Science of the Total Environment

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Anthropogenic acidification effects in primeval forests in the Transcarpathian Mts.,
western Ukraine
F. Oulehle a,
⁎, R. Hleb b
, J. Houška b
, P. Šamonil c
, J. Hofmeister a
, J. Hruška a
a
Department of Environmental Geochemistry and Biogeochemistry, Czech Geological Survey, Klárov 3, Prague 1118 21, Czech Republic
b
Department of Geology and Pedology, Mendel University of Agriculture and Forestry in Brno, Zemědělská 1, 613 00 Brno, Czech Republic
c
Department of Forest Ecology, The Silva Tarouca Research Institute for Landscape and Ornamental Gardening, Lidická 25/27, 657 20 Brno, Czech Republic
a b s t r a c ta r t i c l e i n f o
Article history:
Received 21 July 2009
Received in revised form 16 October 2009
Accepted 20 October 2009
Available online 14 November 2009
Keywords:
Atmospheric deposition
Sulphur
Nitrogen
Soil chemistry
Soil water
Norway spruce
European beech
The precipitation chemistry, deposition, nutrient pools and composition of soils and soil water, as well as an
estimate of historical deposition of sulphur (S) and inorganic nitrogen (N) for the period 1860–2008, were
determined in primeval deciduous and coniferous forests at the sites Javornik and Pop Ivan, respectively.
Measured S throughfall inputs of 10 kg ha−1
year−1
in 2008 were similar to those estimated for the period
1900–1950 at both sites. The highest estimated S inputs were in the 1980s. Measured bulk deposition of N in
2008 was lower at Pop Ivan (5.6 kg ha− 1
year− 1
) compared to Javornik (12 kg ha−1
year−1
). Significantly
lower NO3 deposition was both estimated and measured at Pop Ivan. Higher soil base cation concentrations
were observed at well-buffered Javornik underlain by flysch (Ca pool of 2046 kg ha− 1
and base saturation of
29%) compared to Pop Ivan underlain by crystalline schist (Ca pool of 186 kg ha− 1
and base saturation of 6.5%).
The soil pool of organic carbon (C) was higher at Pop Ivan (212 t ha−1
) compared to Javornik (127 t ha−1
). The
C concentration was positively correlated with organic N in the soil (pb0.001) at both sites, but the mass
average C/N ratio in the forest floor was lower at Javornik (22) than at Pop Ivan (26). High N leaching of
17 kg ha−1
year−1
at the 90 cm depth was measured in the soil water at Javornik, suggesting high
mineralization and nitrification rates in old growth deciduous forests in the area. Despite relatively low Al
concentrations in the soil water, a low soil water Bc/Al ratio (0.9) (Bc=Ca+Mg+K) was found in the upper
mineral soil at Pop Ivan. This suggests that the spruce forest ecosystems in the area are vulnerable to
anthropogenic acidification and to the adverse effects of Al on forest root systems.
© 2009 Elsevier B.V. All rights reserved.
1. Introduction
Mountainous ecosystems of Europe have been exposed to high
acidic deposition for more than a century as a result of the long-range
transport of sulphur (S) and nitrogen (N) compounds from anthro-
pogenic emissions. High loads of strong acid anions (mainly sulphate)
led to acidification and the depletion of base cations (Ca, Mg, Na, K)
from soils and subsequent mobilisation of aluminium (Al), with
adverse effects on both soil and surface water chemistry (Reuss and
Johnson, 1986). International agreements under the United Nations
Economic Council for Europe (UN-ECE) Convention on Long-Range
Transboundary Air Pollution (LTRAP) to reduce emissions of S and N
compounds (Bull et al., 2001) have resulted in a 60–70% reduction in S
and a 20% reduction in N deposition during the period 1980–2000
(Skjelkvåle et al., 2001). These decreases have led to the partial
recovery of surface waters from acidification (Evans et al., 2001).
In the last few decades, the effects of acid deposition on forests have
been widely studied in many mountain regions in Central Europe, with
the exception of the eastern part of the Carpathian Mts. laying mainly
in Ukraine and Romania (e.g. Fagerli and Aas, 2008). Transcarpathia is
among the most forested regions in Europe; however, there is
practically no data concerning the effects of acid deposition on forest
soil conditions in this area. On the other hand, comprehensive
descriptions of these forests (including phytocoenological, dendro-
logical, dendrometrical and also pedological approaches) were already
carried out in the 1930s (Zlatník, 1934, 1935, 1938). In 1996, these
study plots were re-opened, and new field surveys were restored
(Hrubý, 2001; Houška, 2007). In 2007, we started measurements of
deposition, soil and soil solution chemistry in two of those plots with
different tree-species composition and bedrock. Moreover, we
estimated the deposition of S and N compounds for the whole
industrial period (1860–2008) and compared them to other areas in
Central Europe. We attempted to evaluate (1) whether present acid
deposition in this region is lower than in the rest of Central Europe as is
assumed (de Vries et al., 1997; van Leeuwen et al., 1997), and (2)
whether soil condition and soil solution chemistry differ from findings
obtained in other Central European mountain regions.
Science of the Total Environment 408 (2010) 856–864
⁎ Corresponding author. Tel.: +420 251085431; fax: +420 251818748.
E-mail address: filip.oulehle@geology.cz (F. Oulehle).
