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of developed in an ash settling pond at the Be³chatów TPS 49 SCIENCE ANNUAL DOI: 10.2478/ssa-2018-0006 Vol. 69 No. 1/2018: 49–59

£UKASZ UZAROWICZ1*, WOJCIECH KWASOWSKI1, OLGA ŒPIEWAK1, MARCIN ŒWITONIAK2

1 Warsaw University of Life Sciences SGGW, Faculty of and , Department of Soil Environment Sciences, Nowoursynowska Str. 159, building no. 37, 02-776 Warszawa, Poland 2 Nicolaus Copernicus University in Toruñ, Faculty of Sciences, Department of and Landscape Management, Lwowska Str. 1, 87-100 Toruñ, Poland

Indicators of pedogenesis of Technosols developed in an ash settling pond at the Be³chatów thermal power station (central Poland)

Abstract: Technogenic (Technosols) developed in an ash settling pond at the Be³chatów thermal power station, central Poland, were studied in order to identify soil property transformations over 30 years of pedogenesis. Standard pedological methods were applied in order to determine the properties of the studied samples. All investigated soils were classified according to WRB as Spolic Technosols with various supplementary qualifiers (Alcalic/Hypereutric, Arenic/Loamic, Protocalcic, Hyperartefactic, Immisic, Laxic, Ochric, and Protosalic). The studied materials can be arranged into a chronosequence starting from fresh (unweathered) ashes, by young BE1 (age: several months), up to older Technosols BE2 (about 20 years) and BE3 (about 30 years). The studies showed that and soil-forming processes changed properties of ash in soil environment. Fresh ash was characterized by high pH (11.0 – fly ash, 8.7 – bottom ash), low content of carbonates (1.5% in both samples), variable concentrations of TOC (1.2% –1 – fly ash, 6.9% – bottom ash), and very low total nitrogen content (0.04%). Electrical conductivity (ECe) was 2.6 and 2.1 dS·m in fly ash and bottom ash respectively. Young Technosol BE1 had the pH 9.2–10.0, contents of carbonates were in the range 2.4–3.3%, –1 TOC 1.3–1.7%, and total nitrogen less than 0.03%. ECe in young Technosol was in the range 2.7–4.0 dS·m . There was no plant cover present on that soil and no -developed genetic horizons were distinguished in the profile. Finally, old Technosols BE2 and BE3 had lower pH (from 7.9 up to 9.1), and, in general, higher contents of carbonates (from 1.5 to 7.9%) than fresh ash and young Technosol BE1. Old Technosols contained high concentrations of TOC (up to about 38% in Oi horizon) and total nitrogen (up to 0.9%) in the , where O and A horizons developed due to accumulation of . ECe in old Technosols was in the range 0.8–1.5 dS·m–1. All studied ashes and soils were characterized by very low or even absence of total potential acidity. Base cations predominated in the sorption complex of the investigated ash and soils and can be arranged in the following order according to the abundance: Ca>Mg>K>Na. Base saturation (BS) of fresh ashes and Technosols was nearly 100%. The study shows that the first indicators of pedogenesis of the studied technogenic soils within the first 30 years of formation are: (1) changes of consistence of ash material from firm to friable/very friable due to root action, (2) accumulation of soil organic matter in the topsoil and formation of O and A horizons, (3) decrease of pH, (4) formation of pedogenic carbonates in soils and (5) decrease in soil . Key words: Technosols, fly ash, bottom ash, pedogenesis, WRB

INTRODUCTION spontaneous plant succession. The appearance of plant Thermal power stations (TPSs) produce large cover initiates soil formation in the superficial parts quantities of solid wastes from which fly ash and bottom of disposal sites (Tomaszewicz et al. 2017). ash predominate. They are the products of fuel (coal Soil properties and processes of soil formation on or lignite) combustion for the generation of electric ash disposal sites have been studied by Maciak et al. power. The wastes originate because coals and lignites (1976), Zikeli et al. (2002, 2004, 2005), Chudecka contain non-combustible admixtures such as quartz, and Tomaszewicz (2009), Weber et al. (2015), Uza- minerals, carbonates, sulphides, and others rowicz and Zagórski (2015), Tomaszewicz and Chu- (Vassilev and Vassileva 1996) therefore variable decka (2016), Uzarowicz et al. (2017, 2018), and quantities of mineral residues have always been formed Kostiæ et al. (2018). All these studies show that as an effect of fuel combustion. Fly ash and bottom pedogenic processes initiated by natural plant ash are often reused (Ahmaruzzaman 2010). However, succession or reclamation by human lead to the the waste not reused is deposited on land surface in following transformations in the upper layer (from settling ponds or dry landfills where they are subject several to several dozen cm) of soils developed on to weathering (Adriano et al. 1980, Carlson and ash disposal sites: (1) change of morphology of soil, Adriano 1993). After cessation of ash deposition, the (2) accumulation of organic matter, (3) increase in disposal sites are reclaimed or overgrow due to cellulose decomposition constituting an indicator of

