Hydrological, Chemiad and BwbifcalPmcesses of Tranrformatfon and Tran^rt of Contaminate in Aquafc
Environments (Proceeding» of the Rostov-on-Don Symposium, M»y 1993). lAHSPubl. no. 219,1994.
357
Hydrochemical monitoring of a forested catchment with
extremely high aluminium concentrations in runoff: the
Lysina catchment, Czech Republic
JAKUB HRUSKA & PAVEL KRAM
Czech Geological Survey, Malostranské nam. 19, Prague 1, 118 21,
Czech Republic
Abstract The Lysina catchment is a forested area that is extremely
susceptible to adverse impacts from acidic atmospheric deposition. It is
underlain by slow-weathering leucocratic granite covered with basecation deficient, podzolized brown forest soils and peaty gleys. The most
striking feature of the Lysina stream is an extremely high concentration
of total aluminium (weighted mean 68 /*mol l"1 or 1.84 mg l"1).
Monomeric inorganic Al is the dominant fraction present which primarily
contains free Al 3+ and fluoro-complexes. The organic monomeric
aluminium fraction is only about 15% of total monomeric Al. Surface
runoff is dominated by sulphate (84% of anion equivalents) and silica,
accompanied by high concentrations of H + and Al n+ (S 40% of cation
equivalents). Stream-water acidity increases during flood events and
some of the increase is associated with the mobilization of organic acids.
The input of sulphur to the catchment is 26.3 kg ha"1 year"1 (combination
of bulk precipitation and throughfall) and output 28.3 kg ha"1 year"1
(runoff). The critical load of sulphur for adversely impacting surface
water was estimated at 1 kg ha"1 year"1.
INTRODUCTION
The Czech Republic is a country with very serious problems related to acidification.
Adjacent to the North Bohemian Coal Basins is a region with a sulphur deposition
greater than 40 kg ha"1 year"1 (Moldan & Schnoor, 1992), which is the highest in
Europe.
The Lysina catchment, situated in the mountainous area of Slavkovsky les Mts. in
the west of the Czech Republic, was chosen for study because it is underlain by
weathering resistant bedrock and receives emissions of S0 2 from power plants located
nearby. The objective for the study was to investigate changes in the solution chemistry
of water as it percolates through the ecosystem, from precipitation to throughfall, soil
water, groundwater and stream water. The Lysina catchment has been monitored since
September 1989.
CATCHMENT DESCRIPTION
The Lysina catchment lies near the westernmost tip of the Czech Republic, close to
the spa of Mariânské Lâznë, about 120 km west of Prague. The catchment is in the
358
Jakub Hruska & Pavel Krdm
Slavkovsky les Mountains. The region adjacent to the catchment is forested in spruce
and has a relatively low concentration of S0 2 in air but the industrial region with very
high concentration of S0 2 (averaging 60-80 /ig m3 in 1989) is only 10 km away.
Around the city of Sokolov are several open-pit coal mines and two big power plants
(Tisovâ and Vresovâ) where local coal with high sulphur content is burned. The
closest power plant, Tisovâ, is 12 km north of the catchment and the 1990 emissions
from the plant consisted of 88 000 tons of S0 2 , 16 000 tons of NOx and 12 000 tons
of dust (Kurfurst, 1991).
The catchment is in an area of relatively medium pollution load compared to other
areas in the Czech Republic. The mean concentration of S0 2 in the air calculated from
daily measurements in 1989-1990 was 20 ixg m"3. The catchment is located on the
highest part of the Slavkovsky les Mountains, composed of slow-weathering granites.
The catchment represents other areas that are very susceptible to acid rain. Major
characteristics of the catchment are summarized in Table 1.
Table 1 Characteristics of the Lysina catchment.
Location
50°03'N, 12°40'E
Catchment area
0.273 km2
Altitude
829 to 949 m a.s.l.
Mean altitude
884 m a.s.l.
