Water Air Soil Pollut: Focus (2007) 7:301–306

DOI 10.1007/s11267-006-9064-z

Acidification at Plastic Lake, Ontario: Has 20 Years Made

a Difference?
Shaun A. Watmough & Julian Aherne &
M. Catherine Eimers & Peter J. Dillon

Received: 17 June 2005 / Accepted: 3 April 2006 / Published online: 14 February 2007
# Springer Science + Business Media B.V. 2007

Abstract In response to reduced sulphur emissions,
there has been a large decrease in sulphate (SO2
4 ;
−0.97 μeq l−1 year−1) and hydrogen (−1.18 μeq l−1
year−1) ion concentration in bulk precipitation be-
tween 1980 and 2000 at Plastic Lake in central
Ontario. The benefit of this large reduction in SO2

4 acidification and climatic (droughts, increased miner-
deposition on stream water chemistry was assessed
using the gauged outflow from a conifer-forested
catchment (PC1; 23.3 ha), which is influenced by a
small wetland located immediately upstream of the
outflow. Sulphate concentrations declined, but not
significantly due to large inter-annual variation in
SO2
4 concentration. Between 1980 and 2000, there
were significant increases in dissolved organic car-
bon, ammonium and potassium concentration likely
reflecting increased mineralisation in the wetland.
Calcium concentrations in PC1 decreased during the
two decade period (−2.24 μeq l−1 year−1), as a
consequence there was no improvement in stream
pH and the Ca:Al ratio in PC1 continued to decline. A
similar response was noted in an upland-draining sub-
S. A. Watmough (*) : J. Aherne : P. J. Dillon
Environmental and Resource Studies, Trent University,
1600 West Bank Drive,
Peterborough, ON K9J 7B8, Canada
e-mail: swatmough@trentu.ca
M. C. Eimers
Department of Geography, Trent University,
Peterborough, ON K9J 7B8, Canada
catchment of PC1-08 that has been monitored since
1987. Despite large reductions in SO2
4 deposition
and almost complete retention of nitrogen in soil,
there has been no improvement (in terms of pH) in
stream water at PC1 due to a combination of soil
alisation) perturbations.
Keywords acidification . aluminium . calcium .
climate . recovery . sulphate
1 Introduction
Acid rain is recognised as a major environmental
concern in eastern Canada and since the late 1970s
sulphur dioxide (SO2) emissions in Canada and the
United States have decreased in response to various
legislation (e.g., the Acid Rain Control Program,
1985; and the Canada–U.S. Air Quality Agreement,
1991). Nevertheless, recent critical load estimates
indicate that large areas of forest (52% of forest in
eastern Canada; Ouimet, Arp, Watmough, Aherne, &
Demerchant, 2006) and large numbers of lakes in
eastern Canada currently receive acid deposition in
excess of the critical load (Jeffries & Ouimet, 2005).
Jeffries et al. (2003) recently reported that despite
substantial reductions in SO2 emission since 1980
there has been limited improvement in pH and
alkalinity. In Ontario for example, only 13% of 662
lakes analysed exhibited an increase in pH during the
302
1990s. In part, this delay in chemical recovery may be
due to continued soil acidification (Watmough &
Dillon, 2003), although increased organic acid export