* Dr. £. Uzarowicz, [email protected] http://ssa.ptg.sggw.pl/issues/2018/691 50 £UKASZ UZAROWICZ, WOJCIECH KWASOWSKI, OLGA ŒPIEWAK, MARCIN ŒWITONIAK biological soil activity, (4) decrease in ash alkalinity generated in the TPS are deposited in settling ponds and (5) increase in carbonate contents. situated in the close vicinity of the TPS. Despite the growing knowledge about Technosol Previous studies conducted on ash settling ponds pedogenesis developed from TPS ashes further inve- in the vicinity of Be³chatów TPS focused mainly on stigations are still needed. This is because TPSs use and its effect on plants and soil different kind of fuels containing diverse contents of properties (Str¹czyñska and Str¹czyñski 2007, 2008; mineral admixtures. Therefore ashes produced in Str¹czyñska et al. 2009, Pietrzykowski et al. 2010a, TPSs are very heterogeneous materials and their 2010b, 2013, 2015, 2018). However, the development properties can differ from one TPS to another. Ash of soils based on soil chronosequence has not been properties influence the properties of technogenic soil studied until now. The aim of the present study is to developed from ash deposits. Studies in Poland (Ma- characterize the transformations of technogenic soil ciak et al. 1976, Uzarowicz and Zagórski 2015, Uza- (Technosol) properties developed on settling ponds rowicz et al. 2017, 2018) have shown that there are receiving fly ash and bottom ash from the lignite- considerable differences between properties of Tech- firing Be³chatów TPS within 30 years of pedogenesis. nosol developed from ash after combustion of Morphological, physical, and chemical indicators of Carboniferous bituminous coal coming from Upper studied soil pedogenesis are discussed on the basis Silesia Coal Basin (southern Poland) and soil of the obtained results. The results permitted soil clas- properties developed from ash after combustion of sification according to WRB soil system (IUSS Wor- Miocene lignite in the vicinity of the town of Konin king Group WRB 2015). (central Poland). These differences are exhibited among others by different mineral composition, MATERIALS AND METHODS variable contents of CaO in the material, as well as by variable pH of ash and soils developed from them Study area and object (Uzarowicz and Zagórski 2015). However, lignites in Poland are mined not only in Konin region but also The objects of the study were fresh (unweathered) in a few other places (Widera et al. 2016). One of fly ash and bottom ash as well as three soil profiles them is the region of the town of Be³chatów (central developed from ash mixtures. The ashes were taken Poland), where there is a huge open-pit lignite mine. from the Be³chatów TPS (central Poland) combusting This is the greatest open-pit mine in Europe (12 km Miocene lignite immediately after generation. Ashes long, 3 km wide, and about 200 m deep at the deepest were deposited in the settling pond in slurry form, point). Lignite excavated in the mine constitutes i.e. they were mixed with water, transported through a fuel for the Be³chatów TPS located adjacent to the a pipe and sluiced in a pond. Studied soil profiles mine. It is the world’s largest lignite combusting TPS (Fig. 1) were located on the embankment of the with a total maximum power of ~5.47 GW. Ashes