Mean slope
11.5%
Length of brook
900 m
Mean annual precipitation
950 mm (1931-1980)
Mean annual air temperature
5.0°C
Preliminary air movement
West
Bedrock type
Leucocratic granite
Vegetation cover
70% is mature forest,
30% is clear-cut with young forest and grass mainly Calamagrostis villosa
Major tree species
99 % is Norway spruce (Picea abies)
Soil type
Podzolic brown earth, peaty gley
The bedrock underlying the catchment is a base-poor granite. This granite is a
leucocratic (light), and slightly autometamorphic with very low CaO and MgO contents
(Fiala et al., 1961). CaO is only 23% and MgO 17% in comparison with a world
average granite (Paces, 1983). This region was not glaciated and is overlain by soil
derived from residuum. The regolith consists of coarse sand and boulders which is,
on average, 2 m thick. Soils are generally thin, but range from 0.5 to 5 m in depth.
The dominant soils developed in this mantle are podzolic brown forest earth and, in
low lying parts, peaty gleys, but small areas of stagnogleys and peat occur. Originally,
the forest consisted of mixed vegetation with stands of European beech (Fagus
silvahica) and Norway spruce (Picea abies). The original forest was replaced by
Norway spruce 140 years ago. Currently, mature spruce with very small amounts of
Hydrochemical monitoring of a forested catchment with high Al in runoff
359
beech cover 70% of the catchment, and the rest has been clear-cut and recently
reforested.
The present day status of the forest shows signs of problems. Depending on
climatic and pollution changes, we can foresee a dieback of the forest in a time span
of the decade.
METHODS
Daily precipitation was measured at the station Lazy of the Czech
Hydrometeorological Institute (CHMU) 3 km to the northwest of the catchment outlet.
At the same site, S0 2 was measured by the Institute for Forest and Game
Management. Annual volume of precipitation is also recorded at a nearby site (0.7 km
away) by CHMU at the top of Mt. Lysina (982 m a.s.l.).
Precipitation quality was monitored by two bulk deposition collectors. Bulk
precipitation for chemical analysis were collected biweekly at a clearfelled area within
the catchment. Throughfall below the spruce canopy has been monitored at two plots
within the catchment. Ten collectors, of which five were distributed randomly over a
15 by 15 m area in each plot, were sampled monthly. Both the bulk precipitation and
throughfall collectors were fitted with nylon filters to avoid particulate contamination.
The chemistry of atmospheric bulk deposition in the open area and throughfall under
the spruce forest were measured from April 1990 and December 1990, respectively.
Plastic zero-tension lysimeters were installed at one soil plot in the O (5 cm) and
A (15 cm) horizon of podzolized brown forest soil and sampled biweekly.
Groundwater was sampled monthly from one well at the depth of 1.5 m below land
surface near the catchment divide.
The streamflow was monitored continuously at the catchment outlet using a V
notch weir and water level recorder. The stream water was sampled weekly and more
intensively during some high flows.
Volume-weighted mean concentration of constituents in precipitation and
discharge-weighted mean concentration of constituents in the stream water were
multiplied by the associated total water fluxes to determine chemical fluxes.
Atmospheric deposition to the catchment of most constituents was calculated from bulk
precipitation fluxes. Because dry deposition can contribute substantially to the total
atmospheric deposition for some constituents, particularly to forests, and throughfall
can provide an estimate of this deposition, the atmospheric deposition of sulphur,
chloride, sodium and hydrogen ion where computed adding 70% of the throughfall
flux and 30% of bulk precipitation flux, which reflects the forest and clearfelled or
open areas, respectively. The pH was determined using a radiometer combination
electrode. The anions, CI", S042", and N03" were determined by ion chromatography.
Fluoride (F") was determined by ion selective electrode after TISAB addition. The
metals, Ca 2+ , Mg 2+ , Na + , K + , Zn 2+ , Mn 2+ , A1T0T, V^QJ, and Si0 2 were
determined by inductively coupled plasma (ICP). Ammonium (NH4+-N) was
determined by indophenol blue colorimetry. The acid neutralizing capacity (ANC),
sometimes called alkalinity, was determined by strong acid (0.1 M HC1) titration and
Gran plot analysis.
Organic monomeric aluminium (Al0) was separated using ion exchange method
(Driscoll, 1984) and measured as monomeric aluminium (A1M) using pyrocatechol
Jakub Hruska & Pavel Krdm
360
violet method described by Rôgeberg & Henriksen (1985) and modified by LaZerte
et al. (1988). Inorganic monomelic aluminium (A1T) was calculated as the difference
between A1M and Al 0 . Acid soluble aluminium (A1AS) was calculated as the difference
between AlTOT (ICP) and monomelic Al.