0048-9697/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2009.10.059
Contents lists available at ScienceDirect
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2. Materials and methods
2.1. Site description
The Javornik site represents a natural deciduous forest on the
border between Ukraine and Slovakia at 850 m a.s.l. (22°31′ E; 48°55′
N) (Fig. 1). Forest vegetation consists namely of European beech
(Fagus sylvatica L.) and Sycamore (Acer pseudoplatanus L.). Soils are
Cambisols (Michéli et al., 2006) developed on well-buffered bedrock
(flysch). The site is situated on a N-oriented slope, with mean annual
temperature of 5 °C and annual precipitation of 1.1 m. The Pop Ivan
site is a natural coniferous forest situated on the border between
Ukraine and Romania at 1480 m a.s.l. (24°31′ E; 47°57′ N) (Fig. 1). The
forest cover is dominated by Norway spruce (Picea abies (L.) Karsten).
Soils are mostly Podzols in different stages of development as well as
Cambisols. The bedrock consists namely of acid sensitive crystalline
schist and gneiss. The Pop Ivan site is situated on a steep slope
oriented to the W, with mean annual temperature of 2 ° C and annual
precipitation of 1.8 m. Both sites are probably among the most natural
forests of such extent in Central Europe, because direct human
impacts have been minimal in this area.
2.2. Precipitation, soil, and soil water: sampling and chemical analyses
Sampling networks of precipitation collectors (9 at Javornik, 5 at
Pop Ivan) were installed (in May at Javornik, September at Pop Ivan,
2007) in a regular grid for throughfall measurements. Bulk precipi-
tation was sampled at nearby open fields (2 collectors at each site).
Precipitation was collected monthly by polyethylene funnels (area of
122 cm2
) which were replaced in winter by open plastic vessels (area
of 167 cm2
) at Javornik. During the winter season (October–April),
high snow depth and unapproachable trail conditions lead us to use
high volume samplers (area of 990 cm2
) for bulk and throughfall
(area of 179 cm2
) at Pop Ivan. At each site, the contents of throughfall
samplers were combined to create one sample for chemical analysis,
bulk precipitation collectors were analyzed separately.
Soil water has been collected since May (September at Pop Ivan)
2007 using suction lysimeters at depths of 30 and 90 cm in the
mineral soil (6 lysimeters in each depth at Javornik and 3 lysimeters in
each depth at Pop Ivan). Zero-tension lysimeters were installed under
the forest floor at both sites (6 and 3 replications). All lysimeter
samples were collected monthly and combined to create one sample
from each depth for each month.
Water pH was measured using a pH meter with a combination
electrode (Radiometer model GK-2401C). Cl, SO4 and NO3 were
measured by exchange ion chromatography. Ca, Mg, Na, K, Si and Al
were determined by flame atomic absorption spectrometry (FAAS),
and NH4 by indophenol blue colorimetry. Alkalinity was measured by
strong acid (0.1 M HCl) titration with Gran plot analysis. Samples
processing and analysis were made in the Accredited Testing
Laboratory according to criteria of the ISO/IEC 17025:2005.
Quantitative soil samples were based on eight (Javornik) and four
(Pop Ivan) pits. Soil masses were estimated by excavating 0.5 m2
pits
using the method described in Huntington et al. (1988). This
technique entails collection of the Ol plus Of (litter plus fermented)
horizons as a single sample, and then the Oh (humus) horizon.
Mineral soil was collected for the depths of: 0–10, 10–20, 20–40 and
40–80 cm. The soil samples were weighed, and then sieved after air-
drying (mesh size of 5 mm for organic horizons and 2 mm for mineral
horizons). Soil moisture was determined gravimetrically by drying at
105 °C. Soil pH was determined in both deionized water and 1 M KCl.
Exchangeable cations were analyzed in 0.1 M BaCl2 extracts by FAAS.
Total exchangeable acidity (TEA) was determined by titration of 0.1 M
BaCl2 extracts with 0.1 M NaOH. Cation exchange capacity (CEC) was
calculated as the sum of exchangeable Ca, Mg, Na, K and TEA. Base
saturation (BS) was determined as the fraction of CEC associated with
base cations. Total carbon (C) and total nitrogen were determined
using a Carlo-Erba Fisons 1108 analyzer.
2.3. Water and element fluxes of the soil solution
To assess the water and element fluxes through the soil profiles we
used a measurement of the chloride (Cl) mass budget. Chlorine
compounds tend to be highly soluble in water and mobile in soils, so
atmospheric deposition and transport through terrestrial ecosystems
is rapid if there is active hydrologic flow. In addition, small-watershed
studies assume that weathering of Cl is negligible compared to
atmospheric deposition (Juang and Johnson, 1967). The water flux
through different soil horizon was calculated as follows:
water flux ðxÞðmmÞ =
Cl throughfall flux ðmg m−1
Þ
Soil Solution ðxCl concÞðmg L−1
Þ
where: x is the water flux in the respective soil horizon and xCl is the
respective soil horizon Cl concentration. Solute fluxes were calculated
by multiplying the annual average of each solute by the water flux.
2.4. Trends in emissions of sulphur and nitrogen
Historical Czech (CZ) emissions of SO2 and NOx were taken from the
Yearbooks of the Czech Statistical Office and REZZO register (Registry
of atmospheric pollution sources; www.chmi.cz) for the period 1980–
2006. The CZ emissions were tightly correlated with total emissions
from Poland, Slovakia and Romania (Berge, 1997) in the period 1980–
2006 (R2
=0.98; pb0.001 for SO2 and R2
=0.93; pb0.001 for NOx).