FIGURE 1. Soil profiles subject to study Pedogenesis of Technosols developed in an ash settling pond at the Be³chatów TPS 51 lairetamlioscinagrohtiwdeximdna,liosfo lairetamlioscinagrohtiwdeximdna,liosfo ecafrusehtnodetisoped,sdnopgniltteshsa ecafrusehtnodetisoped,sdnopgniltteshsa lairetamcinagrodesopmocedyletaredoM morfyawanwolblairetamydnasdnaytliS morfyawanwolblairetamydnasdnaytliS nozirohCOmorflairetamehtybdeirub sgnitaocetanobrachsitihwnommoC morflairetamydnassuonohthcotuA dnopgnilttesehtfotnemesabeht serutaefcitsiretcarahcrehtO setagerggano gniylrednu yradnuoB ehthtiw noziroh raelC raelC urbA – – ecnadnubA )cilasotorpodnE,cirhcO,cimaoL,cixaL,cisimmiipE,citc nommoC – laudarG nommoC – laudarG nommoC – laudarG nommoc nommoc nommoc stoorfo ynaM – laudarG ynaM – – yreV elttildesrepsidhtiwniargelgniS elttildesrepsidhtiwniargelgniS elttildesrepsidhtiwniargelgniS elttildesrepsidhtiwniargelgniS yaplawyclrlgAenoN tpurbA – )ytalpylkaew(ykcolbralugnA )cirhcO,cixaL,cisimmiipE,citcafetrarepyH,cirtuerepy skcolbralugna skcolbralugna skcolbralugna skcolbralugna erutcurtslioS )cilasotorpipE,cimaoL,cixaL,citcafetrarepyH,cilaclA aeW ecnetsisnoC ssamliosfo afetrarepyH,cirtuerepyH,ciclacotorP(losonhceTcilopS erutsioM sutats yrD esooL yrD esooL ruoloclioS dleifehtni 1/4dna 1/4dna H,cinerA(losonhceTcilopS (losonhceTcilopS WRB classification of the investigated soils )mc( CA 51–5 1/3RY01 elbairfyreV tsiomylthgilS ykcolbkaeW CA 52–01 1/3RY01 elbairF tsiomylthgilS ykcolbralugnabusk eO 01–3 2/3RY01 erbiF elbairfyreV tsiomylthgilS yreV iOCO 1–0 5–1 N/31YELG enoN elbairfyreV tsiomylthgilS rettilfaeldesopmocedylkaeW weF raelC iOCO 1–0 3–1 N/31YELG enoN elbairfyreV tsiomylthgilS rettilfaeldesopmocedylkaeW enoN raelC 1C 53–51 yrD 1/5RY01 esooL 3C 09–06 3/5RY01 2C 06–53 3/5RY01 C3 08–85 mriF N/41YELG tsiomylthgilS ykcolbralugnA enoN – – C2 85–21 mriF N/31YELG tsiomylthgilS ykcolbralugnA enoN tp C2 07–06 yrD 4/5RY01 esooL niargelgniS yreV C 06–52 yrD 1/5RY01 elbairfyreV C 21–0 mriF N/41YELG tsiomylthgilS eliforP noziroH htpeD 1EB 2EB 3EB ABLE 1. Morphology and T 52 £UKASZ UZAROWICZ, WOJCIECH KWASOWSKI, OLGA ŒPIEWAK, MARCIN ŒWITONIAK

Bagno-Lubieñ settling pond adjacent to the Be³cha- fine earth (< 2 mm) of the samples were determined tów TPS. by means of common pedological methods (Pansu The embankment of the Bagno-Lubieñ settling and Gautheyrou 2006). pond consists of a system of levels in the form of A content of rock fragments (>2 mm) was deter- successive escarpments and flat shelves (Str¹czyñ- mined by dry-sieving. Particle size distribution was ska et al. 2004). The embankment creates eight 4 m determined by means of the Bouyoucos and Casa- wide shelves. The escarpments between the shelves grande areometric method in the Prószyñski modifi- are about 3.5 m high. The lowest level (the basement cation using calgon and gum arabic as dispersing of the embankment) was created in 1980 and is com- agents. Soil textural classes were defined according posed of sandy deposits (autochthonous material to the U.S.D.A. classification ( Division occurring in the basement of the settling pond) Staff 1993). Soil was examined by mixed up in the construction process. In the second collecting 100 cm3 of undisturbed soil samples by construction phase (1985–1989), five levels were for- means of metal cores and weighting the sample after med, and in the third phase (1993–1995) two more drying in 105°C. Particle density was measured by were created. Starting from 1985, escarpments and means of pycnometer method. Total was shelves were formed from ash and furnace slag calculated based on bulk and particle density values. obtained from internal parts of the settling pond. In The pH was analysed potentiometrically in H2O order to protect the settling pond and its embankment and 1 mol·dm–3 KCl based on air-dry fine earth samples against , shelves and escarpments were planted using a soil/solution ratio of 1:2.5. Carbonate with various species of trees and shrubs between contents were determined by means of the Scheibler which grass mixtures were sown. Plantings occurred volumetric method (reagent: 10% w/w HCl). Total successively between 1986–1998 (Str¹czyñska et al. organic carbon (TOC) contents were determined by 2004). the 680°C combustion catalytic oxidation method The investigated profiles can be arranged into using a Shimadzu 5000A TOC analyser. Carbonates a chronosequence as follows (from the youngest to were removed from the samples prior to TOC analyses the oldest) BE1

