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Influence of Redox Processes on Clay Mineral Transformation in Retisols in the Carpathian Foothills in Poland

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Influence of Redox Processes on Clay Mineral Transformation in Retisols in the Carpathian Foothills in Poland J Soils Sediments DOI 10.1007/s11368-016-1531-1 SOILS, SEC 4 • ECOTOXICOLOGY • RESEARCH ARTICLE Influence of redox processes on clay mineral transformation in Retisols in the Carpathian Foothills in Poland. Is a ferrolysis process present? Wojciech Szymański1 & Michał Skiba 2 & Artur Błachowski3 Received: 16 May 2016 /Accepted: 18 August 2016 # The Author(s) 2016. This article is published with open access at Springerlink.com Abstract differences in bleaching (strong, moderate, weak, and lack Purpose Ferrolysis is a soil-forming process, which involves of bleaching) caused by periodic stagnation of water above destruction of clay minerals due to cyclic reduction and oxi- a slowly permeable fragipan and cyclic redox processes are dation in acidic and periodically wet soils. The main objec- the same. The E and Eg horizons are characterized by the tives of this study were as follows: (1) to determine the influ- presence of 2:1 clay minerals with likely organic interlayer ence of redox processes on clay mineral transformation in fillings, dioctahedral mica, kaolinite, and chlorite. Retisols (Albeluvisols) in the Carpathian Foothills in Poland Conclusions The results indicate that (1) redox processes and (2) to verify the occurrence of ferrolysis in Retisols show- occurring in the soils do not affect clay mineral transfor- ing various degrees of bleaching. mation in Retisols of the Carpathian Foothills in Poland Materials and methods Twelve representative soil profiles and (2) ferrolysis is not the main soil-forming process op- were selected for analysis. All were formed entirely from erating in these soils. This is most likely because iron- loess except for two profiles, in which the lowermost ho- bearing minerals are not abundant in the Retisols and/or rizons (2C) had developed from weathered flysch rocks undergo eluviation to the lower part of the soil profiles. residuum. Soil mineral analysis was done using x-ray dif- The lower content of the clay fraction in the E and Eg fraction (XRD), Fourier-transform infrared (FTIR) spec- horizons versus that in the lower soil horizons of the troscopy, and Mössbauer spectroscopy (MS). Retisols is related to clay illuviation (lessivage), and not Results and discussion The obtained results indicate that the to clay decomposition due to ferrolysis. qualitative and quantitative mineral compositions of the clay fraction in the E and Eg horizons obtained from . Retisols in the Carpathian Foothills exhibiting marked Keywords Carpathian Foothills Clay minerals Ferrolysis Redox processes . Retisols . X-ray diffraction Responsible editor: Dong-Mei Zhou 1 Introduction * Wojciech Szymański [email protected] Soils with a contrasting texture are very common around the world (Kemp and McIntosh 1989; Phillips 2001, 2004, 2007; Świtoniak 2008, 2014; Świtoniak et al. 2016). 1 Institute of Geography and Spatial Management, Department of Pedology and Soil Geography, Jagiellonian University, ul. According to the literature, such soils could be the result Gronostajowa 7, 30-387 Kraków, Poland of different geologic and/or pedologic processes including 2 Institute of Geological Sciences, Department of Mineralogy, sedimentation of different parent material (Phillips 2007; Petrology and Geochemistry, Jagiellonian University, ul. Oleandry Świtoniak 2008, 2014; Świtoniak et al. 2016); clay 2a, 30-063 Kraków, Poland eluviation-illuviation (Van Ranst and De Coninck 2002; 3 Institute of Physics, Department of Mössbauer Spectroscopy, Boivin et al. 2004; Świtoniak 2008, 2014; Świtoniak Pedagogical University, ul. Podchorążych 2, 30-084 Kraków, Poland et al. 2016); bioturbation (Leigh 1998; Peacock and Fant J Soils Sediments 2002; Phillips 2007); and ferrolysis (Brinkman 1970, color pattern from Western Europe and in Planosols from 1977, 1979; Brinkman et al. 1973). Ethiopia. Ferrolysis is a soil-forming process, which was first pro- Despite the fact that the redox processes are very com- posedbyBrinkman(1970). It involves destruction of clay mon in various soils (Retisols, Stagnosols, Planosols, minerals due to cyclic reduction and oxidation in acidic Gleysols, Fluvisols, paddy soils), very few is known about and periodically wet soils (Brinkman 1970;Barbiero their impact on soil minerals and especially on clay min- et al. 2010). Ferrolysis involves biochemical reduction of erals. In addition, very little studies present the results of Fe3+ taking place during wet seasons and leading to mobi- qualitative and quantitative mineral composition of hydro- lization of Fe and substitution of exchangeable cations morphic soils in the context of their genesis. Due to within clay