Historical anthropogenic emissions of SO2 were calculated on the basis
of brown coal mining, which was the major source of SO2 emissions in
the 20th century (Kopáček and Veselý, 2005). Anthropogenic SO2
emissions in the period 1960–1994 were calculated using a linear
regression model between coal mining and SO2 emission inventories
(R2
=0.89; pb0.001), and according to the linear regression model
between coal mining and SO2 emissions estimated by Mylona (1993)
(R2
=0.92; pb0.001) for the period 1860–1959 (Fig. 2A). Trends in
SO2 emissions were used to estimate S deposition.
Energy production through fuel combustion has been the major
source of NOx emissions in the Czech Republic and Slovakia. During the
first half of the 20th century, burning of solid fuel (black and brown
coal) was the main source of energy production (almost 90%). Since
the 1960s the role of liquid and gaseous fuels have continuously
Fig. 1. Locations of the research sites Javornik and Pop Ivan (circles), the meteorological
stations Chopok and Starina (squares) and research sites in the Czech Republic and
Slovakia (triangles).
857F. Oulehle et al. / Science of the Total Environment 408 (2010) 856–864

4. Author's personal copy
increased, up to 40% in the 1990s (Kopáček and Veselý, 2005).
However, Czech NOx emissions between 1980 and 2006 (REZZO
inventory) were still tightly correlated with brown coal mining
(R2
=0.89; pb0.001). We used 3% of the anthropogenic NOx emission
in the 1980s as an estimation of the emission from natural sources (soil
processes, burning of straw and stubble) (Pacyna et al., 1991) (Fig. 2B).
Historical Czech and Slovak emission trends for NH3 were calculated
for the whole 1860–2006 period according to Asman et al. (1988), using
livestock production data (cattle, pigs, sheep, goats, horses and poultry)
and the production and consumption of nitrogenous fertilisers. Data on
livestock production and fertiliser usage were derived from Kopáček
and Veselý (2005) and recalculated for the Transcarpathian region
according to the status of livestock in the 1870–1904 period (Zlatník,
1934) (Fig. 2C) to obtain more realistic estimations of emission sources
in this agricultural area. These calculated emissions of NH3 were used to
estimate N–NH4 deposition (Fig. 2D).
2.5. Trends in deposition of sulphur and nitrogen
Data on the atmospheric deposition and precipitation concentra-
tions of SO4, NO3 and NH4 were taken from the following sources: (1)
bulk concentrations and deposition in Slovakia from the Chopok
Station, situated at 2008 m a.s.l. ~300 km west of Javornik (1978–
2006 period, www.emep.int) and the Starina Station, situated at
345 m a.s.l. ~30 km west of Javornik (1994–2006, www.emep.int)
(Fig. 1); (2) bulk deposition and concentrations from Javornik and Pop
Ivan (2007–2008); (3) throughfall deposition and concentrations
from Javornik and Pop Ivan (2007–2008).
The relationship used for the estimate of bulk SO4 concentrations at
the Starina Station from 1978 to 2006 was based on a linear regression
between the Chopok and Starina Stations for 1994–2006 (R2
=0.70;
pb0.001). The relationship used for the estimation of SO4 concentrations
at Starina for the entire 1860–2006 period was based on a linear
regression between the Starina SO4 bulk concentration and respective
1978–2006 SO2 emissions (R2
=0.85; pb0.001). The Starina bulk S
deposition was calculated by multiplying the estimated SO4 concentra-
tion by average precipitation amount (Fig. 3A). Because there was no
significant difference between measured monthly bulk SO4 concentra-
tions at Starina (2005–2006), Javornik (2007–2008) and Pop Ivan
(2008), we used the Starina SO4 concentrations as a measure of S
deposition at Javornik and Pop Ivan (Fig. 6A). Total S deposition was
calculated using the dry deposition factor (DDF) obtained from through-
fall to bulk deposition at Javornik and Pop Ivan in 2008. At Javornik, a ratio
of 1 was used prior to 1940, followed by a gradual increase to the
measured ratio of 1.4 between 1950 and 2006 (Fig. 3B). At Pop Ivan, a
ratio of 1 was used prior to 1940, followed by a ratio of 1.1 for the 1940s,
then 1.2 between 1950 and 2006 (Fig. 3C). The DDF was scaled according
to anthropogenic SO2 emission temporal change. We assumed that DDF
was equalled 1 before ca. 1940 as a result of significantly lower coal
burning (Fig. 2) and consequently low particle emissions.
Similarly, the relationship used for the estimation of bulk NO3
concentrations at the Starina Station in 1978–2006 was based on a
linear regression between the Chopok and Starina Station for 1994–
2006 (R2
=0.51; pb0.01). The relationship used for the estimation of
NO3 concentrations at Starina for the entire 1860–2006 period was
based on a linear regression between Starina NO3 bulk concentrations
and respective NO3 emissions (R2
=0.60; pb0.001) (Fig. 4A). No
significant difference between measured monthly bulk concentration
of NO3 at Starina and Javornik was observed (Fig. 6B). Therefore,
historical bulk N–NO3 concentration from Starina was used for
Javornik deposition calculation. The throughfall flux was based on
the ratio of throughfall to bulk deposition at Javornik measured in
2008. A DDF of 1 was applied for 1860–1940, increasing to 1.1 in 1950
and then to 1.4 for the 1970–2008 period (Fig. 4B). Measured monthly
bulk NO3 concentrations at Pop Ivan (2008) significantly differed from
those at Starina (Fig. 6B). Based on the ratio of NO3 bulk
Fig. 2. Coal mining and estimated emissions of SO2 (A), NOx (B) and NH4 (D), plus cattle production in the Czech Republic, Slovakia and Ukraine (C).
