Anthropogenic acidification effects in primeval forests in the transcarpathian

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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 Republicb Department of Geology and Pedology, Mendel University of Agriculture and Forestry in Brno, Zemědělská 1, 613 00 Brno, Czech Republicc 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 2009Received in revised form 16 October 2009Accepted 20 October 2009Available online 14 November 2009

Keywords:Atmospheric depositionSulphurNitrogenSoil chemistrySoil waterNorway spruceEuropean beech

The precipitation chemistry, deposition, nutrient pools and composition of soils and soil water, as well as anestimate of historical deposition of sulphur (S) and inorganic nitrogen (N) for the period 1860–2008, weredetermined in primeval deciduous and coniferous forests at the sites Javornik and Pop Ivan, respectively.Measured S throughfall inputs of 10 kg ha−1year−1 in 2008 were similar to those estimated for the period1900–1950 at both sites. The highest estimated S inputs were in the 1980s. Measured bulk deposition of N in2008 was lower at Pop Ivan (5.6 kg ha−1year−1) compared to Javornik (12 kg ha−1year−1). Significantlylower NO3 deposition was both estimated and measured at Pop Ivan. Higher soil base cation concentrationswere observed at well-buffered Javornik underlain by flysch (Ca pool of 2046 kg ha−1 and base saturation of29%) 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). TheC concentration was positively correlated with organic N in the soil (pb0.001) at both sites, but the massaverage C/N ratio in the forest floor was lower at Javornik (22) than at Pop Ivan (26). High N leaching of17 kg ha−1year−1 at the 90 cm depth was measured in the soil water at Javornik, suggesting highmineralization and nitrification rates in old growth deciduous forests in the area. Despite relatively low Alconcentrations in the soil water, a low soil water Bc/Al ratio (0.9) (Bc=Ca+Mg+K) was found in the uppermineral soil at Pop Ivan. This suggests that the spruce forest ecosystems in the area are vulnerable toanthropogenic 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 highacidic deposition for more than a century as a result of the long-rangetransport 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), withadverse effects on both soil and surface water chemistry (Reuss andJohnson, 1986). International agreements under the United NationsEconomic Council for Europe (UN-ECE) Convention on Long-RangeTransboundary Air Pollution (LTRAP) to reduce emissions of S and Ncompounds (Bull et al., 2001) have resulted in a 60–70% reduction in Sand a 20% reduction in N deposition during the period 1980–2000(Skjelkvåle et al., 2001). These decreases have led to the partialrecovery of surface waters from acidification (Evans et al., 2001).

In the last fewdecades, the effects of acid deposition on forests havebeenwidely studied inmanymountain regions in Central Europe,withthe exception of the eastern part of the Carpathian Mts. laying mainlyin Ukraine and Romania (e.g. Fagerli and Aas, 2008). Transcarpathia isamong the most forested regions in Europe; however, there ispractically no data concerning the effects of acid deposition on forestsoil conditions in this area. On the other hand, comprehensivedescriptions of these forests (including phytocoenological, dendro-logical, dendrometrical and also pedological approaches)were alreadycarried out in the 1930s (Zlatník, 1934, 1935, 1938). In 1996, thesestudy plots were re-opened, and new field surveys were restored(Hrubý, 2001; Houška, 2007). In 2007, we started measurements ofdeposition, soil and soil solution chemistry in two of those plots withdifferent tree-species composition and bedrock. Moreover, weestimated the deposition of S and N compounds for the wholeindustrial period (1860–2008) and compared them to other areas inCentral Europe. We attempted to evaluate (1) whether present aciddeposition in this region is lower than in the rest of Central Europe as isassumed (de Vries et al., 1997; van Leeuwen et al., 1997), and (2)whether soil condition and soil solution chemistry differ from findingsobtained 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: [email protected] (F. Oulehle).