minerals with Fe2+. During dry periods, Fe2+ the above-mentioned contrasting results and reports oxidizes forming ferric hydroxides and protons which at- concerning ferrolysis process in soil environment and still tacks structures of clay minerals. Thus, cyclic reduction lacking of sufficient detailed mineralogical data from hy- and oxidation may cause decomposition of clay minerals dromorphic soils, we have decided to fill this gap. leading to release of the lattice cations (e.g., Al, Mg, Fe). The main objectives of this study were the following: (1) to Except for the dissolution, soil clay minerals may undergo determine the influence of redox processes on clay mineral transformation due to the formation of Al- and/or Fe- transformation in Retisols (Albeluvisols) in the Carpathian hydroxy polymers within the interlayer space (Rich 1968; Foothills in Poland and (2) to verify the occurrence of Brinkman 1970, 1977;GerstlandBanin1980). The trans- ferrolysis in Retisols showing various degrees of bleaching formation of 2:1 clay minerals due to the cyclic reduction by means of qualitative and quantitative mineralogical and oxidation and formation of the clays with interlayer analyses. fillings is responsible for lowering their cation exchange capacity, mineral solubility, and swelling ability (Rich 1968;Brinkman1979; Nakao et al. 2009;Szymański et al. 2014). 2 Materials and methods Ferrolysis is a common process in seasonally wet and acidic soils containing a hardly permeable horizon such as 2.1 Study area a plughpan (Brinkman 1977) and duripan (Hobson and Dahlgren 1998). Ferrolysis may also occur in soils with a The present study was carried out in the Carpathian Foothills fragipan. Fragipan shows low permeability which may lead in southern Poland (Fig. 1). The region is formed of a thick to periodic water stagnation causing seasonal anaerobic mantle of non-calcareous loess, which covers interbedded conditions which favor reduction of iron oxides and their layers of sandstone, siltstone, and shale of turbiditic origin subsequent translocation and oxidation. Thus, it is very (i.e., Carpathian flysch). According to Klimaszewski (1967), likely that ferrolysis may take place in Retisols containing the loess was transported on a short distance and accumulated a fragipan, because of the high bulk density and low po- during the last phase of glaciation (Vistulian) in the rosity of the pan (e.g., Witty and Knox 1989;Lindboetal. Pleistocene. The studied area is characterized by hilly relief 1994;Ciolkoszetal.1995;Szymańskietal.2011). The with wide and flat hills showing elevation between 300 and seasonal stagnation of water within Retisols causes the 500 m a.s.l. (Starkel 1972). A moderately humid climate with bleaching of soil material indicating reduction and disso- mean annual air temperature between 6 and 8 °C and total lution of iron oxides and their subsequent re-oxidation and annual precipitation from 700 to 900 mm (Hess 1965)aswell immobilization in the form of iron nodules, concretions, as a lack of carbonates in the loess cover serve as the main soft masses, and pore linings (Cescas et al. 1970; reasons for the prevalence of Luvisols and Retisols (which Schwertmann and Fanning 1976;Rhotonetal.1993; until recently were called Albeluvisols) across the Zhang and Karathanasis 1997; Lindbo et al. 2000;Dixon Carpathian Foothills (Skiba and Drewnik 2003; Szymański and White 2002;Szymański et al. 2011, 2012, 2014; et al. 2011, 2012). The vegetation of the study area can be Szymański and Skiba 2013). Similar changes in the va- characterized by a mosaic of broadleaf forests (Tilio- lence of iron may occur within the structures of clay min- Carpinetum) showing a prevalence of hornbeam (Carpinus erals containing iron in the octahedral sheet (e.g., Rich betulus L.), lime (Tilia cordata Mill.), oak (Quercus sessilis 1968;Brinkman1977; Rozenson and Heller-Kallai 1978; Ehrh. and Quercus robur L.), and beech (Fagus sylvatica L.) Gerstl and Banin 1980; Hardy et al. 1999; Kohut and as well as arable land, with potatoes (Solanum tuberosum L.), Warren 2002). However, Van Ranst and De Coninck wheat (Triticum aestivum L.), and rye (Secale cereale)being (2002)aswellasVanRanstetal.(2011) have recently the most popular crops. In some places, mixed forests (Pino- reported that ferrolysis does not take place in Retisols (pre- Quercetum)withoak(Q. robur L.) and pine (Pinus silvestris viously called Albeluvisols) and soils exhibiting a stagnic L.) are also present (Towpasz and Zemanek 1995). J Soils Sediments Fig. 1 Location of the soil profiles and occurrence of Luvisols and Retisols in the Polish part of the Carpathians (based on Skiba and Drewnik 2003) 2.2 Methods absorption spectrometry (AAS) (Schlichting and Blume 1966). Amorphous forms of iron and aluminum (Feo,Alo, Twelve representative soil profiles were selected for analysis. respectively) were extracted with acid ammonium
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