RESULTS salic. Tephric or Vitric qualifiers expected for studied soils (Zikeli et al. 2005, Uzarowicz et al. 2017) were Morphology and classification of studied soils not used because oxalate forms of Al and Fe, as well as phosphate retention, were not determined during Profile BE1 (age: several months) was developed the present study. from ashes recently deposited on the surface of a settling pond. The material in the profile has no developed Physical properties of ash and soils genetic soil horizon (Table 1, Fig. 1). Layers of different portions of ashes (labelled as C1, C2, and C3) could The studied fresh fly ash had a texture of , be distinguished by slight change of colours in the whereas fresh bottom ash was a (Table 2). All profile. Soil material was massive and uniform and studied soils had a texture of sandy loam or loamy had firm consistence. sand. A layer of autochthonous material in the The morphology of profiles BE2 and BE3 (age: of BE3 (i.e. 2C horizon) had a texture of sand. Cha- ~20 and ~30 years respectively) was apparently trans- racteristic feature of all studied ashes and soils was formed by pedogenesis. Soil material was loosened the occurrence of very low contents of clay fraction in these profiles by thick net of roots (Fig. 1). Moreover, (< 0.002 mm) not exceeding 5% (Table 2). O and A horizons occurred in the topsoil. The typical Investigated soils were characterized by very low feature of both profiles was the occurrence of silty bulk density ranging from 0.69 to 0.93 g⋅cm–3 (Table 2). and sandy material that was blown away from ash Bulk density did not differ much in all studied profiles. settling ponds, deposited on the surface of soil and Total porosity was high (61.4–76.0%). Particle density mixed with organic soil material. Furthermore, whitish was in the range from 2.28 to 3.00 g⋅cm–3 (Table 2). carbonate coatings on aggregates were very common in C horizon of profile BE3 (Table 1). Chemical properties and salinity All studied soils were classified as Spolic Tech- of ashes and soils nosols (IUSS Working Group WRB 2015) with various supplementary qualifiers (Table 1) such as Fresh ashes were alkaline materials having the pH Alcalic/Hypereutric, Arenic/Loamic, Protocalcic, of 11.0 (fly ash) and 8.7 (bottom ash) (Table 3). They Hyperartefactic, Immisic, Laxic, Ochric, and Proto- contained low concentrations of carbonates (1.5% in

