The Distribution of Sequentially Extracted Cu, Pb, and Zn Fractions in Podzol Profiles Under Dwarf Pine of Different Stages of D

J Soils Sediments DOI 10.1007/s11368-017-1715-3

RECLAMATION AND MANAGEMENT OF POLLUTED SOILS: OPTIONS AND CASE STUDIES

The distribution of sequentially extracted Cu, Pb, and Zn fractions in Podzol profiles under dwarf pine of different stages of degradation in subalpine zone of Karkonosze Mts (central Europe)

Jerzy Weber1 & Agnieszka Dradrach2 & Anna Karczewska 1 & Andrzej Kocowicz1

Received: 31 January 2017 /Accepted: 14 April 2017 # The Author(s) 2017. This article is an open access publication

Abstract The Pb concentrations in the surface organic horizons were Purpose Here, we aimed to assess the contamination of clearly higher than those in similar horizons of European low- Podzol soils in a subalpine zone of the Karkonosze land forest soils. This distribution of Pb in the mineral hori- Mountains. Cu, Pb, and Zn concentrations in the soil and the zons was apparently associated with soil colloid distribution patterns of their speciation are discussed in relation to the that developed in the process of podzolization, indicating the possible influence of airborne industrial emissions and the minimum concentrations in eluvial E horizons and enhanced stage of degradation of dwarf mountain pine stands. concentrations in illuvial Bh horizons. The organically bound Materials and methods The study was conducted in the fraction made up about 40% of total Pb in the Bh horizons. Zn Karkonosze, a mountain range in the Sudetes, on the bound- concentrations were highest in the deepest parts of the soil, ary between Poland and the Czech Republic. We examined where the predominant fraction was residual, while relatively Podzols derived from granites under dwarf mountain pine high amounts of easily mobilizable Zn were present in stands at two stages of degradation (without visible degrada- ectohumus. tion vs. dead). These two sites were 100 m apart, at an altitude Conclusions Very high concentrations of Pb in ectohumus of 1400 m above sea level (upper mountain forest zone). Soil have most likely been caused by a long-distance transport of samples were collected from all distinguished soil horizons anthropogenic emissions. The concentrations of Pb or other and their basic soil properties and heavy metal (Cu, Pb, and metals found in soils cannot be considered to have been the Zn) concentrations (and their speciation) determined by se- principal causes of the ecological disaster observed in the quential extraction according to the method of Zeien and Karkonosze Mountains. The highest concentrations of Pb in Brümmer. ectohumus, as well as its high contributions in the organically Results and discussion The Cu concentrations in these soils bound fraction, confirm a crucial role of organic matter in Pb were relatively low, typical for soils derived from granite and accumulation in soils. did not differ considerably within soil profiles. The residual Cu fraction was a predominant one in all mineral horizons. Keywords Heavy metal . Soil . Podzol . Pollution . Sequential extraction . Speciation Responsible editor: Claudio Bini

* Jerzy Weber 1 Introduction [email protected] The Karkonosze, a mountain range in the Sudetes (central Europe), was subject to widespread deterioration of forest com- 1 Institute of Soil Science and Environmental Protection, Wroclaw University of Environmental and Life Sciences, Grunwaldzka 53, plexes during the last decades of the twentieth century. The 50-357 Wroclaw, Poland stands of spruce (Picea abies (L) H. Karst) and, to a lesser 2 Department of Agroecosystems and Green Areas Management, extent, of mountain dwarf pine (Pinus mugo Turra) were main- Wroclaw University of Environmental and Life Sciences, pl. ly affected. Forests in the Sudety Mountains were referred to as Grunwaldzki 24A, 53-363 Wrocław, Poland in a state of total disaster and reported as strongly damaged J Soils Sediments

Fig. 1 Location of the investigated site on the map of Europe

(Mazurski 1986;Grodzińska and Szarek-Łukaszewska 1997; and SO2 emissions, remain of considerable importance. Fabiszewski and Wojtuń 2000; Godek et al. 2008). Such effects Therefore, the effects of potentially toxic concentrations of were caused by complex interactions of multiple factors, in- metals, and particularly their mobile forms, on mountain habi- cluding (1) adverse climatic, geological, and soil conditions; tats need close examination. (2) the intensity of anthropogenic impact; (3) the level of air The total concentrations of trace metals in soils are primar- pollution from industrial emissions; and (4) the occurrence of ily determined by soil parent rocks and anthropogenic inputs insect pests and parasitic fungi (Sobik and Błaś 2008). Air (Fernandez et al. 2000;Kabata-Pendias2011;Alloway2013). pollution caused by local emissions in the Sudetes, together The fate of airborne metals in soils and their distribution in the with a long-distance atmospheric transport of dust and gases, soil profile are conditioned by soil properties and usually re- in particular SO2, from various industrial- and transport-related flect the course of soil formation (Abollino et al. 2002a; sources, was considered the most degrading factors (Bochenek Kabata-Pendias 2011;Alloway2013; Wang and Xu 2015). et al. 1997;Doreetal.1999;Błaś and Sobik 2000;Donisaetal. The latter are usually particularly well recorded in Podzols. 2000;StachurskiandZimka2002; Bytnerowicz et al. 2004, Consequently, the distribution of trace metals in soil profiles,