858 F. Oulehle et al. / Science of the Total Environment 408 (2010) 856–864

5. Author's personal copy
concentrations between Pop Ivan and Starina in 2008 (0.26), a N–NO3
deposition trend was calculated for the Pop Ivan site from 1860 to
2008. The throughfall flux was calculated according to the ratio
between throughfall to bulk deposition in 2008 (0.7). This ratio was
applied for the whole period from 1860 to 2008 (Fig. 4C), because of
lower flux in throughfall compared to bulk deposition.
For the estimation of N–NH4 bulk concentrations at the Starina
Station we used a linear regression between Starina (1994–2006) and
the respective NH3 emissions (R2
=0.47; pb0.01) (Fig. 5A). No
significant difference was found between monthly N–NH4 bulk
concentrations at Starina and Javornik (Fig. 6C); therefore, bulk N–
NH4 deposition at Javornik was estimated based on bulk chemistry at
Starina (Fig. 5B). In contrast, bulk N–NH4 concentrations at Pop Ivan
significantly differed from those at Starina (average 0.19 mg L−1
vs.
0.41 mg L−1
) (Fig. 6C). The ratio of 0.5 was used for the calculation of
N–NH4 deposition at Pop Ivan. Throughfall fluxes were calculated
from the ratio between throughfall to bulk deposition in 2008. The
ratio of 0.8 was used for the Javornik site (1860–2008) and 1.2 for the
Pop Ivan site (1860–2008) (Fig. 5C).
Estimation of S–SO4, N–NO3 and N–NH4 bulk deposition at
Javornik and Pop Ivan were based on precipitation chemistry in the
Starina Station. Uncertainty associated with the deposition estimates
was calculated as a difference between mean concentrations of the
respective solutes at Starina Station, Javornik and Pop Ivan. For SO4
the uncertainty was estimated less than 30% and for NO3 and NH4 less
than 10% according to available data.
3. Results and discussion
3.1. Sulphur
3.1.1. Trends in emissions and deposition rates of sulphur
The burning of brown coal in Central European power plants has
been the main source of anthropogenic SO2 emissions in the area
(Berge et al., 1999). SO2 emissions started to increase after World War
II as a result of industrial development. The highest SO2 emissions in
the Czech Republic were measured in the first half of the 1980s
(2.3 million of tons per year). A rapid decline has occurred since the
Fig. 3. Estimated and measured bulk deposition of S–SO4 at Starina Station
(A), estimated and measured bulk and throughfall deposition of S–SO4 at Javornik
(B) and Pop Ivan (C).
Fig. 4. Estimated and measured bulk deposition of N–NO3 at Starina Station
(A), estimated and measured bulk deposition and throughfall flux of N–NO3 at Javornik
(B) and Pop Ivan (C).
859F. Oulehle et al. / Science of the Total Environment 408 (2010) 856–864

6. Author's personal copy
mid 1980s caused by industrial declines and desulphurization of
power plants in the 1990s. Recent CZ emissions of SO2 are similar to
those in the 1890s (Fig. 2A).
The estimated trend of S bulk deposition at the Starina Station
(Slovakia), which was estimated from the CZ emissions of SO2, agrees
well with the measured data (pb0.001; Fig. 3A). Deposition trends of
bulk S at Javornik and Pop Ivan, which were estimated from the
Starina bulk S deposition trend, peaked in the early 1980s with 25 and
33 kg ha−1
year−1
, respectively (Fig. 3B,C). Throughfall deposition
was estimated as 35 and 40 kg ha−1
year−1
in the 1980s. In 2008,
measured bulk S deposition was 7.4 kg ha−1
year−1
at Javornik and
8.8 kg ha−1
year−1
at Pop Ivan, while throughfall deposition of S was
10.5 at Javornik and 10.6 kg ha−1
year−1
at Pop Ivan (Fig. 3B,C). The
bulk and throughfall deposition of S at Javornik was higher than that
measured in a beech forest in the Czech Republic (Table 1) even
though the Transcarpathian Mts. have frequently been reported as
being a less polluted area. For example, at the formerly highly polluted
Načetín site in the Krušné hory (50 kg ha−1
year−1
of total S deposition
in 1994–1996, NW Czech Republic, Fig. 1) only 5.4 kg ha−1
year−1
in
bulk and 7.6 kg ha−1
year−1
in throughfall was measured in 2008
(Table 1). Bulk deposition of S at Pop Ivan is similar to that in the High
Tatra Mts., Slovakia (Kopáček et al., 2004) but again higher than bulk
deposition in the Czech Republic (Table 1). Throughfall S deposition
under the spruce canopy at Pop Ivan is slightly higher than at the Czech
sites (Table 1). The reason explaining the higher deposition at sites in
Ukraine was higher precipitation amounts there, particularly at Pop Ivan,
compared to Czech sites (Table 1). Cumulative S deposition between
1860 and 2008 was estimated as 1700 kg ha−1
and 2250 kg ha−1
for
bulk deposition, and 2095 kg ha−1
and 2530 kg ha−1
for throughfall
deposition, at Javornik and Pop Ivan, respectively.