TABLE 2. Physical properties of the studied ash and soils

eliforP noziroH htpeD kluB elcitraP latoT kcorfo% snoitcarffoegatnecreP larutxetlioS )mc( ytisned ytisned ytisorop stnemgarf )mmni( ssalc 3– 3– g( ⋅ mc ) g( ⋅ mc ) )%( 50.0–0.2 200.0–50.0 200.0< ).A.D.S.U( hsaylfhserF – – – 0 13 86 1 maoLtliS hsamottobhserF – – – 0.41 39 6 1 dnaS 1EB C 21–0 37.0 03.2 4.86 0 05 54 5 maoLydnaS C2 85–21 27.0 00.3 0.67 0 84 84 4 maoLydnaS C3 08–85 27.0 82.2 6.86 0 94 84 3 maoLydnaS 2EB iO 1–0 – – – – – – – – CO 5–1 – – – 0 94 84 3 maoLydnaS CA 51–5 96.0 35.2 8.27 7.0 97 91 2 dnaSymaoL 1C 53–51 – – – 6.2 77 12 2 dnaSymaoL 2C 06–53 88.0 92.2 4.16 1.1 68 21 2 dnaSymaoL 3C 09–06 39.0 56.2 0.56 2.1 28 61 2 dnaSymaoL 3EB iO 1–0 – – – – – – – – CO 3–1 – – – 0 45 54 1 maoLydnaS eO 01–3 – – – 0 56 33 2 maoLydnaS CA 52–01 07.0 03.2 6.96 4.1 36 33 4 maoLydnaS C 06–52 56.0 24.2 2.37 6.4 86 03 2 maoLydnaS C2 07–06 – – – 1.51 19 5 4 dnaS Explanations: – not determined; 0 – below detection limit. 54 £UKASZ UZAROWICZ, WOJCIECH KWASOWSKI, OLGA ŒPIEWAK, MARCIN ŒWITONIAK both ashes), variable contents of TOC (1.2% – fly Upper Silesia region, southern Poland, as well as ash, 6.9% – bottom ash) related with the residues of lignite ashes from TPSs from Konin region, central unburned lignite, and very low contents of TN (0.03% Poland (Uzarowicz et al. 2017). in both ashes). The C:N ratio was high (33.6 – fly The soils under study are characterized by high ash, 197.2 – bottom ash). Electrical conductivity (ECe) cation exchange capacity (CEC), which is constituted was 2.6 and 2.1 dS·m–1 in fly ash and bottom ash, in major part by exchangeable bases (EB) (Table 4) respectively. where Ca and Mg predominated. Although the samples Profile BE1 indicated pH from 9.2 to 10.0 (Table 3). were washed using deionised water prior to extraction Contents of carbonates were in the range 2.4–3.3%, of EB, the contents of EB were still high. This feature TOC 1.3–1.7%, and TN less than 0.04%. The C:N is likely a result not only of the occurrence of ratio was very high and ranged from 63.3 to 1361.8. exchangeable cations, but also is an effect of partial –1 ECe in profile BE1 was in a range of 2.7–4.0 dS·m . dissolution of the most soluble minerals (e.g. calcium Profiles BE2 and BE3 had the pH from 7.9 to 9.1. sulphates and carbonates) by the extracting solution They contained higher contents of carbonates (from (ammonium chloride). Therefore, on the one hand it 1.5 to 7.9%, 4.3% on average) than fresh ashes and seems that CEC values for the investigated soils can ashes in profile BE1. Profiles BE2 and BE3 had be overestimated while on the other, the results obtained O horizons developed in the topsoil in which TOC in the present study are comparable with the results reached about 38%, whereas contents of TOC in by Zikeli et al. (2004), who studied CEC of soils A horizons of these profiles was in the range 1–2%. derived from lignite ashes in Germany and found that –1 ECe in profiles BE2 and BE3 was in the range 0.8– mean CECpot ranges from 25.1 to 88.8 cmol⋅kg . 1.5 dS·m–1. The results presented herein shows that Technosols developed from lignite ashes from Be³chatów TPS Sorption properties of ashes and soils are different from similar soils developed from lignite ashes from the P¹tnów and Konin TPSs (Uzarowicz The studied ashes and soils were characterized by et al. 2017, 2018). First of all, the former soils are not very low or even absence of total potential acidity so alkaline (pHKCl from 8.0 to 9.4) as the latter Tech- –1 (PA), which was in the range from 0 to 1.2 cmol⋅kg nosols (pHKCl from 8.9 to 12.1). Secondly, common (Table 4). PA was the highest in the oldest Technosol feature of soils developed from lignite ashes from the (profile BE3). Base cations predominated in sorption P¹tnów and Konin TPSs is a strong cementation of complex of the investigated ashes and soils. Calcium ash material due to crystallization of Ca carbonates was the most abundant base cation, followed by the contents of which were up to 82.7% (Uzarowicz et magnesium, potassium, and sodium (Table 4). Cation al. 2017). Such cementation was not observed in Tech- exchange capacity (CEC) was 97.1 cmol⋅kg–1 in fresh nosols studied herein where contents of carbonates were fly ash and 34.7 cmol⋅kg–1 in fresh bottom ash. The from 0.3 to 7.9% (Table 3). Properties similar to those CEC in soils was in the range 18.2–82.7 cmol⋅kg–1. found in Technosols near Be³chatów TPS were typi- Base saturation (BS) of fresh ashes and profile BE1 cal of Technosols developed on ash landfill of the was nearly 100%, whereas in older Technosols (pro- Adamów TPS located near the town of Turek, central files BE2 and BE3) it was slightly lower (from 98.2 Poland (Weber et al. 2015). This shows that there are to 99.1%) (Table 4). strong differences in properties between ashes from different TPS combusting lignite. These differences DISCUSSION depend among other on quality of lignite and contents of admixtures (e.g. chalk, clay) in lignites. Specific features of studied Technosols and comparison of studied Technosols with similar Indicators of pedogenesis in the studied soils developed from lignite ashes in Poland soil sequence

Technosols developed from ashes originated in In the conducted study, it was assumed that analysis TPSs have specific physical properties. For example, of the sequence of samples comprising fresh ashes low bulk density seems to be a typical feature of such generated in the Be³chatów TPS and a chronosequence soils (Weber et al. 2015, Uzarowicz et al. 2017). Another of soils developed from these ashes on settling pond characteristic feature is a very low content of clay can show the directions of transformations of parent ash fraction (< 0.002 mm). This feature was typical of material in soil environment. It seems this assumption the studied soils (Table 2), but was also observed in is correct in case of the investigated samples. The Technosols developed from bituminous coal ashes in present study showed that 30 years of pedogenesis le- Pedogenesis of Technosols developed in an ash settling pond at the Be³chatów TPS 55