2008;Małek and Astel 2008). Direct impacts of SO2 deposition together with data on their speciation in the soil solid phase, on tree needles contributed to their deterioration, while soil provides valuable information on the origin of metals, as well acidification, together with other stressors, affected the growth as on the factors and mechanisms responsible for their of roots (Ulrich 1986; Markert et al. 1996;Lorenzetal.2008). increased mobility and related bioavailability. Speciation of Several studies reported increased concentrations of some trace elements in soils was defined by Tack and Verloo heavy metals in soils of the Karkonosze (Borkowski et al. (1995) as the identification and quantification of the different, 1993; Drozd et al. 1996;Szopkaetal.2013) and supposed that defined species, forms, or phases in which an element occurs. heavy metals should be considered as highly disadvantageous Although several advanced methods have been recently components of pollution that affect biota, including plants, and developed to investigate the behavior of metals in soils, in- destroy natural ecosystems (Salemaa et al. 2001;Gualaetal. cluding micromorphological and isotopic studies (D’Amore 2010;Chaietal.2014). Environmental pollution with heavy et al. 2005;Bińczycki et al. 2014), chemical extraction metals was therefore suggested to be an important factor of methods are still commonly used. Numerous procedures of forest degradation in the Karkonosze. It should be stressed that chemical extraction have been tested to provide information although a large-scale dieback of coniferous forests has already on the actual and potential solubility of metals in soils in been overcome, this problem continues to arise in various loca- various environmental conditions. Consequently, hundreds tions, indicating that several other factors, other than acid rains of operationally defined sequential extraction methods have J Soils Sediments

Fig. 2 Area I. Mountain dwarf pine (Pinus mugo Turra) stand without signs of degradation

been described that recognize the main soil components that correspond with the following species of metals: (1) mobile, bind metals in soils (Tessier et al. 1979; Zeien and Bruemmer (2) exchangeable and specifically bound, (3) bound to man- 1989;TackandVerloo1995; Gleyzes et al. 2002; Pueyo et al. ganese oxides, (4) organically bound, (5) occluded in amor-

2003; Rao et al. 2008; Hass and Fine 2010). To quantify the phous FeOx, (6) occluded in crystalline FeOx,and(7)residual. contributions of particular fractions, chemical solutions of Mobile and exchangeable fractions of metals are considered as varying strength and reactivity are applied to soils in order easily bioavailable and leachable, whereas metals associated to release metals bound to different soil components. A com- with organic matter, as well as those occluded in MnOx and monly used, relatively simple BCR method, developed by the FeOx, might be released from soils under changing conditions Community Bureau of Reference (Ure et al. 1993;Mossop and, thus, indicate medium- to long-term availability. The re- and Davidson 2003) determines four fractions of metals (acid sidual fraction is considered entirely non-available and immo- soluble, reducible, oxidizable, and residual). A method by bile, as it is confined to silicates that remain stable over time. Zeien and Bruemmer (1989, 1991), which is more laborious, Here, we aimed to assess the contamination of Podzols in a provides greater insight into the mechanisms of metal binding subalpine zone of the Karkonosze Mountains. The Cu, Pb, in soils and, therefore, has been widely applied to both non- and Zn concentrations in these soils and their speciation are polluted and variously polluted soils (Karczewska 1996; discussed in relation to the possible influence of industrial Wenzel and Jockwer 1999;KabałaandSzerszeń 2002; emissions and the stage of degradation of dwarf mountain Marschner et al. 2006; Rao et al. 2008;Kabalaetal.2011). pine stands. Speciation of metals in soil profiles was The Zeien and Brümmer method involves the determination examined by sequential extraction according to Zeien and of seven operationally defined fractions, believed to Bruemmer (1991) to indicate the most likely sources of the

Fig. 3 Area II. Strongly degraded mountain dwarf pine (Pinus mugo Turra) stand J Soils Sediments

Table 1 Procedure of sequential extraction according to Zeien and Fraction Description Extracting agent pH Reaction time and Bruemmer (1989) temperature

F1 Mobile 1 M NH4NO3 Not 24 h, temp 20 °C buffered F2 Exchangeable 1 M NH4-acetate 6.0 24 h, temp 20 °C