0048-9697/$ – see front matter © 2009 Elsevier B.V. All rights reserved.doi:10.1016/j.scitotenv.2009.10.059

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2. Materials and methods

2.1. Site description

The Javornik site represents a natural deciduous forest on theborder 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 areCambisols (Michéli et al., 2006) developed on well-buffered bedrock(flysch). The site is situated on a N-oriented slope, with mean annualtemperature of 5 °C and annual precipitation of 1.1 m. The Pop Ivansite is a natural coniferous forest situated on the border betweenUkraine and Romania at 1480 m a.s.l. (24°31′ E; 47°57′N) (Fig. 1). Theforest cover is dominated by Norway spruce (Picea abies (L.) Karsten).Soils are mostly Podzols in different stages of development as well asCambisols. The bedrock consists namely of acid sensitive crystallineschist and gneiss. The Pop Ivan site is situated on a steep slopeoriented to the W, with mean annual temperature of 2 ° C and annualprecipitation of 1.8 m. Both sites are probably among themost naturalforests of such extent in Central Europe, because direct humanimpacts 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 atPop 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 of122 cm2) which were replaced in winter by open plastic vessels (areaof 167 cm2) at Javornik. During the winter season (October–April),high snow depth and unapproachable trail conditions lead us to usehigh volume samplers (area of 990 cm2) for bulk and throughfall(area of 179 cm2) at Pop Ivan. At each site, the contents of throughfallsamplers 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 themineral soil (6 lysimeters in each depth at Javornik and 3 lysimeters ineach depth at Pop Ivan). Zero-tension lysimeters were installed underthe forest floor at both sites (6 and 3 replications). All lysimetersamples were collected monthly and combined to create one samplefrom each depth for each month.

Water pH was measured using a pH meter with a combinationelectrode (Radiometer model GK-2401C). Cl, SO4 and NO3 weremeasured by exchange ion chromatography. Ca, Mg, Na, K, Si and Alwere determined by flame atomic absorption spectrometry (FAAS),and NH4 by indophenol blue colorimetry. Alkalinity was measured bystrong acid (0.1 M HCl) titration with Gran plot analysis. Samplesprocessing and analysis were made in the Accredited TestingLaboratory 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 pitsusing the method described in Huntington et al. (1988). Thistechnique 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 and40–80 cm. The soil samples were weighed, and then sieved after air-drying (mesh size of 5 mm for organic horizons and 2 mm for mineralhorizons). Soil moisture was determined gravimetrically by drying at105 °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 MBaCl2 extracts with 0.1 M NaOH. Cation exchange capacity (CEC) wascalculated as the sum of exchangeable Ca, Mg, Na, K and TEA. Basesaturation (BS) was determined as the fraction of CEC associated withbase cations. Total carbon (C) and total nitrogen were determinedusing 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 weused a measurement of the chloride (Cl) mass budget. Chlorinecompounds tend to be highly soluble in water and mobile in soils, soatmospheric deposition and transport through terrestrial ecosystemsis rapid if there is active hydrologic flow. In addition, small-watershedstudies assume that weathering of Cl is negligible compared toatmospheric deposition (Juang and Johnson, 1967). The water fluxthrough different soil horizon was calculated as follows:

water flux ðxÞ ðmmÞ = Cl throughfall flux ðmgm−1ÞSoil Solution ðxCl concÞ ðmg L−1Þ

where: x is the water flux in the respective soil horizon and xCl is therespective soil horizon Cl concentration. Solute fluxes were calculatedby 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 andNOxwere taken from theYearbooks of the Czech Statistical Office and REZZO register (Registryof atmospheric pollution sources; www.chmi.cz) for the period 1980–2006. The CZ emissions were tightly correlated with total emissionsfrom 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 SO2were calculated on the basisof brown coal mining, which was the major source of SO2 emissions inthe 20th century (Kopáček and Veselý, 2005). Anthropogenic SO2

emissions in the period 1960–1994 were calculated using a linearregression model between coal mining and SO2 emission inventories(R2=0.89; pb0.001), and according to the linear regression modelbetween coal mining and SO2 emissions estimated by Mylona (1993)(R2=0.92; pb0.001) for the period 1860–1959 (Fig. 2A). Trends inSO2 emissions were used to estimate S deposition.