TABLE 3. Chemical properties and salinity of the studied ash and soils

eliforP noziroH htpeD Hp Hp OCaCqe 3 COT NT N:C eCE 1– )mc( H( 2 )O )lCK( )%( )%( )%( m·Sd( ) hsaylfhserF 0.11 1.11 5.1 2.1 30.0 33 65.2 hsamottobhserF 7.8 8.8 5.1 9.6 30.0 791 90.2 1EB C 21–0 2.9 4.9 0.3 3.1 20.0 86 30.4 C2 85–21 4.9 9.8 3.3 7.1 30.0 36 89.2 C3 08–85 0.01 3.9 3.2 7.1 0 1631 37.2 2EB iO 1–0 – – – 8.83 09.0 24 – CO 5–1 5.8 5.8 9.7 2.2 61.0 31 23.1 CA 51–5 7.8 5.8 6.2 9.1 90.0 02 84.1 1C 53–51 8.8 0.8 0.4 1.1 10.0 141 98.0 2C 06–53 1.9 4.8 0.2 2.1 10.0 751 38.0 3C 09–06 9.8 1.8 5.1 6.1 10.0 352 80.1 3EB iO 1–0 – – – 1.73 88.0 24 – CO 3–1 9.7 5.8 0.7 9.2 71.0 71 70.1 eO 01–3 0.9 6.8 0.4 4.6 14.0 51 53.1 CA 52–01 9.8 7.8 2.4 3.1 20.0 65 64.1 C 06–52 0.8 5.8 2.5 4.1 40.0 43 87.0 C2 07–06 8.8 9.8 3.0 4.0 10.0 92 12.6 Explanations: – not determined; 0 – below detection limit.

TABLE 4. Sorption properties of the studied ash and soils

eliforP noziroH htpeD AP aC +2 gM +2 K+ aN + BE CEC )%(SB )mc( lomc ⋅ gk 1– hsaylfhserF 0 6.68 1.01 1.0 4.0 1.79 1.79 001 hsamottobhserF 2.0 4.92 5.4 1.0 4.0 5.43 7.43 4.99 1EB C 21–0 0 2.63 5.11 2.0 5.0 4.84 4.84 001 C2 85–21 0 9.43 6.8 2.0 5.0 3.44 3.44 001 C3 08–85 0 6.37 4.8 2.0 5.0 7.28 7.28 001 2EB iO 1–0 – – – – – – – – CO 5–1 6.0 6.75 2.7 8.0 6.0 2.66 8.66 1.99 CA 51–5 6.0 5.74 2.6 8.0 5.0 0.55 6.55 9.89 1C 53–51 6.0 0.05 8.5 3.0 5.0 6.65 2.75 9.89 2C 06–53 6.0 7.13 9.3 1.0 1.0 8.53 4.63 2.89 3C 09–06 6.0 3.63 0.6 3.0 5.0 0.34 5.34 7.89 3EB iO 1–0 – – – – – – – – CO 3–1 6.0 0.26 2.8 0.1 5.0 7.17 3.27 2.99 eO 01–3 2.1 4.54 9.81 5.0 4.0 2.56 4.66 2.89 CA 52–01 6.0 4.64 1.4 3.0 3.0 1.15 7.15 9.89 C 06–52 6.0 2.84 6.5 2.0 1.0 0.45 6.45 8.89 C2 07–06 3.0 3.61 9.0 1.0 4.0 8.71 2.81 3.89 Explanations: – not determined; 0 – below detection limit. ads to the transformation of parent ash material into topsoil and formation of O and A horizons, (3) decrease a soil (Fig. 2). The indicators of these transformations of pH, (4) formation of pedogenic carbonates in soils are as follows: (1) changes of consistence of ash and (5) decrease of soil salinity. material from firm to friable/very friable due to root The study shows that the major soil-forming factor action, (2) accumulation of soil organic matter in the influencing soil formation is the development of 56 £UKASZ UZAROWICZ, WOJCIECH KWASOWSKI, OLGA ŒPIEWAK, MARCIN ŒWITONIAK