F3 Easily reducible/bound to 1MNH2OH-HCl and 1 M 6.0 30 min, temp MnOx NH4-acetate 20 °C

F4 Oxidizable/organically 0.025 M NH4EDTA 4.6 90 min, temp bound 20 °C

F5 Reducible/amorphous 0.2 M NH4-oxalate (in dark) 3.25 4 h, temp 20 °C FeOx bound F6 Reducible/crystalline 0.1 M ascorbic acid and 0.2 M 3.25 30 min, temp FeOx bound NH4-oxalate 96 °C

F7 Residual Aqua regia (3HCl + HNO3) ––

metals, to assess the environmental risk associated with their forest zone). The climatic conditions of the investigated area presence, and to predict potential changes in their mobility are characterized by a very high precipitation (1430 mm/year) under changing environmental conditions. and low mean annual temperature +1.5 °C (Głowicki 2005). Two sites were selected for investigation that differed in the deterioration stage of dwarf pine stands: area I had no signs of 2 Materials and methods degradation (Fig. 2), whereas area II was affected by dwarf mountain pine dieback. A thicket of dead dwarf pine The study was conducted in the Karkonosze Mountains, a branches and trunks remained there, without any living range of the Sudetes, located on the boundary between shrubs, and the area was entirely colonized by herbaceous Poland and Czech Republic (Fig. 1). The profiles of soils plants typical for mountain meadow, dominated by a derived from granites in the zone occupied by dwarf mountain Festuca ovina L. grass that covered the soil surface under- pine (P. mugo Turra) were examined. The parent rock is typ- neath dead dwarf pine branches (Fig. 3). Areas I and II were ical biotite granite (Weber et al. 2012) and contains the fol- 100 m apart. Within each of those two areas, two soil profiles lowing amounts of analyzed heavy metals: Cu 11– were analyzed: profiles I/1 and I/2 in the stand with dwarf 22 mg kg−1, Pb 0.1–0.3 mg kg−1, and Zn 32–65 mg kg−1 pine in good condition and profiles II/1 and II/2 in the area (Tyszka et al. 2012). The sites were located at an altitude of with dead dwarf mountain pines. 1400 m above sea level (corresponding to upper mountain Soil samples were collected from all of the horizons distinguished in soil profiles. The samples were air-dried, ground, and passed through a stainless steel 2-mm sieve. The basic soil properties were determined. Particle size distribution was analyzed in mineral samples by the sieve and hydrometric method (Pansu and Gautheyrou 2006), following the pretreatment that involved removal of organic matter and chemical dispersion with sodium hexametaphosphate. The content of organic carbon (Corg) was determined using a CS-MAT 5500 analyzer (Ströhlein GmbH & Co., Kaarst, Germany, currently Bruker AXS Inc., Madison, WI, USA). Soil pH was measured potentiometrically in a 1:2.5 sus- pension of soil and 1 M KCl; soil acidity (Hh) was determined in 1 mol dm−3 KCl (Kappen 1929), and exchangeable base (EB) −3 cationswereextractedby1moldm NH4Ac and measured by atomic emission spectroscopy (AES) (K+,Na+,andCa2+)and atomic absorption spectroscopy (AAS) (Mg2+). Effective cation exchange capacity (CEC) and base saturation (BS) were calcu- lated on the basis of the acidity (Hh) and exchangeable base cations. For analysis of total Cu, Pb, and Zn concentrations in Fig. 4 Profile of Podzol derived under mountain dwarf pine stand (object the mineral soil horizons, the samples were wet digested in con- I/2) centrated perchloric acid, in an open system with reflux, while J Soils Sediments

Table 2 Basic properties of the tested soils

Pro-file Soil horizons pH C N C/N Hh EB CEC BS No. (g kg−1) (g kg−1) (cmol(+) kg−1) (cmol(+) kg−1) (cmol(+) kg−1) (%) Symbols Depth Color (cm)

