more acid-forming emissions than winter heating.

Junge (

content of

) s that rainout efficiency is proportional to the liquid

clouds, Rainout is the incorporation of 502 or sulfate

aerosols into the physical processes of the cloud and subsequent fallout in

rain (Swnmers and Hitchon 1973). In Alberta the liquid content of winter

snow-producing clouds -is typicarly one-tenth of the value found 'in summertime

cumulus. In addition, the oxidation rate of 502 is lower in the presence

of cloud droplets in summertime clouds. These factors account for much of

the difference in rain and snow sulfate concentrations (Summers and Hitchon

1973). vJork by Bushtueva (1954,1957) -indicates that oxidation of 502 to

H2S04 occurs more readily in high relative humidity conditions.

Wet deposit-ion of pollutants may be greater than dry depos-it-jon. Garland

(1974) found from the literature that annual wet deposition of sulfur

compounds Vias 1.5 to 6.4 times greater than dry deposition of SO') gas and(..

S04 particles. f\ d-ispers'ion model used to estimate the amount of dry

deposition in Nor'way showed that VJet deposition of 502 ;s about three times

Pa

as 1a s dry depo -i"Uon (Dovland et ale 1976). Other scientis

hO\'1ever that dr-'j'

(Kramer 1976b)<

-i tion"' a

is approxima ly equal to wet deposition

Dry fa 11 out of OX"j is relatively greater near the emission sources,

whereas depos i ti on -j s more -j mportant hundreds or thousands of ki -1ometers

from the sources (Overrein 1975). Thus, Norway, which is a greater' distance

from the major sources of sulfur dioxide and nitrogen oxide emissions in

Europe, recei yes a gr'eater \-'<Iet depos it i on of po 11 utants than dry depos i t ion.

It should noted t Figure 1 and Table 1 include both wet and bulk

deposit"jon , as well as some seasonal da Based on the information

and ble

-I rIg pa

not be di

SO~ concentration values in the figure"'

1y cornparab"le

ACID BUFFER NG--,_._~_.~_._. ---~~,-==-

The acidity of precipitation can be neutralized by various substances in

the atmosphere. Additions of even small amounts of particulates to the

atmospher'e may raise the pH of precipitation because their surfaces have

+the ability to adsorb H (Kramer 1976a). Norton (1975) reports that most

inorganic particulates tend to react with and consume acid in precipitation.

In -areas where there is abundant windblown dust, pH values for precipitation

of 7 to 8 are not unconmon (Kramer 1976a). Gorham (1975) found differences

in sno\;/ acidity in Ivjinnesota during 1974-1975, presumably related to greater

dustfall in the western cultivated area than in the eastern forested area.

Western snow was alkaline (pH up to 9.5) with a high particulate content

and eastern snow was acid (pH 4.5-5.6) with a low particulate content.

Bases in the atmospher'e which are capable of neutral'izing acid precipitation

Page 2~)

inc"lude sea sp

~ested as sources

and al1ll1l0lria (Gorham 1975). Da"l

a:trnospher"i c arrllnOlrl a in pa

nns have been sug-

of Denmark and southern

Sweden (Barrett and Brodin 1955).

Likens and Bormann (1974) found th the sulfur content of rain and snow in

Ne\'1 York State 70 pe t lower now than prior to 1950, while precipi-

tation acidity has increased since 1950. They hypothesize that a conversion

of fuel source from wood and coal natural gas has caused this change.