FIGURE 2. Changes of soil properties in the investigated soil sequence vegetation. That factor causes the accumulation of The decrease of pH seems to be one of the most plant remnants in the topsoil, which is accompanied important chemical indicators of pedogenesis in Tech- with the formation of organic (O) and (A) nosols developing from ashes from TPSs (Maciak et horizons. Accumulation of soil organic matter is one al. 1976, Zikeli et al. 2002, Uzarowicz et al. 2017). of the first soil-forming processes occurring in initial The study herein shows that 30 years of pedogenesis technogenic soils developed from industrial wastes caused the drop of pH from 9.2–10.0 in young Tech- (e.g. Maciak et al. 1976; Œwitoniak et al. 2011; Uza- nosol (profile BE1) to 7.9–9.1 in old Technosols (pro- rowicz et al. 2017). Moreover, the development of files BE2 and BE3) (Table 3). Initially high pH is roots changes physical properties of parent ash material. related with the formation of Ca and Mg hydroxides After deposition in a settling pond, ash has a firm in the first stage of weathering of ashes in a settling consistence, and after development of plant cover, the pond (Warren and Dudas 1984; Uzarowicz et al. consistence of soil material becomes very friable or 2017). Subsequent decrease of alkalinity is most loose. likely caused by partial of Ca and Mg from Pedogenesis of Technosols developed in an ash settling pond at the Be³chatów TPS 57 soils or transformations of Ca and Mg hydroxides into to soil changes its chemical properties (pH, content carbonates. Moreover, organic acids forming due to of available forms of nutrients, content of soil orga- decomposition of soil organic matter in the topsoil nic matter) (Cieæko et al. 2015). are most likely agents causing the decrease of alkalinity. Another indicator of pedogenesis of the investi- CONCLUSIONS gated Technosols is a formation of pedogenic carbo- nates. Similar conclusion was drawn for another soils The following conclusions can be drawn from the developed from ashes from TPSs (Maciak et al. 1976; obtained results: Zikeli et al. 2002; Uzarowicz et al. 2017). Well-deve- 1. The results indicate that 30 years of pedogenesis loped efflorescences of carbonates were found in changed the original properties of fresh (unweathe- profile BE3 (Table 1, Fig. 2). Carbonates originate red) ashes deposited on land surface. because soil solutions are rich in Ca coming from ash 2. The major morphological and physical indicator 2– weathering. The CO3 ion form most likely due to of pedogenesis of Technosols developed on settling adsorption of CO2 from atmosphere or ponds receiving lignite ashes originated in the Be³- by . Leaching of carbonates from topsoil is chatów TPS is the change of consistence of soil a frequent phenomenon in soils developed from ashes material due to root action. Plant roots mix soil from TPSs (Maciak et al. 1976; Zikeli et al. 2002; material and change initially firm ash material into Uzarowicz et al. 2017). However, this phenomenon a soil having very friable or loose consistence. was not found in the studied Technosols because the 3. The main chemical indicators of pedogenesis of eolian input of ashes that enriched topsoil in carbo- the studied Technosols are (a) the decrease of pH, nates coming from the deposited ash. (b) the increase of contents of total organic carbon Pedogenesis decreases soil salinity. Initially, fresh and total nitrogen in the topsoil due to accumulation ashes are slightly saline (ECe in the range about 2.0– of soil organic matter, (c) formation of pedogenic 2.5 dS·m–1) according to the classification of FAO carbonates as well as (d) a decrease of salinity. (Jackson 1958). After deposition of ashes in a settling pond, they become moderately saline (ECe slightly exceeding the value of 4 dS·m–1) most likely due to ACKNOWLEDGMENTS accumulation of salts from slurry waters. However, Research was funded by the NCN (the Polish the ECe in Technosols after 30 years of pedogenesis drops below the values of 2 dS·m–1, which permits National Science Centre), decision no. DEC-2011/03/ the classification of old Technosols as non-saline D/ST10/04599. The authors would like to thank the reviewers for constructive comments and suggestions. soils (Jackson 1958). 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WskaŸniki pedogenezy w glebach technogenicznych (Technosols) ukszta³towanych na sk³adowisku popio³ów przy Elektrowni Be³chatów