or climate induced releases of SO2
4 or nitrate (NO3 )
may also delay chemical recovery of forest soils and
surface waters (Eimers & Dillon, 2002; Evans,
Freeman, Monteith, Reynolds, & Fenner, 2002;
Watmough, Eimers, Aherne, & Dillon, 2004). Chem-
ical recovery of surface waters from acidification has
been reported in other parts of the world where
emission reductions have occurred. In a comprehen-
sive review of surface water data from 12 geograph-
ical regions in Europe and North America, Skjelkvale
et al. (2005) reported that improvements in pH and
alkalinity are widely observed in response to emission
control programs and decreasing acidic deposition.
Given that the implementation of emission reductions
is extremely costly it is important to characterise the
impact of acid deposition on sensitive ecosystems and
identify reasons for the delay of (or lack of) chemical
and subsequent biological recovery in Ontario.
In an attempt to assess the impact of reduced SO2
emissions in eastern Canada in recent decades, we
report elemental fluxes in bulk deposition and stream
export from a forested catchment (PC1) containing a
small Sphagnum-conifer swamp in central Ontario for
the periods 1980–85 and 1995–2000. We also report
elemental export from an upland sub-catchment (PC1-
08) for the years 1989–1991 and 1999–2001.
2 Materials and Methods
2.1 Study Site
Plastic Lake (PC) is located in Haliburton County on
a southern extension of the Precambrian Shield in
central Ontario, Canada (45°11′ N, 78°50′ W), and is
typical of acid-sensitive lakes in this region. The
32 ha headwater lake is fed by one major stream
(PC1) and six ephemeral streams, which together
drain an area of approximately 90 ha. Plastic Lake-1
(PC1) is the largest sub-catchment (23.3 ha) in the
watershed, and is characterised by thin (average depth
0.37 m to bedrock) orthic humo-ferric and ferro-
humic podzols, formed from thin, sandy basal tills
(Neary, Mistray, & Vanderstar, 1987). The uneven-
aged forest at PC1 is dominated by white pine (Pinus
strobus L.), eastern hemlock (Tsuga canadensis L.),
Water Air Soil Pollut: Focus (2007) 7:301–306
red oak (Quercus rubra L.), red maple (Acer rubrum
L.) and large toothed aspen (Populus grandidentata
Michx.) in the upland areas, and by white cedar
(Thuja occidentalis L.) and black spruce (Picea
mariana (Mill.) BSP) in the swamp regions. A
2.2 ha conifer-Sphagnum swamp is located approxi-
mately 50 m above the catchment outflow and more
than 85% of the runoff from the PC1 catchment drains
through the swamp before discharging to Plastic
Lake. A short (<250 m) ephemeral stream (PC1-08),
which has been monitored periodically since 1987,
drains the northeastern part of PC1 before discharging
into the swamp.
2.2 Bulk Deposition
Deposition data were obtained from collections of
bulk deposition, defined as that caught in a continu-
ously open, 0.25 m2 collector. The collectors were
fitted with Teflon-coated funnels that are screened
(80 μm Nitex mesh) to prevent contamination by
insects and debris. Precipitation samples were re-
moved from collectors when there was sufficient
volume for chemical analyses, typically weekly.
Analytical methods for Ca2+, Mg2+, K+, Na+, SO2
4 ,
NO
3 and NH þ
4 are outlined in detail in Ontario
Ministry of Environment (1983) and were unchanged
during the study period. Briefly, base cations were
measured by atomic absorption spectophotometry,


SO2
4 by ion chromatography and NHþ 4 and NO3
were determined colourimetrically. Precipitation vol-
ume and volume-weighted concentrations were cal-
culated for each water year (June 1–May 31). On the
rare occasions when data were missing the average
precipitation values from three nearby (within 50 km)
bulk collectors (or stream flow from nearby weirs
with highly correlated discharge relationships) were
used.
2.3 Stream Export
Water level or stage was recorded continuously at a
V-notched weir installed at the catchment outflow
(PC1) and PC1-08, and daily stream discharge (m3
day−1) was computed using established stage–dis-
charge relationships (Hutchinson, Scott, Futter, &
Morgan, 1994). Water samples for chemical analyses
were collected at the weir at regular intervals (at least
biweekly) when there was flow, although sampling
Water Air Soil Pollut: Focus (2007) 7:301–306 303

was more frequent during the spring melt period.
Water samples were filtered through 80 μm Nitex
mesh in the field, and transported to the laboratory for
chemical analyses in insulated containers. Filters
(Nitex mesh) were rinsed in deionised water in the
laboratory and rinsed in stream water immediately
prior to sampling. Samples were analysed for Ca2+,