3.2. Nitrogen
3.2.1. Trends in emission and deposition rates of oxidised nitrogen
Solid fuel and wood combustion in the Czech Republic and Slovakia
were the main sources of NOx emissions until 1950s and solid fuel
combustion contributed to the total NOx emissions by ca 50% in late
Fig. 5. Estimated and measured bulk deposition of N–NH4 at Starina Station
(A), estimated and measured bulk deposition and throughfall flux of N–NH4 at Javornik
(B) and Pop Ivan (C).
Fig. 6. Concentrations of S–SO4 (A), N–NO3 (B) and N–NH4 (C) in monthly bulk
precipitation at Starina Station (2005–2006), Javornik (2007–2008) and Pop Ivan
(2007–2008). Different letters indicated statistically different chemistry (One-Way
ANOVA, pb0.05).
860 F. Oulehle et al. / Science of the Total Environment 408 (2010) 856–864

7. Author's personal copy
1990s (Kopáček and Veselý, 2005). The highest emissions were
estimated for the 1980s (Fig. 2B). Recent emissions are similar to those
in the 1960s, with decreases since 1980s primarily due to the
optimization of combustion in power plants (Kopáček and Veselý, 2005).
The estimated trend of N–NO3 bulk deposition at Starina was based on
NOx emissions and corresponds with the measured deposition (Fig. 4A).
Bulk deposition of N–NO3 at Javornik increased sharply between the
1960s and 1970s, and reached their maximum of 8 kg ha−1
year−1
in
the 1980s. Significantly lower bulk deposition was estimated for Pop
Ivan, with a maximum of 2.8 kg ha−1
year−1
in the 1980s (Fig. 4B,C).
The throughfall flux of N–NO3 was estimated to be higher than bulk
deposition at Javornik and lower at Pop Ivan (Fig. 4B,C). The measured
N–NO3 bulk deposition and throughfall flux in 2008 was 4.9 and
7.4 kg ha−1
year−1
and 1.9 and 1.4 kg ha−1
year−1
at Javornik and Pop
Ivan, respectively (Table 1). Low NO3 throughfall concentrations at Pop
Ivan, mostly under detection limit of 0.05 mg L−1
, were measured
during the summer season. Thus lower N–NO3 throughfall flux than bulk
deposition at Pop Ivan could be explained by nitrate consumption and
the production of organic N in the canopy (Lovett and Lindberg, 1993).
Measured N–NO3 bulk deposition at Javornik was similar to that
measured in the Czech Republic and higher than in the High Tatra Mts.,
Slovakia (Table 1). On the other hand, bulk deposition of N–NO3 was
markedly lower at Pop Ivan compared to that in the Czech Republic and
Slovakia (Table 1). This could be due to the long distance from large
stationary sources of NOx emissions and the low population density
(meaning sparse mobile sources of emissions). Cumulative N–NO3
deposition was estimated to be 560 and 190 kg ha−1
for bulk deposition
and 700 and 135 kg ha−1
for throughfall flux at Javornik and Pop Ivan,
respectively, for the period 1860–2008.
3.2.2. Trends in emission and deposition rates of reduced nitrogen
In contrast to NOx and SO2, NH3 emissions are mostly derived from
agricultural production. Estimated emissions in the Transcarpathian
area (Fig. 2D) were about 30% lower than reconstructed emissions for
the Czech Republic and Slovakia (Kopáček and Veselý, 2005). The
emission rate was relatively high from 1860 to 1950 and increased by
50% up to the 1980s. Recent emissions of NH3 are comparable to those
estimated for the period 1860–1950. The NH3 emissions have
decreased since the 1980s primarily due to a 55% reduction in cattle
production and the fertilisation of farmland in the Czech Republic and
Slovakia (Kopáček and Veselý, 2005). We suppose that a similar
situation has also occurred in the western Ukraine, where there have
been declines in planned agriculture since the late 1980s.
The estimated trend of N–NH4 bulk deposition at Starina corre-
sponded with measured data (Fig. 5A), and provided a reasonable basis
for the estimate of N–NH4 bulk deposition trends at Javornik and Pop
Ivan. At both sites, stable N–NH4 depositionwasestimatedfor theperiod
1860–1950, with averages of 8 and 5 kg ha−1
year−1
, followed by
estimated increases to 22 and 15 kg ha−1
year−1
in the 1980s and
decreases by 30% during the 1990s (Fig. 5B,C). The measured throughfall
flux in 2008 (5.8 kg ha−1
year−1
at the Javornik and 4.6 kg ha−1
year−1
at the Pop Ivan, Table 1) was lower than bulk deposition at Javornik and
higher than at Pop Ivan. Recent deposition is equal to the reconstructed
deposition between 1860 and 1950. Measured bulk deposition at
Javornik (7.2 kg ha−1
year−1
) is similar to that measured in the Czech
Republic, while bulk deposition at Pop Ivan (3.7 kg ha−1
year−1
) is
similar to that in the Tatra Mts. (Table 1). From 1860 to 2008, cumulative
N–NH4 deposition was estimated to be 1520 and 1000 kg ha−1
for bulk
deposition and 1220 and 1200 kg ha−1
for throughfall flux at Javornik
and Pop Ivan, respectively.
3.3. Soil chemistry
Soils at Javornik are Haplic Cambisols with dry fine soil (b2.0 mm)
comprising 45–60% of the total soil pool. Soils at Pop Ivan are mostly
Entic and Haplic Podzols with dry fine soil comprising 75% of the
uppermost mineral profile (0–20 cm) and comprising 35% at the 40–
80 cm depth. Concentrations of exchangeable base cations were the
highest in the organic soil layers at both sites, but ca. 4–6 times higher
at Javornik compared to Pop Ivan (Table 2). This difference was also
manifested in base saturation — 87–91% and 21–51% in the forest floor
layer (Ol +Of and Oh) at Javornik and Pop Ivan, respectively (Table 2).