Energy production through fuel combustion has been the majorsource of NOx emissions in the Czech Republic and Slovakia. During thefirst half of the 20th century, burning of solid fuel (black and browncoal) was the main source of energy production (almost 90%). Sincethe 1960s the role of liquid and gaseous fuels have continuously

Fig. 1. Locations of the research sites Javornik and Pop Ivan (circles), the meteorologicalstations Chopok and Starina (squares) and research sites in the Czech Republic andSlovakia (triangles).

857F. Oulehle et al. / Science of the Total Environment 408 (2010) 856–864


increased, up to 40% in the 1990s (Kopáček and Veselý, 2005).However, Czech NOx emissions between 1980 and 2006 (REZZOinventory) were still tightly correlated with brown coal mining(R2=0.89; pb0.001). We used 3% of the anthropogenic NOx emissionin the 1980s as an estimation of the emission fromnatural sources (soilprocesses, burning of straw and stubble) (Pacyna et al., 1991) (Fig. 2B).

Historical Czech and Slovak emission trends for NH3were calculatedfor thewhole 1860–2006 period according to Asman et al. (1988), usinglivestock production data (cattle, pigs, sheep, goats, horses and poultry)and the production and consumption of nitrogenous fertilisers. Data onlivestock production and fertiliser usage were derived from Kopáčekand Veselý (2005) and recalculated for the Transcarpathian regionaccording to the status of livestock in the 1870–1904 period (Zlatník,1934) (Fig. 2C) to obtain more realistic estimations of emission sourcesin this agricultural area. These calculated emissions of NH3were used toestimate 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 ChopokStation, situated at 2008 m a.s.l. ~300 km west of Javornik (1978–2006 period, www.emep.int) and the Starina Station, situated at345 m a.s.l. ~30 km west of Javornik (1994–2006, www.emep.int)(Fig. 1); (2) bulk deposition and concentrations from Javornik and PopIvan (2007–2008); (3) throughfall deposition and concentrationsfrom Javornik and Pop Ivan (2007–2008).

The relationship used for the estimate of bulk SO4 concentrations atthe Starina Station from 1978 to 2006 was based on a linear regressionbetween the Chopok and Starina Stations for 1994–2006 (R2=0.70;pb0.001). The relationship used for the estimation of SO4 concentrationsat Starina for the entire 1860–2006 period was based on a linear

regression between the Starina SO4 bulk concentration and respective1978–2006 SO2 emissions (R2=0.85; pb0.001). The Starina bulk Sdeposition was calculated by multiplying the estimated SO4 concentra-tion by average precipitation amount (Fig. 3A). Because there was nosignificant 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 Sdeposition at Javornik and Pop Ivan (Fig. 6A). Total S deposition wascalculated using the dry deposition factor (DDF) obtained from through-fall to bulkdeposition at Javornik andPop Ivan in2008.At Javornik, a ratioof 1 was used prior to 1940, followed by a gradual increase to themeasured ratio of 1.4 between 1950 and 2006 (Fig. 3B). At Pop Ivan, aratio 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). TheDDFwas scaled accordingto anthropogenic SO2 emission temporal change. We assumed that DDFwas equalled 1 before ca. 1940 as a result of significantly lower coalburning (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 alinear regression between the Chopok and Starina Station for 1994–2006 (R2=0.51; pb0.01). The relationship used for the estimation ofNO3 concentrations at Starina for the entire 1860–2006 period wasbased on a linear regression between Starina NO3 bulk concentrationsand respective NO3 emissions (R2=0.60; pb0.001) (Fig. 4A). Nosignificant difference between measured monthly bulk concentrationof NO3 at Starina and Javornik was observed (Fig. 6B). Therefore,historical bulk N–NO3 concentration from Starina was used forJavornik deposition calculation. The throughfall flux was based onthe ratio of throughfall to bulk deposition at Javornik measured in2008. A DDF of 1 was applied for 1860–1940, increasing to 1.1 in 1950and then to 1.4 for the 1970–2008 period (Fig. 4B). Measuredmonthlybulk NO3 concentrations at Pop Ivan (2008) significantly differed fromthose 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


concentrations between Pop Ivan and Starina in 2008 (0.26), a N–NO3

deposition trend was calculated for the Pop Ivan site from 1860 to2008. The throughfall flux was calculated according to the ratiobetween throughfall to bulk deposition in 2008 (0.7). This ratio wasapplied for the whole period from 1860 to 2008 (Fig. 4C), because oflower flux in throughfall compared to bulk deposition.