þ
Mg2+, K+, Na+, SO2
4 , NO3 and NH4 as outlined
above. In addition, samples were analysed for
Kjeldahl N (TKN) and dissolved organic carbon
(DOC) using standard methods (Ontario Ministry of
Environment, 1983). The contribution of organic
acids to the ion balance was estimated from measured
DOC concentrations and pH (Oliver, Thurman, &
Malcolm, 1983). Labile monomeric aluminium (Al3+)
concentrations in PC1 and PC1-08 were only deter-
mined for a short period of time during the study
(1985–1995) LaZerte, Chun, Evans and Tomassini
(1988) and relationships between H+ and Al3+ in
PC1 and PC1-08 were used to estimate Al3+ concen-
tration outside this period. These estimates were
based on a generalisation of the accepted gibbsite
H–Al relationship.
½Al ¼ KAlox ½ H a
where KAlox =0.38, a=1.27, r2 =0.51 (PC1-08) and
KAlox =0.20, a=0.86 (PC1), r2 =0.40.
A Seasonal Kendall test (treating months as
seasons) was used to determine trends in stream water
and bulk deposition chemistry (Hirsch & Slack,
1984). This method was chosen as it is robust against
seasonality, missing values and autocorrelation and
has been used extensively for assessing the chemical
response of surface waters to declining acid deposi-
tion (e.g. see Hydrology and Earth System Sciences,
2001, vol. 5). In order to facilitate comparison of data
at the beginning and end of the study period and to
reduce the impact of year-to-year variation in chem-
istry data 5 year average volume-weighted values for
1980–1985 and 1995–2000 are presented.
3 Results and Discussion
3.1 Trends in Deposition and Stream Chemistry
Between 1980 and 2000, SO2
4 concentration in bulk
precipitation at PC1 has declined by approximately
30% (Table 1). Five-year annual average SO2
4
concentrations (1980/85) were 61.3 μeq l−1 compared
with 42.1 μeq l−1 (1995–2000) (Table 1). The large
decrease in SO2
4 was almost completely balanced by
large reductions in H+ concentration, which decreased
from 62.0 to 41.l μeq l−1 over the same time period
(Table 1). There were small decreases in Na+ and Cl−
concentration but no significant change in concentra-
tion of any of the other major ions (Table 1). The
large reduction in SO2
4 and H+ ion concentration
typifies recent reports in eastern North America and

Table 1 Mean annual volume-weighted major anion and cation concentrations in bulk deposition and PC1 outflow in 1980–85 and
1995–2000

Bulk deposition PC1

1980/85 1995/00 Trend 1980/85 1995/00 Trend

SO2

4 61.3 42.1 −0.97*** 158.1 116.3 n.s.
NO

3 36.1 37.4 n.s. 1.7 1.5 n.s.
Cl− 4.0 3.6 −0.05* 9.4 10.3 n.s.
DOC n.d. n.d. n.d. 8.3 10.3 +0.13**
H+ 62.0 41.1 −1.18*** 46.5 41.9 n.s.
Ca2+ 13.4 11.8 n.s. 105.3 68.4 −2.24*
Mg2+ 3.7 3.3 n.s. 39.7 30.1 n.s.
K+ 1.8 1.6 n.s. 3.2 4.2 +0.10*
Na+ 2.8 2.4 −0.04* 22.5 24.8 n.s.
NHþ 4 24.8 26.5 n.s. 0.3 0.9 +0.03*
PPT/Q 1.07 0.98 n.s. 0.62 0.54 n.s.

* p<0.05; ** p<0.01, *** p<0.001; n.s. not significant (p<0.05); n.d. not measured.
Units: μeq l−1 , except Dissolved Organic Carbon (DOC: mg l−1 ) and rainfall and runoff volume (PPT and Q: m). Significant trends
and annual slope between 1980 and 2000 are shown.
304 Water Air Soil Pollut: Focus (2007) 7:301–306