I/1 Oi 0–3 7.5YR 5/2 2.4 361 15.1 23.9 14.5 4.8 19.3 24.8 Oe 3–13 7.5YR 5/0 2.0 333 17.1 19.5 22.1 3.3 25.4 13.0 Oa 13–15 7.5YR 4/0 2.3 275 14.0 19.6 23.8 2.5 26.3 9.6 E15–33 7.5YR 7/0 2.4 17 1.0 16.6 4.0 1.3 5.3 25.0 Bh 33–35 7.5YR 3/0 2.6 46 2.2 20.8 8.6 1.1 9.7 11.4 Bs 35–45 7.5YR 4/4 2.9 26 1.0 25.9 15.8 0.9 16.8 5.4 C >45 7.5YR 5/6 3.0 19 0.9 20.6 7.5 1.1 8.5 12.5 II/2 Oi 0–4 7.5YR 5/2 2.9 374 18.2 20.5 7.5 5.9 13.4 44.0 Oe 4–9 7.5YR 5/0 2.2 343 12.8 26.9 21.0 3.8 24.8 15.2 Oa 9–12 7.5YR 4/0 2.4 166 10.4 15.9 15.4 2.6 18.0 14.4 E12–16 7.5YR 7/0 2.3 22 2.2 9.7 3.9 1.5 5.3 27.5 Bh 16–36 7.5YR 3/0 2.7 33 2.2 15.2 9.4 1.3 10.7 12.5 Bs 36–42 7.5YR 4/4 3.0 48 2.1 23.0 9.7 1.1 10.7 10.1 C >42 7.5YR 5/6 3.4 11 0.5 23.8 2.0 0.9 2.9 31.3 II/1 Oi 0–3 7.5YR 5/2 3.4 326 10.9 29.8 6.9 5.6 12.5 44.8 Oe 3–5 7.5YR 5/0 2.6 304 18.0 16.9 17.0 4.3 21.3 20.0 Oa 5–9 7.5YR 4/0 2.9 161 9.2 17.6 10.8 2.2 13.0 17.1 E9–18 7.5YR 7/0 2.8 21 1.2 17.0 2.2 1.4 3.6 38.4 Bh 18–31 7.5YR 3/0 3.4 75 4.3 17.4 2.5 1.2 3.7 33.0 Bs 31–58 7.5YR 4/4 3.5 43 1.8 24.7 8.1 1.1 9.2 11.5 C >58 7.5YR 5/6 4.0 16 0.7 23.0 3.8 1.1 4.9 22.4 II/2 Oi 0–2 7.5YR 5/2 3.0 334 21.5 15.5 12.0 5.5 17.5 31.3 Oe 2–4 7.5YR 5/0 2.7 312 16.1 19.4 24.7 2.8 27.5 10.2 Oa 4–8 7.5YR 4/0 3.2 247 11.4 21.6 23.8 2.0 25.8 7.8 E8–15 7.5YR 7/0 3.2 27 1.3 21.1 3.9 1.3 5.2 25.1 Bh 15–25 7.5YR 3/0 3.4 36 2.5 14.3 7.6 1.2 8.7 13.3 Bs 25–48 7.5YR 4/4 4.0 39 1.3 29.7 4.7 1.0 5.7 17.7 C >48 7.5YR 5/6 4.0 12 0.4 26.4 2.3 1.1 3.4 33.0 the samples of organic horizons were ashed in an oven prior to available species of metals, without further steps of fractionation. acid dissolution in nitric acid. The concentrations of Cu and Zn in All extractions were carried out in duplicates, of which the mean the digests were determined by AAS and the concentrations of values are reported in tables and diagrams. Pb by optical emission spectroscopy (OES-ICP). Two certified reference materials, NIST RSM 2711 (Montana Soil) and RSM 2709 (San Joaquin Soil), were used for analytical validation. 3 Results and discussion The sequential extraction procedure according to the method by Zeien and Bruemmer (1989) was applied to determine seven All soils examined in this study represented shallow operationally defined fractions of metals: mobile (F1), exchange- mountain soils derived from granite, with properties typ- able and specifically sorbed (F2), occluded in Mn oxides (F3), ical for Haplic Podzols (Fig. 4) (WRB IUSS Working organically bound (F4), occluded in amorphous Fe oxides (F5), Group 2014). They contained considerable amounts of occluded in crystalline Fe oxides (F6), and residual (F7). A brief gravel (over 50% in the mineral part of the profile), which summary of the procedure is given in Table 1. Concentrations of tended to increase as progressing downward through the Cu and Zn in soil extracts were determined by AAS and concen- soil profile; up to 90% is in a parent rock (C horizon). trations of Pb by OES-ICP. In the samples of ectohumus, built Soil earthy fractions indicated a sandy loam texture and mainly of organic matter, the procedure was simplified so that differed slightly among horizons. All of the soil properties only the F1 and F2 fractions were isolated to determine the most were found to be strongly influenced by a podzolization J Soils Sediments process (Table 2). The soils indicated strongly acidic re- predominantly natural origin of the Cu in these soils action through all horizons, and the lowest pH values (Karczewska 1996). However, a profile distribution of Cu in (pH 2.0–2.7) were found in the Oe horizons, which is soils indicated significant enrichment of surface horizons, typical for humus under conifers, due to the transforma- which can only partly be attributed to natural bioaccumulation tion of organic compounds. Strong soil acidification (Kabata-Pendias 2011; Alloway 2013). The high share of re- should be considered as an important factor of increased sidual Cu fraction (F7), which is similar between areas I and II, bioavailability and toxicity of heavy metals (Huchinson indicates that neither the total nor soluble Cu concentrations and Whilby 1977; Han et al. 2002; Kabata-Pendias affected the status and condition of dwarf pine. Relatively high 2011;Alloway2013). BS of soil material was low concentrations (27–30 mg kg−1)ofCuintheBhhorizonsofthe (Table 2), which is typical for Podzols, particularly in area II soils should be considered as evidence of past conditions mountain soils (Kabala et al. 2011). However, the effec- that most likely facilitated Cu mobilization and leaching, such tive cation sorption capacity (CEC) in the organic hori- as particularly low pH (Tyler 1978) or accelerated decomposi- zons was considerably high, much higher than in mineral tion of organic matter associated with a release of chelating horizons (Table 2), thus indicating a potential for the ac- compounds (Alloway 2013; Karczewska et al. 2013). cumulation of heavy metals. The total concentrations of Pb in the organic horizons The total concentrations of Cu in the soils varied between reached a maximum of 315 mg kg−1 and were clearly higher 5.54 and 32.0 mg kg−1 and did not differ from natural concen- than in similar horizons of European lowland forest or mead- trations of Cu in European forest soils developed from granitic ow soils (Kabata-Pendias 2011; Kabata-Pendias and Szteke rocks (Kabata-Pendias and Szteke 2015). The Cu distribution 2015), in which they rarely exceed 50 mg kg−1.Particularly indicated small variations through the soil profiles (Table 3). high Pb concentrations, over 265 mg kg−1, were found in Oe The highest concentrations of Cu were found in organic hori- horizons of all soil profiles (Table 4). A similar enrichment of zons, as well as in the illuvial Bh horizon, especially in area II. organic top horizons in mountain soils, including the soils of By sequential fractionation of Cu in soils (Fig. 5), we found that Karkonosze Mountains, has been reported by various authors the mobile (F1) and exchangeable (F2) fractions constituted (KabałaandSzerszeń 2002; Szopka et al. 2013). The Pb con- roughly about 10% of the total concentrations of that element, centrations in the ectohumus (Oi, Oe, and Oa) were higher while the residual (F7) fraction of Cu dominated in all mineral than those in lower, mineral parts of the soil profiles but with horizons. This fact might be considered as a proof of a a secondary accumulation of Pb in the Bh horizons (Table 4).