For the estimation of N–NH4 bulk concentrations at the StarinaStation we used a linear regression between Starina (1994–2006) andthe respective NH3 emissions (R2=0.47; pb0.01) (Fig. 5A). Nosignificant difference was found between monthly N–NH4 bulkconcentrations at Starina and Javornik (Fig. 6C); therefore, bulk N–NH4 deposition at Javornik was estimated based on bulk chemistry atStarina (Fig. 5B). In contrast, bulk N–NH4 concentrations at Pop Ivansignificantly 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 ofN–NH4 deposition at Pop Ivan. Throughfall fluxes were calculatedfrom the ratio between throughfall to bulk deposition in 2008. Theratio of 0.8 was used for the Javornik site (1860–2008) and 1.2 for thePop Ivan site (1860–2008) (Fig. 5C).

Estimation of S–SO4, N–NO3 and N–NH4 bulk deposition atJavornik and Pop Ivan were based on precipitation chemistry in theStarina Station. Uncertainty associated with the deposition estimateswas calculated as a difference between mean concentrations of therespective solutes at Starina Station, Javornik and Pop Ivan. For SO4

the uncertainty was estimated less than 30% and for NO3 and NH4 lessthan 10% according to available data.

3. Results and discussion

3.1. Sulphur

3.1.1. Trends in emissions and deposition rates of sulphurThe 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 afterWorldWarII as a result of industrial development. The highest SO2 emissions inthe 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).



mid 1980s caused by industrial declines and desulphurization ofpower plants in the 1990s. Recent CZ emissions of SO2 are similar tothose 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, agreeswell with the measured data (pb0.001; Fig. 3A). Deposition trends ofbulk S at Javornik and Pop Ivan, which were estimated from theStarina bulk S deposition trend, peaked in the early 1980s with 25 and33 kg ha−1year−1, respectively (Fig. 3B,C). Throughfall depositionwas estimated as 35 and 40 kg ha−1year−1 in the 1980s. In 2008,measured bulk S deposition was 7.4 kg ha−1year−1 at Javornik and8.8 kg ha−1year−1 at Pop Ivan, while throughfall deposition of S was10.5 at Javornik and 10.6 kg ha−1year−1 at Pop Ivan (Fig. 3B,C). Thebulk and throughfall deposition of S at Javornik was higher than thatmeasured in a beech forest in the Czech Republic (Table 1) eventhough the Transcarpathian Mts. have frequently been reported asbeing a less polluted area. For example, at the formerly highly pollutedNačetín site in the Krušné hory (50 kg ha−1year−1 of total S depositionin 1994–1996, NW Czech Republic, Fig. 1) only 5.4 kg ha−1year−1 in

bulk and 7.6 kg ha−1year−1 in throughfall was measured in 2008(Table 1). Bulk deposition of S at Pop Ivan is similar to that in the HighTatra Mts., Slovakia (Kopáček et al., 2004) but again higher than bulkdeposition in the Czech Republic (Table 1). Throughfall S depositionunder the spruce canopy at Pop Ivan is slightly higher than at the Czechsites (Table 1). The reason explaining the higher deposition at sites inUkrainewas higher precipitation amounts there, particularly at Pop Ivan,compared to Czech sites (Table 1). Cumulative S deposition between1860 and 2008 was estimated as 1700 kg ha−1 and 2250 kg ha−1 forbulk deposition, and 2095 kg ha−1 and 2530 kg ha−1 for throughfalldeposition, at Javornik and Pop Ivan, respectively.