Particu"la when eoa'i was burned neutra"1 i zed the aei d formed by

502 emissions. Present use of natural gas produces less 502' but also fewer

neutralizing componen Tall s cks, equipped with precipitators to remove

pa l"ti c ates, ca use 50<,)L

transported to long distances The

auth0 r's conc "j ud(; t hat 10 ca -I II s() at prob1ems Ii have transf~rmed into a

b"1 ern, II

Befot(0 a.cid precipita"Uon Y'eaches a "lake or' stream~ 'it may be additionally

neutralized in the watershed. Henriksen and Wright (1977) found that 75

percent of the incoming acid was neutrailzed in the watershed of a small

acid lake in Norway. When rain fell through the forest canopy in the

Hubbard Brook Experimental Forest in New Hampshire, the pH rose from 4.0-4.1

to LL7~5.0 (Hornbeck et a"l. 1975). Soils also have a neutralizing capability,

especially those derived from carbonate-rich sedimentary rocks (Gar-ham 1975).

Gjessing et al. (1976) found that runoff in Norway has an average weighted

pH of 0.2 to 0.9 units higher than precipitation.

Finally, acid precipitation may be neutralized in lakes. Lakes in drainage

basins high in easily weathered calcareous material (such as dolomite or

limestone) are generally well buffered due to the presence of carbonate and

PdSje

bicarbonate ions (Wright and Gjessing 1976). OH- ions formed from the

hydrolysis of C0 3 2 and HC0 3- cause the water to be alkaline (Wetzel 1975).

in areas of this type have pH values above 6.5, regardless

of acid loading.

Lakes <in drainage basins composed of rdghly resistant crysta'll'ine rocks are

poorly buffered, on the other hand, and in Norway have pH levels of 5.5 to

6.0 if they do not receive acid precipitation, and pH levels ,below 5 0 if

they do receive acid precipitation (Wright and Gjessing 1976, Gjessing et 0.1.

1976, Wright and Henriksen 1976).

Cation-Al-silicates and weak organic acids are also H+ sinks (Kramer 1973b).

The cation-Al-silica buffering system involves a slower reaction than the

HCO? system, and will fix the system near pH 6. Weak organic systems..)

generally buffer be pH 4 and 5 (Kramer 1973b).

Trophic sta has an effect on buffering capacity. High concentrations of

phosphate, silicate, and bora may impart alkalinity. Eutrophic lakes

are, therefore! more strongly buffered than mesotrophic and oligotrophic

lakes (Lenhart 1976).

EFFECTS OF ACID PRECIPITATION ON LAKES.-------_.

Poorly buffered lakes will eventually become acidic if they receive

continued input of acid precipitation. This has happened in parts of the

northeastern U.S. (Likens 1976, Cogbill and Likens 1974), Ontario, Canada

(Conroy et ale 1975, Beamish 1975), and Scandanavia (Dovland et ale 1976,

Bolin 1971). Long distance transport of pollutants has been found to cause

acid precipitation and subsequent acidification of lakes downwind of

27.~ f

industrial areas (Conroy Likens 1976, Dovland 0.1. 1976).

Figures 6 and 7 are an examp"c: of hOVI ttris tyP(~ of impact is determined.

The direction of preva"j"ling \'/inds in Sudbury (Figure 6) can be matched

vJith the zone of low pH lakes (Figure 7). Smelters in Sudbury emit

1.5 X 106 metric tons of 502 per year, and this pollutant has apparently

been the co. e of the acid lakes (Conroy et 0.1. 1975).

The ra of lake pH change is slow, often less than seasonal variations or

analytical reproducib-il-ity (Almer' et 0.1. 1974). Because of this, irrever-

sib"le ecological damage may occur before acidifying trends are established

(Kramer 1 Rates of lake pH change. reported in the literature were

-.01 to .17 pH units per year (Table 3). The remote lakes within and to

tile eas t the La Cloche Mountains in Ontario were among th~ lakes which

exper"j en most rap"fd acidifica.t·jon. These lakes are about 65 km

southwest of SudbuY'j! and receive no v"isib"le surface effluent of industrial

origi~ (Beamish and Harvey 1972). pH measurements were available for 11 of

the 22 lakes from 1961 or earlier. Each of these lakes showed a ten-fold

to mote than one hundred-fold increase in H+ ions by 1971 (Beamish and

Harvey 1971, Beamish 1974). Input of acid precipitation to a group of

"lakes in southern Norway caused a 30 to 60-fold -increase in acidity from

1941 to 1975 (Gj essinget a1. 1976 ) .