Table 3 Cu fractions sequentially extracted according to the method by Zeien and Brümmer

Profile No. Soil horizon Fractions Total

F1 (mg kg−1)F2(mgkg−1) F3 (mg kg−1)F4(mgkg−1)F5(mgkg−1) F6 (mg kg−1)F7(mgkg−1)

I/1 Oi 1.6 0.8 n.d. n.d. n.d. n.d. n.d. 28.5 Oe 1.2 0.6 n.d. n.d. n.d. n.d. n.d. 32.0 Oa 0.9 0.0 n.d. n.d. n.d. n.d. n.d. 13.6 E 0.0 0.0 1.2 2.2 1.6 0.9 7.8 14.8 Bh 0.0 0.0 0.0 3.1 2.2 0.5 9.0 18.3 Bs 0.0 0.5 0.7 2.9 2.1 0.4 11.8 19.0 C 0.0 0.5 0.9 2.5 2.0 0.9 12.0 28.5 II/2 Oi 1.5 1.1 n.d. n.d. n.d. n.d. n.d. 22.0 Oe 0.8 0.8 n.d. n.d. n.d. n.d. n.d. 19.5 Oa 0.5 0.4 n.d. n.d. n.d. n.d. n.d. 15.0 E 0.0 0.0 0.0 1.3 0.7 0.8 2.8 5.5 Bh 0.0 0.5 0.0 1.5 2.2 0.6 4.8 9.6 Bs 0.0 0.5 0.0 1.5 2.0 0.5 5.4 9.8 C 0.0 0.4 0.0 2.8 1.9 0.7 5.7 11.5 II/1 Oi 1.4 0.5 n.d. n.d. n.d. n.d. n.d. 23.0 Oe 1.0 0.5 n.d. n.d. n.d. n.d. n.d. 27.0 Oa 0.6 0.0 n.d. n.d. 95.8 n.d. n.d. 13.0 E 0.0 0.0 0.7 1.6 0.0 0.0 6.1 8.4 Bh 0.0 0.0 0.7 2.7 0.0 0.0 6.8 10.2 Bs 0.0 0.0 0.7 1.0 0.0 0.0 8.4 10.1 C 0.0 0.0 0.6 2.1 0.0 1.9 13.0 17.5 II/2 Oi 0.8 1.1 n.d. n.d. n.d. n.d. n.d. 27.0 Oe 0.8 1.1 n.d. n.d. n.d. n.d. n.d. 30.0 Oa 0.3 0.8 n.d. n.d. n.d. n.d. n.d. 18.0 E 0.0 0.0 0.0 0.8 0.0 0.0 6.0 6.7 Bh 0.0 0.0 1.3 1.1 0.0 0.0 6.3 8.7 Bs 0.0 0.0 0.9 0.4 0.0 1.7 5.8 8.7 C 0.0 0.0 0.9 0.0 0.0 1.9 10.3 13.1 n.d. not determined J Soils Sediments