3.2. Nitrogen

3.2.1. Trends in emission and deposition rates of oxidised nitrogenSolid fuel and wood combustion in the Czech Republic and Slovakia

were the main sources of NOx emissions until 1950s and solid fuelcombustion 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 bulkprecipitation at Starina Station (2005–2006), Javornik (2007–2008) and Pop Ivan(2007–2008). Different letters indicated statistically different chemistry (One-WayANOVA, pb0.05).



1990s (Kopáček and Veselý, 2005). The highest emissions wereestimated for the 1980s (Fig. 2B). Recent emissions are similar to thosein the 1960s, with decreases since 1980s primarily due to theoptimization of combustion in power plants (Kopáček andVeselý, 2005).

The estimated trendofN–NO3bulk deposition at Starinawas based onNOx emissions and corresponds with the measured deposition (Fig. 4A).Bulk deposition of N–NO3 at Javornik increased sharply between the1960s and 1970s, and reached their maximum of 8 kg ha−1year−1 inthe 1980s. Significantly lower bulk deposition was estimated for PopIvan, with a maximum of 2.8 kg ha−1year−1 in the 1980s (Fig. 4B,C).The throughfall flux of N–NO3 was estimated to be higher than bulkdeposition at Javornik and lower at Pop Ivan (Fig. 4B,C). The measuredN–NO3 bulk deposition and throughfall flux in 2008 was 4.9 and7.4 kg ha−1year−1 and 1.9 and 1.4 kg ha−1year−1 at Javornik and PopIvan, respectively (Table 1). Low NO3 throughfall concentrations at PopIvan, mostly under detection limit of 0.05 mg L−1, were measuredduring the summer season. Thus lower N–NO3 throughfall flux than bulkdeposition at Pop Ivan could be explained by nitrate consumption andthe production of organic N in the canopy (Lovett and Lindberg, 1993).Measured N–NO3 bulk deposition at Javornik was similar to thatmeasured in the Czech Republic and higher than in the High Tatra Mts.,Slovakia (Table 1). On the other hand, bulk deposition of N–NO3 wasmarkedly lower at Pop Ivan compared to that in the Czech Republic andSlovakia (Table 1). This could be due to the long distance from largestationary 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 depositionand 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 nitrogenIn contrast to NOx and SO2, NH3 emissions are mostly derived from

agricultural production. Estimated emissions in the Transcarpathianarea (Fig. 2D) were about 30% lower than reconstructed emissions forthe Czech Republic and Slovakia (Kopáček and Veselý, 2005). Theemission rate was relatively high from 1860 to 1950 and increased by50% up to the 1980s. Recent emissions of NH3 are comparable to thoseestimated for the period 1860–1950. The NH3 emissions havedecreased since the 1980s primarily due to a 55% reduction in cattleproduction and the fertilisation of farmland in the Czech Republic andSlovakia (Kopáček and Veselý, 2005). We suppose that a similarsituation has also occurred in the western Ukraine, where there havebeen declines in planned agriculture since the late 1980s.

The estimated trend of N–NH4 bulk deposition at Starina corre-spondedwith measured data (Fig. 5A), and provided a reasonable basisfor the estimate of N–NH4 bulk deposition trends at Javornik and PopIvan. At both sites, stableN–NH4depositionwasestimated for theperiod1860–1950, with averages of 8 and 5 kg ha−1year−1, followed byestimated increases to 22 and 15 kg ha−1year−1 in the 1980s anddecreases by30%during the1990s (Fig. 5B,C). Themeasured throughfallflux in 2008 (5.8 kg ha−1year−1 at the Javornik and 4.6 kg ha−1year−1