In the mineral soil, concentrations of exchangeable cations mainly
reflected the bedrock composition (Table 2; Houška, 2007), and base
cation concentrations were almost an order of magnitude higher for
Ca and 2–3 times higher for Mg at Javornik. Such difference in base
cation concentrations resulted in very different base saturation: 30–
37% at Javornik versus only 5–8% at Pop Ivan in the mineral soil
(Table 2). Also, soil pHKCl was much higher at Javornik in the Ol +Of
layer — 4.88 compared to 2.74 at Pop Ivan. In the mineral soil, pH
differences were not so pronounced, and in the deepest horizons soil
pH was higher at Pop Ivan (Table 2). This was the result of the
extremely low CEC at Pop Ivan (19 mmol+kg−1
) in these deepest
horizons. CEC was generally higher at Javornik (70 mmol+kg−1
)
compared to Pop Ivan (47 mmol+kg−1
).
Pools of base cations in the whole soil profile (0–90 cm) were
significantly higher at Javornik, similar to the proportions of exchange-
able base cation concentrations (Table 2). Concentrations of C and N
were highest in the organic layers and in the top of the mineral soil
profile. The total pool of C was higher at the acidic and colder Pop Ivan
(Table 2). The C concentrations positively correlated with N (pb0.001)
at both sites. The C/N mass ratio was between 21 and 25 at Javornik and
24 and 28 at Pop Ivan in the Ol +Of and Oh horizons. The C/N ratio was
lower in the mineral soil, varying between 13 and 16 at Javornik
(through the whole profile) and between 15 and 18 at Pop Ivan (0–
40 cm) but with a ratio of 29 in the lowermost 40–80 cm depth.
The soil chemistry at Javornik does not show symptoms of
acidification with respect to high concentration of TEA (Table 2), most
probably due to the high base cation weathering rate from the flysch
bedrock. Compared to the Červík catchment (Beskydy Mts., Fig. 1) in the
eastern Czech Republic (Fottová, unpublished data), also underlain by
flysch but receiving an approximately two times higher deposition of S,
Table 1
Measured precipitation chemistry and deposition at Javornik, Pop Ivan, Načetín in 2008, Čertovo Lake (Kopáček et al., 2006) and the Tatra Mts. (Kopáček et al., 2004).
Water
(mm)
pH Alkalinity Na Mg K Ca N–NH4
+
N–NO3
–
S–SO4
2–
Cl–
ueq L−1
kg ha−1
year−1
Javornik Bulk 1340 4.86 −6 2.3 0.7 2.2 5.3 7.2 4.9 7.4 3.1
THFbeech 1002 5.13 49 2.3 2.1 29.6 9.5 5.7 7.4 10.5 4.2
Pop Ivan Bulk 2190 5.00 −9 1.8 0.8 3.4 6.2 3.8 1.9 8.8 3.3
THFspruce 1583 5.04 −3 3.1 1.6 8.6 9.7 4.6 1.4 10.6 4.9
Načetín (2008) Bulk 1034 4.93 −10 3.7 0.8 1.0 2.4 6.3 3.7 5.4 5.9
THFspruce 644 4.38 −36 6.3 1.9 13.5 7.6 6.7 7.3 10.2 12.0
THFbeech 645 4.69 3 3.5 1.9 9.6 6.2 5.1 6.5 7.6 8.9
Čertovo Lake (2005) Bulk 1368 4.73 −22 2.2 0.4 1.0 2.6 4.7 5.2 5.2 3.1
THFspruce 1347 4.58 −27 4.1 1.5 10.0 6.5 6.8 9.1 9.2 7.6
Tatra Mts. Bulk 1340 4.55 – 1.0 0.5 0.5 3.2 4.5 3.7 10.4 1.8
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8. Author's personal copy
base saturation at Javornik is ca. 2 times higher through the whole soil
profile. On the other hand, Houška (2007) confirmed positive influence
of acidic deposition on loss of neutralizing capacity by significant
lowering of soil pH in the period 1935–1998 (average pHKCl dropped
from 4.5 to 3.5 in A horizon and from 4.0 to 3.7 in B horizon).
In contrast, the soil chemistry at Pop Ivan shows symptoms of
acidification, and is quite similar to the Czech sites underlain by
similar igneous acidic bedrocks. For example, the Lysina catchment in
the western Czech Republic (Fig. 1) with granite bedrock has mineral
soil base saturation between 4–7% (Hruška et al., 2002). The forest
plot Načetín in the Krušné hory (underlain by gneiss) also only has
mineral soil base saturation between 5 and 8% (Oulehle et al., 2006).
Nevertheless, the high average precipitation (1.8 m) and low
temperature could be natural factors accelerating soil depletion at
Pop Ivan, and the role of anthropogenic acidification requires future
study (e.g. by biogeochemical models).
3.4. Soil water chemistry and element fluxes
Water fluxes in the soil profile at Javornik decreased with depth as
a result of forest transpiration in the topsoil where the majority of
roots are present. In contrast, at Pop Ivan the water flux (calculated
using the Cl balance) increased with depth, probably as a result of
lateral water movement on the steep slope (Table 3). The reasons of
the relatively high interception in the Pop Ivan spruce forest (28%
of precipitation in 2008, Table 1) were after short term measurements
of water fluxes in open field and throughfall uncertain.