This was apparently caused by leaching of organically bound organic matter and is in line with the commonly accepted Pb complexes from the topsoil. The very high concentrations theory that it is chelation by low molecular weight compounds of Pb in organic horizons of all soils examined are undoubt- rather than acidification that determines the high solubility of edly from atmospheric pollution and absorption of airborne anthropogenic Pb in acid forest soils (Tyler 1978;Steinnesand particles rich in Pb, which has already been widely reported Friedland 2006). High shares of the mobile (F1) and poten- and proven (Donisa et al. 2000; Kaste et al. 2006;Steinnesand tially soluble (F2) fractions of Pb in ectohumus, which reach Friedland 2006; Shotyk 2008; Nygard et al. 2012; Tyszka up to 50% in the Oi horizon of the I/1 profile, confirm an et al. 2012). The Karkonosze mountain range was under the anthropogenic origin of the Pb in these soils (Abollino et al. influence of long-distance pollution, mainly from lignite- 2002b;Luetal.2003;Neeletal.2007; Agbenin et al. 2010; based power plants and metal smelters (Grodzińska and Szolnoki and Farsang 2013). Szarek-Łukaszewska 1997; Dore et al. 1999; Godek et al. Comparison of the results obtained from the areas I and II, 2008; Tyszka et al. 2012). The distribution of Pb in the soil with different degradation of dwarf pine stands, indicated that was clearly affected by the podzolization process, so that the there were no apparent differences in total concentrations of eluvial E horizons were apparently impoverished in Pb (14.8– Pb or in their mobile (F1) and easily mobilizable (F2) fractions 38.1 mg kg−1), whereas the upper illuvial horizons Bh were between these two areas. This result indicates that a forest considerably enriched (67.2–94.2 mg kg−1). The sequential dieback should not be attributed to enhanced concentrations fractionation of Pb showed that a predominating part of Pb of Pb in the soil. Then again, possible adverse effects of sol- accumulated in the soils was in the F4 fraction, defined as uble Pb on plants or other biota in ecosystems cannot be def- bound with organic matter (Fig. 6). The organically bound initely excluded, particularly in relation to the past, because fraction (F4) made up 13.2–44.7% of the total Pb in the soil, several ecotoxicological studies set the threshold of Pb and its contributions were particularly high in illuvial Bh ho- ecotoxicity at the level of 70–150 mg kg−1 (Szopka et al. rizons. This effect demonstrates a high affinity of Pb to 2013). Unfortunately, the properties of the soils in the sites

Fig. 5 Percentage of Cu extracted from soils in fractions 1–7 according to the Zeien and Bruemmer (1989) method. The soils were collected either under a dwarf mountain pine without signs of degradation (I/1, I/2) or under dead dwarf pine (II/1, II/2) J Soils Sediments

Table 4 Pb fractions sequentially extracted according to the method by Zeien and Brümmer

Profile No. Soil horizon Fractions Total

F1 (mg kg−1)F2(mgkg−1) F3 (mg kg−1) F4 (mg kg−1)F5(mgkg−1)F6(mgkg−1)F7(mgkg−1)