at the Pop Ivan, Table 1) was lower than bulk deposition at Javornik andhigher than at Pop Ivan. Recent deposition is equal to the reconstructeddeposition between 1860 and 1950. Measured bulk deposition atJavornik (7.2 kg ha−1year−1) is similar to that measured in the CzechRepublic, while bulk deposition at Pop Ivan (3.7 kg ha−1year−1) issimilar to that in theTatraMts. (Table 1). From1860 to2008, cumulativeN–NH4 depositionwas estimated to be 1520 and 1000 kg ha−1 for bulkdeposition and 1220 and 1200 kg ha−1 for throughfall flux at Javornikand 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 mostlyEntic and Haplic Podzols with dry fine soil comprising 75% of theuppermost mineral profile (0–20 cm) and comprising 35% at the 40–80 cm depth. Concentrations of exchangeable base cations were thehighest in the organic soil layers at both sites, but ca. 4–6 times higherat Javornik compared to Pop Ivan (Table 2). This difference was alsomanifested in base saturation— 87–91% and 21–51% in the forest floorlayer (Ol+Of and Oh) at Javornik and Pop Ivan, respectively (Table 2).In the mineral soil, concentrations of exchangeable cations mainlyreflected the bedrock composition (Table 2; Houška, 2007), and basecation concentrations were almost an order of magnitude higher forCa and 2–3 times higher for Mg at Javornik. Such difference in basecation 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, pHdifferences were not so pronounced, and in the deepest horizons soilpH was higher at Pop Ivan (Table 2). This was the result of theextremely low CEC at Pop Ivan (19 mmol+kg−1) in these deepesthorizons. 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) weresignificantly higher at Javornik, similar to the proportions of exchange-able base cation concentrations (Table 2). Concentrations of C and Nwere highest in the organic layers and in the top of the mineral soilprofile. 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/Nmass ratio was between 21 and 25 at Javornik and24 and 28 at Pop Ivan in the Ol+Of and Oh horizons. The C/N ratio waslower 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 ofacidification with respect to high concentration of TEA (Table 2), mostprobably due to the high base cation weathering rate from the flyschbedrock. Compared to theČervík catchment (BeskydyMts., Fig. 1) in theeastern Czech Republic (Fottová, unpublished data), also underlain byflysch but receiving an approximately two times higher deposition of S,

Table 1Measured 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–SO42– Cl–

ueq L−1 kg ha−1year−1

Javornik Bulk 1340 4.86 −6 2.3 0.7 2.2 5.3 7.2 4.9 7.4 3.1THFbeech 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 3.3THFspruce 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 5.9THFspruce 644 4.38 −36 6.3 1.9 13.5 7.6 6.7 7.3 10.2 12.0THFbeech 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 3.1THFspruce 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



base saturation at Javornik is ca. 2 times higher through the whole soilprofile. On the other hand, Houška (2007) confirmed positive influenceof acidic deposition on loss of neutralizing capacity by significantlowering of soil pH in the period 1935–1998 (average pHKCl droppedfrom 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 ofacidification, and is quite similar to the Czech sites underlain bysimilar igneous acidic bedrocks. For example, the Lysina catchment inthe western Czech Republic (Fig. 1) with granite bedrock has mineralsoil base saturation between 4–7% (Hruška et al., 2002). The forestplot Načetín in the Krušné hory (underlain by gneiss) also only hasmineral soil base saturation between 5 and 8% (Oulehle et al., 2006).Nevertheless, the high average precipitation (1.8 m) and lowtemperature could be natural factors accelerating soil depletion atPop Ivan, and the role of anthropogenic acidification requires futurestudy (e.g. by biogeochemical models).

3.4. Soil water chemistry and element fluxes

Water fluxes in the soil profile at Javornik decreased with depth asa result of forest transpiration in the topsoil where the majority ofroots are present. In contrast, at Pop Ivan the water flux (calculated

using the Cl balance) increased with depth, probably as a result oflateral water movement on the steep slope (Table 3). The reasons ofthe relatively high interception in the Pop Ivan spruce forest (28%of precipitation in 2008, Table 1) were after short termmeasurementsof water fluxes in open field and throughfall uncertain.