Most "lakes and streams in southeastern Norv/ay now have pH values below 5

(Gjessing et ale 1976). Some high a.ltitude lakes in the Adirondacks have

pH levels of about 4.3 (Sawyer 1977). Figure 8 and Table 4 show lake pH

in other areas of the world as reported in the literature. The pH of lakes

in the Copper-Nickel Study area ranges from 6.4 to 7.6 (~1EQB 1977).

Page 28

s E: . 975

Page 29

0)-(]) -- V'lanapitei

0) '- Ollaping

G) - Quirke

® - Nipissingo ~ North Shore

G) - Manitoulin Island

Km

Miles

Figure 7. Sketch map of Sudbury area showing a contour for lakes vith pH~5.5.For geographical reference the numbers indicated are:

1) Sudbury2) Lake Wahnapitae3) Lake Ollaping4) Quirke Lake

5) Lake Nipissing6) North Channel - Lake Huron7) Manitoulin Island

Note the northeast-southwest trend corresponding to the windrose depicted in

Figure 6.

SOURCE: Conroy et al. 1975.I

Table 3. F~te of lake pH change due to acid precipitation.

Location

SwedenSouthwestern

WestcentralSouthcentralSouthernmost

NorwayEast Central

OntarioIn and east of La ClocheMountains

North of La Cloche Hountains

Number of Lakes

8655

51

1011

2226

Years

1963-6919L}3-711933-711937-731933-731935-71

1941-751941-75

1953-71

1959-711970-71

plL_Cpgngej'Jr _(p_H~unit s )

-0.01 to -0.16-D.Ol"-0.03-0.06-0.03-0.015

-0.04-0.05

-0.03 to -0.09

-0.16-0.08

Reference

Oden and fu~l 1970Dickson et 2 1 • 1973

Grahn et al. 19Dickson et a1. 1975MaImer 1975

Gjessing et a1. 1976

Conroy and Keller 1972

Beamish and Harvey 1972

uOJtoI'D

wo

Page 31

Figure 8. Lake pH.

9 t

Acid input.

Easily weathered terrain

Sudbury

Sweden

Northeastern Minnesota

7

Remote

Carbonate rich terrain

Resistant terrain(Sweden)

Northeastern Minnesota

ELA

Non.my

Northeastern }linnesota; Sweden

Carbonate poor bedrock,no acid input

RemoteCarbonate poor bedrock,no acid input

Nonvay

ELANOTIvay

Carbonate poor bedrock, c:Jacid input

Acid input

Acid input

___ Nonvay; La Cloche Hts. (Lake George)__-SvJeden West Coast

La Cloche Mts. (Lumsden Lake)West Central STvJeden; La Cloche Mts. (Muriel Lake)

La Cloche Mts. (O.S.A. Lake); Sudbury

Acid input West Coast SwedenAcid input ---- ----Sudbury

pH L~ <'

~ake pH.

Number orName of Lakes

~tal Lake Area, Ontario 40102

rn Minnesota 26

as of highly resistante poor bedrock andcipitationighly resistante poor bedrock withoutcipitationarbonate rich terrain'\.;rithout acid.ation

pH

5.6-6.76.5

6.3-7.77.0 ave.