I/1 Oi 43.0 28.1 n.d. n.d. n.d. n.d. n.d. 142.0 Oe 4.8 3.9 n.d. n.d. n.d. n.d. n.d. 265.5 Oa 38.0 29.6 n.d. n.d. n.d. n.d. n.d. 256.5 E 1.6 4.9 6.8 7.0 3.4 2.0 7.0 32.7 Bh 11.4 15.8 15.3 38.8 5.1 3.4 4.5 94.2 Bs 2.9 3.6 8.5 17.5 5.4 3.2 6.8 47.9 C 4.6 8.6 9.8 17.5 5.1 4.6 6.4 56.6 II/2 Oi 12.4 20.8 n.d. n.d. n.d. n.d. n.d. 142.0 Oe 28.9 24.8 n.d. n.d. n.d. n.d. n.d. 297.0 Oa 6.8 1.3 n.d. n.d. n.d. n.d. n.d. 54.0 E 1.4 5.6 7.5 6.8 4.1 2.7 10.0 38.1 Bh 10.4 12.8 9.3 14.2 8.8 4.6 18.5 78.6 Bs 3.3 3.3 7.0 6.3 7.3 3.6 16.6 47.3 C 2.6 3.4 5.3 6.0 3.3 4.8 10.3 35.6 II/1 Oi 4.3 10.1 n.d. n.d. n.d. n.d. n.d. 145.0 Oe 34.3 27.8 n.d. n.d. n.d. n.d. n.d. 315.0 Oa 24.3 18.9 n.d. n.d. 95.8 n.d. n.d. 160.5 E 0.6 6.2 1.9 3.6 0.9 0.0 1.7 14.8 Bh 3.6 5.7 7.7 33.0 14.1 8.0 1.7 73.9 Bs 0.0 2.0 2.7 11.6 11.6 6.1 1.7 35.6 C 0.0 0.0 0.0 2.2 6.4 4.7 1.9 15.1 II/2 Oi 7.8 18.4 n.d. n.d. n.d. n.d. n.d. 196.5 Oe 20.5 15.4 n.d. n.d. n.d. n.d. n.d. 288.0 Oa 15.5 7.9 n.d. n.d. n.d. n.d. n.d. 178.5 E 0.8 7.3 1.8 5.2 1.4 4.7 1.5 22.5 Bh 6.0 6.7 6.5 23.6 14.5 8.1 1.8 67.2 Bs 0.2 2.9 3.8 17.1 12.2 6.2 1.5 43.8 C 0.1 0.5 0.2 4.4 6.8 6.0 1.9 19.9 n.d. not determined

Fig. 6 Percentage of Pb extracted from soils in fractions 1–7 according to the Zeien and Bruemmer (1989) method. The soils were collected either under a dwarf mountain pine without signs of degradation (I/1, I/2) or under dead dwarf pine (II/1, II/2) J Soils Sediments

Fig. 7 Percentage of Zn extracted from soils in fractions 1–7 according to the Zeien and Bruemmer (1989) method. The soils were collected either under a dwarf mountain pine without signs of degradation (I/1, I/2) or under dead dwarf pine (III/1, II/2) subject to dwarf pine dieback have apparently changed com- This effect must have been caused by a recent succession of pared to past decades, so that present soil properties do not grasses that replaced dead coniferous dwarf pine shrubs provide a basis for an explanation of past phenomena (Drozd et al. 1996). Therefore, it should be stressed that the (Fabiszewski and Wojtuń 2000). present soil concentrations of Zn, a particularly easily mobi- The concentrations of Zn in the soil profiles were in a broad lized element, cannot be used to illustrate Zn solubility and range 24.8–202.4 mg kg−1, with the highest values in the leaching in the past. The sequential extraction of Zn in the deepest parts of soil profiles, namely in C and Bs horizons samples of organic horizons revealed that fractions F1 and (Table 5). The distribution of Zn was apparently influenced by F2 of this element made up a predominating part of total Zn, podzolization, and minimum Zn concentrations were found in up to 66% (Fig. 7). No simple correlations were, however, the eluvial horizons E or in overlying organic horizon Oa. found between the contributions of soluble or potentially sol- Such a distribution clearly indicates an enrichment of the top uble Zn and soil pH (or related concentrations of H+ ions). The soil layers, most likely from atmospheric depositions total concentrations of Zn were low in the top soil horizons, (Steinnes and Friedland 2006), and confirms a high suscepti- and the residual fraction (F7) of Zn and Cu was a bility of Zn to leaching (Tyler 1978; Kabata-Pendias 2011; predominating one in all the mineral parts of soil profiles. Alloway 2013). There were no substantial differences be- Moreover, the absolute concentrations of Zn in the F7 fraction tween the profiles located in the areas with different stages (expressedinmgkg−1) tended to increase progressively of dwarf pine degradation. However, the total concentrations downward through the soil profile, being much higher in the of Zn in the bottom horizons of soils, that were clearly higher C horizon than in the geochemical background in granites. in area II, may have resulted from more intensive leaching in Similar patterns were also reported by Kabała and Szerszeń the past, possibly associated with a higher solubility of Zn. (2002) from Haplic Cambisols. This effect requires closer in- Such a hypothesis cannot be now checked, as at the time of vestigation but might be explained by a mechanical transport soil sampling for the present study, soil pH values in II/1 and of tiny Zn-bearing particles of airborne origin and simulta- II/2 profiles were considerably higher compared to area I. neous leaching of mobile Zn fractions out of the soil profiles. J Soils Sediments