Streszczenie: Badaniami objêto gleby technogeniczne (Technosols) ukszta³towane na sk³adowisku popio³u przy elektrowni Be³- chatów w centralnej Polsce. Celem badañ by³a identyfikacja przemian w³aœciwoœci gleb w ci¹gu 30 lat pedogenezy. Analizom poddano œwie¿e odpady z elektrowni (tj. popió³ lotny i ¿u¿el), a tak¿e materia³y pochodz¹ce z trzech profili glebowych na sk³adowi- sku Bagno-Lubieñ, ró¿ni¹cych siê wiekiem (od kilku miesiêcy do oko³o 30 lat). W celu okreœlenia w³aœciwoœci badanych odpadów i gleb zastosowano standardowe metody u¿ywane w nauce o glebie. Wszystkie badane utwory glebowe zosta³y sklasyfikowane wed³ug WRB jako Spolic Technosols z ró¿nymi kwalifikatorami uzupe³niaj¹cymi (Alcalic/Hypereutric, Arenic/Loamic, Protocalcic, Hyperartefactic, Immisic, Laxic, Ochric i Protosalic). Badane materia³y wystêpowa³y w chronosekwencji pocz¹wszy od œwie¿ych (niezwietrza³ych) odpadów, przez m³ody profil BE1 (wiek: kilka miesiêcy), a¿ do starszych utworów glebowych BE2 (oko³o 20 lat) i BE3 (oko³o 30 lat). Badania wykaza³y, ¿e procesy wietrzeniowe i glebotwórcze zmieni³y w³aœciwoœci materia³u popio³owo-¿u¿lo- wego w œrodowisku glebowym. Œwie¿y popió³ charakteryzowa³ siê wysokim wartoœciami pH (11,0 – popió³ lotny, 8,7 – ¿u¿el), nisk¹ zawartoœci¹ wêglanów (1,5% w obu próbkach), zmienn¹ zawartoœci¹ wêgla organicznego (1,2% – popió³ lotny, 6,9% – ¿u¿el), oraz bardzo nisk¹ ca³kowit¹ zawartoœci¹ azotu ogólnego (do 0,03%). Przewodnoœæ elektryczna (ECe) wynosi³a odpowiednio 2,6 i 2,1 dS·m–1 w popiele lotnym i ¿u¿lu. M³ody profil gleby technogenicznej BE1 mia³ pH 9,2–10,0, zawartoœæ wêglanów mieœci³a siê w przedziale 2,4–3,3%, wêgla organicznego 1,3–1,7%, a zawartoœæ azotu ogólnego wynosi³a <0,04%. Wartoœæ ECe w profilu BE1 mieœci³a siê w przedziale 2,7–4,0 dS·m–1. Profil ten nie by³ pokryty roœlinnoœci¹, nie wystêpowa³y w nim dobrze rozwiniête poziomy genetyczne. Starsze gleby technogeniczne BE2 i BE3 mia³y ni¿sze pH (od 7,9 do 9,1) i generalnie wiêksz¹ zawartoœæ wêglanów (od 1,5 do 7,9%) ni¿ œwie¿e odpady i profil BE1. Profile BE2 i BE3 zawiera³y du¿e iloœci wêgla organicznego (do oko³o 38% w poziomie Oi) i azotu ca³kowitego (do 0,9%) w wierzchniej warstwie gleby, gdzie w wyniku akumulacji materii organicznej ukszta³- –1 towa³y siê poziomy O i A. Wartoœæ ECe w profilach BE2 i BE3 mieœci³a siê w zakresie 0,8–1,5 dS·m . Wszystkie badane odpady i utwory glebowe charakteryzowa³y siê bardzo nisk¹ lub wrêcz brakiem kwasowoœci hydrolitycznej. Kationy zasadowe dominowa³y w kompleksie sorpcyjnym badanych odpadów i gleb. Kationy te mog¹ byæ u³o¿one w nastêpuj¹cej kolejnoœci w zale¿noœci od zawar- toœci: Ca>Mg>K>Na. Stopieñ wysycenia kompleksu sorpcyjnego kationami zasadowymi w badanych odpadach i utworach glebowych wynosi³ prawie 100%. Badania wykaza³y, ¿e pierwszymi wskaŸnikami procesów glebotwórczych w badanych glebach technogenicznych w ci¹gu pierwszych 30 lat pedogenezy s¹: (1) zmiany zwiêz³oœci materia³u popio³owo-¿u¿lowego ze zwiêz³ego na luŸny z powodu dzia³ania korzeni roœlin, (2) akumulacja glebowej materii organicznej w wierzchniej warstwie gleby i tworzenie siê poziomów O i A, (3) spadek pH, (4) powstawanie pedogenicznych wêglanów i (5) spadek zasolenia gleby. S³owa kluczowe: technogeniczne utwory glebowe, popió³ lotny, ¿u¿el, proces glebotwórczy, WRB