<5.0

5.5-6.0

>6.5

Reference

Armstrong and Schindler 1971Beamish et ale 1975

}'IEQB 1977

Gjessing et al. 1976

vOJtoCD

WN

.pitation areaslst S\.vedenl tral SwedenIe l'iountains, Ontario

~eathered terrainlt terrain3.st area

11264

o. S. A.MurielGeorgeLumsden48 within 200 km

673

4.374.664.7

4.5Lf • 75.04.84.54.3-8.3

8.16.34.9

Hornstrom et al. 1973Grahn et a1. 1974

Beamish 1974

Beamish et ale 1975Beamish and Van Loon 1975Scheider et al. 1975Conroy et a1. 1975

Dickson 1975

'"

Hydrogen ion loading in di rent areas of the world was not reported in

the literature; however, sulfa loading was reported and is shown in

Figure 9 and Tab"le 5. T~'JO remote Canadian stations t(~ceive load'ings of

less than 365 mg/m2/year. Most rural station values are less than 5000

mg/m2/year. Continued input of sulfate via acid precipitation to acidified

Norwegian lakes has caused a change from bicarbonate to sulfate as the

rna j 0 r 1ake viateran ion (~\1r -j 911 t eta1. 1975).

Fluctuations in Lake pH- . _._---~._---=-

Periodically, extren~ly acid precipitation events occur and large amounts

of acid are deposi "i n 1a and streams over ShOi·'t per'iods of time. In

the Birkenes watershed in Norway 25 of the entire excess sulfate

deposition of three yea occurred in acid precipitation during 15 days

(Dovland al. 1976). After one of these events the H+ concentration in

one stream rose 300 percent, 504 concentration rose 20 percent and N03concentration rose 90 percent (Gjessing et al. 1976). While these increases

occurred wi th'j n a few hours ~ recovery to pre-epi sodi c concentr'ati ons of I-tand 504 took weeks. Nitrate returned rapidly to low concentrations,

presumably due to biological imnobilization in the forest ecosystem

(Gjess-ing et ale 1976). lkid precipitation episodes in Norway occur most

frequently in the fall, when precipitation is greatest (Gjessing et ale 1976).

Spring snowmelt also supplies large amounts of acid and other pollutants to

lakes and streams (Air Pollution Across National Boundaries 1971). Lab and

field stud'ies by Johannessen et ale (1975) showed that concentrat-ions of

+H , 504' N0:is and heavy metals were tv/a to three times greater- in the first

meltwater than in snow. Minimum annual pH levels in Finish rivers occur

Pa.ge

Figure 9. Sulfa loadIng from bulk tion.

10000

lL~OOO

12000 I

I8000

Cottered U.Ie

Wagenigen, Netherlands

Vert-Ie-Petit, France

Den Helder, Netherlands

Wittevan, Netherlands

-1~ Europe, 20 stations

• Northern OntarioUrban(U.S.) 6000 11. Nort}lcastern u.s.; Soyland, Norway; Bredkalen, Sweden

_---Puumala, F'inJ and

j

Great Lakes:-- ~nibel1, Denmark; Finsland, Non'Jay; Ryda, Sweden__--Tange, Denmark; Dueodde, Denmark

Coastal(U.S.) Northeastern U.S.; Keldsnor, DenmarkRural LIOOO : Nor theas tern U. S .

Rernote(Finland)--____Remote(U. S.) 'k--.-=-----.,.

Remote

Grand Marais, MN; Two Harbors, }lli

__--Faroe Island, Finland; Sjuangen, Sweden___U. S.; Thunder Bay, Ontario

Sodankyla, Finland

Remote

Remote

mg/m 2 /yr

2000

joI

Northeas tern }linnesotaU.S.

Ram Plateau, CanadaNorthern Ontario

Table 5. Sulfate loading from bulk precipitation.

Location

Remote backgroundRam Plateau, N.W.T.Faroe Island, DenmarkSj~anjen, SwedenSodankyla, FinlandContinental U.S.

Northeastern U.S.Rural inland stations

Coastal stations

Urban station

CanadaGreat LakesNorthern Ontario

Europe Hanstholm, DenmarkTange, Der.markKeldsnor, DanmarkGniben, DenmarkDueodde, DenmarkVert-Ie-Petit, FranceRj'upnah&ed, IcelandFinsland, NorwaySoyland, NonHayWagenigan, NetherlandsWittevan, NetherlandsDen Helder, NetherlandsRyda, .. SwedenBredkalen, SwedenJomala, FinlandJokioinen, FinlandPuu~ala, FinlandAhtari, FinlandCottered U.K.Eskdalenuir, U.K.