4Conclusions 5. Profile distributions of all metals examined have been influenced by soil properties that developed 1. Very high Pb concentrations in the ectohumus of the during the podzolization processes. It was particular- Karkonosze soils tested here have most likely been caused ly well expressed in the case of Pb, a metal that by a long-distance transport of anthropogenic emissions. strongly accumulated in Bh horizons, predominantly 2. The total concentrations of Cu, Pb, and Zn found in soils in organically bound (F4) fraction that made up cannot be considered as essential factors of the ecological about 40% of total Pb. disaster that affected Karkonosze Mountains. 6. Low concentrations of Cu throughout the soil profiles and 3. This study did not reveal any remarkable differences in the predominance of residual (F7) fraction present in soil the patterns of profile distribution or in the fractionation of mineral horizons support a lithogenic origin of Cu in these Cu, Pb, and Zn between the areas differing in the deteri- soils. oration stage of dwarf pine stands. 7. High contributions of easily mobilizable (F1 and F2) frac- 4. High concentrations of Pb in the ectohumus horizons, as tions of Zn in ectohumus, as well as the prevalence of its well as very high contributions of its organically bound residual (F7) form in deeper mineral horizons, indicate (F4) fraction in mineral horizons, confirm a crucial role of that a considerable part of the Zn pool is subject to organic matter in the processes of Pb accumulation. leaching out of the soil profile.

Table 5 Zn fractions sequentially extracted according to the method by Zeien and Brümmer

Profile No. Soil horizon Fractions Total

F1 (mg kg−1)F2(mgkg−1)F3(mgkg−1)F4(mgkg−1)F5(mgkg−1)F6(mgkg−1) F7 (mg kg−1)

I/1 Oi 36.8 2.1 n.d. n.d. n.d. n.d. n.d. 64.0 Oe 16.4 2.1 n.d. n.d. n.d. n.d. n.d. 86.5 Oa 34.6 1.5 n.d. n.d. n.d. n.d. n.d. 78.0 E 4.8 6.7 4.0 9.1 11.0 7.5 11.4 54.5 Bh 7.8 2.1 3.7 9.0 15.5 7.5 40.1 85.7 Bs 8.1 2.4 4.0 9.6 20.3 6.0 58.1 108.4 C 6.7 2.9 3.0 8.4 22.8 12.0 74.8 130.5 I/2 Oi 7.1 40.3 n.d. n.d. n.d. n.d. n.d. 64.0 Oe 3.4 35.0 n.d. n.d. n.d. n.d. n.d. 80.5 Oa 1.1 16.0 n.d. n.d. n.d. n.d. n.d. 46.0 E 4.1 1.1 1.0 3.6 2.3 5.3 7.5 24.8 Bh 4.8 2.4 2.0 4.1 2.3 15.0 38.0 68.6 Bs 4.5 1.3 1.0 4.1 2.3 4.9 36.5 54.6 C 2.1 1.3 0.5 3.6 3.4 3.8 42.3 56.9 II/1 Oi 4.1 3.6 n.d. n.d. n.d. n.d. n.d. 80.0 Oe 2.5 0.9 n.d. n.d. n.d. n.d. n.d. 81.0 Oa 9.8 0.3 n.d. n.d. 95.8 n.d. n.d. 34.5 E 5.1 3.0 3.4 3.5 4.2 3.9 10.8 33.9 Bh 5.0 0.8 2.0 4.4 6.9 10.2 32.2 61.5 Bs 6.0 1.7 2.8 4.4 8.1 9.7 83.8 116.5 C 4.3 1.8 2.2 2.9 6.9 12.3 172.0 202.4 II/2 Oi 43.0 7.9 n.d. n.d. n.d. n.d. n.d. 76.5 Oe 50.0 3.0 n.d. n.d. n.d. n.d. n.d. 81.0 Oa 20.3 0.8 n.d. n.d. n.d. n.d. n.d. 39.0 E 14.3 6.6 7.0 5.4 4.5 4.7 18.0 60.4 Bh 15.3 8.6 9.3 10.1 9.2 8.1 74.3 134.7 Bs 11.0 5.8 8.0 9.6 9.4 6.2 109.8 159.7 C 9.1 4.4 6.8 6.8 9.0 7.5 119.8 163.3 n.d. not determined J Soils Sediments

Open Access This article is distributed under the terms of the Creative Głowicki B (2005) Klimat Karkonoszy. In: Mierzejewski M (ed) Commons Attribution 4.0 International License (http:// Karkonosze. Przyroda nieo żywiona iczłowiek. Wyd. creativecommons.org/licenses/by/4.0/), which permits unrestricted use, Uniwersytetu Wrocławskiego, Poland, Wrocław distribution, and reproduction in any medium, provided you give appro- Godek M, Migała K, Sobik M (2008) Air pollution and forest disaster in priate credit to the original author(s) and the source, provide a link to the the Western Sudetes in the light of high elevation spruce tree-ring Creative Commons license, and indicate if changes were made. data TRACE - Tree Rings in Archaeology, Climatology and Ecology, Vol. 7: Proceedings of the Dendrosymposium 2008, April 27th – 30th 2008, Zakopane, Poland. 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