From the calculated A1I; and measured temperature and ion concentrations in
water, the speciation of inorganic aluminium was calculated with the chemical
equilibrium model ALCHEMI 4.0 (Schecher & Driscoll, 1988).
RESULTS AND DISCUSSION
Deposition
Bulk precipitation inputs to the catchment were dominated by nitrate, ammonium,
hydrogen ion, and sulphate (Table 2). Hydrogen ion concentration was highly
correlated with sulphate, nitrate, and fluoride. Chloride concentration was poorly
correlated with hydrogen ion concentration. Annual precipitation and throughfall
quantities from November 1990 through October 1991 were 793 and 396 mm,
respectively.
Table 2 Annual volume-weighted ion concentrations, in /tmol l"1 except pH, and mass fluxes in bulk
precipitation and throughfall measured at the Lysina catchment for the period November 1990 through
October 1991.
Constituent
Concentrations:
Bulk precipitation
Fluxes:
Throughfall Bulk precipitation:
1
Throughfall:
2
(kg ha" ) (mmol m" )
pH
H+
Na+
K+
Ca2+
Mg 2+
Al n+
Mn 2+
Zn 2+
Fe2+
NH 4 + -N
NCV-N
SO/'-S
cr
p
Si02-Si
4.32
47.7
8.7
2.5
8.7
2.2
1.8
0.1
0.3
0.5
51.7
51.8
41.9
11.3
2.8
1.7
3.56
274.8
21.8
80.5
60.8
14.2
10.3
3.2
0.6
1.8
62.0
99.4
258.5
35.5
10.3
6.8
0.4
1.6
0.8
2.9
0.4
0.4
0.04
0.1
0.2
6.1
5.9
11.0
3.3
0.4
0.4
39.0
7.12
2.00
7.10
1.77
1.49
0.08
0.21
0.38
42.2
42.3
34.3
9.21
2.27
1.35
(kg ha"1)
1.1
2.0
12.5
9.7
1.4
1.1
0.7
0.1
0.4
3.4
5.6
32.9
5.0
0.8
0.8
(mmol m"2)
108.9
8.64
31.9
24.1
5.62
4.07
1.26
0.22
0.70
24.5
39.4
102.4
14.1
4.1
2.69
Throughfall was dominated by hydrogen ion, sulphate, nitrate, potassium,
ammonium, and calcium. All constituent concentrations increased as the precipitation
passed through the spruce canopy. Also, although throughfall volumes were less than
precipitation due to interception losses, the flux for each constituent except N was
greater under the canopy than in the precipitation. The volume-weighted average
precipitation acidity increased rather markedly as it passed through the canopy from
Hydrochemical monitoring of a forested catchment with high Al in runoff
361
47.7 to 274.8 ^mol l"1 (pH decreased from 4.32 to 3.56) and was accompanied by
similar increases in S042" (Table 2).
The S042"-S deposition in throughfall below the Norway spruce was 33 kg ha"1
year"1, whereas S042"-S in bulk deposition in the open area was only 11 kg ha"1 year"1.
The estimated total atmospheric deposition of S042"-S to the Lysina catchment (70%
throughfall plus 30% bulk precipitation) was 26 kg ha"1 year"1.
Soil water and groundwater
The mean weighted annual concentrations of constituents in soil water from the O and
A horizons from the zero-tension lysimeters are summarized in Table 3. In general,
the highest constituent concentrations in soil solutions were in the summer and the
early autumn. Concentrations were lower in winter than in summer. Large amounts
of Al was released to the soil solution which create toxic conditions for plant roots.
The inorganic monomeric aluminium (A1T) ranged from 30% to 60% in the O horizon
Table 3 Volume-weighted concentrations, in mmol l"1 except pH, of soil water, shallow groundwater,
and stream water.