Europe and reflects the success of programs imple-
mented to reduce SO2 emissions (Hedin et al., 1994).
In some areas (or over certain time periods) part of the
benefit of reduced SO2
4 deposition has been offset by
decreased base cation deposition (Hedin et al., 1994),
although this is not the case at PC1 where the
reduction in SO2
4 has produced an equivalent
reduction in H+ concentration.
The annual average SO2
4 concentration in PC1
was 158.1 μeq l−1 in 1980/85 period compared with
116.3 μeq l−1 in the 1995/00 period, a reduction of
26%, which is similar in magnitude to the SO2
4 creased mineralisation or declining SO2
4 concentra-
reduction in bulk deposition (Table 1). However there
was no significant monotonic trend in SO2
4 detected
due to large inter-annual variations in SO2
4 concen-
tration that occur as a result of drought-induced SO2
4
release from the wetland (Eimers & Dillon, 2002).
During summer droughts, sulphur stored in the
wetland is re-oxidised as the water table drops and
the SO2
4 is released when rains resume (Eimers &
Dillon, 2002).
There was a significant increase in DOC, NHþ 4 and
+
K concentration in PC1 between 1980 and 2000
(Table 1). At PC1, there has been no net increase in
forest biomass and the 1980s and 1990s were the
warmest two decades on record (IPCC, 2001), which
will likely stimulate mineralisation in the wetland and
lead to increased DOC, NHþ 4 and K
+
leaching.
Several studies in Europe and eastern North America
have reported increased concentrations of DOC
(Driscoll, Driscoll, Roy, & Mitchell, 2003; Evans
et al., 2005), although the cause of the increases
remains under debate. For example, the increases in
DOC may be caused by climate warming and in-
tions (acidity and/or ionic strength) (Clark, Chapman,
Adamson, & Lane, 2005; Evans et al. 2005; Hejzlar
et al., 2003; Krug & Frink, 1983).
Between 1980 and 2000 there was a large,
significant decline in Ca2+ concentration in PC1
(−2.24 μeq l−1 year−1); annual average Ca2+ concen-
trations decreased from 105.3 μeq l−1 in the 1980/85
period to 68.4 μeq l−1 in the 1995/00 period, a
decrease of 35% (Table 1). The decrease in Ca2+ has
almost completely offset the reduction in SO2
4
concentration and as a result there has been no

Fig. 1 Mean annual cation Bulk Deposition PC1 Streamwater

PC1 Streamwater PC108PC108
Streamwater
Streamwater
Bulk Deposition
(upper) and anion (lower) 100%
balance (%) in bulk precip-
itation and PC1 stream
80%
water during the periods
1980–1985 and 1995–2000;
and PC1-08 stream water 60%
Cations

during the periods 1989–

1991 and 1999–2001
40%
AL
20% H
NH4
0% BC

100%

80%

60%
Anions

40%

ORG
20% NO3
CL
0% SO4
1980–1985 1995–2000 1980–1985 1995–2000 1989–1991 1999–2001
Water Air Soil Pollut: Focus (2007) 7:301–306
significant decrease in H+ ion concentration over the
two-decades (Table 1). The large decrease in Ca2+ is
likely attributed to continued soil acidification at PC1
(Watmough & Dillon, 2003). Mass balance estimates
indicate that Ca2+ leaching from PC1 exceeds the
combined Ca2+ inputs from deposition and mineral
weathering leading to a decline in exchangeable soil
Ca2+, which was supported by repeated field measure-
ments in 1983 and 1999 (Watmough & Dillon, 2003).
Declining exchangeable soil Ca2+ will result in a
greater than expected decline in stream Ca2+ in
response to declining SO2
4 concentrations (Kirchner
& Lydersen, 1995). Despite high concentrations of
NO
þ

3 and NH4 in bulk deposition, NO3 concentra-
tions in PC1 (and PC1-08) are very low (<5 μeq l−1)
and have not increased over the 20-year period
(Table 1).
3.2 Ion Budgets
In 1980/85 SO2
4 was the dominant anion in bulk
deposition, accounting for 60% of the anions in bulk
deposition (Fig. 1). At the end of the study period

1980s to values around two at the end of the study
(1995/00), SO2
4 and NO3 were present in approxi-
mately equivalent amounts reflecting the increasing
relative importance of NO
3 deposition as sulphur
emissions decline in eastern North America. In 1980/
85 H+ was the dominant cation in precipitation,
accounting for almost 60% of the total cations
(Fig. 1). However, by the end of the study period,
H+ represented less than half of the total cations,
reflecting the improvement in atmospheric deposition.
In contrast to bulk deposition, SO2