2(J s tJ~on,s

804 (mg/m2/yr)

(3653000300025001300-2600

2L~65-6363

414-0 ave.2921-56124382 ave.5663-66216042 ave.

5110183-6205

450047004400500047001280048005000600013600800092005000600056006800550042001600060006 0

Comments

anthropogenically uninfluencedanthropogenically uninfluencedanthropogenically uninfluencedanthropogenically uninfluenced

14 stations

3 stations

1 station (Albany, NY)

Reference

Kramer 1975Benarie 1975

Wolaver and Lieth 1972

Pearson and Fisher 1971

Shiomi and Kuntz 1973-Kramer 1975

Benarie 1975

vOJ

La(D

WU1

Table 5. contd.

Location

Thunder Bay, Onta.rio

Grand 11arais, 11inn.

Two Harbors, l1inn.

Northeastern YdnnesotaHoyt LakesDunka RoadSpruce RoadFernberg Roadaverage, 4 stations

so~. (mg/m2 /yr)

2599

3285

3281

16001800130018001600

Comments

average, 2 samplers, 10/73-6/75

average, 2 samplers, 5/74-2/75

average, 2 samplers, 4/74- 75

geometric means of monthlyrates, 1977

Reference

Acres 1975

Acres 1975

Acres 1975

MEQB 1977n 21

11

'-,p;

C0C'l

Page 37

during spring melt clue to acid rne-ltvwter (Haapala et al. 1975). Gjessing

+et al. (1976) found that "large amounts of H are r(~lea.sed into south

centra 1 NorvJegi an 1akes -j n the f-i rs t phases of sno\\~ne1t. The me"' t~freeze

cycles that occur during snowmelt increase the concentration of pollutants

(Kramer 19?6a, Gjessing et al. 1976).

Natural, seasonal, and diurnal pH changes do occur in lakes because of

photosynthetic activity (Oden and Ahl 1970, Johannessen et ale 1975)~ pH

generally increases during growing periods (daylight, spring bloom,

August bloom)(Kramer 1976a) In acidic lakes which have lost their

bicarbonate buffering systems, however, large pH fluctuations can occur in

l"esponse to episodic inputs of a.cid n~right and Gjessing 1976, Gjess"ing

et al. 1976).

Acid precipitation may cause changes. in lake water' chemistry in addition to

acidification. Acid precipitation is usually high in trace elements such

as Cu~ Ni, Pb, Zn, and As from urban and industrial areas (Gorham 1975).

Extremely high eu and Ni concentrat-jons occur in precipitation near Sudbur'y

(Conroy et a~l. 1975). Concentrations of metals in lakes are, therefore,

elevated due to direct deposition by precipitat-ion (Conroy et ale 1975).

Organic toxins and nutrients, particularly phosphorus, nitrogen, calcium,

and potassium, may also accompany acid precipitation (Gorham 1975).

Runoff of acid precipitation across land surfaces also adds chemical

components to lakes (Wright and Gjessing 1976). Acid precipitation may

affect soils in various ways, including:

1) increase the mobility of most elements,2) increase the loss of clay minerals,

Po.

3)4)5)

change the cation exchagenerally increase the raincrease flux nutri

Sf'-; nd through aquatic

ca ci increase or reaseof removal all cclt--ion~~ from the soil,

ugh eeo contiguous with theecosys telns 1).