Constituent
Soil water:
Shallow groundwater
Surface
O horizon
A horizon
3.27
3.23
5.27
3.82
0.539
0.594
0.0054
0.151
0.036
0.087
0.207
0.091
0.112
0.183
0.040
0.025
0.029
0.540
0.057
0.031
0.119
0.287
0.248
0.101
NH 4 -N
0.182
0.476
<0.0011
0.0002
+
0.030
0.082
0.023
0.068
2+
0.003
0.005
< 0.0004
0.0075
0.031
0.064
0.0016
0.0039
0.001
0.003
0.0002
0.0007
cr
0.071
0.149
0.066
0.022
F
0.016
0.033
0.034
0.042
N03--N
0.336
0.364
0.198
0.027
2
0.325
0.810
0.308
0.271
Si02-Si
0.283
0.203
ANC
0.021
-0.161
pH (from H
H
+
Na
+
K+
Mg
2+
2+
Ca
+
Aln
Fe
Mn
Zn
2+
2+
so 4 --s
a
+)
unweighted concentrations
Jakub Hruska & Pavel Krâm
362
and from 70% to 95% in the A horizon. Likewise, the A1T0T concentration in
groundwater was high, whereas ANC concentration was low.
Runoff
Stream water is dominated by sulphate, silica, hydrogen ion, and calcium and has high
aluminium concentrations. Stream water pH varied from 3.68 to 4.46 with a volumeweighted mean H + concentration 151 peq l"1 or pH of 3.84. An ion balance for the
measured constituents indicates that on average cations exceed anions by about 10%
anion and the difference is probably caused by unmeasured organic anions.
Concentrations of H + and Al increase with increasing streamflow while those ionic
species originating dominantly from mineral weathering (Na, Ca, Mg, Si) decrease
with increasing streamflow (Fig. 1). Also, pH was highly correlated with AlTOT
concentration: a linear regression of AlTOT concentration on pH was highly significant
(p < 0.01: r2 = 0.84). During high flows, the stream pH has decreased to less than
3.7 and aluminium has increased to greater than 82 mmol Ï1. The increases in acidity
are accompanied by increases in organic acid concentrations and decreases in base
cations concentrations. In contrast to results from other studies, Al and H +
concentrations were also high during baseflow conditions. Apparently, the stream
water was not well buffered because the pH was consistently less than 4.5. Contrary
to many anthropogenically acidified sites, there is a negative correlation between S042~
and H + concentrations in stream water. Concentration of these ions are relatively
stable over time and hydrologie condition. Also CI" concentration shows remarkably
little variation in the stream water.
The stream-water N03~ concentrations vary seasonally and were less than the
detection limit (5 /*mol l"1) in the summer months.
400
4.5
350i
I-4.4
300
4.3
043 0
250-
ÏK
4.2 _^
*%K
|
200-
•4.1 I
ffr
S o ^
X
150-
a
100-
-1
4
o
0°
-0.5
Al
0
0.5
1
Log of discharge l/s
PH
°"
-3.9
SËjïfij*» •» *
500
o a
cP S
aci
*s
•_, cfa
-3.8
3.7
1.5
base cations
Fig. 1 Relations between aluminium, pH, sum of base cations concentrations
(Ca + Mg + Na + K) and discharge in the Lysina catchment stream.
Hydrochemical monitoring of a forested catchment with high Al in runoff
363
Budget of elements
A summary of element budgets for the Lysina catchment are summarized in Table 4
for hydrological year 1991 (November 1990 through October 1991). Rainfall for the
period was 793 mm and stream runoff was equivalent to 327 mm. Throughfall for the
70% forested area plus precipitation to the open areas totalled 515 mm for the period.
As noted previously, throughfall and bulk precipitation inputs for S042", CI", Na +
and H + were combined in proportion to the respective areas in the catchment.
Comparing the stream-water output in Table 4 to the respective atmospheric inputs in
Table 2, it is apparent that if bulk deposition were the only input then the catchment
would have sources of S042% CI" and H + . However, when additional dry deposition
inputs of these constituents, as estimated by the throughfall flux, were considered then
the inputs and outputs for S042" and CI- were closely balanced. If these flux
measurements are accurate then the transport of sulphur and chloride through the
Lysina catchment was conservative.
Table 4 Element fluxes from the Lysina catchment for the period November 1990 through October
1991.