4 and organic
anions are dominant in stream water, but the relative
contribution of SO2
4 in PC1 declined over the study
period reflecting the change in SO2
4 deposition
(Fig. 1). At the PC1-08 upland draining stream
between 1989/91 and 1999/01 the magnitude of
chemical change was smaller due to the shorter time
period considered and the contribution of organic
anions was lower (Fig. 1). Despite reductions in
+ 3+
SO2
4 , the relative contribution of both H and Al
the cation balance in PC1 increased slightly (even
though there was no change in H + and Al 3+
concentration) due to the large decrease in Ca2+
concentration. A decline in Ca2+ concentration was
also noted in PC1-08 between 1989/91 and 1999/01
(Fig. 1).
305
3.3 Calcium: Aluminum Ratios in PC1 and PC1-08
Critical load calculations for forest soils usually set a
critical acid neutralising capacity leaching based on a
molar ratio of base cations or calcium to aluminium in
soil solution. Cronan and Grigal (1995) suggested that
there is a risk of adverse impacts on tree growth or
nutrition when the soil solution Ca:Al molar ratio ≤1.0.
Although the use of critical chemical limits has been
the subject of great debate, the Ca:Al ratio can be con-
sidered to be an indicator of the acid status of forest
soils. Because there has been a large decline in Ca2+
concentration in both PC1 and PC1-08 streams and
no change in H+ concentration, estimated Ca:Al mo-
lar ratios (Al estimated using H–Al relationships) in
both PC1 and PC1-08 have decreased during the
study period (Fig. 2). It should be noted that error
associated with estimation of Al3+ from pH (H+) will
be constant throughout the study period. Ca:Al ratios
in PC1 were higher than in PC1-08 due to the large
influence of the wetland and decreased from between
approximately 8 and 10 in the early 1980s to as low
as 5 by the end of the study period. Ca:Al ratios in
PC1-08 decreased from approximately four in the mid-
period. While these values are higher than the critical
values reported by Cronan and Grigal (1995) and there
14
12
Calcium:Aluminium molar ratio
PC1
10
8
6
4
PC108
2
to
0
1975 1980 1985 1990 1995 2000
Fig. 2 Temporal trend in calcium:aluminium molar ratio for
PC1 (thin line) and PC1-08 (thick line) for the period 1980–
2000. Relationship between H–Al was used to predict the
temporal trend for labile monomeric aluminium (see text)
306
is some uncertainty in the estimates based on pH
measurements, it is possible that Ca:Al ratios in
mineral soil may be approaching values that pose a
risk to forest health.
4 Conclusion
Despite large reductions in SO2
4 and corresponding
decreases in H+ ion concentration in bulk deposition
there has been little improvement in the chemical
status of streams at PC between 1980 and 2000 and
Ca:Al ratios in stream water continue to decline. In
addition, any further increases in organic acid release
or future increased NO
3 leaching could potentially
offset the benefits of predicted further declining SO2