Thefluxof S through the soil profile at Javornikwas similar to currentdeposition (Table 2), and at 90 cmwas calculated as9.8 kg ha−1year−1.Similar concentrations of soil water SO4 were measured at Pop Ivan(Table 3). The SO4 concentrations at Javornik and Pop Ivan (Table 3)weremarkedly lower compared toNačetín (Oulehle et al., 2006), wheresoil water SO4 concentration in 90 cm depth were 22 mg L−1 in spruceforest and 12mg L−1 in beech forest. Nevertheless, high export of S atthe 90 cm depth was caused by the high water flux calculated by the Clbalance model. Nitrogen flux (based mainly or only on the N–NO3

concentration under the forestfloor/mineral soil)washighest under theforest floor at Javornik (37 kg ha−1year−1), likely as a result of highmineralization and nitrification rates in the old beech forest. Even at90 cm the N fluxwas estimated to be 17 kg ha−1year−1, which ismorethan current deposition (Tables 2 and 3). On the other hand, Hedin et al.(1995) showed that nitrogen loss in unpolluted old growth forests isdriven primarily by dissolved organic nitrogen, rather than inorganicforms. The high leaching of N–NO3 could be attributable to the low soil

Table 3Soil 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

− SO42− 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 20.730 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 15.890 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 4.830 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 0.990 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−1year−1

Javornik Forest floor 726 1.5 40.4 44.3 6.1 17.6 3.1 4.2 7.7 36.730 cm 540 2.3 1.7 25.5 3.4 26.0 1.4 4.2 7.9 12.290 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 11.730 cm 1326 5.5 1.4 4.6 4.5 50.6 10.5 4.9 16.3 5.790 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 2Soil 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 25Oh 4.26 4.05 3260 258 302 68 26 218 87 17 0.8 210–10 3.98 3.84 574 62 115 401 62 99 37 5.4 0.4 1410–20 4.11 3.98 276 30 62 419 59 77 22 3.1 0.2 1320–40 4.31 4.13 275 25 43 377 50 67 24 2.1 0.2 1340–85 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 28Oh 3.33 2.69 448 120 140 757 131 168 21 34 1.4 240–10 3.82 3.18 73 46 61 835 119 128 8 13 0.7 1810–20 4.35 3.60 35 22 39 615 83 88 6 6.7 0.4 1520–40 4.69 4.09 18 8.0 18 293 45 47 5 4.0 0.2 1840–80 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 14Pop Ivan Mineral soil 186 65 105 1220 212,164 10,569 20

TEA (Total Exchangeable Acidity), CEC (Cation Exchange Capacity), BS (Base Saturation).



C/N ratio (Dise et al., 1998; Gundersen et al., 1998). The weightedaverage soil C/N ratio at Javornikwas calculated to be 14 (22 at the forestfloor). This low C/N ratio could be partly due to high N deposition in thepast. Total deposition of N during the period 1860–2008 was estimatedto be 2080 kg ha−1. On the basis of the nitrogen saturation typologypresented by Stoddard (1994), the Javornik site fits Stage 2, which ischaracterized by distinct seasonality andhigh concentrations during thegrowing season. This suggests nitrogen saturation of old growthdeciduous forests in the area.

Significantly lower concentrations of NO3 (3–4 times, Table 3) wereobserved at Pop Ivan, despite the fact that leaching was also high(Table 3). Total N deposition at Pop Ivanwas estimated as 1190 kg ha−1