Constituent"
Atmospheric input (J):
1
H+
Na
Stream output (0):
2
1
Net
2
(kg ha" )
(mmolnï )
(kg ha )
(mmol m )
Oil
0.9
87.9
0.49
49.0
0.6
8.2
6.8
29.6
3.6
0.8
2.0
3.2
8.2
4.1
2.9
7.1
13.2
32.9
4.6
0.4
1.8
2.4
9.9
5.5
0.4
1.5
6.0
22.2
15
+
1.9
K+
Ca
2+
Mg
Al
2+
n+
2+
0.04
0.08
0.7
1.3
16
2+
0.14
0.21
0.15
0.23
1.1
2+
0.2
0.38
1.4
2.5
6.6
NH 4 -N
6.1
42.2
0.01
0.06
0.0014
NCV-N
5.9
42.3
1.2
7.7
0.2
so 4 --s
26.3
82.0
28.3
88.4
1.1
ci-
4.3
12.0
4.9
13.8
1.2
F
0.4
2.3
1.4
7.4
3.2
SiQ2-Si
0.4
18.5
66.1
47
Mn
Zn
Fe
+
2
1.4
2_
+
+
"Atmospheric inputs for S0 4 , Cr, Na and H were calculated by summing the throughfall flux
(70%) and the bulk deposition (30%) and for all other constituents were equal to the bulk deposition.
Jakub HruSka & Pavel Krdm
364
However, other elements were not in balance. Most of the H + and nitrogen input
(NH4+ and N03") was retained within the catchment. In contrast, the catchment was
a source for the other constituents.
Critical loads
The Steady-State Water Chemistry Model (Henriksen et al, 1990) was used to
determine the critical load for sulphur to stream water of the Lysina catchment. Model
results indicated that the critical load of S is about 1 kg ha"1 year"1. Because the S
transport in stream water at Lysina was 28 kg ha"1 year"1, the critical load of S for the
study period was exceeded by 27 kg ha"1 year"1.
Table 5 Volume-weighted total Al concentrations and pH of some catchments with high concentrations
of Al.
Catchment
Location
Al
pH
Reference
1
Oimol l" )
Robinette
Belgium
119
3.57
Hambucker, 1987"
Lysina
CSFR
68
3.84
Krâm & Hruska, 1991
Pancake Hall"
USA, NY
33
4.65
Cronan <*«/., 1990
Gârdsjôn
Sweden
32
4.16
Nilsson, 1985
Beddgelert
UK, Wales
26
4.30
Stevens et al., 1989
Jizerka
CSFR
25
3.90
Kreêek, personal communication 1991
Schluchsee
Germany
24
5.40
Feger et al., 1990
Birkenes
Norway
23
4.55
Abrahamsen et al., 1989
Loch Ard'Kelty
UK, Scotland
16
4.02
Miller et al., 1990
CSFR
16
5.20
Jezeri X16
a
Woods Lake
a
b
a
USA, NY
b
15
4.75
Kinkor, 1988
b
Schofield et al., 1985; Cronan, 1985
unweighted concentrations,
rough estimate.
Aluminium
The weighted average AlTOT concentration in stream water at the Lysina catchment
was much higher than that reported stream waters from small catchments in other
areas (Corell, 1977; Driscoll et al, 1984; Schofield et al, 1985; Moldan & Paces,
1987; Fottovâ, 1988; Cronan & Schofield, 1990; Hornung et al, 1990; Cerny et al,
1992). Only one exception is the aluminium concentrations in the Robinette catchment,
Belgium, for which the volume-weighted mean concentration of H202-hydrolysable
aluminium was reported to be 119 /nmol l"1 (Hambucker, 1987; Hornung et al., 1990).
Hydrochemical monitoring of a forested catchment with high Al in runoff
365
Aluminium equilibria may be an important buffering process in the Lysina
catchment. The main process regulating Al concentrations in stream water at the
Lysina catchment was probably the dissolution of jurbanite (Al(OH)(SO)4.H20). The
solubility of Al with respect to mineral phase equilibria was evaluated using saturation
indices IP (Paces, 1978; Johnson et al., 1981): IP > 0 indicates that the system is
oversaturated with respect to mineral phase, IP < 0 indicates undersaturation and Ip
= 0 indicates that the system is in equilibrium with respect to the mineral. The
saturation index (IP = —0.21 + 0.22) for the stream water at the Lysina catchment
suggests that the water may be in equilibrium with jurbanite Al(OH)S04.H20
(Nordstrom, 1982).