The fluxof S through thesoil profile at Javornik wassimilar to current
deposition (Table 2), and at 90 cm was calculated as 9.8 kg ha−1
year−1
.
Similar concentrations of soil water SO4 were measured at Pop Ivan
(Table 3). The SO4 concentrations at Javornik and Pop Ivan (Table 3)
were markedly lower compared to Načetín (Oulehle et al., 2006), where
soil water SO4 concentration in 90 cm depth were 22 mg L−1
in spruce
forest and 12 mg L−1
in beech forest. Nevertheless, high export of S at
the 90 cm depth was caused by the high water flux calculated by the Cl
balance model. Nitrogen flux (based mainly or only on the N–NO3
concentration under the forest floor/mineral soil) was highest under the
forest floor at Javornik (37 kg ha−1
year−1
), likely as a result of high
mineralization and nitrification rates in the old beech forest. Even at
90 cm the N flux was estimated to be 17 kg ha−1
year−1
, which is more
than current deposition (Tables 2 and 3). On the other hand, Hedin et al.
(1995) showed that nitrogen loss in unpolluted old growth forests is
driven primarily by dissolved organic nitrogen, rather than inorganic
forms. The high leaching of N–NO3 could be attributable to the low soil
Table 3
Soil water concentrations (upper panel) and fluxes (lower panel) at different soil profile depths (forest floor, 30 and 90 cm) at Javornik and Pop Ivan.
2008 pH Alkalinity Na K Ca Mg SiO2 Al NH4
+
NO3
−
SO4
2−
Cl−
Bc/Al
ueq L−1
mg L− 1
mol/mol
Javornik Forest floor 4.82 36.5 0.20 5.56 6.10 0.84 2.42 0.43 0.63 20.20 3.18 0.58 20.7
30 cm 4.87 4.3 0.43 0.32 4.72 0.63 4.82 0.26 0.14 9.55 4.39 0.78 15.8
90 cm 5.62 41.7 0.78 0.49 5.31 0.99 5.23 0.05 0.18 12.80 5.39 0.77 105.7
Pop Ivan Forest floor 4.06 −93.0 0.22 1.40 1.18 0.43 3.68 0.46 0.57 4.67 3.82 0.63 4.8
30 cm 4.47 −26.3 0.41 0.11 0.35 0.34 3.81 0.79 0.03 1.80 3.69 0.37 0.9
90 cm 4.57 −20.5 0.48 0.15 0.65 0.44 4.90 0.64 0.02 3.07 4.18 0.23 1.6
2008 Water Na K Ca Mg SiO2 Al Cl S N
mm kg ha−1
year−1
Javornik Forest floor 726 1.5 40.4 44.3 6.1 17.6 3.1 4.2 7.7 36.7
30 cm 540 2.3 1.7 25.5 3.4 26.0 1.4 4.2 7.9 12.2
90 cm 547 4.3 2.7 29.1 5.4 28.6 0.3 4.2 9.8 16.6
Pop Ivan Forest floor 779 1.7 10.9 9.2 3.3 28.7 3.6 4.9 9.9 11.7
30 cm 1326 5.5 1.4 4.6 4.5 50.6 10.5 4.9 16.3 5.7
90 cm 2133 10.2 3.1 13.9 9.3 104.5 13.7 4.9 29.7 15.1
Forest floor layer included Ol, Of and Oh horizon.
Table 2
Soil chemistry (upper panel) and pools (lower panel) at Javornik and Pop Ivan.
Horizon pH(H2O) pH(KCl) Ca2+
Mg2+
K+
Aln+
TEA CEC BS C N C/N
mg kg−1
mmolc kg−1
%
Javornik Ol+Of 4.86 4.88 6860 718 1024 8.3 44 472 91 42 1.7 25
Oh 4.26 4.05 3260 258 302 68 26 218 87 17 0.8 21
0–10 3.98 3.84 574 62 115 401 62 99 37 5.4 0.4 14
10–20 4.11 3.98 276 30 62 419 59 77 22 3.1 0.2 13
20–40 4.31 4.13 275 25 43 377 50 67 24 2.1 0.2 13
40–85 4.61 4.31 323 36 36 262 39 60 30 1.1 0.1 16
Pop Ivan Ol+Of 3.71 2.74 1200 232 273 312 81 168 51 43 1.6 28
Oh 3.33 2.69 448 120 140 757 131 168 21 34 1.4 24
0–10 3.82 3.18 73 46 61 835 119 128 8 13 0.7 18
10–20 4.35 3.60 35 22 39 615 83 88 6 6.7 0.4 15
20–40 4.69 4.09 18 8.0 18 293 45 47 5 4.0 0.2 18
40–80 4.98 4.48 10 2.5 7.3 74 18 19 6 1.5 0.1 29
POOL Ca2+
Mg2+
K+
Aln+
C N C/N
kg ha−1
mass ratio
Javornik Forest floor + 2046 211 328 2015 126,744 9020 14
Pop Ivan Mineral soil 186 65 105 1220 212,164 10,569 20
TEA (Total Exchangeable Acidity), CEC (Cation Exchange Capacity), BS (Base Saturation).
862 F. Oulehle et al. / Science of the Total Environment 408 (2010) 856–864

9. Author's personal copy
C/N ratio (Dise et al., 1998; Gundersen et al., 1998). The weighted
average soil C/N ratio at Javornik was calculated to be 14 (22 at the forest
floor). This low C/N ratio could be partly due to high N deposition in the
past. Total deposition of N during the period 1860–2008 was estimated
to be 2080 kg ha−1
. On the basis of the nitrogen saturation typology
presented by Stoddard (1994), the Javornik site fits Stage 2, which is
characterized by distinct seasonality and high concentrations during the
growing season. This suggests nitrogen saturation of old growth
deciduous forests in the area.