4
concentrations and the chemical and subsequent biol-
ogical recovery at PC1 could be further delayed.
Acknowledgements The authors acknowledge the hard work
of staff at the Dorset Environmental Science Centre and the
Ontario Ministry of Environment.
References
Clark, J. M., Chapman, P. J., Adamson, J. K., & Lane, S. N.
(2005). Influence of drought-induced acidification on the
mobility of dissolved organic carbon in peat soils. Global
Change Biology, 11, 791–809.
Cronan, C. S., & Grigal, D. F. (1995). Use of calcium/
aluminum ratios as indicators of stress in forest ecosys-
tems. Journal of Environmental Quality, 24, 209–226.
Driscoll, C. T., Driscoll, K. M., Roy, K. M., & Mitchell, M. J.
(2003). Chemical response of lakes in the Adirondack
Region of New York to declines in acidic deposition.
Environmental Science and Technology, 37, 2036–2042.
Eimers, M. C., & Dillon, P. J. (2002). Climate effects on
sulphate flux from forested catchments in south-central
Ontario. Biogeochemistry, 61, 337–355.
Evans, C. D., Freeman, C., Monteith, D. T., Reynolds, B., &
Fenner, N. (2002). Climate change – terrestrial export of
organic carbon: Communication arising. Nature, 415, 862.
Evans, C. D., Monteith, D. T., & Cooper, D. M. (2005). Long
term increases in surface water dissolved organic carbon,
possible causes and environmental impacts. Environmental
Pollution, 137, 55–71.
Hedin, L. O., Granat, L., Likens, G. E., Buishand, T. A.,
Galloway, J. N., Butler, T. J., et al. (1994). Steep declines
in atmospheric base cations in regions of North America.
Nature, 367, 351–354.
Water Air Soil Pollut: Focus (2007) 7:301–306
Hejzlar, J., Dubrovsky, M., Buchtele, J., & Ruzicka, M. (2003).
The apparent and potential effects of climate change on
the inferred concentration of dissolved organic matter in a
temperate stream (the Malse River, South Bohemia).
Science of the Total Environment, 310, 143–152.
Hirsch, R. M., & Slack, J. R. (1984). A nonparametric trend test
for seasonal data with serial dependence. Water Resources
Research, 20, 727–732.
Hutchinson, B. A., Scott, L. D., Futter, M. N., & Morgan, A.
(1994). Hydrology data for lakes and catchments in
Muskoka/Haliburton (1980–1992). Ontario Ministry of
Environment data report DR93/5, ISBN 0-7778-2535-X
PIBS 3017 17pp.
IPCC (2001). Third Assessment Report: Climate Change 2001.
Jeffries, D. S., Clair, T. C., Couture, S., Dillon, P. J., Dupont, J.,
Keller, W., et al. (2003). Assessing the recovery of lakes in
southeastern Canada from the effects of acid deposition.
Ambio, 32, 176–182.
Jeffries, D. S., & Ouimet, R. (2005). Critical loads: Are they
being exceeded? In H. A. Morrison (Ed.), Canadian acid
deposition science assessment. Canada: Environment
Canada.
Kirchner, J. W., & Lydersen, E. (1995). Base cation depletion
and potential long-term acidification of Norwegian catch-
ments. Environmental Science and Technology, 29, 1953–
1960.
Krug, E. C., & Frink, C. R. (1983). Acid rain on acid soil: A
new perspective. Science, 221, 520–525.
LaZerte, B. D., Chun, C., Evans, D., & Tomassini, F. (1988).
Measurement of aqueous aluminum species: Comparison
of dialysis and ion-exchange techniques. Environmental
Science and Technology, 22, 1106–1108.
Neary, A. J., Mistray, E., & Vanderstar, L. (1987). Sulphate
relationships in some central Ontario forest soils. Canadian
Journal of Soil Science, 67, 341–352.
Oliver, B. G., Thurman, E. M., & Malcolm, R. L. (1983). The
contribution of humic substances to the acidity of colored
natural waters. Geochimica et Cosmochimica Acta, 47,
2031–2035.
Ontario Ministry of the Environment (1983). Handbook of
analytical methods for environmental samples. Rexdale,
Ontario, Canada.
Ouimet, R., Arp, P., Watmough, S., Aherne, J., & Demerchant,
I. (2006). Determination and mapping of critical loads and
exceedances for upland forest soils in Eastern Canada.
Water, Air, & Soil Pollution, 172, 57–66.
Skjelkvale, B. A., Stoddard, J. L., Jeffries, D. S., Torseth, K.,
Hogasen, T., Bowman, J., et al. (2005). Regional scale
evidence for improvements in surface water chemistry
1990–2001. Environmental Pollution, 137, 165–176.
Watmough, S. A., & Dillon, P. J. (2003). Major element fluxes
from a coniferous catchment in central Ontario, 1983–
1999. Biogeochemistry, 67, 369–398.
Watmough, S. A., Eimers, M. C., Aherne, J., & Dillon, P. J.
(2004). Climate effects on nitrate export from forested
catchments in south-central Ontario. Environmental Sci-
ence and Technology, 38, 2383–2388.