Prenzel (1983) suggested that jurbanite may form as an intermediate step in Al
mobilization. Ionic activity in seepage water of a spruce forest soil in Germany was
reported to be in accordance with the solubility product of jurbanite. Formation of
jurbanite is typical for sulphate stressed groundwater and soil water, and may be an
intermediate step in proton storage (Nordstrom, 1982; Prenzel, 1983; Gundersen &
Rasmussen, 1988). But this equilibrium has not been reported often for surface waters,
for which models usually suggest waters to be in equilibrium with gibbsite (Driscoll
et ah, 1984; Nilsson, 1985; Schofield etal, 1985; Cronan etal., 1990). Furthermore,
Seip et al. (1990) reported that stream water in the Birkenes catchment, Norway,
equilibrium with gibbsite for stream water with pHs from 4.6 to 5.3 and
undersaturation with respect to jurbanite (IP about - 1 ) .
The dominant aluminium fraction in the stream water under all hydrological
conditions and seasons was inorganic monomeric aluminium (Alin) ranging from 92%
of AlTOT in autumn baseflow to 75% during a snowmelt event in January 1992.
Concentrations of the organic monomeric aluminium (Al0) were correlated with
hydrologie conditions. During high flow periods, humic substances were leached from
organic soil horizons and peat. The Al 0 concentrations increased proportionally with
increased A1T concentrations. Acid soluble Al fraction did not contain suspended
3.79
3.95
4.04
4.34
4.46
pH
g^g Al-org
H I AI-S04
H I Al 3+
[ m Al-Si
£~} Al-F
B U AI acid soluble
Fig. 2 Aluminium speciation in stream water from the Lysina catchment.
366
Jakub Hruska & Pavel Krâm
Al(OH)3 because the stream pH was too low for this type of suspended matter to have
existed (Schecher & Driscoll, 1988). This A1AS fraction ranged from 0 to 10% of
A1 T0T . The A1AS decreased with increased pH and when pH was greater than or equal
to 4.1, the A1AS was essentially zero (Fig. 2). Small suspended soil and clay particles
also could have affected the A1AS fraction, particularly during high flows.
When stream water pH was low, free Al 3+ was calculated to be a major proportion
(about 50%) of the Alr (Fig. 2). The total free Al 3+ was limited by the fluoride concentration. Although concentration of Al is strongly dependent on pH, F concentrations
were relatively constant over the observed pH range. The model results suggest that
almost 100% of F was complexed with aluminium and that the total concentration of
Al-F complexes was relatively stable in the stream water at the Lysina catchment.
Furthermore, free Al 3+ and. Al-F complexes were about 50 and 40% of Alj ,
respectively, in the stream during the low pH event. For high pH stream water, free
Al 3+ decreased to 10% and Al-F increased to 80% of Alt. Total concentration of Al-F
ranged from 24 to 12 jttmol l"1, while Al3+decreased from 42 to 3 /*mol T1. Based on the
discharge weighted total aluminium concentration, the average charge per aluminium
ion was estimated to be 1.95 (AlDand A1AS were assumed to carry no charge).
CONCLUSIONS
The Lysina catchment received only average atmospheric deposition of sulphur typical
of the Czech Republic. Nevertheless, concentrations of total Al and other toxic forms,
mainly inorganic monomeric Al in surface water are extremely high. The aluminium is
derived from granite and podzolized brown forest soils in this catchment which has an
extremely low buffering capacity. Acid input also increased markedly as precipitation
passed through the spruce canopy. Critical load for adversely impacting surface waters
in this environment is very low and, under the current stress, it is many times exceeded.
We hope to continue collecting time series information of inputs and outputs from
the Lysina catchment to assess the effects of forest health and environmental changes on
catchment processes. Severe damage to Norway spruce has not been observed in the
Lysina catchment but has been observed at Mt. Lesny (983 m a.s.l.) 5 km from the
Lysina catchment. The reasons that forest health has not declined as rapidly in the
catchment is also the subject of on-going research.
Acknowledgements This research was funded by the Czech Geological Survey, Prague.
We thank Dr J. Cerny, Dr T. Paces, Dr D. Fottovâ and Dr J. Vesely for their support
of this research. We also thank Dr J. Cerny for constructive criticism of this paper. The
chemical analysis was done by Z. Valny, P. Pokorny, H. Vitkovâ, Dr A. Galfk, Dr L.
Dempfrovâ and M. Miksovsky from laboratories of the Geological Survey.
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