Significantly lower concentrations of NO3 (3–4 times, Table 3) were
observed at Pop Ivan, despite the fact that leaching was also high
(Table 3). Total N deposition at Pop Ivan was estimated as 1190 kg ha−1
for the period 1860–2008. The non-linear nature of the relationship
between soil C/N and NO3 export makes it difficult to perform robust
predictions, as small (and difficult to detect) changes in soil C/N can
result in large NO3 increases once the threshold for accelerated NO3
leaching (a C/N of approximately 22–25) has been passed (Dise et al.,
1998; Gundersen et al., 1998).
The concentrations of base cations in the soil water reflected the soil
chemistry. High concentrations of Ca (ca. 4–7 times) and Mg (ca. 2 times)
were observed at Javornik compared to Pop Ivan (Table 3). Ca and Mg soil
water fluxes were estimated to be 29 and 5 kg ha−1
year−1
, at Javornik
and 14 kg ha−1
year−1
and 9 kg ha−1
year−1
at Pop Ivan at 90 cm. The
highest fluxes were observed under the forest floor at Javornik (Table 3).
Forest floor soil water concentrations of Ca and Mg were higher compared
to the mineral soil at Pop Ivan, but fluxes of Ca and Mg were highest in the
mineral soil at the 90 cm depth (Table 3). The highest concentrations and
fluxes of K were observed under the forest floor at both sites. Intensive
internal cycling of K between the forest canopy and the forest floor is clear
when comparing the throughfall flux to bulk deposition. Leaching of
aluminium was negligible at Javornik site at 90 cm because of the high soil
water pH (average pH=5.62) and positive alkalinity (Table 3). Lower soil
water pH and negative alkalinity was observed at Pop Ivan (average
pH=4.57), with consequently higher Al leaching (Table 3). Compared to
acidified sites in Central Europe (e.g. Načetín and Lysina, Fig. 1) with
mineral soil water Al concentrations of ca. 3 mg L−1
(Oulehle et al., 2006)
and stream water concentrations of 1 mg L−1
(Hruška et al., 2009; Krám
et al., 2009), Pop Ivan had significantly lower Al soil water concentrations
(Table 3). Relatively high past deposition of S together with acid sensitive
bedrock and high water fluxes depletes base cations from soils, resulting
in low base saturation at the Pop Ivan. High concentrations of total
aluminium, or low base cation to total aluminium ratios (Bc/Al, where
Bc=K+Ca+Mg), in the soil solution can cause physiological stress for
the spruce root system (Puhe and Ulrich, 2001). In particular, a Bc/Al ratio
below 1 has been proposed as a threshold value, below which there is risk
of significant damage of plants (Sverdrup and Warfvinge, 1993; Cronan
and Grigal, 1995). At Pop Ivan, a soil water Bc/Al of 0.9 was measured at
the 30 cm soil depth (Table 3) where a majority of roots are present,
suggesting that coniferous forests in the area are vulnerable to acidic
deposition due to the adverse effect of aluminium on roots.
4. Conclusions
Estimated emissions of SO2, NOx and NH3 were used to calculate S
and N deposition at primeval forest ecosystems in the Ukrainian
Transcarpathian Mts. between 1860 and 2008. The deciduous forest at
Javornik received an estimated total S deposition of 2095 kg ha−1
during the period 1860–2008. The current measured S bulk deposition
of 7.4 kg ha−1
year−1
is similar to that estimated for the 1st half of the
20th century. The old growth coniferous forest at Pop Ivan received an
estimated total S deposition of 2530 kg ha−1
during the period 1860–
2008. The current measured S bulk deposition of 8.8 kg ha−1
year−1
is
similar to that measured at the end of the 19th century. Total N
deposition was lower at Pop Ivan compared to Javornik, namely
because of significantly lower NO3 deposition. The estimated
cumulative N bulk deposition was 2080 and 1190 kg ha−1
between
1860 and 2008 at Javornik and Pop Ivan, respectively. High leaching of
N was observed at the Javornik site, suggesting N saturation of the old
growth forests in the area. The C/N ratio of the forest floor was 22 and
26 at Javornik and Pop Ivan, respectively. A relatively high base
saturation of the mineral soil (29%) and a high concentration of base
cations in the soil solution were observed at Javornik, where high
weathering of the flysch bedrock was likely responsible for mitigating
the adverse effects of acidic deposition. In contrast, a low soil base
saturation of 6.5% was measured at Pop Ivan. This depletion of base
cations was likely caused primarily by low weathering rates of the
bedrock, the high water flux and the relatively high past S deposition.
Despite relatively low Al concentrations in the soil water compared
with highly acidified sites in the Czech Republic, a low soil water Bc/Al
ratio (0.9) was found in the upper mineral soil. This suggests that the
spruce forest ecosystems in the area are vulnerable to anthropogenic
acidification and to the adverse effects of Al on forest root systems.
Acknowledgments
We thank David Hardekopf for proofreading. This study was
supported by Czech Science Foundation (project No. 526/07/1187)
and by the research plans of the Czech Geological Survey (MZP
0002579801) and The Silva Tarouca Research Institute for Landscape
and Ornamental Gardening (MSM 6293359101).
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