Unusually high aluminum and magnesium levels have been found in the acidic

La CI 0 che t~0 un t aina Sea nd-! nav-I an 1a s (1iJ r -j SJ ht eta1. 1975) . Sin ce t hf~

solubility Qf Al is negligible at pH above 5, the appearance of Al in lakes

is probably due to vJashout from t sedl. by acid precipitation (Norton 1975,

vJr';ght et 0.1. 1975). Co. and i~g are a.1so leached f}"om scrj'ls by acid rain

(Overrein 1972, Henriksen 1972).

In acid lakes, a greater portion of trace meta'is are -in the soluble fr-action

from desorption (Kramer 1976a, Onto. 0 ter Resources Commission 1970).

Manganese and zinc levels are high in the La Cloche Mountain"lakes and

Swedish lakes, pparently as a res t of increased solubility (Beamish and

Van Loon 1975). Gal 1oV-J a.y 0.1. (1 6b) found that both Al and f\1n are

impo~~rished in sediments of an acid lake in the Adirondack Mountains,

indicating that lake sediments may act as a source of these elements to

lake water.

Kramer (19760.) suggests that pH should be considered the master variable in

lake chemistry because -it affects, dit~ectly or indirectly, primary and

secondary aquatic production and lake product-Ion. The residence time of

trace metals and nutrients increases in acid lakes because of decreased

biological production and decay (Kramer 19760.). pH of less than 5.5 has

an adverse effect on the aquat-ic bio'logica"l community (Conroy et al. 1975),

and sudden pH drops due to spring meltwater or acid precipitation episodes

may cause a severe shock to aquatic life at higher pH levels (Wright et al.

Page 39

1975). The add-itive effects of heavy rnetals and acid may cause stress at

a higher pH than if metals are not present (Beamish 1975, Dickson 1975).

CONCLUSION

Acid precipitation has caused damage to terrestrial and aquatic ecosystems

in several areas of the VJOY'ld, notab'ly Scandinavia, the northeastern U.S.,

and Ontario, Canada (Li 1976; Cogbill and Likens 1974, Conroy et ale

1975, Beamish 1975, Dovland et al. 1976, Bolin 1971, Kramer 1976a).

Precipitation has become increasingly acidic over the past two decades and

pH values of four or lower are now not unusual in the areas mentioned above

(Likens 1976, Dovland et al. 1976, Hutchinson and Whitby 1974). Additional

areas can be expected re ve acid precipitation if acid~forming pollu-

tants, particularly sulfur dioxi and nitrogen oxides, continue to be

released to the atmosphere in increasing amounts. Especially vulnerable to

acid"precipitatio'n 3.1"2 <lakes v,rhich are poorly buffered due to geo·logic

environment and are located downwind of areas of high pollutant emissions

(Wright and Gjessing 1976). These lakes may suffer from, or continue to

suffer from, acidification and other associated chemical changes, and

subsequent loss of fish populations and other aquatic life.

Pa IJO

and B.t.

i on onreferred to as

Acres Consult"in19 /\Appendices.

Earth ience Consultants, Inc.t La kes Vo 1. 3.

I~domai

chaPr'oc

cal.\ ands.

Air' pollanlLN. conC-j in

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flJtshull

Andersson fLSwedishSVleden.Cited in

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7

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Page 41

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T.1\. '1acid p.jDochi

acid ip tationL. Dochinsymposium onre asDar'by, Pa

, R.:J.fvio un ta. inRes. Boa r'cl

1972.resu·j

1

Aciding

cation ofsh mortalities.

C~j ocheJ sh

Beamish, R.J., L. Milanese. and G.A. Me rlane. 19survey of 110 ELA lakes th appended repoerrors and northwes Onta 0 it fisTech. . (in s). Ci in Beamish, 19

A fish and chemicalon white sh aging

Fish Res. Board Can

Beamish, R J. and J.e. Van Loon. ipi tion loading acid,heavy m(~ ls, and other subs nces smarl 1a near Sudbury,Ontario, Canada (Manuscript in preparation) Ci d in Beamish 1975.

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Pa 42

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Pa 45

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