for the period 1860–2008. The non-linear nature of the relationshipbetween soil C/N and NO3 export makes it difficult to perform robustpredictions, as small (and difficult to detect) changes in soil C/N canresult 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 soilchemistry. High concentrations of Ca (ca. 4–7 times) andMg (ca. 2 times)were observed at Javornik compared to Pop Ivan (Table 3). Ca andMg soilwater fluxes were estimated to be 29 and 5 kg ha−1year−1, at Javornikand 14 kg ha−1year−1 and 9 kg ha−1year−1 at Pop Ivan at 90 cm. Thehighest fluxes were observed under the forest floor at Javornik (Table 3).Forestfloor soilwater concentrations of Ca andMgwere higher comparedto themineral soil at Pop Ivan, butfluxes of Ca andMgwere highest in themineral soil at the 90 cm depth (Table 3). The highest concentrations andfluxes of K were observed under the forest floor at both sites. Intensiveinternal cycling of K between the forest canopy and the forestfloor is clearwhen comparing the throughfall flux to bulk deposition. Leaching ofaluminiumwasnegligible at Javornik site at 90 cmbecause of thehigh soilwater pH (average pH=5.62) and positive alkalinity (Table 3). Lower soilwater pH and negative alkalinity was observed at Pop Ivan (averagepH=4.57), with consequently higher Al leaching (Table 3). Compared toacidified sites in Central Europe (e.g. Načetín and Lysina, Fig. 1) withmineral soil water Al concentrations of ca. 3 mg L−1 (Oulehle et al., 2006)and streamwater concentrations of 1 mg L−1 (Hruška et al., 2009; Krámet al., 2009), Pop Ivan had significantly lower Al soil water concentrations(Table 3). Relatively high past deposition of S together with acid sensitivebedrock and high water fluxes depletes base cations from soils, resultingin low base saturation at the Pop Ivan. High concentrations of totalaluminium, or low base cation to total aluminium ratios (Bc/Al, whereBc=K+Ca+Mg), in the soil solution can cause physiological stress forthe spruce root system (Puhe andUlrich, 2001). In particular, a Bc/Al ratiobelow1has been proposed as a threshold value, belowwhich there is riskof significant damage of plants (Sverdrup and Warfvinge, 1993; Cronanand Grigal, 1995). At Pop Ivan, a soil water Bc/Al of 0.9 was measured atthe 30 cm soil depth (Table 3) where a majority of roots are present,suggesting that coniferous forests in the area are vulnerable to acidicdeposition due to the adverse effect of aluminium on roots.

4. Conclusions

Estimated emissions of SO2, NOx and NH3 were used to calculate Sand N deposition at primeval forest ecosystems in the UkrainianTranscarpathianMts. between 1860 and 2008. The deciduous forest atJavornik received an estimated total S deposition of 2095 kg ha−1

during the period 1860–2008. The currentmeasured S bulk depositionof 7.4 kg ha−1year−1 is similar to that estimated for the 1st half of the20th century. The old growth coniferous forest at Pop Ivan received anestimated total S deposition of 2530 kg ha−1 during the period 1860–2008. The currentmeasured S bulk deposition of 8.8 kg ha−1year−1 issimilar to that measured at the end of the 19th century. Total Ndeposition was lower at Pop Ivan compared to Javornik, namelybecause of significantly lower NO3 deposition. The estimatedcumulative N bulk deposition was 2080 and 1190 kg ha−1 between

1860 and 2008 at Javornik and Pop Ivan, respectively. High leaching ofN was observed at the Javornik site, suggesting N saturation of the oldgrowth forests in the area. The C/N ratio of the forest floor was 22 and26 at Javornik and Pop Ivan, respectively. A relatively high basesaturation of the mineral soil (29%) and a high concentration of basecations in the soil solution were observed at Javornik, where highweathering of the flysch bedrock was likely responsible for mitigatingthe adverse effects of acidic deposition. In contrast, a low soil basesaturation of 6.5% was measured at Pop Ivan. This depletion of basecations was likely caused primarily by low weathering rates of thebedrock, the high water flux and the relatively high past S deposition.Despite relatively low Al concentrations in the soil water comparedwith highly acidified sites in the Czech Republic, a low soil water Bc/Alratio (0.9) was found in the upper mineral soil. This suggests that thespruce forest ecosystems in the area are vulnerable to anthropogenicacidification and to the adverse effects of Al on forest root systems.

Acknowledgments

We thank David Hardekopf for proofreading. This study wassupported by Czech Science Foundation (project No. 526/07/1187)and by the research plans of the Czech Geological Survey (MZP0002579801) and The Silva Tarouca Research Institute for Landscapeand Ornamental Gardening (MSM 6293359101).

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Data & Analytics

Anthropogenic acidification effects in primeval forests in the transcarpathian